Aqueous Redox Flow Cells Utilizing Verdazyl Cations enabled by Polybenzimidazole Membranes.

Non-aqueous organic redox flow batteries (RFB) utilizing verdazyl radicals are increasingly explored as energy storage technology. Verdazyl cations in RFBs with acidic aqueous electrolytes, however, have not been investigated yet. To advance the application in aqueous RFBs it is crucial to examine the interaction with the utilized membranes. Herein, the interactions between the 1,3,5-triphenylverdazyl cation and commercial Nafion 211 and self-casted polybenzimidazole (PBI) membranes are systematically investigated to improve the performance in RFBs. The impact of polymer backbones is studied by using mPBI and OPBI as well as different pre-treatments with KOH and H3PO4. Nafion 211 shows substantial absorption of the 1,3,5-triphenylverdazylium cation resulting in loss of conductivity. In contrast, mPBI and OPBI are chemically stable against the verdazylium cation without noticeable absorption. Pre-treatment with KOH leads to a significant increase in ionic conductivity as well as low absorption and permeation of the verdazylium cation. Symmetrical RFB cell tests on lab-scale highlight the beneficial impact of PBI membranes in terms of capacity retention and I-V curves over Nafion 211. With only 2 % d-1 capacity fading 1,3,5-triphenylverdazyl cations in acidic electrolytes with low-cost PBI based membranes exhibit a higher cycling stability compared to state-of-the-art batteries using verdazyl derivatives in non-aqueous electrolytes.

Recent Development of Electrolytes for Aqueous Organic Redox Flow Batteries (Aorfbs): Current Status, Challenges, and Prospects.

In recent years, aqueous organic redox flow batteries (AORFBs) have attracted considerable attention due to advancements in grid-level energy storage capacity research. These batteries offer remarkable benefits, including outstanding capacity retention, excellent cell performance, high energy density, and cost-effectiveness. The organic electrolytes in AORFBs exhibit adjustable redox potentials and tunable solubilities in water. Previously, various types of organic electrolytes, such as quinones, organometallic complexes, viologens, redox-active polymers, and organic salts, were extensively investigated for their electrochemical performance and stability. This study presents an overview of recently published novel organic electrolytes for AORFBs in acidic, alkaline, and neutral environments. Furthermore, it delves into the current status, challenges, and prospects of AORFBs, highlighting different strategies to overcome these challenges, with special emphasis placed on their design, composition, functionalities, and cost. A brief techno-economic analysis of various aqueous RFBs is also outlined, considering their potential scalability and integration with renewable energy systems.

Recent Developments on Electroactive Organic Electrolytes for Non-Aqueous Redox Flow Batteries: Current Status, Challenges, and Prospects.

The ever-increasing threat of climate change and the depletion of fossil fuel resources necessitate the use of solar- and wind-based renewable energy sources. Large-scale energy storage technologies, such as redox flow batteries (RFBs), offer a continuous supply of energy. Depending on the nature of the electrolytes used, RFBs are broadly categorized into aqueous redox flow batteries (ARFBs) and non-aqueous redox flow batteries (NARFBs). ARFBs suffer from various problems, including low conductivity of electrolytes, inferior charge/discharge current densities, high-capacity fading, and lower energy densities. NARFBs offer a wider potential window and range of operating temperatures, faster electron transfer kinetics, and higher energy densities. In this review article, a critical analysis is provided on the design of organic electroactive molecules, their physiochemical/electrochemical properties, and various organic solvents used in NARFBs. Furthermore, various redox-active organic materials, such as metal-based coordination complexes, quinones, radicals, polymers, and miscellaneous electroactive species, explored for NARFBs during 2012-2023 are discussed. Finally, the current challenges and prospects of NARFBs are summarized.

Enhanced Photocatalytic H2 Generation by Light-Induced Carbon Modification of TiO2 Nanotubes.

