Electronic and Optical Property Control of Polycation/MXene Layer-by-Layer Assemblies with Chemically Diverse MXenes.

MXenes, 2D nanomaterials derived from ceramic MAX phases, have drawn considerable interest in a wide variety of fields including energy storage, catalysis, and sensing. There are many possible MXene compositions due to the chemical and structural diversity of parent MAX phases, which can bear different possible metal atoms "M", number of layers, and carbon or nitrogen "X" constituents. Despite the potential variety in MXene types, the bulk of MXene research focuses upon the first MXene discovered, Ti3C2T. With the recent discovery of polymer/MXene multilayer assemblies as thin films and coatings, there is a need to broaden the accessible types of multilayers by including MXenes other than Ti3C2Tz; however, it is not clear how altering the MXene type influences the resulting multilayer growth and properties. Here, we report on the first use of MXenes other than Ti3C2Tz, specifically Ti2CTz and Nb2CTz, for the layer-by-layer (LbL) assembly of polycation/MXene multilayers. By comparing these MXenes, we evaluate both how changing M (Ti vs Nb) and "n" (Ti3C2Tzvs Ti2CTz) affect the growth and properties of the resulting multilayer. Specifically, the aqueous LbL assembly of each MXene with poly(diallyldimethylammonium) into films and coatings is examined. Further, we compare the oxidative stability, optoelectronic properties (refractive index, absorption coefficient, optical conductivity, and direct and indirect optical band gaps), and the radio frequency heating response of each multilayer. We observe that MXene multilayers with higher "n" are more electrically conductive and oxidatively stable. We also demonstrate that Nb2CTz containing films have lower optical band gaps and refractive indices at the cost of lower electrical conductivities as compared to their Ti2CTz counterparts. Our work demonstrates that the properties of MXene/polycation multilayers are highly dependent on the choice of constituent MXene and that the MXene type can be altered to suit specific applications.

Layer-by-Layer Assembly of Reduced Graphene Oxide and MXene Nanosheets for Wire-Shaped Flexible Supercapacitors.

As the demand for wearable electronic devices increases, interest in small, light, and deformable energy storage devices follows suit. Among these devices, wire-shaped supercapacitors (WSCs) are considered key components of wearable technology due to their geometric similarity to woven fiber. One potential method for creating WSC devices is the layer-by-layer (LbL) assembly technique, which is a "bottom-up" method for electrode fabrication. WSCs require conformal and adhesive coatings of the functional material to the wire-shaped substrate, which is difficult to obtain with other processing techniques such as vacuum filtration or spray-coating. However, the LbL assembly technique produces conformal and robust coatings that can be deposited onto a variety of substrates and shapes, including wires. In this study, we report WSCs made using the LbL assembly of alternating layers of positively charged reduced graphene oxide functionalized with poly(diallyldimethylammonium chloride) and negatively charged Ti3C2Tx MXene nanosheets conformally deposited on activated carbon yarns. In this construct, the added LbL film enhances capacitance, energy density, and power density by 240, 227, and 109%, respectively, relative to the uncoated activated carbon yarn, yielding high specific and volumetric capacitances (237 F g-1, 2193 F cm-3). In addition, the WSC possesses good mechanical stability, retaining 90% of its initial capacity after 200 bending cycles. This study demonstrates that LbL coatings on carbon yarns are promising as linear energy storage devices for fibrous electronics.

Synthesis and Electronic Applications of Particle-Templated Ti3C2Tz MXene-Polymer Films via Pickering Emulsion Polymerization.

