Downplaying the role of water in the rheological changes of conducting polymers by using water-in-salt electrolytes.

Volumetric changes associated with solvent/electrolyte exchange in electronic conducting polymers (ECPs) play an important role in the mechanical stability of the polymers, as these changes are a critical factor in ECP-based energy storage devices. Thus, the present work explores the hindering of such volumetric deformations for polypyrrole films doped with dodecylbenzenesulphonate (PPy(DBS)) by employing highly concentrated aqueous electrolytes (or water-in-salt electrolytes, WiSEs), and their effects over the corresponding electrochemical capacitor cell energy retention. Electrochemical quartz crystal microbalance with dissipation monitoring measurements for thin PPy(DBS) films in the WiSEs revealed negligible dissipation changes (ΔDn ≈ 0), in contrast with those in dilute aqueous electrolyte (ΔDn ≠ 0), indicating inexpressive structural deformation of PPy(DBS) in the WiSE. This phenomenon is observed for thick freestanding PPy(DBS) films, which presented a maximum bending angle decay from ∼56° (diluted aqueous electrolyte) to 3.5° when working in the WiSE, thus proving the hindering of film bending. The observed trends are reflected in the PPy(DBS) cell energy retention, where the use of a WiSE decreased cell energy fading by 30% after 600 cycles, in comparison with cells based on diluted electrolytes.

An Overview on the Development of Electrochemical Capacitors and Batteries - part II.

In the second part of the review on electrochemical energy storage, the devolvement of batteries is explored. First, fundamental aspects of battery operation will be given, then, different materials and chemistry of rechargeable batteries will be explored, including each component of the cell. In negative electrodes, metallic, intercalation and transformation materials will be addressed. Examples are Li or Na metal batteries, graphite and other carbonaceous materials (such as graphene) for intercalation of metal-ions and transition metal oxides and silicon for transformation. In the positive electrode section, materials for intercalation and transformation will be reviewed. The state-of-the-art on intercalation as lithium cobalt oxide and nickel containing oxides will be approached for intercalation materials, whereas sulfur and metal-air will also be explored for transformation. Alongside, the role of electrolyte will be discussed concerning performance and safety, with examples for the next generation devices. Finally, a general future perspective will address both electrochemical capacitors and batteries.

An Overview on the Development of Electrochemical Capacitors and Batteries - Part I.

The Nobel Prize in Chemistry 2019 recognized the importance of Li-ion batteries and the revolution they allowed to happen during the past three decades. They are part of a broader class of electrochemical energy storage devices, which are employed where electrical energy is needed on demand and so, the electrochemical energy is converted into electrical energy as required by the application. This opens a variety of possibilities on the utilization of energy storage devices, beyond the well-known mobile applications, assisting on the decarbonization of energy production and distribution. In this series of reviews in two parts, two main types of energy storage devices will be explored: electrochemical capacitors (part I) and rechargeable batteries (part II). More specifically, we will discuss about the materials used in each type of device, their main role in the energy storage process, their advantages and drawbacks and, especially, strategies to improve their performance. In the present part, electrochemical capacitors will be addressed. Their fundamental difference to batteries is explained considering the process at the electrode/electrolyte surface and the impact in performance. Materials used in electrochemical capacitors, including double layer capacitors and pseudocapacitive materials will be reviewed, highlighting the importance of electrolytes. As an important part of these strategies, synthetic routes for the production of nanoparticles will also be approached (part I).

Kinetics, Assembling, and Conformation Control of L-Cysteine Adsorption on Pt Investigated by in situ FTIR Spectroscopy and QCM-D.

A quartz crystal microbalance method with dissipation (QCM-D) and attenuated total reflection Fourier-transform infrared (ATR-FTIRS) spectroscopy were used to study the adsorption of L-cysteine (L-Cys) on Pt. Through QCM-D, it was possible to verify that the viscoelastic properties of the adsorbed species play an important role in the adsorption, rendering Sauerbrey's equation inapplicable. The modelling of QCM-D data exposed two different processes for the adsorption reaction. The first one had an activation time and is fast, whereas the second is slow. These processes were also resolved by ATR-FTIRS and identified to be water and anion adsorption preceded by L-Cys adsorption. Both techniques reveal that the degree of surface coverage is pH dependent. Spectroscopic data indicate that the conformation of L-Cys(ads) changes with pH and that the structures do not fully agree with those proposed in literature for other metallic surfaces. The assembling of the adsorbed monolayer appeared to be very fast, and it was not possible to determine or quantify this kinetics. The conformation is also controlled by applied potential, and the anion adsorption and interfacial water depends on the conformation of the adsorbed molecules.

