Viscosity Of Electrolyte Research Articles

Sustainable Electrochemical Synthesis of Dry Formaldehyde from Anhydrous Methanol

Facing climate change, we switch our energy sources from fossil fuels to renewable electricity. This often requires the electrification of industrial processes that have so far been thermally driven. One of these large-scale processes is the methanol oxidation to formaldehyde with a yearly production of ca 45 MT worldwide. Formaldehyde is a versatile C1 building block that is used, for example, in the syntheses of polymers, resins and complex organic molecules. Conventionally, it is obtained by methanol oxidation with air to formaldehyde and water.[1] Attempts to electrify this process have been mainly studied in aqueous electrolytes, where a reasonable formaldehyde production was proven on the lab scale, but these reactions still struggle with the subsequent oxidation to CO or CO2 due to the presence of water.[2] Furthermore, for many products, formaldehyde is required in its dry form, such that energy intensive drying processes are needed subsequently.[3] The first promising results for the electrochemical conversion of anhydrous methanol to formaldehyde on platinum electrodes were obtained in the 1960s. Faraday efficiencies of up to 75% were reported at low current densities (~3 mA cm-2) for batch systems under ice-bath cooling.[4] In this work, we report the successful oxidation of anhydrous methanol to formaldehyde and hydrogen.[5] We not only verify the initial reports, now with modern reference electrodes and reliable measurement procedures, but also make the next step in the scaling of the process. Based on the reported setup, we changed to a non-aqueous reference electrode and worked at room temperature. Chronoamperometries over 2 hours yielded Faraday efficiencies of up to 78% at current densities of up to 10 mA cm-2, which already surpassed the reported results. To scale the reaction up, we switched from an H-cell to a flow reactor with a surface area of 12 cm2 and applied current densities of up to 100 mA cm-2, i.e. a total of 1.2 A. This scaled-up system performed even better and reached Faraday efficiencies of up to 91% (Figure 1) and formaldehyde concentrations of up to 7.5 g L-1 in 30 minutes. Studying the impact of various reaction parameters, like current density, flow rate and electrolyte concentration, we furthermore reveal a fascinating potential dependent reactivity for the oxidation of anhydrous methanol. Our experiments indicate a vastly different behavior for the two mechanisms regarding mass transport and electrolyte viscosity and basicity. Our results proof that the electrochemical synthesis of formaldehyde is selective and able to produce significant amounts of formaldehyde. The whole synthesis can be carried out anhydrously, which avoids energy intensive water removal for the industrial synthesis of resins, glues and polymers, and further recycles H2 from methanol as the cathode product. The robust behavior at elevated current densities is vital for further scale up and shows potential for industrial application.

Challenges and Prospects of Low-Temperature Rechargeable Batteries: Electrolytes, Interfaces, and Electrodes.

Rechargeable batteries have been indispensable for various portable devices, electric vehicles, and energy storage stations. The operation of rechargeable batteries at low temperatures has been challenging due to increasing electrolyte viscosity and rising electrode resistance, which lead to sluggish ion transfer and large voltage hysteresis. Advanced electrolyte design and feasible electrode engineering to achieve desirable performance at low temperatures are crucial for the practical application of rechargeable batteries. Herein, the failure mechanism of the batteries at low temperature is discussed in detail from atomic perspectives, and deep insights on the solvent-solvent, solvent-ion, and ion-ion interactions in the electrolytes at low temperatures are provided. The evolution of electrode interfaces is discussed in detail. The electrochemical reactions of the electrodes at low temperatures are elucidated, and the approaches to accelerate the internal ion diffusion kinetics of the electrodes are highlighted. This review aims to deepen the understanding of the working mechanism of low-temperature batteries at the atomic scale to shed light on the future development of low-temperature rechargeable batteries.

Effect of Triton X-100 surfactant concentration on the wettability of polyethylene-based separators used in supercapacitors