MXene/polymer composites have gained widespread attention due to their high electrical conductivity and extensive applications, including electromagnetic interference (EMI) shielding, energy storage, and catalysis. However, due to the difficulty of dispersing MXenes in common polymers, the fabrication of MXene/polymer composites with high electrical conductivity and satisfactory EMI shielding properties is challenging, especially at low MXene loadings. Here, we report the fabrication of MXene-armored polymer particles using dispersion polymerization in Pickering emulsions and demonstrate that these composite powders can be used as feedstocks for MXene/polymer composite films with excellent EMI shielding performance. Ti3C2Tz nanosheets are used as the representative MXene, and three different monomers are used to prepare the armored particles. The presence of nanosheets on the particle surface was confirmed by X-ray photoelectron spectroscopy and scanning electron microscopy. Hot pressing the armored particles above Tg of the polymer produced Ti3C2Tz/polymer composite films; the films are electrically conductive because of the network of nanosheets templated by the particle feedstocks. For example, the particle-templated Ti3C2Tz/polystyrene film had an electrical conductivity of 0.011 S/cm with 1.2 wt % of Ti3C2Tz, which resulted in a high radio frequency heating rate of 13-15 °C/s in the range of 135-150 MHz and an EMI shielding effectiveness of ∼21 dB within the X band. This work provides a new approach to fabricate MXene/polymer composite films with a templated electrical network at low MXene loadings.

Quantifying internal charge transfer and mixed ion-electron transfer in conjugated radical polymers.

Macromolecular radicals are receiving growing interest as functional materials in energy storage devices and in electronics. With the need for enhanced conductivity, researchers have turned to macromolecular radicals bearing conjugated backbones, but results thus far have yielded conjugated radical polymers that are inferior in comparison to their non-conjugated partners. The emerging explanation is that the radical unit and the conjugated backbone (both being redox active) transfer electrons between each other, essentially "quenching" conductivity or capacity. Here, the internal charge transfer process is quantified using a polythiophene loaded with 0, 25, or 100% nitroxide radicals (2,2,6,6-tetramethyl-1-piperidinyloxy [TEMPO]). Importantly, deconvolution of the cyclic voltammograms shows mixed faradaic and non-faradaic contributions that contribute to the internal charge transfer process. Further, mixed ion-electron transfer is determined for the 100% TEMPO-loaded conjugated radical polymer, from which it is estimated that one triflate anion and one propylene carbone molecule are exchanged for every electron. Although these findings indicate the reason behind their poor conductivity and capacity, they point to how these materials might be used as voltage regulators in the future.

Layer-by-Layer Assembly of Polyaniline Nanofibers and MXene Thin-Film Electrodes for Electrochemical Energy Storage.

The growing demand for compact energy storage devices may be met through the use of thin-film microbatteries, which generally rely on charge storage in thin or conformal layers. A promising technique for creating thin-film electrodes is layer-by-layer (LbL) assembly, based on the alternating adsorption of oppositely charged species to a surface to form a nanostructured electrode. Thin-film energy storage devices must have a high energy density within a limited space, so new electrode structures, materials, and assembly methods are important. To this end, both two-dimensional MXenes and polyaniline nanofibers (PNFs) have shown promising energy storage properties. Here, we report on the LbL assembly of positively charged PNFs and negatively charged Ti3C2Tx MXenes into hybrid electrodes for thin-film energy storage devices. The successful assembly is demonstrated in which MXenes and PNFs are deposited in films of 49 nm/layer pair thickness. The resulting composition was 77 wt % PNFs and 23 wt % MXenes. The charge storage process was deconvoluted into faradaic/non-faradaic contributions and separated into contributions from PNFs and MXenes. A sandwich cell showed a maximum areal capacity, energy, and power of 17.6 µA h cm-2, 22.1 µW h cm-2, and 1.5 mW cm-2, respectively, for PNF/MXene multilayers of about 2 µm thickness. This work suggests the possibility of using LbL PNF/MXene thin films as electrode materials for thin-film energy storage devices used in next-generation small electronics.

Wire-Shaped Supercapacitors with Organic Electrolytes Fabricated via Layer-by-Layer Assembly.

