Maintaining Cytocompatibility of Biopolymers Through a Graphene Layer for Electrical Stimulation of Nerve Cells

Here, the utility of large‐area graphene as a flexible, biocompatible electrode to stimulate cell growth is demonstrated. Chemical vapor deposition allows the production of highly crystalline, single, double, or few‐layered graphene on copper substrates. The subsequent transfer to a biopolymer support, such as polylactic acid (PLA) or polylactic‐co‐glycolic acid (PLGA) copolymers, provides a unique electrode structure retaining the flexibility and surface properties of the underlying materials with a conductive graphene layer sufficient to enable electrical communication with excitable cells. The growth and compatibility of PC‐12 cells on these graphene‐biopolymer (GPB) electrodes is influenced more by the underlying polymer than the presence of graphene, demonstrating that the characteristics influencing biocompatibility have been retained after graphene modification. Differentiation of these cells into neural phenotypes is enhanced using electrical stimulation through the graphene conductive layer, confirming that the conductivity of graphene is sufficient to electrically communicate with cells grown on the surface. The process described herein demonstrates that non‐conducting, flexible biopolymer surfaces can be easily coated with graphene without changing the biocompatibility of the materials. This could be used to create electrodes from non‐conducting materials with optimized cell compatibility with graphene providing electrical properties suitable for stimulation of cells without greatly changing the surface properties.     

Multifunctional Nanobiomaterials for Neural Interfaces

Neural electrodes are designed to interface with the nervous system and provide control signals for neural prostheses. However, robust and reliable chronic recording and stimulation remains a challenge for neural electrodes. Here, a novel method for the fabrication of soft, low impedance, high charge density, and controlled releasing nanobiomaterials that can be used for the surface modification of neural microelectrodes to stabilize the electrode/tissue interface is reported. The fabrication process includes electrospinning of anti‐inflammatory drug‐incorporated biodegradable nanofibers, encapsulation of these nanofibers by an alginate hydrogel layer, followed by electrochemical polymerization of conducting polymers around the electrospun drug‐loaded nanofibers to form nanotubes and within the alginate hydrogel scaffold to form cloud‐like nanostructures. The three‐dimensional conducting polymer nanostructures significantly decrease the electrode impedance and increase the charge capacity density. Dexamethasone release profiles show that the alginate hydrogel coating slows down the release of the drug, significantly reducing the burst effect. These multifunctional materials are expected to be of interest for a variety of electrode/tissue interfaces in biomedical devices.     

Poly(5-nitroindole) Thin Film as Conductive and Adhesive Interfacial Layer for Robust Neural Interface

Poly(3,4-ethylenedioxythiophene) (PEDOT) has emerged as a promising neural interface material, but the weak adhesion of PEDOT to substrates adversely affects its reliability and practical application. Although adhesive interfacial layers have been explored to enhance the adhesion of PEDOT, their poor conductivity seriously compromises the performance of neural electrodes. It is a great challenge to develop an adhesive interfacial layer with excellent electrical properties. Herein, utilizing the advantages of polyindole derivatives, conductive polymers which have various functional groups for potential interface bonding, a conductive, adhesive, and biocompatible poly(5-nitroindole) (PIN-5NO₂) interfacial layer is developed to enhance the adhesion of PEDOT to metal electrodes. The conjugated PIN-5NO₂ with its superior electrical property can be prepared by electropolymerization of 5-nitroindole; however, the electrografting of amino groups, which is reduced from nitro groups in 5-nitroindole can provide strong adhesion with the gold (Au) substrate. With PIN-5NO₂ as an adhesive interfacial layer, the resultant Au/PIN-5NO₂/PEDOT electrode exhibits excellent electrochemical property, superb stability, and biocompatibility for high-performance neural interface. The in vivo evaluation of Au/PIN-5NO₂/PEDOT electrocorticographic microelectrodes demonstrates superior capacity to capture the neural dynamics of the brain. The novel strategy would offer a new insight for the construction of high-performance neural electrodes with high stability for neural interface application.     

