Size-Selective Ionic Crosslinking Provides Stretchable Mixed Ionic-Electronic Conductors.

Mechanically compliant conductors are of utmost importance for the emerging fields of soft electronics and robotics. However, the development of intrinsically deformable organic conductors remains a challenge due to the trade-off between mechanical performance and charge mobility. In this study, we report a solution to this issue based on size-selective ionic crosslinking. This rationally designed crosslinking mediated by length-regulated oligo(ethylene glycol) pendant groups and metal ions simultaneously improved the softness and toughness and ensured excellent mixed ionic-electronic conductivity in poly(3,4-ethylenedioxythiophene):polystyrene sulfonate composite materials. Moreover, the added ions remarkably promoted accumulation of charge carriers in response to temperature gradient, thus offering a viable approach to stretchable thermoelectric generators with enhanced stability against humidity.

Dual Buffering Inverse Design of Three-Dimensional Graphene-Supported Sn-TiO2 Anodes for Durable Lithium-Ion Batteries.

Stable battery operation involving high-capacity electrode materials such as tin (Sn) has been plagued by dimensional instability-driven battery degradation despite the potentially accessible high energy density of batteries. Rational design of Sn-based electrodes inevitably requires buffering or passivation layers mostly in a multi-stacked manner with sufficient void inside the shells. However, undesirable void engineering incurs energy loss and shell fracture during the strong calendaring process. Here, this study reports an inverse design of freestanding 3D graphene electrodes sequentially passivated by capacity-contributing Sn and protective/buffering TiO2 . Monodisperse polymer bead templates coated with inner TiO2 and outer SnO2 layers generate regular macropores and 3D interconnected graphene framework while the inner TiO2 shell turns inside out to fully passivate the surface of Sn nanoparticles during the thermal annealing process. The prepared 3D freestanding electrodes are simultaneously buffered by electronically conductive and flexible graphene support and ion-permeable/mechanically stable TiO2 nanoshells, thus greatly extending the cycle life of batteries more than 5000 cycles at 5 C with a reversible capacity of ≈520 mAh g-1 with a high volumetric energy density.

Toughening Self-Healing Elastomers with Chain Mobility.

Enhancing fracture toughness and self-healing within soft elastomers is crucial to prolonging the operational lifetimes of soft devices. Herein, it is revealed that tuning the polymer chain mobilities of carboxylated-functionalized polyurethane through incorporating plasticizers or thermal treatment can enhance these properties. Self-healing is promoted as polymer chains gain greater mobility toward the broken interface to reassociate their bonds. Raising the temperature from 80 to 120 °C, the recovered work of fracture is increased from 2.86 to 123.7 MJ m-3. Improved fracture toughness is realized through two effects. First, strong carboxyl hydrogen bonds dissipate large energies when broken. Second, chain mobilities enable the redistribution of localized stress concentrations to allow crack blunting, enlarging the size of dissipation zones. At optimal conditions of plasticizers (3 wt.%) or temperature (40 °C) to promote chain mobilities, fracture toughness improves from 16.3 to 19.9 and 25.6 kJ m-2, respectively. Insights of fracture properties at healed soft interfaces are revealed through double cantilever beam tests. These measurements indicate that fracture mechanics play a critical role in delaying complete failure at partial self-healing. By imparting optimal polymer chain mobilities within tough and self-healing elastomers, effective prevention against damage and better recovery are realized.

The Role of 3D Printing Technologies in Soft Grippers.

Soft grippers are essential for precise and gentle handling of delicate, fragile, and easy-to-break objects, such as glassware, electronic components, food items, and biological samples, without causing any damage or deformation. This is especially important in industries such as healthcare, manufacturing, agriculture, food handling, and biomedical, where accuracy, safety, and preservation of the objects being handled are critical. This article reviews the use of 3D printing technologies in soft grippers, including those made of functional materials, nonfunctional materials, and those with sensors. 3D printing processes that can be used to fabricate each class of soft grippers are discussed. Available 3D printing technologies that are often used in soft grippers are primarily extrusion-based printing (fused deposition modeling and direct ink writing), jet-based printing (polymer jet), and immersion printing (stereolithography and digital light processing). The materials selected for fabricating soft grippers include thermoplastic polymers, UV-curable polymers, polymer gels, soft conductive composites, and hydrogels. It is conclude that 3D printing technologies revolutionize the way soft grippers are being fabricated, expanding their application domains and reducing the difficulties in customization, fabrication, and production.

Effective Surface Modification of 2D MXene toward Thermal Energy Conversion and Management.

Thermal energy management is a crucial aspect of many research developments, such as hybrid and soft electronics, aerospace, and electric vehicles. The selection of materials is of critical importance in these applications to manage thermal energy effectively. From this perspective, MXene, a new type of 2D material, has attracted considerable attention in thermal energy management, including thermal conduction and conversion, owing to its unique electrical and thermal properties. However, tailored surface modification of 2D MXenes is required to meet the application requirements or overcome specific limitations. Herein, a comprehensive review of surface modification of 2D MXenes for thermal energy management is discussed. First, this work discusses the current progress in the surface modification of 2D MXenes, including termination with functional groups, small-molecule organic compound functionalization, and polymer modification and composites. Subsequently, an in situ analysis of surface-modified 2D MXenes is presented. This is followed by an overview of the recent progress in the thermal energy management of 2D MXenes and their composites, such as Joule heating, heat dissipation, thermoelectric energy conversion, and photothermal conversion. Finally, some challenges facing the application of 2D MXenes are discussed, and an outlook on surface-modified 2D MXenes is provided.