Polyethylene-based separators are generally unsuitable for aqueous supercapacitors due to their poor wettability with the electrolyte, which impedes ion transport. However, incorporating Triton X-100 (2-[4-(2,4,4-trimethylpentan-2-yl)phenoxy]ethanol) into the aqueous sulfuric acid (H2SO4) electrolyte improves the wettability of polyethylene and facilitates ionic movement through its pores. In this study, Triton X-100 was added to 1.0 M H2SO4 at various concentrations (0.122%–1.210% V/V) to evaluate its impact on supercapacitor performance. Supercapacitors were assembled using activated carbon-filled carbon cloth electrodes, each of the above electrolytes and polyethylene sheet separators. Scanning electron microscopy revealed that the carbon cloth exhibited a uniform fiber distribution and high surface area for activated carbon integration. The polyethylene separator displayed a porous structure with an average pore size of 165 ± 35 nm. Triton X-100 significantly reduced the water contact angle from 101.5° (without surfactant) to 30.2° (with 1.21% V/V Triton X-100), enhancing polyethylene’s wettability. This change from hydrophobic to hydrophilic characteristics enabled the formation of an electrical double layer at the separator/electrolyte interface, improving ionic transport. However, higher Triton X-100 concentrations increased the electrolyte's viscosity, which impeded ion movement. The highest specific capacitance of 55.3 F/g (at a scan rate of 0.005 V s−1) was achieved with 0.488% V/V Triton X-100. The specific capacitance varied with surfactant concentration in a complex manner, influenced by micelle formation and precipitation. These findings were corroborated by cyclic voltammetry and AC impedance spectroscopy.

Low‐temperature performance of Na‐ion batteries

AbstractSodium‐ion batteries (NIBs) have become an ideal alternative to lithium‐ion batteries in the field of electrochemical energy storage due to their abundant raw materials and cost‐effectiveness. With the progress of human society, the requirements for energy storage systems in extreme environments, such as deep‐sea exploration, aerospace missions, and tunnel operations, have become more stringent. The comprehensive performance of NIBs at low temperatures (LTs) has also become an important consideration. Under LT conditions, challenges such as increased viscosity of electrolyte, abnormal growth of solid electrolyte interface, and poor contact between collector and electrode materials emerge. The aforementioned issues hinder the diffusion kinetics of sodium ions (Na+) at the electrode/electrolyte interface and cause rapid degradation of battery performance. Consequently, the optimization of electrolyte composition and cathode/anode materials becomes an effective approach to improve LT performance. This review discusses the conduction behavior and limiting factors of Na+ in both solid electrodes and liquid electrolytes at LT. Furthermore, it systematically reviews the recent research progress of LT NIBs from three aspects: cathode materials, anode materials, and electrolyte components. This review aims to provide a valuable reference for developing high‐performance LT NIBs.

Refractive Laser Beam Measuring Diffusion Coefficient of Concentrated Battery Electrolytes

A thorough understanding of electrolyte transport properties is crucial in the development of alternative battery technology. As a key parameter, the diffusion coefficient offers important insights into the behavior of electrolytes, especially for fast charge of high-energy batteries. Existing methods of measurement are often limited by redox species or offer questionable accuracy due to side reactions and/or disruption of the diffusion profile. A highly sensitive optical method was developed using a refractive laser beam through triangular diffusion column to measure the diffusion coefficient of concentrated battery electrolytes. The method based on Snell’s law can be applied to all liquid phase electrolytes since the refractive index is concentration dependent for all liquid electrolytes. This universal method relies on the deflection of a refractive laser beam passing through an electrolyte of a minor concentration gradient in a triangular diffusion column (Figure 1). A polarized HeNe laser was arranged to pass the beam through a right-angled triangular quartz precision cell, slightly rotated to the normal. The exact position of the refracted beam was located by a silicon photodiode-based position detector. Deflection calibration curves made simple conversion of beam position to concentration, and during the diffusion of two layered solutions, data points were collected every minute to produce a concentration profile descriptive of the 48-hour diffusion. Diffusion coefficients were calculated using a model based on OSM theory, accounting for multi-component concentrated systems in a restricted diffusion column.1 The measured diffusion coefficients are between 4.12x10-10 m2/s for 0.15 mol/kg ZnSO4 and 0.681x10-10 m2/s for 2.5 mol/kg ZnSO4 at 22.4 °C. The profile of concentration-dependent diffusion coefficients follows a non-linear inverse relationship described by the function D=4.943(1+m)-1.564 (Figure 2).Several other physicochemical properties of the same electrolytes were studied to correlate to the concentration-dependent diffusion coefficients, including refractive index, viscosity, conductivity, and microstructure analysis based on vibrational spectroscopy (Infrared and Raman). High concentration electrolytes with more ion pairs show increased viscosity which ultimately leads to smaller diffusion coefficients. A QCM-I instrument standard flow cell were used to determine the viscosity of ZnSO4 electrolyte and the concentration-dependent viscosity was fitted to the function η=1.06-0.476m+2.13m2-1.01m3+0.204m4. Interionic interactions also led to reduced conductivity at concentrations beyond 1.5mol/kg, despite the increased charge density of concentrated solutions. FT-IR spectrums allowed analyzation of increased charge density, which increased intensity of the O-H stretching peak in concentrated electrolytes, despite the decrease in the ratio of water. Competition between charge density and viscosity continues to challenge the efficiency of concentrated electrolytes.Lastly, we demonstrate the prototype in situ triangular cell to characterize the electrolyte in working batteries. The cell responds to short, low-voltage pulses with beam deflection and relaxation, and offers an opportunity as a novel in situ spectroscopic tool to characterize the battery electrolyte. Acknowledgments This work is supported by a grant from NSF (CBET-2243098).