Titanium dioxide (TiO2 ) is the material of choice for photocatalytic and electrochemical applications owing to its outstanding physicochemical properties. However, its wide bandgap and relatively low conductivity limit its practical application. Modifying TiO2 with carbon species is a promising route to overcome these intrinsic complexities. In this work, we propose a facile method to modify TiO2 nanotubes (NTs) based on the remnant organic electrolyte retained inside the nanotubes after the anodization process, that is, without removing it by immersion in ethanol. Carbon-modified TiO2 NTs (C-TiO2 NTs) showed enhanced H2 evolution in photocatalysis under UV illumination in aqueous solutions. When the C-TiO2 NTs were subjected to UV light illumination, the carbon underwent modification, resulting in higher measured photocurrents in the tube layers. After UV illumination, the IPCE of the C-TiO2 NTs was 4.4-fold higher than that of the carbon-free TiO2 NTs.

Oscillation Charging Dynamics in Nanopore Supercapacitors with Organic Electrolyte.

Nanopore electrodes have the potential to enhance the energy density of supercapacitors but tend to reduce charging dynamics, consequently impacting power density. A comprehensive understanding of their charging mechanisms can provide insights into how to boost charging dynamics. In this work, we conducted constant-potential-based molecular dynamics simulations to explore the charging mechanism of nanopore supercapacitors with organic electrolytes. Contrary to the traditional understanding associating larger pore sizes with faster charging, our results found a complex oscillatory behavior of the charging rate, correlating with nanopore size in organic electrolytes. An anomalously increased charging dynamics was found in the 0.9 nm pore. This anomalous enhancement can be attributed to the improved in-pore ion diffusion and reduced desolvation energy, owing to the orientation transition of the solvate molecules. These results pave a new way for innovative designs of nanoporous electrode supercapacitors that can enlarge both power and energy densities.

Response Patterns of Chromoionophore-Based Bulk Optodes Containing Lipophilic Electrolytes: Toward Background-Independent pH-Sensing.

Despite a number of advantages of ion-selective optical sensors (optodes), their practical application is limited by their response mechanism, which leads to the dependence of the signal on the activity of two ions (analyte ion and the so-called reference ion) in the solution at the same time. Here, we show that the introduction of a lipophilic electrolyte into the polymeric optode membrane allows assessing the ionic activity of H+ cations regardless of the concentration of the background electrolyte containing a hydrophilic cation, with NaCl as an example of such an electrolyte. For the first time, the applicability of this approach is proven theoretically utilizing the numerical simulation of optode response. A correlation between the interfacial potential stability and the single-ion optical response is established. The predicted optical response is independent of background cation concentration to a significant extent. Theoretical conclusions are supported by experimental data obtained with chromoionophore-based optodes doped with various lipophilic electrolytes, including ionic liquids, by thin-film spectrophotometry and macrophotography coupled with digital color analysis. Most of the experimental sensor characteristics, such as the response range and its median, as well as its independence from the background electrolyte concentration are in quantitative agreement with the proposed theoretical description.

Ethylene-Carbonate-Free Electrolytes for Rechargeable Li-Ion Pouch Cells at Sub-Freezing Temperatures.

Sub-freezing temperature presents a significant challenge to the survival of current Li-ion batteries (LIBs) as it leads to low capacity retention and poor cell rechargeability. The electrolyte in commercial LIBs relies too heavily on ethylene carbonate (EC) to produce a stable solid electrolyte interphase (SEI) on graphite (Gr) anodes, but its high melting point (36.4 °C) severely restricts ion transport below 0 °C, causing energy loss and Li plating. Here, a class of EC-free electrolytes that exhibits remarkable low-temperature performance without compromising cell lifespan is reported. It is found that at sub-zero temperatures, EC forms highly resistive SEI that seriously impedes electrode kinetics, whereas EC-free electrolytes create a highly stable, low-impedance SEI through anion decomposition, which boosts capacity retention and eliminates Li plating during charging. Pouch-type LiCoO2 (LCO)|Gr cells with EC-free electrolytes sustain 900 cycles at 25 °C with 1 C charge/discharge, and LiNi0.85 Co0.10 Al0.05 O2 (NCA)|Gr cells last 300 cycles at -15 °C with 0.3 C charge, both among the best-performing in the literature under comparable conditions. Even at -50 °C, the NCA|Gr cell with EC-free electrolytes still delivers 76% of its room-temperature capacity, outperforming EC-based electrolytes.

