Electrolyte | EPFL Graph Search

An electrolyte is a medium containing ions that is electrically conducting through the movement of those ions, but not conducting electrons. This includes most soluble salts, acids, and bases dissolved in a polar solvent, such as water. Upon dissolving, the substance separates into cations and anions, which disperse uniformly throughout the solvent. Solid-state electrolytes also exist. In medicine and sometimes in chemistry, the term electrolyte refers to the substance that is dissolved. Electrically, such a solution is neutral. If an electric potential is applied to such a solution, the cations of the solution are drawn to the electrode that has an abundance of electrons, while the anions are drawn to the electrode that has a deficit of electrons. The movement of anions and cations in opposite directions within the solution amounts to a current. Some gases, such as hydrogen chloride (HCl), under conditions of high temperature or low pressure can also function as electrolytes. Electr

Thermodynamics of organic electrochemical transistors

Hsin Tseng

Though models describing the operating mechanism of organic electrochemical transistors (OECTs) have been developed, these models are unable to accurately reproduce OECT electrical characteristics. Here, the authors report a thermodynamic-based framework that accurately models OECT operation. Despite their increasing usefulness in a wide variety of applications, organic electrochemical transistors still lack a comprehensive and unifying physical framework able to describe the current-voltage characteristics and the polymer/electrolyte interactions simultaneously. Building upon thermodynamic axioms, we present a quantitative analysis of the operation of organic electrochemical transistors. We reveal that the entropy of mixing is the main driving force behind the redox mechanism that rules the transfer properties of such devices in electrolytic environments. In the light of these findings, we show that traditional models used for organic electrochemical transistors, based on the theory of field-effect transistors, fall short as they treat the active material as a simple capacitor while ignoring the material properties and energetic interactions. Finally, by analyzing a large spectrum of solvents and device regimes, we quantify the entropic and enthalpic contributions and put forward an approach for targeted material design and device applications.

NATURE PORTFOLIO2022

Aqueous electrolytes for high-voltage batteries and supercapacitors

David Reber

Lithium-ion batteries are widely implemented as energy storage devices due to their high energy density and low cost. They enabled modern portable electronics and electric ve-hicles, and are key to manage the integration of intermittent renewable electricity sources, such as solar and wind, into the power grid and decentralized microgrids. The use of flam-mable organic electrolytes however raises safety concerns, particularly for large-scale sta-tionary batteries. Furthermore, supply chain risks and the use of critical raw materials are a major challenge for the ongoing battery revolution. Aqueous electrolytes offer promising properties, as they are inherently non-flammable and potentially more cost effective. Combined with electrode materials based on abundant raw materials, aqueous batteries are among the most promising candidates to replace cur-rent battery chemistries relying on critical cobalt and flammable organic electrolytes. How-ever, due to the narrow electrochemical stability window of water (practically ca. 1.5 V), aqueous batteries have not yet met the energy density to be serious competitors to current lithium-ion battery technology. The goal of this thesis was to develop aqueous electrolytes with enhanced electrochem-ical stability, thus enabling new high-voltage cell chemistries. Exploring aqueous electrolytes with high salt concentrations, so-called water-in-salt electrolytes, we significantly increased the electrochemical stability and developed highly stable 2 V class aqueous sodium-ion bat-teries. Operating near the solubility limit of the electrolyte salt, crystallization turned out to be a major challenge for water-in-salt electrolytes. In this thesis, we demonstrated that add-ing highly asymmetric anions into the solution can effectively suppress crystallization, allow-ing stable operation of saturated electrolytes at temperatures as low as -10 °C. We further examined the impact of anion asymmetry on the local solution structure and dynamics using molecular dynamics simulations, relating the enhanced supercooling to sustained rotational motion of the asymmetric anion. Further, we demonstrate that the anion has a crucial impact on solution structure and cell performance. We establish that high salt concentration alone does not guarantee high-voltage stability and that due to the limited solubility of most sodium salts new approaches are needed. We provide guidelines for future work and the evaluation of experimental data in order to spur progress in the field of aqueous batteries.