Solving ZIB Challenges: The Dynamic Role of Water in Deep Eutectic Solvents Electrolyte

Zinc-Ion batteries (ZIBs) are considered one of the most promising technologies in the realm of post-lithium-ion batteries. Rechargeable chemistries with zinc anodes hold significant technological potential due to their high theoretical energy density, lower manufacturing costs, abundant raw materials, and inherent safety. ZIBs typically feature neutral or weakly acidic aqueous electrolytes and exhibit typical drawbacks of Zn anodes: hydrogen evolution, passivation, and shape changes.In aqueous electrolytes, two types of water molecules can be described: free water molecules and solvated water molecules that participate in Zn2+ solvation structure [Zn(H2O)6]2+. The free water easily reacts with metallic Zn at the electrode/electrolyte interface, leading to the aforementioned irreversibilities. Alternative electrolytes such as Deep Eutectic Solvents (DESs) can be used to modulate Zn solvation shell, preserving the green and safe characteristics of aqueous-based ones. DESs show relevant characteristics for battery applications, such as low vapor pressure, good thermal and chemical stability, non-flammability, easy moldability, wide electrochemical window, and structured interface. However, a main drawback for electrochemical applications is the high viscosity, low diffusivity, and sluggish kinetics.Water molecules can be added as a cosolvent to eutectic mixtures to increase the diffusion coefficient of electroactive species and reduce the electrolyte viscosity without destroying the eutectic nature by up to 40%. The hydration percentage of DES can modify the thickness of the electrolyte-electrode interface and the Zn2+ solvation structure. Thus, the tuning capability, on one hand, of the solution chemistry of Zn2+ containing electroactive species, and on the other hand, of the electrode–electrolyte interfacial structure and chemistry by the combined use of DES and water provides a flexible tool to control Zn plating and stripping processes.In this study, we investigate the electrochemistry of Zn in ethaline DES with different percentages of water (0%, 5%, 10%, 25%, 50%, 70%, respectively), transitioning from a water-in-salt structure to a salt-in-water one. Fundamental electrokinetic and electrocrystallization studies based on cyclic voltammetry and chronoamperometry at different cathodic substrates were complemented with galvanostatic cycling tests of Zn|Zn symmetric CR2032 coin cells, SEM imaging of electrodes, and in situ Surface Enhanced Raman spectroscopy (SERS).Moreover, the Zn solvation structure was investigated using spontaneous Raman spectroscopy . The employed methodology provided valuable insights into the Zn plating reaction. Water molecules are present in a "confined" state rather than a free one, directly interacting with choline cations and being trapped in the eutectic framework if the molar fraction is kept below 40%.When ZnSO4 is dissolved in anhydrous ethaline, the [ZnCl4]2− species is formed and stabilized by choline. The peculiarities of Zn2+ coordination were found to result in unusual voltammetric behavior, characterized by a cathodic peak in the cathodic branch of the anodic-going scan.Although tetrachlorozincate is the dominant species, it does not seem to be the complex from which Zn is deposited; indeed, [ZnCl4]2− has a very negative reduction potential. Mechanistic studies of Zn electrodeposition onto different cathodic materials have concluded that the metal is formed by the reduction of an intermediate Zn-containing species. The two organic components of the eutectic solvents can be dehydrogenated at a negative potential, forming RO-, which can replace one or more chloride ligands in [ZnCl4]2−.Hydrated DES exhibits faster kinetics, which, in turn, leads to a lower nucleation overpotential. This phenomenon has been explained with two different mechanisms occurring at the same time. Firstly, by increasing the hydration percentage in the eutectic framework, the coordination of Zn2+ changes, forming [ZnCl3(H2O)]-. The water molecule in the Zn2+ sheath has a lower energy barrier than chlorine in the step-by-step desolvation of Zn2+. Consequently, the [ZnCl3(H2O)]- complex exhibits a lower dissociation energy than [ZnCl4]2- present in anhydrous ethaline, resulting in a faster desolvation process that can reduce nucleation overpotentials.Secondly, water molecules hydrogen-bonded to DES components can be reduced at cathodic potential, forming H· radicals that can then participate in the decomposition of the organic component. This apparent side reaction can aid in the formation of RO- ligands that participate in the Zn-species undergoing reduction, thereby increasing the amount of reactants.This multi-technique approach, also applicable to the study of new electrolytes, leads to the optimization of DES hydration, reducing the presence of free water and addressing the main drawbacks associated with eutectic electrolytes. The nuanced understanding of the interplay between solvent composition, Zn solvation, and electrodeposition mechanisms paves the way for the development of more efficient and sustainable ZIB technologies. Figure 1

A Low-Temperature Na-MoS2 Rechargeable Battery.

