High conductivity Sepia melanin ink films for environmentally benign printed electronics.

Melanins (from the Greek µÎ­λας, mélas, black) are bio-pigments ubiquitous in flora and fauna. Eumelanin is an insoluble brown-black type of melanin, found in vertebrates and invertebrates alike, among which Sepia (cuttlefish) is noteworthy. Sepia melanin is a type of bio-sourced eumelanin that can readily be extracted from the ink sac of cuttlefish. Eumelanin features broadband optical absorption, metal-binding affinity and antioxidative and radical-scavenging properties. It is a prototype of benign material for sustainable organic electronics technologies. Here, we report on an electronic conductivity as high as 10-3 S cm-1 in flexographically printed Sepia melanin films; such values for the conductivity are typical for well-established high-performance organic electronic polymers but quite uncommon for bio-sourced organic materials. Our studies show the potential of bio-sourced materials for emerging electronic technologies with low human- and eco-toxicity.

Air-breathing cathode self-powered supercapacitive microbial fuel cell with human urine as electrolyte.

In this work, a membraneless microbial fuel cell (MFC) with an empty volume of 1.5 mL, fed continuously with hydrolysed urine, was tested in supercapacitive mode (SC-MFC). In order to enhance the power output, a double strategy was used: i) a double cathode was added leading to a decrease in the equivalent series resistance (ESR); ii) the apparent capacitance was boosted up by adding capacitive features on the anode electrode. Galvanostatic (GLV) discharges were performed at different discharge currents. The results showed that both strategies were successful obtaining a maximum power output of 1.59 ± 0.01 mW (1.06 ± 0.01 mW mL-1) at pulse time of 0.01 s and 0.57 ± 0.01 mW (0.38 ± 0.01 mW mL-1) at pulse time of 2 s. The highest energy delivered at ipulse equal to 2 mA was 3.3 ± 0.1 mJ. The best performing SC-MFCs were then connected in series and parallel and tested through GLV discharges. As the power output was similar, the connection in parallel allowed to roughly doubling the current produced. Durability tests over ≈5.6 days showed certain stability despite a light overall decrease.

Increased power generation in supercapacitive microbial fuel cell stack using Fe-N-C cathode catalyst.

The anode and cathode electrodes of a microbial fuel cell (MFC) stack, composed of 28 single MFCs, were used as the negative and positive electrodes, respectively of an internal self-charged supercapacitor. Particularly, carbon veil was used as the negative electrode and activated carbon with a Fe-based catalyst as the positive electrode. The red-ox reactions on the anode and cathode, self-charged these electrodes creating an internal electrochemical double layer capacitor. Galvanostatic discharges were performed at different current and time pulses. Supercapacitive-MFC (SC-MFC) was also tested at four different solution conductivities. SC-MFC had an equivalent series resistance (ESR) decreasing from 6.00â€¯Ω to 3.42â€¯Ω in four solutions with conductivity between 2.5 mScm-1 and 40 mScm-1. The ohmic resistance of the positive electrode corresponded to 75-80% of the overall ESR. The highest performance was achieved with a solution conductivity of 40 mS cm-1 and this was due to the positive electrode potential enhancement for the utilization of Fe-based catalysts. Maximum power was 36.9 mW (36.9 W m-3) that decreased with increasing pulse time. SC-MFC was subjected to 4520 cycles (8 days) with a pulse time of 5 s (ipulse 55 mA) and a self-recharging time of 150 s showing robust reproducibility.

Self-stratified and self-powered micro-supercapacitor integrated into a microbial fuel cell operating in human urine.