A wire-shaped supercapacitor (WSS) has structural advantages of high flexibility and ease of incorporation into conventional textile substrates. In this work, we report a thin reproducible WSS fabricated via layer-by-layer (LbL) assembly of multiwalled carbon nanotubes (MWCNTs), combined with an organic electrolyte of propylene carbonate (PC)-acetonitrile (ACN)-lithium perchlorate (LiClO4)-poly(methyl methacrylate) (PMMA) that extends the voltage window to 1.6 V. The MWCNTs were uniformly deposited on a curved surface of a thin Au wire using an LbL assembly technique, resulting in linearly increased areal capacitance of the fabricated WSS. Vanadium oxide was coated on the LbL-assembled MWCNT electrode to induce pseudocapacitance, hence enhancing the overall capacitance of the fabricated WSS. Both the cyclic stability of the WSS and the viscosity of the electrolyte could be optimized by controlling the mixing ratio of PC to ACN. As a result, the fabricated WSS exhibits an areal capacitance of 5.23 mF cm-2 at 0.2 mA cm-2, an energy density of 1.86 µ W h cm-2, and a power density of 8.5 mW cm-2, in addition to a high cyclic stability with a 94% capacitance retention after 10 000 galvanostatic charge-discharge cycles. This work demonstrates a great potential of the fabricated scalable WSS in the application to high-performance textile electronics as an integrated energy storage device.

Fabrication of High-Sensitivity Skin-Attachable Temperature Sensors with Bioinspired Microstructured Adhesive.

In this study, we demonstrate the fabrication of a highly sensitive flexible temperature sensor with a bioinspired octopus-mimicking adhesive. A resistor-type temperature sensor consisting of a composite of poly(N-isopropylacrylamide) (pNIPAM)-temperature sensitive hydrogel, poly(3,4-ethylenedioxythiophene) polystyrene sulfonate, and carbon nanotubes exhibits a very high thermal sensitivity of 2.6%·°C-1 between 25 and 40 °C so that the change in skin temperature of 0.5 °C can be accurately detected. At the same time, the polydimethylsiloxane adhesive layer of octopus-mimicking rim structure coated with pNIPAM is fabricated through the formation of a single mold by utilizing undercut phenomenon in photolithography. The fabricated sensor shows stable and reproducible detection of skin temperature under repeated attachment/detachment cycles onto skin without any skin irritation for a long time. This work suggests a high potential application of our skin-attachable temperature sensor to wearable devices for medical and health-care monitoring.

Skin-Attachable, Stretchable Electrochemical Sweat Sensor for Glucose and pH Detection.

As part of increased efforts to develop wearable healthcare devices for monitoring and managing physiological and metabolic information, stretchable electrochemical sweat sensors have been investigated. In this study, we report on the fabrication of a stretchable and skin-attachable electrochemical sensor for detecting glucose and pH in sweat. A patterned stretchable electrode was fabricated via layer-by-layer deposition of carbon nanotubes (CNTs) on top of patterned Au nanosheets (AuNS) prepared by filtration onto stretchable substrate. For the detection of glucose and pH, CoWO4/CNT and polyaniline/CNT nanocomposites were coated onto the CNT-AuNS electrodes, respectively. A reference electrode was prepared via chlorination of silver nanowires. Encapsulation of the stretchable sensor with sticky silbione led to a skin-attachable sweat sensor. Our sensor showed high performance with sensitivities of 10.89 µA mM-1 cm-2 and 71.44 mV pH-1 for glucose and pH, respectively, with mechanical stability up to 30% stretching and air stability for 10 days. The sensor also showed good adhesion even to wet skin, allowing the detection of glucose and pH in sweat from running while being attached onto the skin. This work suggests the application of our stretchable and skin-attachable electrochemical sensor to health management as a high-performance healthcare wearable device.

Highly Durable and Flexible Transparent Electrode for Flexible Optoelectronic Applications.

A highly-durable, highly-flexible transparent electrode (FTE) is developed by applying a composite made of a thin metal grid and a doped conducting polymer onto a colorless polyimide-coated NOA63 substrate. The proposed FTE exhibits a transparency of 90.7% at 550 nm including the substrate and a sheet resistance of 30.3 Ω/sq and can withstand both moderately high-temperature annealing (∼180 °C) and acidic solution (70 °C, pH 0.3) processes without performance degradation. The fabricated FTE yielded good mechanical stability under 10 000 cycles of bending deformations at a bending radius less than 1 mm without degradation of electrical conductivity. The high durability of the proposed FTE allows for the fabrication of flexible energy harvesting devices requiring harsh conditions, such as highly flexible perovskite solar cells (FPSCs) with a steady-state power conversion efficiency (PCE) of 12.7%. Notably, 93% of the original PCE is maintained after 2000 bending cycles at an extremely small bending radius of 1.5 mm. The FPSCs installed on curved surfaces of commercial devices drive them under various environments. The applicability of the proposed FTE is further confirmed via the fabrication of a flexible perovskite light-emitting diode. The proposed FTE demonstrates great potential for applications in the field of flexible optoelectronic devices.