It is generally accepted that the low-temperature environment typically augments electrolyte viscosity and impedes electrochemical kinetics, thereby diminishing battery performance. However, this prevailing notion, while valid in certain contexts, lacks universality, particularly regarding cycling stability. In this context, the Na-MoS2 batteries serve as a model to elucidate the impacts of low temperatures. By significantly suppressing the pulverization and amorphization of MoS2, the low-temperature milieu effectively mitigates the risk of micro-short circuits induced by the mass shuttling to the Na metal anode, thereby averting performance degradation by self-discharge. Upon cycling, the generated NaxMo3S4 intermediates only at low temperatures benefit the structural and electrochemical stabilizations to counteract the intrinsic performance degradation. The attenuation of kinetics at low temperatures facilitates the accumulation of Na2S, akin to a sustained-release agent within the electrode, steadily furnishing the capacity in long cycling. Moreover, the suppression of polysulfide dissolution and shuttling emerges as a pivotal factor contributing to the cycling stability at low-temperature. These findings provide a rewarding avenue toward understanding of the influence of low temperature on battery performance, as well as the design of practical electrodes and batteries for low-temperature applications.

Synthesis of a copolymer with a dynamic disulfide network and its application to a lithium-ion capacitor polymer electrolyte

Polymer electrolytes are being actively researched in energy storage applications because of their large operating potential range and cycle stability. Among them, poly(ethylene glycol) (PEG) is most commonly used to take advantage of the high ionic conductivity generated by polar functional groups in the structure. However, the polar functional group in the PEG structure has limitations that not only interfere with the movement of ions through interchain interaction, but also prevent the penetration of the polymer structure into the electrode material. In this paper, a copolymer into which a dynamic disulfide bonding network was introduced based on PEG was synthesized to control the polar functional effect of the polymer chain. The copolymer was then applied as a lithium-ion hybrid capacitor electrolyte. Due to the disconnection of the dynamic disulfide bond, the viscosity of the polymer electrolyte was reduced, allowing smooth penetration into the electrode material. The copolymer-based polymer electrolyte showed better energy storage performance and shorter relaxation time than a commercial PEG-based device (225 F g−1/5.18 × 10−5 s for copolymer and 166 F g−1/7.96 × 10−3 s for PEG). In addition, the copolymer not only preserved excellent ionic conductivity of PEG at a certain level (from 6.3 × 10−4 S cm−1 to 3.73 × 10−4 S cm−1) but also decreased the polarity of the material due to the presence of the nonpolar disulfide chain, thereby reducing crystallinity and dielectric permittivity (from 1460 to 246).

The study of electrochemical stabilization mechanism of Pt, GC, SS304, Ti and Cu as current collectors for aqueous lithium-ion batteries by electrochemical approaches

This paper employs electrochemical methods (linear sweep voltammetry (LSV) and electrochemical impedance spectroscopy (EIS)) to investigate the electrochemical behavior of platinum, glassy carbon, 304 stainless steel, titanium, and copper in 21 and 1 M LiTFSI electrolytes. The LSV results indicate that the electrochemical stability window of the materials varies with the electrolyte concentration, and the stability window is wider in the high-concentration system. Through Tafel polarization curves and EIS analysis, the overpotential of the charge exchange process differs due to the type of material and the concentration of the electrolyte, mainly attributed to the influence of the proportion of free water, electrolyte viscosity, and SEI film formation on electrode process kinetics. After comparative analysis, glassy carbon exhibits a higher overpotential than other materials at both the cathode and anode, effectively suppressing water decomposition. These findings provide theoretical support for the development of high-performance aqueous lithium-ion battery current collector materials.

Deflection and control of the mixing region in membraneless vanadium micro redox flow batteries: Modeling and experimental validation

Membraneless micro redox flow batteries operate within the laminar flow regime to mitigate the convective mixing between catholyte and anolyte. The absence of an ion-exchange membrane reduces manufacturing costs and overall cell resistance, thereby enhancing battery performance. However, it also poses a new challenge: the precise control of the thin mixing layer established between the two co-flowing electrolytes. Undesired displacements of the mixing region lead to increased crossover losses and significant liquid transfer between tanks. This work addresses the deflection of the mixing region under varying flow conditions, considering electrolyte viscosity variations due to the changes in the local state of charge arising during battery operation. This is achieved through a combination of mathematical analysis, numerical simulations, and experimental results. The conservation equations and non-dimensional parameters governing the problem are first written and discussed. The model is then integrated numerically incorporating different inlet and outlet boundary conditions to simulate the effect of various flow control strategies. Next, the numerical results are validated against experimental realizations of the flow. Finally, three case studies are presented and discussed. This work highlights the relevance of variable viscosity in the operation of co-laminar membraneless micro redox flow batteries, and proposes for the first time feasible control methods to mitigate undesired disturbances in the hydraulic circuit, thereby minimizing crossover losses.