Photothermal modulated dielectric elastomer actuator for resilient soft robots.

Soft robots need to be resilient to extend their operation under unpredictable environments. While utilizing elastomers that are tough and healable is promising to achieve this, mechanical enhancements often lead to higher stiffness that deteriorates actuation strains. This work introduces liquid metal nanoparticles into carboxyl polyurethane elastomer to sensitize a dielectric elastomer actuator (DEA) with responsiveness to electric fields and NIR light. The nanocomposite can be healed under NIR illumination to retain high toughness (55 MJ m-3) and can be recycled at lower temperatures and shorter durations due to nanoparticle-elastomer interactions that minimize energy barriers. During co-stimulation, photothermal effects modulate the elastomer moduli to lower driving electric fields of DEAs. Bilayer configurations display synergistic actuation under co-stimulation to improve energy densities, and enable a DEA crawler to achieve longer strides. This work paves the way for a generation of soft robots that achieves both resilience and high actuation performance.

Surface modification of liquid metal as an effective approach for deformable electronics and energy devices.

The fields of flexible or stretchable electronics and energy devices, reconfigurable and compliant soft robotics, wearable e-textiles or health-care devices have paid significant attention to the need of deformable conductive electrodes due to its critical role in device performances. Gallium-based liquid metals, such as the eutectic gallium-indium (EGaIn) being an electrically conductive liquid phase at room temperature, have attracted immense interests as a promising candidate for deformable conductor. However, in the case of bulk liquid metal, there are several limitations such as the need of encapsulation, dispersion in a polymer matrix, or accurate patterning. For these reasons, the preparation of liquid metal particles in harnessing the properties in a non-bulk form and surface modification is crucial for the success of incorporating liquid metal into functional devices. Herein, we discuss the current progress in chemical surface modification and interfacial manipulations of liquid metal particles. The physical and chemical properties of the surface modification-assisted liquid metal polymer composite are also reviewed. Lastly, the applications of the surface-modified liquid metal particles such as flexible electrode, soft robotics, energy storage or harvester, thermal conductor, dielectric sensor, and bioelectronics are discussed, and the corresponding perspectives of deformable electronics and energy devices are provided. In particular, we focus on the functionalization method or requirement of liquid metal particles in each application. The challenging issues and outlook on the applications of surface-modified liquid metal particles are also discussed.

Continuous Tuning of the Fermi Level in Disorder-Engineered Amorphous Films of Li-Doped ZnO for Thermoelectric Applications.

Amorphous metal-oxide semiconductors can be readily prepared by a solution process at low temperatures, and their energy band structures and carrier concentrations can be controlled based on the oxide composition or the addition of dopants in the design of thermoelectric (TE) materials. However, research on the correlation between the charge transport and TE performance of amorphous metal-oxide semiconductors is still in its infancy. Herein, we present the energy-dependent TE performance characteristics of Li-doped ZnO thin films with different doping levels and charge carrier concentrations. Thin films were prepared by the solution process, and the Li doping level was controlled by the Li precursor concentration added to a Zn precursor solution. Subsequently, a field-effect-modulated Seebeck coefficient measurement device was built to study the energy-dependent TE performance. Notably, the higher ratio of interstitial Li (Liinter) and oxygen vacancies (Ova) in the Li-ZnO device indicates an improved n-type TE performance. To investigate more thoroughly the charge transport phenomena, the localized density of states (DOS) was derived from the temperature-dependent transfer curve; the higher ratio of interstitial Li (Liinter) and oxygen vacancy (Ova) induces a reduction in the localized DOS and lowers the degree of disorder in their DOS. The determined energy-dependent TE characteristics can be used as guidance for the design of efficient TE devices with amorphous metal-oxide semiconductors.

Simultaneous Nitrogen Doping and Pore Generation in Thermo-Insulating Graphene Films via Colloidal Templating.

We report a simple method for preparing highly efficient thermoelectric materials through the fabrication of nitrogen-doped reduced graphene oxide (GO) with a porous structure. The samples were produced by thermal annealing of GO/nitrogen-rich polystyrene (N-PS) particle composite films using a colloidal templating method. N-PS particles served as a nitrogen dopant source for the nitrogen-doped thermally reduced graphene oxide (TrGO) as well as sacrificial particles for the porous structure. The S values of the porous TrGO films were negative, indicating that the samples were transformed into n-type materials. Their porous structures simultaneously resulted in materials with high σ values and low in-plane κ values by providing numerous air cavities for phonon scattering and destruction of the anisotropic structure, maintaining an interconnected structure for an electron transport path. Thus, the porous TrGO films exhibited enhanced power factors and low κ values. The highest ZT value of 1.39 × 10-4 was attained for a porous TrGO film annealed at 1100 °C, which was 1200 times higher than that of a nonporous TrGO film. This study emphasizes that an isotropic orientation of two-dimensional materials has a significant effect on the suppression of in-plane κ, leading to their enhanced thermoelectric performance.