Enabling Fluorine-Free Lithium-Ion Capacitors and Lithium-Ion Batteries for High-Temperature Applications by the Implementation of Lithium Bis(oxalato)Borate and Ethyl Isopropyl Sulfone as Electrolyte

A novel fluorine-free electrolyte comprising a solution of lithium bis(oxalato)borate in ethyl isopropyl sulfone is presented. It is characterized by its safety and non-toxic properties, along with the capability to effectively suppress the anodic dissolution of aluminum. Successful high-temperature application of this electrolyte in combination with various capacitor- and battery-like electrode materials is shown. Further utilization in a lithium-ion capacitor and a lithium-ion battery is demonstrated. To the best of the knowledge, the lithium-ion capacitor presented in this work represents the first entirely fluorine-free device suitable for high-temperature applications. When operating at 60 °C, this device delivers a maximum energy output of 169 Wh kg⁻¹_AM at a power of 200 W kg⁻¹_AM and even 80 Wh kg¹_AM at 10 kW kg^-1_AM, along with the ability to retain 80% of its initial capacitance after 3500 cycles at 5 A g⁻¹. As such, this novel electrolyte is a promising alternative to conventional fluorine-containing configurations since its performance is capable to match or even surpass that of most similar laboratory-scale LICs.     

Electrospun Carbon Nanofibers Encapsulated with NiCoP: A Multifunctional Electrode for Supercapattery and Oxygen Reduction,Oxygen Evolution,and Hydrogen Evolution Reactions

Functionalizing nanostructured carbon nanofibers (CNFs) with bimetallic phosphides enables the material to become an active electrode for multifunctional applications. A facile electrospinning technique is utilized for the first time to develop NiCoP nanoparticles encapsulated CNFs that are used as an energy storage system of supercapattery, and as an electrocatalyst for oxygen reduction, oxygen evolution, and hydrogen evolution reaction in KOH electrolyte. Evolving from the inclusion of bimetallic phosphide nanoparticles, the NiCoP/CNF electrode unveils superior‐specific capacitance (333 Fg^?1 at 2 Ag^?1) and rate capability (87%). The fabricated supercapattery device offers a voltage of 1.6 V that supplies a remarkable energy density (36 Wh kg^?1) along with an improved power density (4000 W kg^?1) and unwavering cyclic stability (25 000 cycles). Meanwhile, the NiCoP/CNF electrode has simultaneously performed well as a multifunctional electrocatalyst for oxygen reduction reaction at a half‐wave potential of 0.82 V versus reversible hydrogen electrode and can attain a current density of 10 mA cm^?2 at a very low overpotential of 268 and 130 mV for the oxygen evolution reaction and hydrogen evolution reaction, respectively. Thus, the NiCoP/CNF with all its inimitable electrode properties has profoundly proved its proficiency at handling multifunctional challenges in terms of both storage and conversion.     

A High Energy Density Aqueous Battery Achieved by Dual Dissolution/Deposition Reactions Separated in Acid‐Alkaline Electrolyte

Aqueous batteries are facing big challenges in the context of low working voltages and energy density, which are dictated by the narrow electrochemical window of aqueous electrolytes and low specific capacities of traditional intercalation‐type electrodes, even though they usually represent high safety, low cost, and simple maintenance. For the first time, this work demonstrates a record high‐energy‐density (1503 Wh kg^?1 calculated from the cathode active material) aqueous battery system that derives from a novel electrolyte design to expand the electrochemical window of electrolyte to 3 V and two high‐specific‐capacity electrode reactions. An acid‐alkaline dual electrolyte separated by an ion‐selective membrane enables two dissolution/deposition electrode redox reactions of MnO₂/Mn²⁺ and Zn/Zn(OH)₄^2? with theoretical specific capacities of 616 and 820 mAh g^?1, respectively. The newly proposed Zn–Mn²⁺ aqueous battery shows a high Coulombic efficiency of 98.4% and cycling stability of 97.5% of discharge capacity retention for 1500 cycles. Furthermore, in the flow battery based on Zn–Mn²⁺ pairs, more excellent stability of 99.5% of discharge capacity retention for 6000 cycles is achieved due to greatly improved reversibility of the Zn anode. This work provides a new path for the development of novel aqueous batteries with high voltage and energy density.     