High performance flexible double-sided micro-supercapacitors with an organic gel electrolyte containing a redox-active additive.

In this study, we report the fabrication of a high performance flexible micro-supercapacitor (MSC) with an organic gel electrolyte containing a redox-active additive, referred to as poly(methyl methacrylate)-propylene carbonate-lithium perchlorate-hydroquinone (PMMA-PC-LiClO4-HQ). Hexagonal MSCs fabricated on thin polyethylene terephthalate (PET) films had interdigitated electrodes made of spray-coated multi-walled carbon nanotubes (MWNTs) on Au. The addition of HQ as a redox-active additive enhanced not only the specific capacitance but also the energy density of the MSCs dramatically, which is approximately 35 times higher than that of MSCs without the HQ additive. In addition, both areal capacitance and areal energy density could be doubled by fabrication of double-sided MSCs, where two MSCs are connected in parallel. The double-sided MSCs exhibited stable electrochemical performance during repeated deformation by bending. By dry-transferring the double-sided MSCs based on PMMA-PC-LiClO4-HQ on a deformable polymer substrate, we fabricated a stretchable MSC array, which also retained its electrochemical performance during a uniaxial strain of 40%. Furthermore, a wearable energy storage bracelet made of such an MSC array could operate a µ-LED on the wrist.

Stretchable Active Matrix Temperature Sensor Array of Polyaniline Nanofibers for Electronic Skin.

A stretchable polyaniline nanofiber temperature sensor array with an active matrix consisting of single-walled carbon nanotube thin-film transistors is demonstrated. The integrated temperature sensor array gives mechanical stability under biaxial stretching of 30%, and the resultant spatial temperature mapping does not show any mechanical or electrical degradation.

Stretchable Array of Highly Sensitive Pressure Sensors Consisting of Polyaniline Nanofibers and Au-Coated Polydimethylsiloxane Micropillars.

We report on the facile fabrication of a stretchable array of highly sensitive pressure sensors. The proposed pressure sensor consists of the top layer of Au-deposited polydimethylsiloxane (PDMS) micropillars and the bottom layer of conductive polyaniline nanofibers on a polyethylene terephthalate substrate. The sensors are operated by the changes in contact resistance between Au-coated micropillars and polyaniline according to the varying pressure. The fabricated pressure sensor exhibits a sensitivity of 2.0 kPa(-1) in the pressure range below 0.22 kPa, a low detection limit of 15 Pa, a fast response time of 50 ms, and high stability over 10000 cycles of pressure loading/unloading with a low operating voltage of 1.0 V. The sensor is also capable of noninvasively detecting human-pulse waveforms from carotid and radial artery. A 5 × 5 array of the pressure sensors on the deformable substrate, which consists of PDMS islands for sensors and the mixed thin film of PDMS and Ecoflex with embedded liquid metal interconnections, shows stable sensing of pressure under biaxial stretching by 15%. The strain distribution obtained by the finite element method confirms that the maximum strain applied to the pressure sensor in the strain-suppressed region is less than 0.04% under a 15% biaxial strain of the unit module. This work demonstrates the potential application of our proposed stretchable pressure sensor array for wearable and artificial electronic skin devices.

Fabrication of high performance flexible micro-supercapacitor arrays with hybrid electrodes of MWNT/V2O5 nanowires integrated with a SnO2 nanowire UV sensor.