Double-Microcrack Coupling Stretchable Neural Electrode for Electrophysiological Communication

Developing neural electrodes with high stretchability and stable conductivity is a promising method to explore applications of them in biological medicine and electronic skin. However, considering the poor mechanical stretchability of typical conductive materials, maintaining the connection of electrode conductive paths under high stretching is still a challenge. Herein, for the first time, a double-microcrack coupling strategy for highly stretchable neural electrodes is proposed. Compared with single-layer stretchable microcrack electrodes, the design utilizes the complement between two gold microcrack films to contribute more conductive paths. It shows that the resistance change (R/R₀) of the electrode under 100% strain is about 5.6 times, which is much lower than other electrodes and exhibits a high stretchability of ≈200%. Simultaneously, this design is an encapsulation-free design which avoids the electrode performance degradation caused by encapsulation. Furthermore, it is found that the adhesion strength between metal electrode and substrate is critical to the stretchability and stability of electrodes, so polydimethylsiloxane_0.9-isophorone diisocyanate elastomer (PDMS_0.9-IPDI), whose adhesion to gold electrode is 4.5 times higher than that of the commercial polydimethylsiloxane (PDMS), is synthesized. Finally, the electrophysiological communication between different organisms by electrodes is successfully demonstrated.     

Bench‐Top Fabrication of Hierarchically Structured High‐Surface‐Area Electrodes

Fabrication of hierarchical materials, with highly optimized features from the millimeter to the nanometer scale, is crucial for applications in diverse areas including biosensing, energy storage, photovoltaics, and tissue engineering. In the past, complex material architectures have been achieved using a combination of top‐down and bottom‐up fabrication approaches. A remaining challenge, however, is the rapid, inexpensive, and simple fabrication of such materials systems using bench‐top prototyping methods. To address this challenge, the properties of hierarchically structured electrodes are developed and investigated by combining three bench‐top techniques: top‐down electrode patterning using vinyl masks created by a computer‐aided design (CAD)‐driven cutter, thin film micro/nanostructuring using a shrinkable polymer substrate, and tunable electrodeposition of conductive materials. By combining these methods, controllable electrode arrays are created with features in three distinct length scales: 40 μm to 1 mm, 50 nm to 10 μm, and 20 nm to 2 μm. The electrical and electrochemical properties of these electrodes are analyzed and it is demonstrated that they are excellent candidates for next generation low‐cost electrochemical and electronic devices.     

Mechanism of Phase Propagation During Lithiation in Carbon‐Free Li4Ti5O12 Battery Electrodes

Functional electrodes for batteries share a common design rule by which high electronic and ionic conductivity pathways must exist throughout the electrode in its pristine state. Notable amounts of conductive carbon additive in the composite electrode are usually included to form an electronically conductive matrix. However, excellent high rate cycling performance has been achieved in electrodes composed of the insulating Li₄Ti₅O₁₂ without any conductive additives. This behavior opens the possibility of a new paradigm for designing functional electrodes by which high electronic conductivity in the pristine electrode is not required. The mechanism of operation that enables such unexpected electrochemical behavior is evaluated and discussed. Electronically conductive pathways due to the reduction of Ti⁴⁺ to Ti³⁺ form and percolate throughout the Li₄Ti₅O₁₂ electrode in the early stage of Li insertion, eliminating the need for conductive additives. This work highlights the importance of the mass and charge transport properties of the intermediate states during cycling and of good interparticle ohmic contact in the electrode. This physical behavior can lead to novel system designs with improved battery utilization and energy density.     

A Self‐Standing and Flexible Electrode of Li4Ti5O12 Nanosheets with a N‐Doped Carbon Coating for High Rate Lithium Ion Batteries

Flexible energy‐storage devices have attracted growing attention with the fast development of bendable electronic systems. Thus, the search for reliable electrodes with both high mechanical flexibility and excellent electron and lithium‐ion conductivity has become an urgent task. Carbon‐coated nanostructures of Li₄Ti₅O₁₂ (LTO) have important applications in high‐performance lithium ion batteries (LIBs). However, these materials still need to be mixed with a binder and carbon black and pressed onto metal substrates or, alternatively, by be deposited onto a conductive substrate before they are assembled into batteries, which makes the batteries less flexible and have a low energy density. Herein, a simple and scalable process to fabricate LTO nanosheets with a N‐doped carbon coating is reported. This can be assembled into a film which can be used as a binder‐free and flexible electrode for LIBs that does not require any current collectors. Such a flexible electrode has a long life. More significantly, it exhibits an excellent rate capability due to the thin carbon coating and porous nanosheet structures, which produces a highly conductive pathway for electrons and fast transport channels for lithium ions.     