Electrolytes toward High‐Voltage Na3V2(PO4)2F3 Positive Electrode Durable against Temperature Variation

High power and energy density, long cyclability, and tolerance for wide temperature (seasonal and daily operational temperature differences) must be considered to construct large‐scale sodium secondary batteries. In this regard, Na₃V₂(PO₄)₂F₃ (NVPF) has become a subject of interest as a high‐performance positive electrode material owing to its high energy density. However, the high operating voltage of NVPF causes continuous decomposition of electrolytes during cycles, resulting in significant capacity fading and low Coulombic efficiency. In this study, the electrochemical performance of the NVPF electrode in organic solvent electrolytes with and without additives and an ionic liquid is investigated at high voltage regimes over a wide temperature range (?20 °C to 90 °C). The results reveal that the performance of organic electrolytes is still insufficient even with additives, and the ionic liquid electrolyte demonstrates high electrochemical stability and cyclability with NVPF electrodes over a temperature range from ?20 °C to 90 °C, achieving stable cycling over 500 cycles. The detailed electrochemical analysis combined with X‐ray photoelectron and energy dispersive X‐ray spectroscopy indicates that a sturdy cathode electrolyte interphase layer around the electrode protects it from capacity fading at high voltage and elevated temperature, resulting in high Coulombic efficiency.     

Development of a disposable glucose biosensor using electroless-plated Au/Ni/copper low electrical resistance electrodes

This paper presents a glucose biosensor, which was developed using a Au/Ni/copper electrode. Until now, research regarding the low electrical resistance and uniformity of this biosensor electrode has not been conducted. Glucose oxidase (GOD) immobilized on the electrode effectively plays the role of an electron shuttle, and allows glucose to be detected at 0.055 V with a dramatically reduced resistance to easily oxidizable constituents. The Au/Ni/copper electrode has a low electrical resistance, which is less than 0.01 Ω, and it may be possible to mass produce the biosensor electrode with a uniform electrical resistance. The low electrical resistance has the advantage in that the redox peak occurs at a low applied potential. Using a low operating potential (0.055 V), the GOD/Au/Ni/copper structure creates a good sensitivity to detect glucose, and efficiently excludes interferences from common coexisting substances. The GOD/Au/Ni/copper sensor exhibits a relatively short response time (about 3 s), and a sensitivity of 0.85 μA mM⁻¹ with a linear range of buffer to 33 mM of glucose. The sensor has excellent reproducibility with a correlation coefficient of 0.9989 (n = 100 times) and a total non-linearity error of 3.17%.     

有机硫对生物脱硫过程的抑制机理及其研究进展

作为一种绿色、经济的新兴技术,生物脱硫技术正逐渐受到人们的青睐.然而,处理气体中的有机硫对生物脱硫过程的抑制是一个不容忽视的问题.文中总结了近年来国际上对生物脱硫过程中有机硫影响的相关研究,主要包括有机硫的种类及理化特征、有机硫对脱硫过程的影响、有机硫的作用机理、操作条件与有机硫的相互关系以及耐受有机硫微生物的种类,并...     

Ultralow Ru Loading Transition Metal Phosphides as High‐Efficient Bifunctional Electrocatalyst for a Solar‐to‐Hydrogen Generation System

Water splitting is a promising technology for sustainable conversion of hydrogen energy. The rational design of oxygen evolution reaction (OER) and hydrogen evolution reaction (HER) bifunctional electrocatalysts with superior activity and stability in the same electrolyte is the key to promoting their large‐scale applications. Herein, an ultralow Ru (1.08 wt%) transition metal phosphide on nickel foam (Ru–MnFeP/NF) derived from Prussian blue analogue, that effectively drivies both the OER and the HER in 1 m KOH, is reported. To reach 20 mA cm^?2 for OER and 10 mA cm^?2 for HER, the Ru–MnFeP/NF electrode only requires overpotentials of 191 and 35 mV, respectively. Such high electrocatalytic activity exceeds most transition metal phosphides for the OER and the HER, and even reaches Pt‐like HER electrocatalytic levels. Accordingly, it significantly accelerates full water splitting at 10 mA cm^?2 with 1.470 V, which outperforms that of the integrated RuO₂ and Pt/C couple electrode (1.560 V). In addition, the extremely long operational stability (50 h) and the successful demonstration of a solar‐to‐hydrogen generation system through full water splitting provide more flexibility for large‐scale applications of Ru–MnFeP/NF catalysts.     

Advanced Electrolytes for Fast‐Charging High‐Voltage Lithium‐Ion Batteries in Wide‐Temperature Range

LiNi_xMn_yCo_1?x?yO₂ (NMC) cathode materials with Ni ≥ 0.8 have attracted great interest for high energy‐density lithium‐ion batteries (LIBs) but their practical applications under high charge voltages (e.g., 4.4 V and above) still face significant challenges due to severe capacity fading by the unstable cathode/electrolyte interface. Here, an advanced electrolyte is developed that has a high oxidation potential over 4.9 V and enables NMC811‐based LIBs to achieve excellent cycling stability in 2.5–4.4 V at room temperature and 60 °C, good rate capabilities under fast charging and discharging up to 3C rate (1C = 2.8 mA cm^?2), and superior low‐temperature discharge performance down to ?30 °C with a capacity retention of 85.6% at C/5 rate. It is also demonstrated that the electrode/electrolyte interfaces, not the electrolyte conductivity and viscosity, govern the LIB performance. This work sheds light on a very promising strategy to develop new electrolytes for fast‐charging high‐energy LIBs in a wide‐temperature range.     