Ionic liquids containing tricyanomethanide anions: physicochemical characterisation and performance as electrochemical double-layer capacitor electrolytes.

We investigated the use of fluorine free ionic liquids (ILs) containing the tricyanomethanide anion ([C(CN)3]) as an electrolyte in electrochemical double-layer capacitors (EDLCs). Three cations were used; 1-butyl-3-methylimidazolium ([Im1,4]), N-butyl-N-methylpyrrolidinium ([Pyr1,4]) and N-butyl-N-methylpiperidinium ([Pip1,4]). Their physicochemical properties are discussed alongside with their performance as electrolytes. We found that the cyano-based ILs present higher ionic conductivity (9.4, 8.7 and 4.2 mS cm-1 at 25 °C for [Im1,4], [Pyr1,4] and [Pip1,4], respectively) than the widely studied IL containing the bis(trifluoromethylsulfonyl)imide anion, namely [Pyr1,4][Tf2N] (2.7 mS cm-1 at 25 °C). Of the three ILs investigated, [Pip1,4][C(CN)3] presents the widest electrochemical stability window, 3.0 V, while [Pyr1,4][C(CN)3] is stable up to 2.9 V and its [Tf2N] analogue can operate at 3.5 V. Despite operating at a lower voltage, [Pyr1,4][C(CN)3] EDLC is capable of delivering up to 4.5 W h kg-1 when operating at high specific power of 7.2 kW kg-1, while its [Pyr1,4][Tf2N] counterpart only delivered 3.0 W h kg-1 when operated at similar power.

Two phosphonium ionic liquids with high Li(+) transport number.

This work presents the physicochemical characterization of two ionic liquids (ILs) with small phosphonium cations, triethylpenthylphosphonium bis(trifluoromethanesulfonyl)imide ([P2225][Tf2N]) and (2-methoxyethyl)trimethylphosphonium bis(trifluoromethanesulfonyl)imide ([P222(201)][Tf2N]), and their mixtures with Li(+). Properties such as the electrochemical window, density, viscosity and ionic conductivity are presented. The diffusion coefficient was obtained using two different techniques, PGSE-NMR and Li electrodeposition with microelectrodes. In addition, the Li(+) transport number was calculated using the PGSE-NMR technique and an electrochemical approach. The use of these three techniques showed that the PGSE-NMR technique underestimates the diffusion coefficient for charged species. The Li(+) transport number was found to be as high as 0.54. Raman spectroscopy and molecular dynamics simulations were used to evaluate the short-range structure of the liquids. These experiments suggested that the interaction between the Li(+) and the Tf2N(-) anion is similar to that seen with other ILs containing the same anion. However, the MD simulations also showed that the Li(+) ions interact differently with the cation containing an alkyl ether chain. The results found in this work suggest that these Li(+) mixtures have promising potential to be applied as electrolytes in batteries.

Gel Biopolymer Electrolytes Based on Saline Water and Seaweed to Support the Large-Scale Production of Sustainable Supercapacitors.

Climate change and the demand for clean energy have challenged scientists worldwide to produce/store more energy to reduce carbon emissions. This work proposes a conductive gel biopolymer electrolyte to support the sustainable development of high-power aqueous supercapacitors. The gel uses saline water and seaweed as sustainable resources. Herein, a biopolymer agar-agar, extracted from red algae, is modified to increase gel viscosity up to 17-fold. This occurs due to alkaline treatment and an increase in the concentration of the agar-agar biopolymer, resulting in a strengthened gel with cohesive superfibres. The thermal degradation and agar modification mechanisms are explored. The electrolyte is applied to manufacture sustainable and flexible supercapacitors with satisfactory energy density (0.764 Wh kg-1 ) and power density (230 W kg-1 ). As an electrolyte, the aqueous gel promotes a long device cycle life (3500 cycles) for 1 A g-1 , showing good transport properties and low cost of acquisition and enabling the supercapacitor to be manufactured outside a glove box. These features decrease the cost of production and favor scale-up. To this end, this work provides eco-friendly electrolytes for the next generation of flexible energy storage devices.