Low‐Resistant Electrical and Robust Mechanical Contacts of Self‐Attachable Flexible Transparent Electrodes with Patternable Circuits

Flexible, transparent, conductive electrodes are key elements of emerging flexible electronic and energy devices. Such electrodes should form an intimate physical contact with various active components of flexible devices to ensure stable, low‐resistant electrical contacts. However, contact formation techniques are based largely on conventional soldering, conductive pastes, mechanical clamping, and thin film deposition. These generally result in damaged, contaminated, bulky, and uncontrollable contact interfaces. A self‐attachable, flexible, transparent, and conductive electrode that is based on a distinctive design of regular grid patterns into which bioinspired adhesive architectures and percolating Ag nanowires are integrated is proposed. Based on this integrated design, the proposed electrode forms reliable, low‐resistant electrical contacts; strong mechanical adhesive contacts; and ultra‐clean, damage‐free contact interfaces with active device components by attaching onto the components without using additional conductive pastes, mechanical pressing, or vacuum deposition processes. The contact interfaces of the electrode and device components remain stable even when the electrode is extremely bent. Moreover, specific electronic circuits can be generated on the electrode surface by a selective deposition of Ag nanowires. This enables simple interconnections of diverse electronic components on its surface.     

Challenges and Opportunities of Implantable Neural Interfaces: From Material,Electrochemical and Biological Perspectives

The desirable implantable neural interfaces can accurately record bioelectrical signals from neurons and regulate neural activities with high spatial/time resolution, facilitating the understanding of neuronal functions and dynamics. However, the electrochemical performance (impedance, charge storage/injection capacity) is limited with the miniaturization and integration of neural electrodes. The “crosstalk” caused by the uneven distribution of elctric field leads to lower electrical stimulation/recording efficiency. The mismatch between stiff electrodes and soft tissues exacerbates the inflammatory responses, thus weakening the transmission of signals. Though remarkable breakthroughs have been made through the incorporation of optimizing electrode design and functionalized nanomaterials, the chronic stability, and long-term activity in vivo of the neural electrodes still need further development. In this review, the neural interface challenges mainly on electrochemistry and biology are discussed, followed by summarizing typical electrode optimization technologies and exploring recent advances in the application of nanomaterials, based on traditional metallic materials, emerging 2D materials, conducting polymer hydrogels, etc., for enhancing neural interfaces. The strategies for improving the durability including enhanced adhesion and minimized inflammatory response, are also summarized. The promising directions are finally presented to provide enlightenment for high-performance neural interfaces in future, which will promote profound progress in neuroscience research.     

Silk as a Multifunctional Biomaterial Substrate for Reduced Glial Scarring around Brain‐Penetrating Electrodes

The reliability of chronic, brain‐penetrating electrodes must be improved for these ‐neural recording technologies to be viable in widespread clinical applications. One approach to improving electrode reliability is to reduce the foreign body response at the probe‐tissue interface. In this work, silk fibroin is investigated as a candidate material for fabricating mechanically dynamic neural probes with enhanced biocompatibility compared to traditional electrode materials. Silk coatings are applied to flexible cortical electrodes to produce devices that transition from stiff to flexible upon hydration. Theoretical modeling and in vitro testing show that the silk coatings impart mechanical properties sufficient for the electrodes to penetrate brain tissue. Further, it is demonstrated that silk coatings may reduce some markers of gliosis in an in vitro model and that silk can encapsulate and release the gliosis‐modifying enzyme chondroitinase ABC. This work establishes a basis for future in vivo studies of silk‐based brain‐penetrating electrodes, as well as the use of silk materials for other applications in the central nervous system where gliosis must be controlled.     