A self-stratified microbial fuel cell fed with human urine with a total internal volume of 0.55 ml was investigated as an internal supercapacitor, for the first time. The internal self-stratification allowed the development of two zones within the cell volume. The oxidation reaction occurred on the bottom electrode (anode) and the reduction reaction on the top electrode (cathode). The electrodes were discharged galvanostatically at different currents and the two electrodes were able to recover their initial voltage value due to their red-ox reactions. Anode and cathode apparent capacitance was increased after introducing high surface area activated carbon embedded within the electrodes. Peak power produced was 1.20 ±â€¯0.04 mW (2.19 ±â€¯0.06 mW ml-1) for a pulse time of 0.01 s that decreased to 0.65 ±â€¯0.02 mW (1.18 ±â€¯0.04 mW ml-1) for longer pulse periods (5 s). Durability tests were conducted over 44 h with ≈2600 discharge/recharge cycles. In this relatively long-term test, the equivalent series resistance increased only by 10% and the apparent capacitance decreased by 18%.

Three-dimensional graphene nanosheets as cathode catalysts in standard and supercapacitive microbial fuel cell.

Three-dimensional graphene nanosheets (3D-GNS) were used as cathode catalysts for microbial fuel cells (MFCs) operating in neutral conditions. 3D-GNS catalysts showed high performance towards oxygen electroreduction in neutral media with high current densities and low hydrogen peroxide generation compared to activated carbon (AC). 3D-GNS was incorporated into air-breathing cathodes based on AC with three different loadings (2, 6 and 10 mgcm-2). Performances in MFCs showed that 3D-GNS had the highest performances with power densities of 2.059 ± 0.003 Wm-2, 1.855 ± 0.007 Wm-2 and 1.503 ± 0.005 Wm-2 for loading of 10, 6 and 2 mgcm-2 respectively. Plain AC had the lowest performances (1.017 ± 0.009 Wm-2). The different cathodes were also investigated in supercapacitive MFCs (SC-MFCs). The addition of 3D-GNS decreased the ohmic losses by 14-25%. The decrease in ohmic losses allowed the SC-MFC with 3D-GNS (loading 10 mgcm-2) to have the maximum power (Pmax) of 5.746 ± 0.186 Wm-2. At 5 mA, the SC-MFC featured an "apparent" capacitive response that increased from 0.027 ± 0.007 F with AC to 0.213 ± 0.026 F with 3D-GNS (loading 2 mgcm-2) and further to 1.817 ± 0.040 F with 3D-GNS (loading 10 mgcm-2).

Supercapacitive microbial desalination cells: New class of power generating devices for reduction of salinity content.

In this work, the electrodes of a microbial desalination cell (MDC) are investigated as the positive and negative electrodes of an internal supercapacitor. The resulting system has been named a supercapacitive microbial desalination cell (SC-MDC). The electrodes are self-polarized by the red-ox reactions and therefore the anode acts as a negative electrode and the cathode as a positive electrode of the internal supercapacitor. In order to overcome cathodic losses, an additional capacitive electrode (AdE) was added and short-circuited with the SC-MDC cathode (SC-MDC-AdE). A total of 7600 discharge/self-recharge cycles (equivalent to 44 h of operation) of SC-MDC-AdE with a desalination chamber filled with an aqueous solution of 30 g L-1 NaCl are reported. The same reactor system was operated with real seawater collected from Pacific Ocean for 88 h (15,100 cycles). Maximum power generated was 1.63 ±â€¯0.04 W m-2 for SC-MDC and 3.01 ±â€¯0.01 W m-2 for SC-MDC-AdE. Solution conductivity in the desalination reactor decreased by ∼50% after 23 h and by more than 60% after 44 h. There was no observable change in the pH during cell operation. Power/current pulses were generated without an external power supply.

Miniaturized supercapacitors: key materials and structures towards autonomous and sustainable devices and systems.

Supercapacitors (SCs) are playing a key role for the development of self-powered and self-sustaining integrated systems for different fields ranging from remote sensing, robotics and medical devices. SC miniaturization and integration into more complex systems that include energy harvesters and functional devices are valuable strategies that address system autonomy. Here, we discuss about novel SC fabrication and integration approaches. Specifically, we report about the results of interdisciplinary activities on the development of thin, flexible SCs by an additive technology based on Supersonic Cluster Beam Deposition (SCBD) to be implemented into supercapacitive electrolyte gated transistors and supercapacitive microbial fuel cells. Such systems integrate at materials level the specific functions of devices, like electric switch or energy harvesting with the reversible energy storage capability. These studies might open new frontiers for the development and application of new multifunction-energy storage elements.