Rheological changes and kinetics of water uptake by poly(ionic liquid)-based thin films.

Water uptake by thin films composed of the poly(ionic liquid) poly[diallyldimethylammonium bis(trifluoromethanesulfonyl)imide] (PDDATf2N) and the ionic liquid N,N-butylmethylpyrrolidinium bis(trifluoromethanesulfonyl)imide (Pyr1.4Tf2N) was studied with a quartz crystal microbalance with dissipation. The data obtained for films with different compositions during the passage of dry and wet N2 flow through the films were simulated with the Kevin-Voigt viscoelastic model for assessment of the mass of uptake water as well as the viscoelastic parameters. Our results show that the ionic liquid acts as a plasticizer, reducing the rigidity of the film and decreasing the capacity of water uptake. Introduction to a Li salt (LiTf2N) increases the water uptake capacity and also affects both elastic and viscous parameters due to aggregation among the ions from the ionic liquid and Li(+). However, due to the preferable interaction of Li(+) ions with water molecules, these aggregates are broken when the film is hydrated. In short, the presence of water in such films affects their mechanical properties, which can reflect in their performances as solid state electrolytes and ion-conducting membranes for electrochemical applications.

Electrochromic properties of a metallo-supramolecular polymer derived from tetra(2-pyridyl-1,4-pyrazine) ligands integrated in thin multilayer films.

The electrochromic behavior of iron complexes derived from tetra-2-pyridyl-1,4-pyrazine (TPPZ) and a hexacyanoferrate species in polyelectrolytic multilayer adsorbed films is described for the first time. This complex macromolecule was deposited onto indium-tin oxide (ITO) substrates via self-assembly, and the morphology of the modified electrodes was studied using atomic force microscopy (AFM), which indicated that the hybrid film containing the polyelectrolyte multilayer and the iron complex was highly homogeneous and was approximately 50 nm thick. The modified electrodes exhibited excellent electrochromic behavior with both intense and persistent coloration as well as a chromatic contrast of approximately 70%. In addition, this system achieved high electrochromic efficiency (over 70 cm(2) C(-1) at 630 nm) and a response time that could be measured in milliseconds. The electrode was cycled more than 10(3) times, indicating excellent stability.

Tandem X-ray absorption spectroscopy and scattering for in situ time-resolved monitoring of gold nanoparticle mechanosynthesis.

Current time-resolved in situ approaches limit the scope of mechanochemical investigations possible. Here we develop a new, general approach to simultaneously follow the evolution of bulk atomic and electronic structure during a mechanochemical synthesis. This is achieved by coupling two complementary synchrotron-based X-ray methods: X-ray absorption spectroscopy (XAS) and X-ray diffraction. We apply this method to investigate the bottom-up mechanosynthesis of technologically important Au micro and nanoparticles in the presence of three different reducing agents, hydroquinone, sodium citrate, and NaBH4. Moreover, we show how XAS offers new insight into the early stage generation of growth species (e.g. monomers and clusters), which lead to the subsequent formation of nanoparticles. These processes are beyond the detection capabilities of diffraction methods. This combined X-ray approach paves the way to new directions in mechanochemical research of advanced electronic materials.

Electrochemical quartz crystal microbalance with dissipation investigation of fibronectin adsorption dynamics driven by electrical stimulation onto a conducting and partially biodegradable copolymer.

Functional surface coatings are a key option for biomedical applications, from polymeric supports for tissue engineering to smart matrices for controlled drug delivery. Therefore, the synthesis of new materials for biological applications and developments is promising. Hence, biocompatible and stimuli-responsive polymers are interesting materials, especially when they present conductive properties. PEDOT-co-PDLLA graft copolymer exhibits physicochemical and mechanical characteristics required for biomedical purposes, associated with electroactive, biocompatible, and partially biodegradable properties. Herein, the study of fibronectin (FN) adsorption onto PEDOT-co-PDLLA carried out by an electrochemical quartz crystal microbalance with dissipation is reported. The amount of FN adsorbed onto PEDOT-co-PDLLA was higher than that adsorbed onto the Au surface, with a significant increase when electrical stimulation was applied (either at +0.5 or -0.125 V). Additionally, FN binds to the copolymer interface in an unfolded conformation, which can promote better NIH-3T3 fibroblast cell adhesion and later cell development.