Printing of Highly Integrated Crossbar Junctions

A new process is presented that combines nanoimprint lithography and soft lithography to assemble metal–bridge–metal crossbar junctions at ambient conditions. High density top and bottom metal electrodes with half‐pitches down to 50 nm are fabricated in a parallel process by means of ultraviolet nanoimprint lithography. The top electrodes are realized on top of a sacrificial layer and are embedded in a polymer matrix. The lifting of the top electrodes by dissolving the sacrificial layer in an aqueous solution results in printable electrode stamps. Crossbar arrays are noninvasively assembled with high yield by printing the top electrode stamps onto bare or modified bottom electrodes. A semiconducting and a quasi metal like conducting type of polymer are incorporated in the cross points to form metal‐polymer‐metal junctions. The electrical characterization of the printed junctions revealed that the functional integrity of the electrically addressed conductive polymers is conserved during the assembling process. These findings suggest that printing of electrodes represents an easy and cost effective route to highly integrated nanoscale metal‐bridge‐metal junctions if imprint lithography is used for electrode fabrication.     

High‐Performance Supercapacitor Applications of NiO‐Nanoparticle‐Decorated Millimeter‐Long Vertically Aligned Carbon Nanotube Arrays via an Effective Supercritical CO2‐Assisted Method

Nickel oxide (NiO) nanoparticles are distributed uniformly in the vertically aligned carbon nanotube arrays (VACNTs) with millimeter thickness by an effective supercritical carbon dioxide‐assisted method. The as‐prepared VACNT/NiO hybrid structures are used as electrodes without binders and conducting additives for supercapacitor applications. Due to the synergetic effects of NiO and VACNTs with nanoporous structures and parallel 1D conductive paths for electrons, the supercapacitors exhibit a high capacitance of 1088.44 F g^?1. Furthermore, an asymmetric supercapacitor is assembled using the as‐synthesized VACNTs/NiO hybrids as the positive electrode and the VACNTs as the negative electrode. Remarkably, the energy density of the asymmetric supercapacitor is as high as 90.9 Wh kg^?1 at 3.2 kW kg^?1 and the maximum power density reaches 25.6 kW kg^?1 at 24.9 Wh kg^?1, which are superior to those of the NiO or VACNTs‐based asymmetric supercapacitors. More importantly, the asymmetric supercapacitors exhibit capacitance retention of 87.1% after 2000 cycles at 5 A g^?1. The work provides a novel approach in decorating highly dense and long VACNTs with active materials, which are promising electrodes for supercapacitors with ultrahigh power density and energy density.     

Fabrication of Responsive,Softening Neural Interfaces

A novel processing method is described using photolithography to pattern thin‐film flexible electronics on shape memory polymer substrates with mechanical properties tailored to improve biocompatability and enhance adhesion between the polymer substrate and metal layers. Standard semiconductor wafer processing techniques are adapted to enable robust device design onto a variety of softening substrates with tunable moduli. The resulting devices are stiff enough (shear modulus of ≈700 MPa) to assist with device implantation and then soften in vivo (≈300 kPa) approaching the modulus of brain tissue (≈10 kPa) within 24 h. Acute in vivo studies demonstrate that these materials are capable of recording neural activity. Softening multi‐electrode arrays offer a highly customizable interface, which can be optimized to improve biocompatibility, enabling the development of robust, reliable neural electrodes for neural engineering and neuroscience.     

Antimicrobial Peptide Functionalized Conductive Nanowire Array Electrode as a Promising Candidate for Bacterial Environment Application

Conductive polymer electrodes are widely used for electrical signal detection owing to their unique mechanical, redox, and impedance characteristics. However, the performance of electrodes is compromised due to the interference of adhered bacteria and most of the scientists have not taken the microbial environment into consideration during electrode design. Here, a facile approach to construct antimicrobial peptide (AMP) functionalized polypyrrole nanowire array conductive electrodes (PNW‐AMP) is reported. Instead of compromising the electrochemical properties as the other antibacterial agents do, the PNW‐AMP electrodes exhibit excellent redox and low interfacial impedance properties. More importantly, the PNW‐AMP can eliminate bacterial adhesion and maintain electrochemical stability simultaneously in the microbial microenvironment for a long time. The antibacterial rate of the PNW‐AMP electrode reaches 95.8% after exposing the electrode to air for one month, while the charge transfer resistance ( R_ct) value only increases by 9% at a bacterium (Escherichia. Coli ) concentration of 1 × 10⁴ colony forming unit (CFU) mL^?1. This research makes it possible to construct highly stable conductive polymer electrodes for bacterial environment electrical signal detection.     