Co-generation of hydrogen and power/current pulses from supercapacitive MFCs using novel HER iron-based catalysts.

In this work, four different supercapacitive microbial fuel cells (SC-MFCs) with carbon brush as the anode and an air-breathing cathode with Fe-Aminoantipyrine (Fe-AAPyr) as the catalyst have been investigated using galvanostatic discharges. The maximum power (Pmax) obtained was in the range from 1.7 mW to 1.9 mW for each SC-MFC. This in-series connection of four SC-MFCs almost quadrupled Pmax to an operating voltage of 3025 mV and a Pmax of 8.1 mW, one of the highest power outputs reported in the literature. An additional electrode (AdHER) connected to the anode of the first SC-MFC and placed in the fourth SC-MFC evolved hydrogen. The hydrogen evolution reaction (HER) taking place at the electrode was studied on Pt and two novel platinum group metal-free (PGM-free) catalysts: Fe-Aminoantipyrine (Fe-AAPyr) and Fe-Mebendazole (Fe-MBZ). The amount of H2 produced was estimated using the Faraday law as 0.86 mMd-1cm-2 (0.132 L day-1) for Pt, 0.83 mMd-1cm-2 (0.127 L day-1) for Fe-AAPyr and 0.8 mMd-1cm-2 (0.123 L day-1) for Fe-MBZ. Hydrogen evolution was also detected using gas chromatography. While HER was taking place, galvanostatic discharges were also performed showing simultaneous H2 production and pulsed power generation with no need of external power sources.

Electronic properties of lithium-ion battery cathodes studied in ion-gated transistor configuration.

Electronic and ionic transport governs lithium-ion battery (LIB) operation. The in operando study of electronic transport in lithium-ion transition metal oxide (LMOx) cathodes at different states of charge enables the evaluation of the state of health of LIBs and the optimization of their performance. We report on electronic transport in LIB cathode materials at different states of charge controlled in operando in ion-gated transistor (IGT) configuration. We considered LiNi0.5Mn0.3Co0.2O2 (NMC532)- and LiMn1.5Ni0.5O4 (LNMO)-based composite materials formulated like in conventional LIB cathodes and operated in the organic electrolyte LP30 (1M LiPF6 in ethylene carbonate:dimethyl carbonate 1:1 v/v). NMC532- and LNMO-based cathode materials were used as the transistor channel materials and LP30 as the ion gating medium. Beyond its impact on the field of LIBs, our work advances the design of novel devices based on mixed ionic and electronic transport, including neuromorphic computing.

Biosourced quinones for high-performance environmentally benign electrochemical capacitors via interface engineering.

Biosourced and biodegradable organic electrode materials respond to the need for sustainable storage of renewable energy. Here, we report on electrochemical capacitors based on electrodes made up of quinones, such as Sepia melanin and catechin/tannic acid (Ctn/TA), solution-deposited on carbon paper engineered to create high-performance interfaces. Sepia melanin and Ctn/TA on TCP electrodes exhibit a capacitance as high as 1355 mF cm-2 (452 F g-1) and 898 mF cm-2 (300 F g-1), respectively. Sepia melanin and Ctn/TA symmetric electrochemical capacitors operating in aqueous electrolytes exhibit up to 100% capacitance retention and 100% coulombic efficiency over 50,000 and 10,000 cycles at 150 mA cm-2 (10 A g-1), respectively. Maximum power densities as high as 1274 mW cm-2 (46 kW kg-1) and 727 mW cm-2 (26 kW kg-1) with maximum energy densities of 0.56 mWh cm-2 (20 Wh kg-1) and 0.65 mWh cm-2 (23 Wh kg-1) are obtained for Sepia melanin and Ctn/TA.