Aging effect on vanadium oxide hybrid nanotubes.

Vanadium oxides present a rich magnetic phase diagram depending on the oxidation state of the V ions. In particular the vanadium oxide nanotubes (VO x NTs) present several promising perspectives for different technological applications for which it is essential to know the oxidation state of V ions, as well as to evaluate the stability with the aging time of the tubes. In this work we present a systematic study of the time evolution of the magnetic properties of VO x NTs. For this complete characterization, we used electron spin resonance (ESR) and dc-susceptibility techniques, which were supplemented with TEM microscopy and XANES. We observed that for aging in normal environmental conditions of pressure, temperature and humidity, the V4+ ions oxidize to V5+ . Although the multiwall tubular structure is maintained, this oxidation process produces a marked change in the magnetic properties. We conclude that the aging of the samples affects the V4+ /V5+ relationship in the VO x NTs, which may contribute to explain the significant dispersion of data reported in the bibliography.

Transport coefficients, Raman spectroscopy, and computer simulation of lithium salt solutions in an ionic liquid.

Lithium salt solutions of Li(CF3SO2)2N, LiTFSI, in a room-temperature ionic liquid (RTIL), 1-butyl-2,3-dimethyl-imidazolium cation, BMMI, and the (CF3SO2)2N(-), bis(trifluoromethanesulfonyl)imide anion, [BMMI][TFSI], were prepared in different concentrations. Thermal properties, density, viscosity, ionic conductivity, and self-diffusion coefficients were determined at different temperatures for pure [BMMI][TFSI] and the lithium solutions. Raman spectroscopy measurements and computer simulations were also carried out in order to understand the microscopic origin of the observed changes in transport coefficients. Slopes of Walden plots for conductivity and fluidity, and the ratio between the actual conductivity and the Nernst-Einstein estimate for conductivity, decrease with increasing LiTFSI content. All of these studies indicated the formation of aggregates of different chemical nature, as it is corroborated by the Raman spectra. In addition, molecular dynamics (MD) simulations showed that the coordination of Li+ by oxygen atoms of TFSI anions changes with Li+ concentration producing a remarkable change of the RTIL structure with a concomitant reduction of diffusion coefficients of all species in the solutions.

Shielding of ionic interactions by sulfur dioxide in an ionic liquid.

The effect of adding SO2 on the structure and dynamics of 1-butyl-3-methylimidazolium bromide (BMIBr) was investigated by low-frequency Raman spectroscopy and molecular dynamics (MD) simulations. The MD simulations indicate that the long-range structure of neat BMIBr is disrupted resulting in a liquid with relatively low viscosity and high conductivity, but strong correlation of ionic motion persists in the BMIBr-SO2 mixture due to ionic pairing. Raman spectra within the 5

Immobilization of catalysts of biological interest on porous oxidized silicon surfaces.

The present paper deals with the immobilization of redox mediators and proteins onto protected porous silicon surfaces to obtain their direct electrochemical reactions and to retain their bioactivities. This paper shows that MP-11 and viologens are able to establish chemical bonds with 3-aminopropyltriethoxylsilane-modified porous silicon surface. The functionalization of the surfaces have been fully characterized by energy dispersive X-ray analysis (EDX) and X-ray photoelectron spectroscopy (XPS) to examine the immobilization of these mediators onto the solid surface. Amperometric and open circuit potential measurements have shown the direct electron transfer between glucose oxidase and the electrode in the presence of the viologen mediator covalently linked to the 3-aminopropyltriethoxylsilane (APTES)-modified porous silicon surfaces.

Improved Performance of Ionic Liquid Supercapacitors by using Tetracyanoborate Anions.

Supercapacitors are energy storage devices designed to operate at higher power densities than conventional batteries, but their energy density is still too low for many applications. Efforts are made to design new electrolytes with wider electrochemical windows than aqueous or conventional organic electrolytes in order to increase energy density. Ionic liquids (ILs) with wide electrochemical stability windows are excellent candidates to be employed as supercapacitor electrolytes. ILs containing tetracyanoborate anions [B(CN)4] offer wider electrochemical stability than conventional electrolytes and maintain a high ionic conductivity (6.9 mS cm-1). Herein, we report the use of ILs containing the [B(CN)4] anion for such an application. They presented a high maximum operating voltage of 3.7 V, and two-electrode devices demonstrate high specific capacitances even when operating at relatively high rates (ca. 20 F g-1 @ 15 A g-1). This supercapacitor stored more energy and operated at a higher power at all rates studied when compared with cells using a commonly studied ILs.