Hierarchical Free‐Standing Carbon‐Nanotube Paper Electrodes with Ultrahigh Sulfur‐Loading for Lithium–Sulfur Batteries

The rational combination of conductive nanocarbon with sulfur leads to the formation of composite cathodes that can take full advantage of each building block; this is an effective way to construct cathode materials for lithium–sulfur (Li–S) batteries with high energy density. Generally, the areal sulfur‐loading amount is less than 2.0 mg cm^?2, resulting in a low areal capacity far below the acceptable value for practical applications. In this contribution, a hierarchical free‐standing carbon nanotube (CNT)‐S paper electrode with an ultrahigh sulfur‐loading of 6.3 mg cm^?2 is fabricated using a facile bottom–up strategy. In the CNT–S paper electrode, short multi‐walled CNTs are employed as the short‐range electrical conductive framework for sulfur accommodation, while the super‐long CNTs serve as both the long‐range conductive network and the intercrossed mechanical scaffold. An initial discharge capacity of 6.2 mA·h cm^?2 (995 mA·h g^?1), a 60% utilization of sulfur, and a slow cyclic fading rate of 0.20%/cycle within the initial 150 cycles at a low current density of 0.05 C are achieved. The areal capacity can be further increased to 15.1 mA·h cm^?2 by stacking three CNT–S paper electrodes—resulting in an areal sulfur‐loading of 17.3 mg cm^?2—for the cathode of a Li–S cell. The as‐obtained free‐standing paper electrode are of low cost and provide high energy density, making them promising for flexible electronic devices based on Li–S batteries.     

Redox‐Induced Asymmetric Electrical Characteristics of Ferrocene‐Alkanethiolate Molecular Devices on Rigid and Flexible Substrates

The electrical properties of ferrocene‐alkanethiolate self‐assembled monolayers (SAMs) on a high yield solid‐state device structure are investigated. The devices are fabricated using a conductive polymer interlayer between the top electrode and the SAM on both silicon‐based rigid substrates and plastic‐based flexible substrates. Asymmetric electrical transport characteristics that originate from the ferrocene moieties are observed. In particular, a distinctive temperature dependence of the current (i.e., a decrease in current density as temperature increases) at a large reverse bias, which is associated with the redox reaction of ferrocene groups in the molecular junction, is found. It is further demonstrated that the molecular devices can function on flexible substrates under various mechanical stress configurations with consistent electrical characteristics. This study enhances the understanding of asymmetric molecules and may lead to the development of functional molecular electronic devices on both rigid and flexible substrates.     

Spatially resolved photocurrent mapping of efficient organic solar cells fabricated on a woven mesh electrode

Flexible organic photovoltaic devices may soon find applications in various fields, such as portable electronics or building‐integrated photovoltaics, occupying market niches that are currently not covered by the prevailing photovoltaic technology based on silicon and other inorganic materials. For these applications, there is an urgent need to replace the commonly used indium tin oxide by transparent and electrically conductive materials that can be processed cost‐effectively by large‐area compatible printing and coating processes. Here, we fabricated P3HT/PCBM organic solar cells with a power conversion efficiency of 3.1% on a flexible, transparent and conductive woven fabric electrode. The electrode is produced by a roll‐to‐roll process and consists of a polymer‐embedded fibre/metal wire grid. Metal wires protrude as little as 5 µm from the electrode plane, providing electrical contact points on a smooth surface suitable for thin film deposition. The use of spatially resolved photocurrent mapping experiments showed a high level of detailed information, with the unexpected indication that there probably exists a maximum in the cell performance versus mesh size opening and that woven fabric electrodes with largest geometrical open area do not necessarily perform better. Copyright © 2012 John Wiley & Sons, Ltd.     

