In recent years, tremendous research effort has been aimed at increasing the energy density of supercapacitors without sacrificing high power capability so that they reach the levels achieved in batteries and at lowering fabrication costs For this purpose, two important problems have to be solved: first, it is critical to develop ways to design high performance electrode materials for supercapacitors; second, it is necessary to achieve controllably assembled supercapacitor types (such as symmetric capacitors including double-layer and pseudo-capacitors, asymmetric capacitors, and Li-ion capacitors) The explosive growth of research in this field makes this review timely Recent progress in the research and development of high performance electrode materials and high-energy supercapacitors is summarized Several key issues for improving the energy densities of supercapacitors and some mutual relationships among various effecting parameters are reviewed, and challenges and perspectives in this exciting field are also discussed This provides fundamental insight into supercapacitors and offers an important guideline for future design of advanced next-generation supercapacitors for industrial and consumer applications

Recent Advances in Design and Fabrication of Electrochemical Supercapacitors with High Energy Densities

BACKGROUND Hydrogels are formed through the cross-linking of hydrophilic polymer chains within an aqueous microenvironment. The gelation can be achieved through a variety of mechanisms, spanning physical entanglement of polymer chains, electrostatic interactions, and covalent chemical cross-linking. The water-rich nature of hydrogels makes them broadly applicable to many areas, including tissue engineering, drug delivery, soft electronics, and actuators. Conventional hydrogels usually possess limited mechanical strength and are prone to permanent breakage. The lack of desired dynamic cues and structural complexity within the hydrogels has further limited their functions. Broadened applications of hydrogels, however, require advanced engineering of parameters such as mechanics and spatiotemporal presentation of active or bioactive moieties, as well as manipulation of multiscale shape, structure, and architecture. ADVANCES Hydrogels with substantially improved physicochemical properties have been enabled by rational design at the molecular level and control over multiscale architecture. For example, formulations that combine permanent polymer networks with reversibly bonding chains for energy dissipation show strong toughness and stretchability. Similar strategies may also substantially enhance the bonding affinity of hydrogels at interfaces with solids by covalently anchoring the polymer networks of tough hydrogels onto solid surfaces. Shear-thinning hydrogels that feature reversible bonds impart a fluidic nature upon application of shear forces and return back to their gel states once the forces are released. Self-healing hydrogels based on nanomaterial hybridization, electrostatic interactions, and slide-ring configurations exhibit excellent abilities in spontaneously healing themselves after damages. Additionally, harnessing techniques that can dynamically and precisely configure hydrogels have resulted in flexibility to regulate their architecture, activity, and functionality. Dynamic modulations of polymer chain physics and chemistry can lead to temporal alteration of hydrogel structures in a programmed manner. Three-dimensional printing enables architectural control of hydrogels at high precision, with a potential to further integrate elements that enable change of hydrogel configurations along prescribed paths. OUTLOOK We envision the continuation of innovation in new bioorthogonal chemistries for making hydrogels, enabling their fabrication in the presence of biological species without impairing cellular or biomolecule functions. We also foresee opportunities in the further development of more sophisticated fabrication methods that allow better-controlled hydrogel architecture across multiple length scales. In addition, technologies that precisely regulate the physicochemical properties of hydrogels in spatiotemporally controlled manners are crucial in controlling their dynamics, such as degradation and dynamic presentation of biomolecules. We believe that the fabrication of hydrogels should be coupled with end applications in a feedback loop in order to achieve optimal designs through iterations. In the end, it is the combination of multiscale constituents and complementary strategies that will enable new applications of this important class of materials.

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Advances in engineering hydrogels

Wearable biosensors are garnering substantial interest due to their potential to provide continuous, real-time physiological information via dynamic, noninvasive measurements of biochemical markers in biofluids, such as sweat, tears, saliva and interstitial fluid. Recent developments have focused on electrochemical and optical biosensors, together with advances in the noninvasive monitoring of biomarkers including metabolites, bacteria and hormones. A combination of multiplexed biosensing, microfluidic sampling and transport systems have been integrated, miniaturized and combined with flexible materials for improved wearability and ease of operation. Although wearable biosensors hold promise, a better understanding of the correlations between analyte concentrations in the blood and noninvasive biofluids is needed to improve reliability. An expanded set of on-body bioaffinity assays and more sensing strategies are needed to make more biomarkers accessible to monitoring. Large-cohort validation studies of wearable biosensor performance will be needed to underpin clinical acceptance. Accurate and reliable real-time sensing of physiological information using wearable biosensor technologies would have a broad impact on our daily lives.

