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.

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.

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.

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).

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.

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.

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.

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.

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.

Probing the local environment of hybrid materials designed from ionic liquids and synthetic clay by Raman spectroscopy.

Hybrid organic-inorganic material containing Laponite clay and ionic liquids forming cations have been prepared and characterized by FT-Raman spectroscopy, X-ray diffraction, and thermal analysis. The effect of varying the length of the alkyl side chain and conformations of cations has been investigated by using different ionic liquids based on piperidinium and imidazolium cations. The structure of the N,N-butyl-methyl-piperidinium cation and the assignment of its vibrational spectrum have been further elucidated by quantum chemistry calculations. The X-ray data indicate that the organic cations are intercalated parallel to the layers of the clay. Comparison of Raman spectra of pure ionic liquids with different anions and the resulting solid hybrid materials in which the organic cations have been intercalated into the clay characterizes the local environment experienced by the cations in the hybrid materials. The Raman spectra of hybrid materials suggest that the local environment of all confined cations, in spite of this diversity in properties, resembles the liquid state of ionic liquids with a relatively disordered structure.

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.

Influence of the water content on the structure and physicochemical properties of an ionic liquid and its Li+ mixture.

The effect of water on the hydrophobic ionic liquid (IL) 1-n-butyl-2,3-dimethylimidazolium bis(trifluoromethanesulfonylimide) and its Li(+) mixture was evaluated. The electrochemical stability, density, viscosity, and ionic conductivity were measured for both systems in different concentrations of water. The presence of Li(+) causes a large increase in the water absorption ability of the IL. The experimental results suggest a break of the interactions between Li(+) and Tf2N(-) anions in the strong aggregates formed in dried Li(+) mixtures, modifying the size and physicochemical nature of these aggregates. It is also observed that the size of the ions aggregates with formal charge increases at high temperature and decreases the mobility of the charge carrier, explaining the break in the Walden rules at high temperature. Raman spectroscopy and molecular dynamic simulations show the structural change of these systems. In neat ILs, the water molecules interact mainly among each other, while in the Li(+) mixtures, water interacts preferentially with the metallic cation, causing an important change in the aggregates present in this system.

Ni(ii)-modified solid substrates as a platform to adsorb His-tag proteins.

This work investigated a simple and versatile modification to a solid substrate to develop electrochemical bio-recognition platforms based on bio-affinity interactions between histidine (His)-tagged proteins and Ni(ii) surface sites. Carboxylate (COO)-functionalized substrates were prepared in multiple steps, initiated with an amino-terminated self-assembled monolayer (SAM) on polycrystalline gold. Surface enhanced Raman spectroscopy (SERS), quartz crystal microbalance with dissipation monitoring (QCM-D) and contact angle measurements were used to follow the modification process. Upon completion of the modification process, the surface COO-Ni(ii) chelate complex and the coordination mode used to bind the His-tag proteins were characterized by X-ray absorption near-edge spectroscopy (XANES). Finally, the electrochemical stability and response of the modified substrates were evaluated. The versatility of the modification process was verified using silica as the substrate. QCM-D and SERS results indicated that two types of films were formed: a COO-terminated SAM, which resulted from the reduction of previously incorporated surface aldehyde groups, and a physically adsorbed polymeric glutaraldehyde film, which was produced in the alkaline medium. XANES spectral features indicated that COO-Ni(ii) formed a non-distorted octahedral complex on the substrate. The electrochemical stability and response towards a redox mediator of the COO-Ni(ii)-terminated SAM indicated that this platform could be easily coupled to an electrochemical method to detect bio-recognition events.

Ether-Bond-Containing Ionic Liquids as Supercapacitor Electrolytes.

Electrochemical capacitors (ECs) are electrical energy storage devices that have the potential to be very useful in a wide range of applications, especially where there is a large disparity between peak and average power demands. The use of ionic liquids (ILs) as electrolytes in ECs can increase the energy density of devices; however, the viscosity and conductivity of ILs adversely influence the power density of the device. We present experimental results where several ILs containing different cations have been employed as the electrolyte in cells containing mesoporous carbon electrodes. Specifically, the behavior of ILs containing an ether bond in an alkyl side chain are compared with those of a similar structure and size but containing purely alkyl side chains. Using electrochemical impedance spectroscopy and constant current cycling, we show that the presence of the ether bond can dramatically increase the specific capacitance and reduce device resistance. These results have the important implication that such ILs can be used to tailor the physical properties and electrochemical performance of IL-based electrolytes.

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.

Effect of SO2 on the transport properties of an imidazolium ionic liquid and its lithium solution.

Transport coefficients have been measured as a function of the concentration of sulfur dioxide, SO(2), dissolved in 1-butyl-2,3-dimethylimidazolium bis(trifluoromethylsulfonyl)imide, [BMMI][Tf(2)N], as well as in its lithium salt solution, Li[Tf(2)N]. The SO(2) reduces viscosity and density and increases conductivity and diffusion coefficients in both the neat [BMMI][Tf(2)N] and the [BMMI][Tf(2)N]-Li[Tf(2)N] solution. The conductivity enhancement is not assigned to a simple viscosity effect; the weakening of ionic interactions upon SO(2) addition also plays a role. Microscopic details of the SO(2) effect were unraveled using Raman spectroscopy and molecular dynamics (MD) simulations. The Raman spectra suggest that the Li(+)-[Tf(2)N] interaction is barely affected by SO(2), and the SO(2)-[Tf(2)N] interaction is weaker than previously observed in an investigation of an ionic liquid containing the bromide anion. Transport coefficients calculated by MD simulations show the same trend as the experimental data with respect to SO(2) content. The MD simulations provide structural information on SO(2) molecules around [Tf(2)N], in particular the interaction of the sulfur atom of SO(2) with oxygen and fluorine atoms of the anion. The SO(2)-[BMMI] interaction is also important because the [BMMI] cations with above-average mobility have a larger number of nearest-neighbor SO(2) molecules.

Ether-bond-containing ionic liquids and the relevance of the ether bond position to transport properties.

The ionic liquids (ILs) 1-ethoxyethyl-2,3-dimethylimidazolium bis(trifluoromethanesulfonyl)imide, [EtO(CH(2))(2)MMI][Tf(2)N], and N-(ethoxyethyl)-N-methylmorpholinium bis(trifluoromethanesulfonyl)imide, [EtO(CH(2))(2)MMor][Tf(2)N] were synthesized, and relevant properties, such as thermal stability, density, viscosity, electrochemical behavior, ionic conductivity, and self-diffusion coefficients for both ionic species, were measured and compared with those of their alkyl counterparts, 1-n-butyl-2,3-dimethylimidazolium bis(trifluoromethanesulfonyl)imide, [BMMI][Tf(2)N], and N-n-butyl-N-methylpiperidinium bis(trifluoromethanesulfonyl)imide, [BMP][Tf(2)N] and N-n-butyl-N-methylmorpholinium bis(trifluoromethanesulfonyl)imide [BMMor][Tf(2)N]. This comparison was done to evaluate the effects caused by the presence of the ether bond in either the side chain or in the organic cation ring. The salt, LiTf(2)N, was added to the systems to estimate IL behavior with regard to lithium cation transport. Pure [EtO(CH(2))(2)MMI][Tf(2)N] and their LiTf(2)N solutions showed low viscosity and the highest conductivity among the ILs studied. The H(R) (AC conductivity/NMR calculated conductivity ratio) values showed that, after addition of LiTf(2)N, ILs containing the ether bond seemed to have a greater number of charged species. Structural reasons could explain these high observed H(R) values for [EtO(CH(2))(2)MMor][Tf(2)N].