We report on the on-chip fabrication of high performance flexible micro-supercapacitor (MSC) arrays with hybrid electrodes of multi-walled carbon nanotube (MWNT)/V2O5 nanowire (NW) composites and a solid electrolyte, which could power the SnO2 NW UV sensor integrated on the same flexible substrate. The patterned MSC using hybrid electrodes of MWNT/V2O5 NW composites with 10 vol% of V2O5 NWs exhibited excellent electrochemical performance with a high volume capacitance of 80 F cm(-3) at a scan rate of 10 mV s(-1) in a PVA-LiCl electrolyte and good cycle performance to maintain 82% of the capacitance after 10,000 cycles at a current density of 11.6 A cm(-3). The patterned MSC also showed an excellent energy density of 6.8 mW h cm(-3), comparable to that of a Li-thin film battery (1-10 mW h cm(-3)), and a power density of 80.8 W cm(-3) comparable to that of state-of-the-art MSCs. In addition, the flexible MSC array on a PET substrate showed mechanical stability over bending with a bending radius down to 1.5 mm under both compressive and tensile stress. Even after 1000 bending cycles at a bending radius of 7 mm, 94% of the initial capacitance was maintained. Furthermore, we have shown the operation of a SnO2 NW UV sensor using such a fabricated MSC array integrated into the same circuit on the PET substrate.

High-performance all-solid-state flexible micro-supercapacitor arrays with layer-by-layer assembled MWNT/MnO(x) nanocomposite electrodes.

In this study, we report on the fabrication of high performance planar-type flexible micro-supercapacitor (MSC) arrays using Au electrodes coated with a functionalized multi-walled carbon nanotube (MWNT) film and a layer of MWNT-COOH/MnOx nanoparticle (NP) composite on top. The MWNT thin film was formed via layer-by-layer (LbL) assembly of MWNTs functionalized with amine groups and MWNTs with carboxylic acid groups in water. The hydrothermally synthesized composite of MWNT-COOH/MnOx NPs was coated on top of the MWNT film (LbL-MWNT). The addition of MWNT-COOH/MnOx NP composite as a top layer enhanced the performance of the MSCs dramatically, resulting in a volumetric capacitance of 50 F cm(-3) at a scan rate of 10 mV s(-1) and a coulombic efficiency of ∼100%. By contrast, a volumetric capacitance of 3.6 F cm(-3) was obtained when using only the LbL-MWNT film. After repetitive operation up to ∼10(4) times, the capacitance remained at ∼88.3% of the original value. With a deliberate circuit design consisting of serially connected MSC arrays, various light-emitting diodes operating at different bias voltages could be lit. The MSC circuit fabricated on a polyethylene terephthalate (PET) film showed stable electrochemical properties upon 1000 cycles of bending deformation.

Biaxially stretchable, integrated array of high performance microsupercapacitors.

We report on the fabrication of a biaxially stretchable array of high performance microsupercapacitors (MSCs) on a deformable substrate. The deformable substrate is designed to suppress local strain applied to active devices by locally implanting pieces of stiff polyethylene terephthalate (PET) films within the soft elastomer of Ecoflex. A strain suppressed region is formed on the top surface of the deformable substrate, below which PET films are implanted. Active devices placed within this region can be isolated from the strain. Analysis of strain distribution by finite element method confirms that the maximum strain applied to MSC in the strain suppressed region is smaller than 0.02%, while that on the Ecoflex film is larger than 250% under both uniaxial strain of 70% and biaxial strain of 50%. The all-solid-state planar MSCs, fabricated with layer-by-layer deposited multiwalled carbon nanotube electrodes and patterned ionogel electrolyte of poly(ethylene glycol) diacrylate and 1-ethyl-3-methylimidazolium bis(trifluoromethylsulfonyl)imide having high-potential windows, are dry-transferred onto the deformable substrate and electrically connected in series and parallel via embedded liquid metal interconnection and Ag nanowire contacts. Liquid metal interconnection, formed by injecting liquid metal into the microchannel embedded within the substrate, can endure severe strains and requires no additional encapsulation process. This formed MSC array exhibits high energy and power density of 25 mWh/cm(3) and 32 W/cm(3), and stable electrochemical performance up to 100% uniaxial and 50% biaxial stretching. The high output voltage of the MSC array is used to light micro-light-emitting diode (µ-LED) arrays, even under strain conditions. This work demonstrates the potential application of our stretchable MSC arrays to wearable and bioimplantable electronics with a self-powered system.