Safer lithium-ion batteries realized by electrolyte with thermoresponsive poly(vinylidene fluoride-co-trifluoroethylene)

The increasingly widespread use of electric vehicles has necessitated the development of high-energy batteries capable of operating under harsh conditions, e.g., at elevated temperatures and high charge/discharge rates. Hence, considerable attention has been focused on enhancing the safety of lithium-ion batteries (LIBs). Herein, a thermoresponsive polymer, poly(vinylidene fluoride-co-trifluoroethylene) with 75 mol% vinylidene fluoride and 25 mol% trifluoroethylene (TrFE-25), is employed as an electrolyte additive to enhance the thermal stability of LIBs (LiCoO2/graphite full cells). Under thermal-abuse conditions, i.e., above a certain threshold temperature, the TrFE-25-containing electrolyte turns into a gel, thereby abruptly increasing of the electrolyte viscosity and interfacial resistance. The gel layers block ion transport, suppress exothermic reactions between the electrodes and electrolyte, and hinder separator shrinkage via adhesive bonding to the anode and cathode, thus preventing internal short-circuiting and enhancing battery safety. According to the results of cycling tests, the addition of TrFE-25 to the baseline electrolyte has no negative effects under normal conditions. Therefore, the proposed methodology holds promise for improving the safety of LIBs, particularly those with flammable carbonate-based electrolytes, and paves the way for the widespread use of these batteries in electric vehicles.

Weakly Coordinating Diluent Modulated Solvation Chemistry for High-Performance Sodium Metal Batteries.

Diluents have been extensively employed to overcome the disadvantages of high viscosity and sluggish kinetics of high-concentration electrolytes, but generally do not change the pristine solvation structure. Herein, a weakly coordinating diluent, hexafluoroisopropyl methyl ether (HFME), is applied to regulate the coordination of Na+ with diglyme and anion and form a diluent-participated solvate. This unique solvation structure promotes the accelerated decomposition of anions and diluents, with the construction of robust inorganic-rich electrode-electrolyte interphases. In addition, the introduction of HFME reduces the desolvation energy of Na+, improves ionic conductivity, strengthens the antioxidant, and enhances the safety of the electrolyte. As a result, the assembled Na||Na symmetric cell achieves a stable cycle of over 1800 h. The cell of Na||P'2-Na0.67MnO2 delivers a high capacity retention of 87.3 % with a high average Coulombic efficiency of 99.7 % after 350 cycles. This work provides valuable insights into solvation chemistry for advanced electrolyte engineering.

A correlated multi-observable assessment for vanadium redox flow battery state of charge estimation — Empirical correlations and temperature dependencies

The efficient operation of vanadium redox flow batteries requires the half cell specific monitoring of the state of charge (SOC). Monitoring of the SOC is affected by temperature fluctuations, which need to be distinguished from the SOC signal. Several SOC monitoring approaches have been proposed in the literature and either been evaluated individually or compared to one other approach. The aim of this study is to contribute to SOC sensor development for VRFB by providing a first correlated assessment of several established and new SOC monitoring methods. We perform multi observable measurements of: half cell electrolyte potentials, electrolyte densities, electrolyte volumes, electrolyte viscosity related pressure drops, pH related potentials and UV/Vis absorbances. We determine SOC correlations of these observables in full charge/discharge cycles at constant temperature and derive temperature corrections in additional measurements over a range of 12°C to 32°C at 25%, 50% and 75% SOC. We compare the SOC and temperature sensitivity as well as the accuracy of these monitoring methods at constant and varied temperature. We find that the established half cell electrolyte potentials and UV/Vis absorbances can estimate the SOC at constant temperature with measurement errors of 1.7% and 4%, respectively and with slightly higher errors at varying temperatures. The viscosity related pressure drop and electrolyte density are both suitable for SOC estimation if temperature corrections are included. The pH related potentials for the positive half cell and both half cell electrolyte volumes could be used for a rough SOC estimate, but need accurate temperature corrections and further long term stability evaluation.

Brownian Motion Paving the Way for Molecular Translocation in Nanopores.