Wearable biosensors for healthcare monitoring.

Skin-like electronics that can adhere seamlessly to human skin or within the body are highly desirable for applications such as health monitoring, medical treatment, medical implants and biological studies, and for technologies that include human-machine interfaces, soft robotics and augmented reality. Rendering such electronics soft and stretchable-like human skin-would make them more comfortable to wear, and, through increased contact area, would greatly enhance the fidelity of signals acquired from the skin. Structural engineering of rigid inorganic and organic devices has enabled circuit-level stretchability, but this requires sophisticated fabrication techniques and usually suffers from reduced densities of devices within an array. We reasoned that the desired parameters, such as higher mechanical deformability and robustness, improved skin compatibility and higher device density, could be provided by using intrinsically stretchable polymer materials instead. However, the production of intrinsically stretchable materials and devices is still largely in its infancy: such materials have been reported, but functional, intrinsically stretchable electronics have yet to be demonstrated owing to the lack of a scalable fabrication technology. Here we describe a fabrication process that enables high yield and uniformity from a variety of intrinsically stretchable electronic polymers. We demonstrate an intrinsically stretchable polymer transistor array with an unprecedented device density of 347 transistors per square centimetre. The transistors have an average charge-carrier mobility comparable to that of amorphous silicon, varying only slightly (within one order of magnitude) when subjected to 100 per cent strain for 1,000 cycles, without current-voltage hysteresis. Our transistor arrays thus constitute intrinsically stretchable skin electronics, and include an active matrix for sensory arrays, as well as analogue and digital circuit elements. Our process offers a general platform for incorporating other intrinsically stretchable polymer materials, enabling the fabrication of next-generation stretchable skin electronic devices.

Skin electronics from scalable fabrication of an intrinsically stretchable transistor array.

Plastic bioelectronics is a research field that takes advantage of the inherent properties of polymers and soft organic electronics for applications at the interface of biology and electronics. The resulting electronic materials and devices are soft, stretchable and mechanically conformable, which are important qualities for interacting with biological systems in both wearable and implantable devices. Work is currently aimed at improving these devices with a view to making the electronic-biological interface as seamless as possible.

The rise of plastic bioelectronics

The use of poly(3,4-ethylenedioxythiophene):poly(styrenesulfonate) (PEDOT:PSS) in electrodes and electrical circuits presents a number of challenges that are yet to be overcome, foremost amongst which are its relatively low conductivity, low coatability on hydrophobic substrates, and decreased conductivity at large strains. With this in mind, this study suggests a simple way to simultaneously address all of these issues through the addition of a small amount of a nonionic surfactant (Triton X-100) to commercial PEDOT:PSS solutions. This surfactant is shown to considerably reduce the surface tension of the PEDOT:PSS solution, thus permitting conformal coatings of PEDOT:PSS thin film on a diverse range of hydrophobic substrates. Furthermore, this surfactant induces the formation of PEDOT nanofibrils during coating, which led to the high conductivity values and mechanical stability at large strains (e=10.3%). Taking advantage of the superior characteristics of these PEDOT:PSS thin films, a highly flexible polymer solar cell was fabricated. The power conversion efficiency of this solar cell (3.14% at zero strain) was preserved at large strains (e=7.0%).

Effect of PEDOT Nanofibril Networks on the Conductivity, Flexibility, and Coatability of PEDOT:PSS Films.

The promise of wearable and implantable devices has made stretchable organic semiconductors highly desirable. Though there are increasing attempts to design intrinsically stretchable conjugated polymers, their performance in terms of charge carrier mobility and maximum fracture strain is still lacking behind extrinsic approaches (i.e., buckling, Kirigami interconnects). Here, polymer crosslinking with flexible oligomers is applied as a strategy to reduce the tensile modulus and improve fracture strain, as well as fatigue resistance for a high mobility diketopyrrolopyrrole polymer. These polymers are crosslinked with siloxane oligomers to give stretchable films stable up to a strain e = 150% and 500 strain-and-release cycles of 100% strain without the formation of nanocracks. Organic field-effect transistors are prepared to assess the electrical properties of the crosslinked film under cyclic strain loading. An initial average mobility (μavg) of 0.66 cm2 V−1 s−1 is measured at 0% strain. A steady μavg above 0.40 cm2 V−1 s−1 is obtained in the direction perpendicular to the strain direction after 500 strain-and-release cycles of 20% strain. The μavg in the direction parallel to strain, however, is compromised due to the formation of wrinkles.