The sulfur dioxide-1-butyl-3-methylimidazolium bromide interaction: drastic changes in structural and physical properties.

The contact between minor amounts of SO2 and crystalline 1-butyl-3-methyl-imidazolium bromide (BMIBr) causes the almost immediate melting of the ionic liquid (mp 45 degrees C) as well as a dramatic decrease in its viscosity in comparison to the pure molten phase. The same behavior was observed for other halide ionic liquids of higher melting points (70, 135, and 220 degrees C). The Raman spectrum of BMIBr-SO2 clearly indicates a specific charge transfer interaction involving SO2 and the halide. The measurements of ionic conductivity and diffusion coefficients obtained for the neat BMIBr (molten phase) and for the BMIBr-SO2 strongly suggest a higher degree of ionic association in the presence of SO2. Molecular dynamic simulations indicate that although the cation-anion distance is preserved in the short range, there is a variation in the interionic distances in the second shell, leading to a less organized structure in the long range. The modulation of the structural and physical properties of ionic liquids by SO2 and the convenient choice of the ions for gas absorption are suggested.

Design of molecular wires based on supramolecular structures for application in glucose biosensors.

In the present work, the synthesis and the spectroelectrochemical characterization of a novel iron compound derived of tetra-2-pyridyl-1,4-pyrazine (TPPZ) with hexacyanoferrate species forming a very stable supramolecular complex in the presence of polypyrrole (PPY) matrix, is described. The hybrid material has shown excellent catalytic activity towards H(2)O(2) detection that makes it suitable for being used as redox mediator in a glucose biosensor. The hybrid FeTPPZFeCN/PPY film presents satisfactory detection limits and high sensitivity for H(2)O(2) in the presence of K(+) or Na(+) ions. For the glucose biosensor, a linear range up to 1.1 mmoll(-1) of glucose was observed with no interferences. In this case, the sensitivities obtained were 7.88 and 5.90 microAmmol(-1)lcm(-2) in phosphate buffer or NaCl solutions, respectively. The good sensitivity is related to the presence of a high-dimensional structure based on polypyridine type ligands providing an "electron antennae effect" facilitating electron tunneling between the protein and the electrode.

Layer-by-layer nanostructured hybrid films of polyaniline and vanadium oxide.

Supramolecular structures of polyaniline (PANI) and vanadium oxide (V2O5) have been assembled via the electrostatic layer-by-layer (ELBL) technique. Strong ionic interactions and H-bonding impart unique features to the ELBL films, which are distinct from cast films obtained with the same materials. The interactions were manifested in UV-vis and Fourier transform infrared spectroscopy data. They are enhanced by the intimate contact between the components, as the films are molecularly thin, with 25 A per PANI/V2O5 bilayer.

Physicochemical properties of three ionic liquids containing a tetracyanoborate anion and their lithium salt mixtures.

Given their relevant physicochemical properties, ionic liquids (ILs) are attracting great attention as electrolytes for use in different electrochemical devices, such as capacitors, sensors, and lithium ion batteries. In addition to the advantages of using ILs containing lithium cations as electrolytes in lithium ion batteries, the Li(+) transport in ILs containing the most common anion, bis(trifluoromethanesulfonyl) imide anion ([Tf2N]), is reportedly small; therefore, its contribution to the overall conductivity is also low. In this work, we describe the preparation and characterization of two new and one known IL containing the tetracyanoborate anion ([B(CN)4]) as the anionic species. These ILs have high thermal and chemical stabilities, with almost twice the ionic conductivity of the [Tf2N] ILs and, most importantly, provide a greater role for the Li(+) ion throughout the conductivity process. The experimental ionic conductivity and self-diffusion coefficient data show that the [B(CN)4]-based ILs and their Li(+) mixtures have a higher number of charge carriers. Molecular dynamics simulations showed a weaker interaction between Li(+) and [B(CN)4] than that with [Tf2N]. These results may stimulate new applications for ILs that have good Li(+) transport properties.