Improving the Electrical Percolating Network of Carbonaceous Slurries by Superconcentrated Electrolytes: An Electrochemical Impedance Spectroscopy Study.

Semisolid redox flow batteries simultaneously address the need for high energy density and design flexibility. The electrical percolating network and electrochemical stability of the flowable electrodes are key features that are required to fully exploit the chemistry of the semisolid slurries. Superconcentrated electrolytes are getting much attention for their wide electrochemical stability window that can be exploited to design high-voltage batteries. Here, we report on the effect of the ion concentration of superconcentrated electrolytes on the electronic percolating network of carbonaceous slurries. Slurries based on different concentrations of lithium bis(trifluoromethane)sulfonamide in tetraethylene glycol dimethyl ether (0.5, 3, and 5 mol/kg) at different content of Pureblack carbon (from 2 up to 12 wt %) have been investigated. The study was carried out by coupling electrochemical impedance spectroscopy (EIS), optical fluorescence microscopy, and rheological measurements. A model that describes the complexity and heterogeneity of the semisolid fluids by multiple conductive branches is also proposed. For the first time, to the best of our knowledge, we demonstrate that besides their recognized high electrochemical stability, superconcentrated electrolytes enable more stable and electronically conductive slurry. Indeed, the high ionic strength of the superconcentrated solution shields interparticle interactions and enables better carbon dispersion and connections.

Electronic Transport in the Biopigment Sepia Melanin.

Eumelanin is the most common form of the pigment melanin in the human body, with diverse functions including photoprotection, antioxidant behavior, metal chelation, and free radical scavenging. Melanin also plays a role in melanoma skin cancer and Parkinson's disease. Sepia melanin is a natural eumelanin extracted from the ink sac of cuttlefish. Eumelanin is an ideal candidate to eco-design technologies based on abundant, biosourced, and biodegradable organic electronic materials to alleviate the environmental footprint of the electronics sector. Herein, the focus is on the reversible electrical resistive switching in dry and wet Sepia eumelanin pellets, pointing to the possibility of predominant electronic transport satisfying conditio sine qua non to develop melanin-based electronic devices. These findings shed light on the possibility to describe the transport physics of dry eumelanin using the amorphous semiconductor model. Results are of tremendous importance for the development of sustainable organic electronics.

Combination of bioelectrochemical systems and electrochemical capacitors: Principles, analysis and opportunities.

Bioelectrochemical systems combine electrodes and reactions driven by microorganisms for many different applications. The conversion of organic material in wastewater into electricity occurs in microbial fuel cells (MFCs). The power densities produced by MFCs are still too low for application. One way of increasing their performance is to combine them with electrochemical capacitors, widely used for charge storage purposes. Capacitive MFCs, i.e. the combination of capacitors and MFCs, allow for energy harvesting and storage and have shown to result in improved power densities, which facilitates the up scaling and application of the technology. This manuscript summarizes the state-of-the-art of combining capacitors with MFCs, starting with the theory and working principle of electrochemical capacitors. We address how different electrochemical measurements can be used to determine (bio)electrochemical capacitance and show how the measurement data can be interpreted. In addition, we present examples of the combination of electrochemical capacitors, both internal and external, that have been used to enhance MFC performance. Finally, we discuss the most promising applications and the main existing challenges for capacitive MFCs.

An Electrochemical Study on the Effect of Metal Chelation and Reactive Oxygen Species on a Synthetic Neuromelanin Model.

Neuromelanin is present in the cathecolaminergic neuron cells of the substantia nigra and locus coeruleus of the midbrain of primates. Neuromelanin plays a role in Parkinson's disease (PD). Literature reports that neuromelanin features, among others, antioxidant properties by metal ion chelation and free radical scavenging. The pigment has been reported to have prooxidant properties too, in certain experimental conditions. We propose an explorative electrochemical study of the effect of the presence of metal ions and reactive oxygen species (ROS) on the cyclic voltammograms of a synthetic model of neuromelanin. Our work improves the current understanding on experimental conditions where neuromelanin plays an antioxidant or prooxidant behavior, thus possibly contributing to shed light on factors promoting the appearance of PD.