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Inducing Elasticity through Oligo‐Siloxane Crosslinks for Intrinsically Stretchable Semiconducting Polymers

In spite of the recent successes in transistors and solar cells utilizing poly(3-hexylthiophene) (P3HT) nanofibrils, systematic analysis on the growth kinetics has not been reported due to the lack of analytical tools. This study proposed a simple spectroscopic method to obtain the crystallinity of P3HT in solutions. On the basis of the analytical approach, we found that the crystallinity hysteresis upon temperature is a simple function of the solubility parameter difference (Δδ) between the P3HT and the solvents. When Δδ ≥ 0.7, a cooling (−20 °C)-and-heating (25 °C) process allowed the preparation of solutions including 1D crystal seeds dispersed in the solution. Simple coating of the seeded solutions completed the growth of the seeds into long nanofibrils at the early stage of the coating and thereby achieved almost 100% crystallinity in the resulting films without any postannealing process. The existence of PCBM for bulk-heterojunction (BHJ) solar cells did not affect the nucleation and growth of the n...

Self-Seeded Growth of Poly(3-hexylthiophene) (P3HT) Nanofibrils by a Cycle of Cooling and Heating in Solutions

Lithium-sulfur (Li-S) batteries are experiencing a design shift from a closed structure to an open structure to further improve their performance, expanding the design realm from the development of nanostructured materials for the cathode to the production of functional separators. Rational guidelines for preparing a bifunctional separator with exfoliated MoS2 and CNTs are suggested to deal with two conflicting issues: guaranteeing the electron pathway while strongly trapping polysulfide species. In addition, various exfoliation methods ranging from mechanical to chemical were investigated to identify an adequate method for preparing exfoliated MoS2 based-bifunctional separators. The electrochemical exfoliation method was found to be effective in not only exfoliating high quality MoS2 in terms of the lateral size and number of layers, but also providing a favorable MoS2 phase, 1T metallic MoS2. A bifunctional separator of 1T exfoliated MoS2@CNT in a tandem configuration (layer-by-layer structure)-coated Celgard rather than a hetero-configuration delivered an excellent electrochemical performance of ∼670 mA h g−1 after 500 cycles at a high current density of 1C. In addition, the separator was highly effective in trapping polysulfide species and facilitating electron transfer to the irreversible discharge products. The rational guidelines suggested in this study will be extended to other two-dimensional transition-metal dichalcogenides, and applied to the development of other functional membranes.

Rational design of exfoliated 1T MoS2@CNT-based bifunctional separators for lithium sulfur batteries

We developed a solution-processed indium oxide (In2O3) thin-film transistor (TFT) with a boron-doped peroxo-zirconium (ZrO2:B) dielectric on silicon as well as polyimide substrate at 200 °C, using water as the solvent for the In2O3 precursor. The formation of In2O3 and ZrO2:B films were intensively studied by thermogravimetric differential thermal analysis (TG-DTA), attenuated total reflectance Fourier transform infrared spectroscopy (ATR-FT IR), high-resolution X-ray diffraction (HR-XRD), and X-ray photoelectron spectroscopy (XPS). Boron was selected as a dopant to make a denser ZrO2 film. The ZrO2:B film effectively blocked the leakage current at 200 °C with high breakdown strength. To evaluate the ZrO2:B film as a gate dielectric, we fabricated In2O3 TFTs on the ZrO2:B dielectrics with silicon substrates and annealed the resulting samples at 200 and 250 °C. The resulting mobilities were 1.25 and 39.3 cm(2)/(V s), respectively. Finally, we realized a flexible In2O3 TFT with the ZrO2:B dielectric on a polyimide substrate at 200 °C, and it successfully operated a switching device with a mobility of 4.01 cm(2)/(V s). Our results suggest that aqueous solution-processed In2O3 TFTs on ZrO2:B dielectrics could potentially be used for low-cost, low-temperature, and high-performance flexible devices.

Jin Young Oh

Papers

Effect of PEDOT Nanofibril Networks on the Conductivity, Flexibility, and Coatability of PEDOT:PSS Films.

Inducing Elasticity through Oligo‐Siloxane Crosslinks for Intrinsically Stretchable Semiconducting Polymers

Self-Seeded Growth of Poly(3-hexylthiophene) (P3HT) Nanofibrils by a Cycle of Cooling and Heating in Solutions

Rational design of exfoliated 1T MoS2@CNT-based bifunctional separators for lithium sulfur batteries

Boron-doped peroxo-zirconium oxide dielectric for high-performance, low-temperature, solution-processed indium oxide thin-film transistor