Tracing fast nanopore-translocating analytes requires a high-frequency measurement system that warrants a temporal resolution better than 1µs. This constraint may practically shift the challenge from increasing the sampling bandwidth to dealing with the rapidly growing noise with frequencies typically above 10kHz, potentially making it still uncertain if all translocation events are unambiguously captured. Here, a numerical simulation model is presented as an alternative to discern translocation events with different experimental settings including pore dimension, bias voltage, the charge state of the analyte, salt concentration, and electrolyte viscosity. The model allows for simultaneous analysis of forces exerting on a large analyte cohort along their individual trajectories; these forces are responsible for the analyte movement leading eventually to the nanopore translocation. Through tracing the analyte trajectories, the Brownian force is found to dominate the analyte movement in electrolytes until the last moment at which the electroosmotic force determines the final translocation act. The mean dwell time of analytes mimicking streptavidin decreases from ≈6 to ≈1µs with increasing the bias voltage from ±100 to ±500mV. The simulated translocation events qualitatively agree with the experimental data with streptavidin. The simulation model is also helpful for the design of new solid-state nanopore sensors.

Density and Dynamic Viscosity of Aqueous Electrolytes with Increased Li-Salt Solubility Due to Addition of Ionic Liquids

Density and Dynamic Viscosity of Aqueous Electrolytes with Increased Li-Salt Solubility Due to Addition of Ionic Liquids

Hyperbranched TEMPO-based polymers as catholytes for redox flow battery applications.

Application of redox-active polymers (RAPs) in redox flow batteries (RFBs) can potentially reduce the stack cost through substitution of costly ion-exchange membranes by cheap size-exclusion membranes. However, intermolecular interactions of polymer molecules, i.e., entanglements, particularly in concentrated solutions, result in relatively high electrolyte viscosities. Furthermore, the large size and limited mobility of polymers lead to slow diffusion and more sluggish heterogeneous electron transfer rates compared to quickly diffusing small molecules. Although a number of RAPs with varying electrolyte viscosities have been reported in the literature, the relation between the RAP structure and the hydrodynamic properties has not been thoroughly investigated. Herein, hyperbranched 2,2,6,6-tetramethylpiperidinyloxyl (TEMPO)-based polymers intended for application as low-viscosity catholytes for RFBs are presented and the influence of the structure and the molar mass distribution on the hydrodynamic properties is investigated. A new synthesis approach for TEMPO-based polymers is established based on step-growth polymerization of a TEMPO-containing monomer using an aza-Michael addition followed by a postpolymerization modification to improve solubility in aqueous solutions. The compact structure of hyperbranched polymers was demonstrated using size-exclusion chromatography (SEC) with viscometric detection and the optimum molar mass was found based on the results of viscometric and crossover investigations. The resulting RAP revealed a viscosity of around 21 mPas at a concentration corresponding to around 1 M TEMPO-containing units, according to the calculated mass of the repeating unit, showing potential for high capacity polymer-based catholytes for RFBs. Nevertheless, possible partial deactivation of TEMPO units lowered the active TEMPO concentration of the hyperbranched RAPs. A faster diffusion and higher charge transfer rate were observed for the hyperbranched polymer compared to the previously reported linear polymers. However, in RFB tests, a poor performance was observed, which is attributed to the side reactions of the oxidized TEMPO moieties. Finally, pathways for overcoming the main remaining challenges, i.e., high loss of material during dialysis as an indication of being prone to crossover, the partial deactivation of TEMPO moieties, and the subsequent side reactions under battery conditions, are suggested.

Stabilized four-electron aqueous zinc-iodine batteries by quaternary ammonium complexation.

Four-electron aqueous zinc-iodine batteries (4eZIBs) leveraging the I-/I0/I+ redox couple have garnered attention for their potential high voltage, capacity, and energy density. However, the electrophilic I+ species is highly susceptible to hydrolysis due to the nucleophilic attack by water. Previous endeavors to develop 4eZIBs primarily relied on highly concentrated aqueous electrolytes to mitigate the hydrolysis issue, nonetheless, it introduced challenges associated with dissolution, high electrolyte viscosity, and sluggish electrode kinetics. In this work, we present a novel complexation strategy that capitalizes on quaternary ammonium salts to form solidified compounds with I+ species, rendering them impervious to solubilization and hydrolysis in aqueous environments. The robust interaction in this complexation chemistry facilitates a highly reversible I-/I0/I+ redox process, significantly improving reaction kinetics within a conventional ZnSO4 aqueous electrolyte. The proposed 4eZIB exhibits a superior rate capability and an extended lifespan of up to 2000 cycles. This complexation chemistry offers a promising pathway for the development of advanced 4eZIBs.