Organic Ammonium Ion Battery: A New Strategy for a Nonmetallic Ion Energy Storage System.

Nonmetallic ammonium (NH4 + ) ion batteries are promising candidates for large-scale energy storage systems, which have the merit of low molar mass, sustainability, non-toxicity and non-dendrite. Herein, for the first time, we introduce the novel organic ammonium ion batteries (OAIBs). Significantly, a manganese-based Prussian white analogue (noted as MnHCF) as cathode exhibits a reversible capacity of 104 mAh g-1 with 98 % retention over 100 cycles. We further demonstrate the electrochemical performance of the NH4 + ion full cell, which delivers a reversible capacity of 45 mAh g-1 with a broad electrochemical window. Combining ex situ XPS, ex situ XRD results and electrochemical properties, the NH4 + ion storage mechanism of MnHCF in a non-aqueous electrolyte is clearly revealed. This work verifies the feasibility of employing NH4 + ions as charge carriers in organic energy storage systems and provides new insights for designing organic nonmetallic ion batteries with broad electrochemical windows and high energy density.

Coherent Integration of Organic Gel Polymer Electrolyte and Ambipolar Polyoxometalate Hybrid Nanocomposite Electrode in a Compact High-Performance Supercapacitor.

We report a gel polymer electrolyte (GPE) supercapacitor concept with improved pathways for ion transport, thanks to a facile creation of a coherent continuous distribution of the electrolyte throughout the electrode. Poly(vinylidene fluoride-co-hexafluoropropylene) (PVDF-HFP) was chosen as the polymer framework for organic electrolytes. A permeating distribution of the GPE into the electrodes, acting both as integrated electrolyte and binder, as well as thin separator, promotes ion diffusion and increases the active electrode-electrolyte interface, which leads to improvements both in capacitance and rate capability. An activation process induced during the first charge-discharge cycles was detected, after which, the charge transfer resistance and Warburg impedance decrease. We found that a GPE thickness of 12 µm led to optimal capacitance and rate capability. A novel hybrid nanocomposite material, formed by the tetraethylammonium salt of the 1 nm-sized phosphomolybdate cluster and activated carbon (AC/TEAPMo12), was shown to improve its capacitive performance with this gel electrolyte arrangement. Due to the homogeneous dispersion of PMo12 clusters, its energy storage process is non-diffusion-controlled. In the symmetric capacitors, the hybrid nanocomposite material can perform redox reactions in both the positive and the negative electrodes in an ambipolar mode. The volumetric capacitance of a symmetric supercapacitor made with the hybrid electrodes increased by 40% compared to a cell with parent AC electrodes. Due to the synergy between permeating GPE and the hybrid electrodes, the GPE hybrid symmetric capacitor delivers three times more energy density at higher power densities and equivalent cycle stability compared with conventional AC symmetric capacitors.

Electrolyte formulation strategies for potassium-based batteries.

Potassium (K)-based batteries are viewed as the most promising alternatives to lithium-based batteries, owing to their abundant potassium resource, lower redox potentials (-2.97 V vs. SHE), and low cost. Recently, significant achievements on electrode materials have boosted the development of potassium-based batteries. However, the poor interfacial compatibility between electrode and electrolyte hinders their practical. Hence, rational design of electrolyte/electrode interface by electrolytes is the key to develop K-based batteries. In this review, the principles for formulating organic electrolytes are comprehensively summarized. Then, recent progress of various liquid organic and solid-state K+ electrolytes for potassium-ion batteries and beyond are discussed. Finally, we offer the current challenges that need to be addressed for advanced K-based batteries.