Toward Low-Cost and Sustainable Supercapacitor Electrode Processing: Simultaneous Carbon Grafting and Coating of Mixed-Valence Metal Oxides by Fast Annealing.

There is a rapid market growth for supercapacitors and batteries based on new materials and production strategies that minimize their cost, end-of-life environmental impact, and waste management. Herein, mixed-valence iron oxide (FeOx) and manganese oxide (Mn3O4) and FeOx-carbon black (FeOx-CB) electrodes with excellent pseudocapacitive behavior in 1 M Na2SO4 are produced by a one-step thermal annealing. Due to the in situ grafted carbon black, the FeOx-CB shows a high pseudocapacitance of 408 mF cm-2 (or 128 F g-1), and Mn3O4 after activation shows high pseudocapacitance of 480 mF cm-2 (192 F g-1). The asymmetric supercapacitor based on FeOx-CB and activated-Mn3O4 shows a capacitance of 260 mF cm-2 at 100 mHz and a cycling stability of 97.4% over 800 cycles. Furthermore, due to its facile redox reactions, the supercapacitor can be voltammetrically cycled up to a high rate of 2,000 mV s-1 without a significant distortion of the voltammograms. Overall, our data indicate the feasibility of developing high-performance supercapacitors based on mixed-valence iron and manganese oxide electrodes in a single step.

Oxygen Redox Reaction in Ionic Liquid and Ionic Liquid-like Based Electrolytes: A Scanning Electrochemical Microscopy Study.

Improving the stability of the cathode interface is one of the critical issues for the development of high-performance Li/O2 batteries. The most critical feature to address is the development of electrolytes that mitigate side reactions that bring about cathode passivation. It is well-known that the superoxide anion (O2•-) plays a critical role. Here, we propose scanning electrochemical microscopy (SECM) as an analytical tool to screen the electrolyte of Li/O2 batteries. We demonstrate that by using SECM it is possible to evaluate the stability of O2•- and of the cathode to the passivation process occurring during the oxygen redox reaction. Specifically, we report a study carried out at a glassy carbon electrode in 1-butyl-1-methylpyrrolidinium bis(trifluoromethanesulfonyl)imide (PYR14TFSI) and lithium bis(trifluoromethanesulfonyl)imide (LiTFSI) and in tetraethylene glycol dimethyl ether with LiTFSI, the latter ranging from the salt-in-solvent to solvent-in-salt regions.

Melanin: A Greener Route To Enhance Energy Storage under Solar Light.

The development of technologies integrating solar energy conversion and energy storage functions is critical for limiting the anthropogenic effects on climate change and preventing possible energy shortages related to the increase of the world population. In our work, we explored the possibility to integrate the conversion and storage functions within the same multifunctional biosourced material. We identified the redox-active, quinone-based, melanin pigment, featuring a broadband absorption in the UV-vis region, as the ideal candidate for such an exploration. Electrodes of melanin on carbon paper were investigated for their morphological, optical, and voltammetric characteristics prior to being assembled into symmetric supercapacitors operating in aqueous electrolytes. We observed that, under solar light, the capacity and capacitance of melanin electrodes significantly increase with respect to the dark conditions (by 22 and 39%, respectively). Once in a supercapacitor configuration, besides featuring a Coulombic efficiency close to 100% after 5000 cycles, the capacitance and capacity of the electrodes, rated by the initial values, improve after prolonged illumination, as it is the case for the energy and power density.

Electropolymerized Poly(3,4-ethylenedioxythiophene) (PEDOT) Coatings for Implantable Deep-Brain-Stimulating Microelectrodes.