Anionic Effects on Li-Ion Activity and Intercalation Kinetics in Highly Concentrated Electrolytes

Certain highly concentrated electrolytes (HCEs) enhance the charge-transfer reaction rate at the electrode/electrolyte interface in Li-ion batteries. The solvation structure of Li+ in HCEs significantly affects the electrochemical interfacial reaction kinetics.1 However, the effects of different anions on these kinetics have not yet been fully understood. In this study, we investigated the effects of anionic species on the liquid structure and electrochemical reactions of HCEs composed of various Li salts and propylene carbonate (PC).2 Raman spectra revealed that both PC and anions were coordinated to Li+ ions in HCEs and that the concentration of uncoordinated (free) PC changed depending on the anionic species. Consequently, the activity of Li+ in the electrolyte changed depending on the anionic species. The use of Li salts with weakly Lewis basic anions increased the activity of Li+ and decreased the concentration of free PC in HCEs.The activity of Li+ in the electrolyte significantly affected the Li+ intercalation/deintercalation reaction rate of the LiCoO2 thin-film electrode. Electrochemical impedance spectroscopy revealed that the interfacial reaction rate of LiCoO2 was enhanced in the HCEs with anions having weaker Lewis basicity owing to the higher Li+ ion activity. In addition to the Li+ ion activity, the electrolyte viscosity also gives a significant effect on the charge-transfer kinetics at the electrode/electrolyte interface. The effects of salt concentration and anionic species on Li+ ion activity, electrolyte viscosity, and reaction kinetics in the HCEs will be discussed in detail. Acknowledgements : This study was partially supported by the JSPS KAKENHI (Grant No. JP19H05813, JP21H04697, and JP22H00340). References Y. Kondo et al., ACS Appl. Mater. Interfaces 2022, 14, 22706-22718.Y. Ugata et. al., J. Phys. Chem. C 2023, 127, 3977-3987.

(Invited) Solvation Control in Deep Eutectic Solvent Electrolytes for Stable Plating/Stripping of Zn in Battery Applications

Within the field of battery applications, deep eutectic solvents (DESs) have emerged as innovative electrolytes for rechargeable Zinc-ion batteries (ZIBs) . ZIBs traditionally employ neutral or weakly acidic aqueous electrolytes, which are susceptible to the standard anode drawback such as dendrite formation and passivation. DES-based electrolytes can facilitate the reversible plating and stripping of Zn, mitigating also dendrite growth . One notable benefit of DES solvents over their aqueous counterparts is that the concentration of electroactive species controls the shape evolution of electrodes during electroplating. For this reason, the coordination chemistry and metal complex formed between the Lewis acid of the metal and the Lewis base of the DES play a central role. Moreover, water can be added to the eutectic mixtures to increase the diffusion coefficient of the electroactive species and lower the electrolyte viscosity without destroying the eutectic nature if the concentration is kept under 40%.Regarding metal plating/stripping processes, DESs offer a notable advantage due to their high capacity to dissolve metal salts, oxides, and hydroxides, inhibiting the formation of insoluble oxides and hydroxides . Moreover, the unique coordination properties of Zn2+ in DESs lead to an atypical voltammetric behavior, characterized by a cathodic peak in the cathodic branch of the anodic-going scan. The mechanistic studies of Zn electrodeposition onto glassy carbon (GC) from DESs have concluded that the metal is formed by the reduction of an intermediate Zn-containing species. Finally, the reactivity of choline chloride and ethylene glycol can impact coordination in that these species can be dehydrogenated at negative potential forming RO¯, which can replace one or more chloride ligands in [ZnCl4]2− . The correlation between the chemistry of Zn2+ solutions and DESs is elucidated, and the peculiarities of Zn electrochemistry can be rationalized in terms of the DES–electrode interface structure. Although few studies on hydrated DESs have been conducted, the literature remains scant.Shi et al. conducted a study on DES composed of ZnCl2 and acetamide with different concentration of water. The authors employed various spectroscopic techniques, including FT-IR, Raman, and 17O NMR, to investigate the effect of water on the coordination geometry of Zn2+ and its consequent impact on Zn plating. Interestingly, the authors observed that the addition of small amounts of water, below the threshold for direct water-water interaction, resulted in significant alterations of the Zn2+ coordination geometry. In fact, based on the accepted view that Zn electrodeposition is a process that involves desolvation and charge-transfer steps, [ZnCl(acetamide)2(H2O)]+ was shown to undergo successive deamidation and dehydration, yielding [ZnCl(acetamide)]+ from which the metal center is finally reduced. Although [ZnCl(acetamide)3]+ is the most stable species, the energy barrier for dehydration is significantly lower than that for deamidation. Therefore, [ZnCl(acetamide)2(H2O)]+ with lower dissociation energy is the actual electroactive species . The solvation of Zn also affects the nucleation overpotential, as Zn2+ in hydrated DES exhibits faster desolvation kinetics, resulting in a lower nucleation overpotential. In addition, Zhao et al. investigated the properties of a “water-in-DES” electrolyte (~30 mol.% H2O) based on the urea/LiTFSI/Zn(TFSI)2 mixture and discovered that the preferential interaction between water and metal cations promotes interfacial charge transfer. Notwithstanding the important contribution of these papers, the mechanism of Zn electrodeposition in DES has not been conclusively assessed. To address this knowledge gap, our research aims to investigate Zn electrodeposition from two distinct, hydrated DESs: ChU and ChEG with approximately 30% H2O content. To gain control of the impact of the cathode material, we carried out our electrochemical tests by employing GC, Zn, Pt and Au electrodes. Furthermore, to evaluate the performance of these electrolytes under realistic device conditions, electrochemical cycling tests were conducted on symmetric CR2023 coin cells.In this study, we have demonstrated the beneficial effect of water addition on reducing the electrolyte viscosity, which consequently resulted in lower anodic and cathodic overpotentials and improved charge/discharge cyclability. Specifically, the electrolytes ChEG and ChU failed due to passivation and short circuits, respectively. The ChU electrolyte showed regular chronopotentiometric transients until cell failure, and this was supported by multiple cyclic voltammetry (CV) measurements, which showed reversible Zn plating/stripping in this system. Notably, our cell cycling tests were performed at higher current densities and exhibited longer lifetimes compared to previous literature reports. The unusual CV patterns observed with gold and glassy carbon (GC) electrodes, featuring cathodic peaks on both forward and backward scans, were elucidated using complementary electrochemical and in situ Raman spectroscopy measurements. Figure 1