EPFL2020

Chemical and electrochemical promotion of supported rhodium catalyst

Olena Baranova

The chemical and electrochemical promotion of highly dispersed nanofilm Rh catalysts (dispersion: about 10 %, film thickness: 40 nm) has been investigated for the first time. To this end Rh metal was sputter-deposited, either on a purely ionic conductor (8 % Y2O3-stabilized ZrO2) or on a mixed ionic-electronic conductor (TiO2), the latter being a highly dispersed layer of TiO2 (4 µm) deposited on YSZ. These catalysts are designated as Rh/YSZ and Rh/TiO2/YSZ, respectively. It was established analytically that both in the Rh/YSZ and in the Rh/TiO2/YSZ system, the catalyst films have a nanoparticle-size grain structure. The Rh supported on titania is rather porous, exhibiting a higher dispersion and surface area than Rh on YSZ. Both after reduction (H2, T=400 °C) and after oxidation (O2, T=400 °C), Rh supported on TiO2 was found to be in a more highly reduced state than Rh on YSZ. After reducing treatment, the Rh/TiO2/YSZ samples contain a larger amount of weakly bonded oxygen, which can be attributed to oxygen "backspillover" from the TiO2. A major feature of this research was the electrochemical characterization of the oxygen/Rh/solid electrolyte three-phase boundary by steady-state polarization measurements and by impedance spectroscopy. These are powerful techniques for extracting experimental trends and details that are useful for an understanding of the electrochemical promotion principles. It was shown that the exchange current densities at the Rh/solid electrolyte interface are lower on account of the TiO2 layer. The exchange current densities are more than twice lower at Rh/TiO2(4 µm)/YSZ than at Rh/YSZ, demonstrating that the former interface is much more polarizable. The mechanism of oxygen exchange occurring close to equilibrium (O2/O2- couple) was investigated for the first time at Rh catalyst electrodes interfaced with solid electrolyte. The processes of cathodic oxygen reduction and anodic oxygen evolution are not symmetric, but they are similar in the two systems, Rh/YSZ and Rh/TiO2(4 µm)/YSZ. The cathodic process consists of three steps: dissociative adsorption of oxygen at the gas-exposed Rh surface, atomic oxygen diffusion to the electrochemical reaction sites (ERS), and a two-electron transfer to this oxygen on the ERS. The cathodic process is limited by interfacial diffusion of oxygen atoms from the gas-exposed metal surface to the ERS. The anodic process includes two steps: two-electron transfer reaction, which is the rate-determining step, and oxygen desorption to the gas phase. With data obtained from impedance spectroscopy at the equilibrium potential, it was possible to confirm the reaction scheme proposed. It was demonstrated that Rh nanofilm catalysts interfaced with YSZ or TiO2/YSZ can be electrochemically promoted for the reaction of ethylene oxidation. Small anodic currents cause periodic oscillations in catalytic rate and potential of the Rh/YSZ catalyst, while at Rh/TiO2/YSZ they give rise to a stable and reversible rate enhancement by up to a factor 80. The increase in ethylene oxidation rate is up to 2000 times larger than the electrochemical rate, I/2F, of O2- oxidation. The pronounced electrochemical promotion behavior that has been observed is due to the anodically controlled migration of O2- species from the electrolyte to the Rh/gas interface. At the Rh surface, these species destabilize the formation of rhodium surface oxide (Rh2O3). The existence of backspillover oxygen species has been confirmed by impedance measurements under positive applied potential. Another significant result for heterogeneous catalysis is the finding that thick as well as thin films of Rh/TiO2/YSZ catalyst are open to chemical promotion of ethylene oxidation and partial methane oxidation, ie, they offer a higher catalytic activity and stability than the Rh/YSZ catalysts. The modification of catalytic activity observed for Rh/TiO2/YSZ was attributed to either a "long-range" electronic-type SMSI mechanism or to a self-driven electrochemical promotion mechanism. In both cases, the ultimate cause of promotion are different work functions of catalyst and support. Equilibration of the work functions of two solids in contact induces surface charging, a migration of O2- ions to the catalyst/gas interface, and a weakening of the Rh-O chemisorptive bonds. It facilitates reduction of oxidized surface sites. Another important achievement of the present work was that of exploring and confirming the possibilities of current-assisted activation of Rh/TiO2/YSZ catalysts. In partial methane oxidation using close to stoichiometric gas compositions (CH4 : O2 = 2 : 1) at 550 °C, the inactive (oxidized) Rh/TiO2/YSZ catalyst was successfully activated by applied currents, either positive or negative. This phenomenon is an example of "permanent" electrochemical promotion furnishing a permanent rate enhancement ratio of γ = 11. The activation by negative currents is explained in terms of an electrochemical reduction of rhodium surface oxide, while the activation by positive currents can be explained by the mechanism of electrochemical promotion.

EPFL2005