Conducting polymers have been widely explored as coating materials for metal electrodes to improve neural signal recording and stimulation because of their mixed electronic-ionic conduction and biocompatibility. In particular, the conducting polymer poly(3,4-ethylenedioxythiophene) (PEDOT) is one of the best candidates for biomedical applications due to its high conductivity and good electrochemical stability. Coating metal electrodes with PEDOT has shown to enhance the electrode's performance by decreasing the impedance and increasing the charge storage capacity. However, PEDOT-coated metal electrodes often have issues with delamination and stability, resulting in decreased device performance and lifetime. In this work, we were able to electropolymerize PEDOT coatings on sharp platinum-iridium recording and stimulating neural electrodes and demonstrated its mechanical and electrochemical stability. Electropolymerization of PEDOT:tetrafluoroborate was carried out in three different solvents: propylene carbonate, acetonitrile, and water. The stability of the coatings was assessed via ultrasonication, phosphate buffer solution soaking test, autoclave sterilization, and electrical pulsing. Coatings prepared with propylene carbonate or acetonitrile possessed excellent electrochemical stability and survived autoclave sterilization, prolonged soaking, and electrical stimulation without major changes in electrochemical properties. Stimulating microelectrodes were implanted in rats and stimulated daily, for 7 and 15 days. The electrochemical properties monitored in vivo demonstrated that the stimulation procedure for both coated and uncoated electrodes decreased the impedance.

Poly(3,4-ethylenedioxythiophene) (PEDOT) Coatings for High-Quality Electromyography Recording.

Conducting polymer coatings on metal electrodes are an efficient solution to improve neural signal recording and stimulation, due to their mixed electronic-ionic conduction and biocompatibility. To date, only a few studies have been reported on conducting polymer coatings on metallic wire electrodes for muscle signal recording. Chronic muscle signal recording of freely moving animals can be challenging to acquire with coated electrodes, due to muscle movement around the electrode that can increase instances of coating delamination and device failure. The poor adhesion of conducting polymers to some inorganic substrates and the possible degradation of their electrochemical properties after harsh treatments, such as sterilization, or during implantation limits their use for biomedical applications. Here, we demonstrate the mechanical and electrochemical stability of the conducting polymer, poly(3,4-ethylenedioxythiophene) (PEDOT) doped with LiClO4, deposited on stainless steel multistranded wire electrodes for invasive muscle signal recording in mice. The mechanical and electrochemical stability was achieved by tuning the electropolymerization conditions. PEDOT-coated and bare stainless steel electrodes were implanted in the neck muscle of five mice for electromyographic (EMG) activity recording over a period of 6 weeks. The PEDOT coating improved the electrochemical properties of the stainless steel electrodes, lowering the impedance, resulting in an enhanced signal-to-noise ratio during in vivo EMG recording compared to bare electrodes.

Electrolyte-gated transistors based on phenyl-C61-butyric acid methyl ester (PCBM) films: bridging redox properties, charge carrier transport and device performance.

The n-type organic semiconductor phenyl-C61-butyric acid methyl ester (PCBM), a soluble fullerene derivative well investigated for organic solar cells and transistors, can undergo several successive reversible, diffusion-controlled, one-electron reduction processes. We exploited such processes to shed light on the correlation between electron transfer properties, ionic and electronic transport as well as device performance in ionic liquid (IL)-gated transistors. Two ILs were considered, based on bis(trifluoromethylsulfonyl)imide [TFSI] as the anion and 1-ethyl-3-methylimidazolium [EMIM] or 1-butyl-1-methylpyrrolidinium [PYR14] as the cation. The aromatic structure of [EMIM] and its lower steric hindrance with respect to [PYR14] favor a 3D (bulk) electrochemical doping. As opposed to this, for [PYR14] the doping seems to be 2D (surface-confined). If the n-doping of the PCBM is pursued beyond the first electrochemical process, the transistor current vs. gate-source voltage plots in [PYR14][TFSI] feature a maximum that points to the presence of finite windows of high conductivity in IL-gated PCBM transistors.