Recent Advances in Electrolytes for "Beyond Aqueous" Zinc-Ion Batteries.

With the growing demands for large-scale energy storage, Zn-ion batteries (ZIBs) with distinct advantages, including resource abundance, low-cost, high-safety, and acceptable energy density, are considered as potential substitutes for Li-ion batteries. Although numerous efforts are devoted to design and develop high performance cathodes and aqueous electrolytes for ZIBs, many challenges, such as hydrogen evolution reaction, water evaporation, and liquid leakage, have greatly hindered the development of aqueous ZIBs. Developing "beyond aqueous" electrolytes can be able to avoid these issues due to the absence of water, which are beneficial for the achieving of highly efficient ZIBs. In this review, the recent development of the "beyond aqueous" electrolytes, including conventional organic electrolytes, ionic liquid, all-solid-state, quasi-solid-state electrolytes, and deep eutectic electrolytes are presented. The critical issues and the corresponding strategies of the designing of "beyond aqueous" electrolytes for ZIBs are also summarized.

Long-Chain Ionic Liquids Based on Monoquaternary DABCO Cations and TFSI Anions: Towards Stable Electrolytes for Electrochemical Capacitors.

The desirable properties of ionic liquids (ILs) enable their use in various branches of chemistry, through a wide range of applications, e. g. as organic electrolytes. In the present study, an efficient two-step method was developed for the synthesis of long-chain ionic liquids with alkyl derivatives of DABCO as cations and bis(trifluoromethane)sulfonimide as anions. ILs obtained with high yields (≥91 %) were solids with melting points that increased with the rise in the number of carbon atoms of the alkyl substituent in the bicyclic cation. The structure of the compounds was confirmed by spectroscopic methods and elemental analysis. All compounds were soluble in the main solvents except water and hexane. The solubility in organic solvents such as acetonitrile allowed the use of synthesized ILs in electrochemical capacitors. Electrochemical tests revealed that the ILs enhanced the conductivity of organic electrolytes. This phenomenon improved the cyclability and reduced the internal resistance of the electrochemical capacitors.

Charge-Transfer Kinetics of The Solid-Electrolyte Interphase on Li4 Ti5 O12 Thin-Film Electrodes.

Charge-transfer kinetics between electrodes and electrolytes critically determines the performance of lithium-ion batteries (LIBs). Lithium titanate defect spinel (Li4 Ti5 O12 , LTO) is a safe and durable anode material, but its relatively low energy density limits the range of applications. Utilizing the low potential region of LTO is a straightforward strategy for increasing energy density. However, the electrochemical characteristics of LTO at low potentials and the properties of the solid-electrolyte interphase (SEI) on LTO are not well understood. Here, we investigate the charge-transfer kinetics of the SEI formed between model LTO thin-film electrodes and organic electrolytes with distinct solvation ability using AC impedance spectroscopy whereas their stability was assessed by cyclic voltammetry of ferrocene. With the SEI film on LTO, the Li+ desolvation was rate-determining step but with larger activation energies, which showed a strong dependence on the solvation ability of electrolyte. The activation energies of desolvation for the fluoroethylene carbonate+dimethyl carbonate- and ethylene carbonate+diethyl carbonate-based systems increased from 35 and 55 to 44 and 67 kJ mol-1 , respectively, and that for the propylene carbonate-based system did not noticeably change at around 67 kJ mol-1 . In addition, the SEI passivation of LTO was much slower than that of graphite, and the rate also strongly depended on the solvation ability of the electrolyte. Understanding the surface properties of LTO at low potentials opens the door for high-energy-density LTO-based LIBs.