Ultrafast Self‐Assembly of Graphene Oxide‐Induced Monolithic NiCo–Carbonate Hydroxide Nanowire Architectures with a Superior Volumetric Capacitance for Supercapacitors

The monolithic electrodes with high volumetric capacitance demonstrate a great potential in practical industrial applications for supercapacitors. Herein, a novel strategy for ultrafast self‐assembly of graphene oxides (GO)‐induced monolithic NiCo–carbonate hydroxide (NiCo–CH) nanowire composite films (G–CH) is reported. The oxygen‐containing functional groups on the GO surface help effectively to induce formation of the monodisperse NiCo–CH nanowires. Such a nanowire‐shaped structure further functions as a scaffold and/or support, leading to 25 s of ultrafast self‐assembly for G–CH composite films and a relatively loose and open channel that contributes to fast electrolyte transport. The as‐obtained monolithic G–CH architectures show an excellent supercapacitor performance as binder‐ and conductive agent‐free electrode, evidenced by a superior volumetric capacitance of 2936 F cm^?3 and good electrochemical stability. Combining highly conductive carbon nanotubes (CNTs) into the monolithic composite films can further create well‐interconnected conductive networks within the electrode matrix, thus to improve the reaction kinetics and rate capability. The present strategy that can modulate the growth of the high‐electroactive pseudocapacitive hydroxides and achieve an ultrafast self‐assembly of monolithic composites may pave a promising new way for development of high‐performance supercapacitors and shed a new light on the configuration of carbon‐based electrode materials in energy storage and conversion devices.     

Dual Support System Ensuring Porous Co–Al Hydroxide Nanosheets with Ultrahigh Rate Performance and High Energy Density for Supercapacitors

Layered double hydroxides (LDHs) are promising supercapacitor electrode materials due to their high specific capacitances. However, their electrochemical performances such as rate performance and energy density at a high current density, are rather poor. Accordingly, a facile strategy is demonstrated for the synthesis of the integrated porous Co–Al hydroxide nanosheets (named as GSP‐LDH) with dual support system using dodecyl sulfate anions and graphene sheets as structural and conductive supports, respectively. Owing to fast ion/electron transport, porous and integrated structure, the GSP‐LDH electrode exhibits remarkably improved electrochemical characteristics such as high specific capacitance (1043 F g^?1 at 1 A g^?1) and ultra‐high rate performance capability (912 F g^?1 at 20 A g^?1). Moreover, the assembled sandwiched graphene/porous carbon (SGC)//GSP‐LDH asymmetric supercapacitor delivers a high energy density up to 20.4 Wh kg^?1 at a very high power density of 9.3 kW kg^?1, higher than those of previously reported asymmetric supercapacitors. The strategy provides a facile and effective method to achieve high rate performance LDH based electrode materials for supercapacitors.     

Pyrolysed 3D‐Carbon Scaffolds Induce Spontaneous Differentiation of Human Neural Stem Cells and Facilitate Real‐Time Dopamine Detection

Structurally patterned pyrolysed three‐dimensional carbon scaffolds (p3D‐carbon) are fabricated and applied for differentiation of human neural stem cells (hNSCs) developed for cell replacement therapy and sensing of released dopamine. In the absence of differentiation factors (DF) the pyrolysed carbon material induces spontaneous hNSC differentiation into mature dopamine‐producing neurons and the 3D‐topography promotes neurite elongation. In the presence and absence of DF, ≈73–82% of the hNSCs obtain dopaminergic properties on pyrolysed carbon, a to‐date unseen efficiency in both two‐dimensional (2D) and 3D environment. Due to conductive properties and 3D environment, the p3D‐carbon serves as a neurotransmitter trap, enabling electrochemical detection of a significantly larger dopamine fraction released by the hNSC derived neurons than on conventional 2D electrodes. This is the first study of its kind, presenting new conductive 3D scaffolds that provide highly efficient hNSC differentiation to dopaminergic phenotype combined with real‐time in situ confirmation of the fate of the hNSC‐derived neurons.