(Battery Division Postdoctoral Associate Research Award Sponsored by MTI Corporation and the Jiang Family Foundation) Aqueous Batteries for Grid-Scale Storage: Beyond Highly Concentrated Electrolytes

Aqueous electrolytes offer significant advantages over their organic counterparts, particularly for large-scale applications that prioritize non-flammability, scalability, and sustainability. However, the narrow electrochemical stability window of water imposes voltage limitations, resulting in low energy densities of aqueous batteries. Highly concentrated electrolytes have enabled high-voltage, mostly intercalation-type, aqueous battery chemistries, and over the past decade many additives, coatings, and highly soluble salts have been developed to manipulate the solution structure of the electrolyte and the interphasial chemistry at the electrode surfaces. However, the large amounts of specialized salts required in this approach, put into question whether GWh-scale storage is really the best application of this technology.Storage at such very large scale, however, is required for further integration of renewables and complete decarbonization of power grids. Flow batteries that decouple energy storage from power generation were developed to simplify scaling of very large batteries while maintaining cost and safety benefits of aqueous electrolytes. Here, the solubility of active materials governs the achievable energy density, which is typically an order of magnitude lower for aqueous flow batteries compared to state-of-the-art lithium-ion cells.Capitalizing on our experience with highly concentrated electrolytes and the impact of molecular symmetry and ion-pairing on electrolyte properties,1–5 we manipulate the solution structure of flow battery electrolytes to maximize active material concentration. We manipulate the hydrogen-bonding environment in the electrolyte and mediate anion-cation interactions via cation-engineering and additives, enabling more than four-fold higher concentrations for a series of metal-organic chelates and ferrocyanides than previously reported.6–8 We further developed a simple flame emission spectroscopy setup to track cation ratios in solution and study cation-dependent instabilities of presumably highly stable ferrocyanide anions.8,9 Achieving very high concentrations, however, presents a series of challenges for flow batteries. A two-molar lithium ferrocyanide electrolyte, for example, has an ionic strength comparable to a twenty-molar lithium chloride solution.8 Managing osmotic balance across the membrane thus becomes very challenging in a flow cell. Additionally, the high viscosity of concentrated electrolytes results in significant efficiency and power losses, suggesting that the “dissolve-as-much-as-possible” approach may not necessarily lead to better flow batteries.We thus studied the importance of energy density for real-world MWh-scale batteries by using satellite images to estimate the footprint of such large-scale deployments. We find that installations using lithium-ion batteries often have a comparable footprint to sodium-sulfur batteries and even demonstrator-stage flow batteries.10 This implies that low cell level energy density of flow batteries is not the key limitation of the technology, challenging the common narrative. For applications such as residential use, on the other hand, energy density certainly plays a critical role, and we discuss approaches that could enable much more compact systems.