Above 800 mV Open-Circuit Voltage in Solid-State Photovoltaic Devices Using Phosphonium Cation-Based Solid Ionic Conductors.

Here, we report phosphonium-based two solid ionic conductors (SICs), namely, triphenylphosphonium methyl iodide (TPPMeI) and triphenylphosphonium iodide (TPPHI), prepared via simple protocol at room temperature and were used as an electrolyte for solid-state photovoltaic devices (ss-PVDs) with open-circuit voltage (Voc) exceeding 800 mV. Here, for the first time, detailed electrochemical investigations with theoretical aspects of phosphonium electrolytes were conducted, where PVDs prepared from these SICs, TPPMeI, showed the highest power conversion efficiency (PCE) of 4.08% with a Voc of 810 mV. However, this performance was further improved up to the PCE of 6.71% with 824 mV of Voc in the presence of additives like LiI and tert-butyl pyridine. This work leads to find the best alternative of liquid and quaternary ammonium ion-based electrolytes that suffers from problems like lower Voc (<800 mV) and stability, leakage, etc.

Willow Bark for Sustainable Energy Storage Systems.

Willow bark is a byproduct from forestry and is obtained at an industrial scale. We upcycled this byproduct in a two-step procedure into sustainable electrode materials for symmetrical supercapacitors using organic electrolytes. The procedure employed precarbonization followed by carbonization using different types of KOH activation protocols. The obtained electrode materials had a hierarchically organized pore structure and featured a high specific surface area (>2500 m2 g-1) and pore volume (up to 1.48 cm3 g-1). The assembled supercapacitors exhibited capacitances up to 147 F g-1 in organic electrolytes concomitant with excellent cycling performance over 10,000 cycles at 0.6 A g-1 using coin cells. The best materials exhibited a capacity retention of 75% when changing scan rates from 2 to 100 mV s-1.

Large Variations in the Composition of Ionic Liquid-Solvent Mixtures in Nanoscale Confinement.

Mixtures of an ionic liquid with an organic solvent are widely used as electrolytes in supercapacitors where they are often confined in porous electrodes with pore widths only slightly larger than the sizes of bare ions or solvent molecules. The composition of the electrolyte inside these pores, which may depend on the pore width and choice of electrolyte, can affect supercapacitor performance but remains poorly understood. Here, we perform all-atom molecular dynamics simulations of solutions of two different ionic liquids in acetonitrile under confinement between graphene sheets forming slit pores of various widths. We observe significant oscillations in the in-pore ionic liquid mole fraction with varying pore widths. Ions are excluded from very narrow pores, while for pore widths that tightly fit a single layer of ions, we observe an in-pore ionic liquid mole fraction over three times greater than that in the bulk. At slightly larger pore widths, we observe for different ionic liquids either a nearly complete exclusion of ions from the pore or a slight depletion of ions, while ion population again increases as pore width further increases. We develop an analytical model that can qualitatively predict the in-pore ionic liquid mole fraction based on the effective molar volumes and the pore wall interaction energies of each species. Our work suggests a new avenue for tuning the ionic liquid mole fraction in nanopores with potentially significant implications for designing systems involving nanoconfined liquid electrolytes such as supercapacitors where in-pore ion population can affect charging dynamics.

Betavoltaic Enhancement Using Defect-Engineered TiO2 Nanotube Arrays through Electrochemical Reduction in Organic Electrolytes.

Utilizing high-energy beta particles emitted from radioisotopes for long-lifetime betavoltaic cells is a great challenge due to low energy conversion efficiency. Here, we report a betavoltaic cell fabricated using TiO2 nanotube arrays (TNTAs) electrochemically reduced in ethylene glycol electrolyte (EGECR-TNTAs) for the enhancement of the betavoltaic effect. The electrochemical reduction of TNTAs using high cathodic bias in organic electrolytes is indeed a facile and effective strategy to induce in situ self-doping of oxygen vacancy (OV) and Ti3+ defects. The black EGECR-TNTAs are highly stable with a significantly narrower band gap and higher electrical conductivity as well as UV-vis-NIR light absorption. A 20 mCi of 63Ni betavoltaic cell based on the reduced TNTAs exhibits a maximum ECE of 3.79% with open-circuit voltage of 1.04 V, short-circuit current density of 117.5 nA cm-2, and a maximum power density of 39.2 nW cm-2. The betavoltaic enhancement can be attributed to the enhanced charge carrier transport and separation as well as multiple exciton generation of electron-hole pairs due the generation of OV and Ti3+ interstitial bands below the conductive band of TiO2.

Protected Lithium-Metal Anodes in Batteries: From Liquid to Solid.

High-energy lithium-metal batteries are among the most promising candidates for next-generation energy storage systems. With a high specific capacity and a low reduction potential, the Li-metal anode has attracted extensive interest for decades. Dendritic Li formation, uncontrolled interfacial reactions, and huge volume effect are major hurdles to the commercial application of Li-metal anodes. Recent studies have shown that the performance and safety of Li-metal anodes can be significantly improved via organic electrolyte modification, Li-metal interface protection, Li-electrode framework design, separator coating, and so on. Superior to the liquid electrolytes, solid-state electrolytes are considered able to inhibit problematic Li dendrites and build safe solid Li-metal batteries. Inspired by the bright prospects of solid Li-metal batteries, increasing efforts have been devoted to overcoming the obstacles of solid Li-metal batteries, such as low ionic conductivity of the electrolyte and Li-electrolyte interfacial problems. Here, the approaches to protect Li-metal anodes from liquid batteries to solid-state batteries are outlined and analyzed in detail. Perspectives regarding the strategies for developing Li-metal anodes are discussed to facilitate the practical application of Li-metal batteries.

1D and 2D NMR Spectroscopy of Bonding Interactions within Stable and Phase-Separating Organic Electrolyte-Cellulose Solutions.

Organic electrolyte solutions (i.e. mixtures containing an ionic liquid and a polar, molecular co-solvent) are highly versatile solvents for cellulose. However, the underlying solvent-solvent and solvent-solute interactions are not yet fully understood. Herein, mixtures of the ionic liquid 1-ethyl-3-methylimidazolium acetate, the co-solvent 1,3-dimethyl-2-imidazolidinone, and cellulose are investigated using 1D and 2D NMR spectroscopy. The use of a triply-13 C-labelled ionic liquid enhances the signal-to-noise ratio for 13 C NMR spectroscopy, enabling changes in bonding interactions to be accurately pinpointed. Current observations reveal an additional degree of complexity regarding the distinct roles of cation, anion, and co-solvent toward maintaining cellulose solubility and phase stability. Unexpectedly, the interactions between the dialkylimidazolium ring C2 -H substituent and cellulose become more pronounced at high temperatures, counteracted by a net weakening of acetate-cellulose interactions. Moreover, for mixtures that exhibit critical solution behavior, phase separation is accompanied by the apparent recombination of cation-anion pairs.

Structure-Property Relationships of Organic Electrolytes and Their Effects on Li/S Battery Performance.

Electrolytes, which are a key component in electrochemical devices, transport ions between the sulfur/carbon composite cathode and the lithium anode in lithium-sulfur batteries (LSBs). The performance of a LSB mostly depends on the electrolyte due to the dissolution of polysulfides into the electrolyte, along with the formation of a solid-electrolyte interphase. The selection of the electrolyte and its functionality during charging and discharging is intricate and involves multiple reactions and processes. The selection of the proper electrolyte, including solvents and salts, for LSBs strongly depends on its physical and chemical properties, which is heavily controlled by its molecular structure. In this review, the fundamental properties of organic electrolytes for LSBs are presented, and an attempt is made to determine the relationship between the molecular structure and the properties of common organic electrolytes, along with their effects on the LSB performance.