Improving Electrochemical Stability and Low‐Temperature Performance with Water/Acetonitrile Hybrid Electrolytes

Although the “water‐in‐salt” electrolyte has significantly expanded the electrochemical stability window of aqueous electrolytes from 1.23 to 3 V, its inevitable hydrogen evolution under 1.9 V versus Li⁺/Li prevents the practical use of many energy‐dense anodes. Meanwhile, its liquidus temperature at 17 °C restricts its application below ambient temperatures. An advanced hybrid electrolyte is proposed in this work by introducing acetonitrile (AN) as co‐solvent, which minimizes the presence of interfacial water at the negatively charged electrode surface, and generates a thin and uniform interphase consisting of an organic outer layer based on nitrile (C?N) and sulfamide (R‐S‐N‐S) species and an inner layer rich in LiF. Such an interphase significantly suppresses water reduction and expands the electrochemical stability window to an unprecedented width of 4.5 V. Thanks to the low freezing point (?48 °C) and low viscosity of AN, the hybrid electrolyte is highly conductive in a wide temperature range, and enables a LiMn₂O₄/Li₄Ti₅O₁₂ full cell at both ambient and sub‐ambient temperatures with excellent cycling stability and rate capability. Meanwhile, such a hybrid electrolyte also inherits the nonflammable nature of aqueous electrolyte. The well‐balanced merits of the developed electrolyte make it suitable for high energy density aqueous batteries.     

Formation of Solid–Electrolyte Interfaces in Aqueous Electrolytes by Altering Cation‐Solvation Shell Structure

Aqueous lithium/sodium‐ion batteries (AIBs) have received increasing attention because of their intrinsic safety. However, the narrow electrochemical stability window (1.23 V) of the aqueous electrolyte significantly hinders the development of AIBs, especially the choice of electrode materials. Here, an aqueous electrolyte composed of LiClO₄, urea, and H₂O, which allows the electrochemical stability window to be expanded to 3.0 V, is developed. Novel [Li (H₂O)_x(organic)_y]⁺ primary solvation sheath structures are developed in this aqueous electrolyte, which contribute to the formation of solid–electrolyte interface layers on the surfaces of both the cathode and anode. The expanded electrochemical stability window enables the construction of full aqueous Li‐ion batteries with LiMn₂O₄ cathodes and Mo₆S₈ anodes, demonstrating an operating voltage of 2.1 V and stability over 2000 cycles. Furthermore, a symmetric aqueous Na‐ion battery using Na₃V₂(PO₄)₃ as both the cathode and anode exhibits operating voltage of 1.7 V and stability over 1000 cycles at a rate of 5 C.     

A Novel High Capacity Positive Electrode Material with Tunnel‐Type Structure for Aqueous Sodium‐Ion Batteries

Aqueous sodium‐ion batteries have shown desired properties of high safety characteristics and low‐cost for large‐scale energy storage applications such as smart grid, because of the abundant sodium resources as well as the inherently safer aqueous electrolytes. Among various Na insertion electrode materials, tunnel‐type Na_0.44MnO₂ has been widely investigated as a positive electrode for aqueous sodium‐ion batteries. However, the low achievable capacity hinders its practical applications. Here, a novel sodium rich tunnel‐type positive material with a nominal composition of Na_0.66[Mn_0.66Ti_0.34]O₂ is reported. The tunnel‐type structure of Na_0.44MnO₂ obtained for this compound is confirmed by X‐ray diffraction and atomic‐scale spherical aberration‐corrected scanning transmission electron microscopy/electron energy‐loss spectrum. When cycled as positive electrode in full cells using NaTi₂(PO₄)₃/C as negative electrode in 1 m Na₂SO₄ aqueous electrolyte, this material shows the highest capacity of 76 mAh g^?1 among the Na insertion oxides with an average operating voltage of 1.2 V at a current rate of 2 C. These results demonstrate that Na_0.66[Mn_0.66Ti_0.34]O₂ is a promising positive electrode material for rechargeable aqueous sodium‐ion batteries.     

Solid Polymer Electrolytes with Enhanced Electrochemical Stability for High-Capacity Aluminum Batteries

Chloroaluminate ionic liquids are commonly used electrolytes in rechargeable aluminum batteries due to their ability to reversibly electrodeposit aluminum at room temperature. Progress in aluminum batteries is currently hindered by the limited electrochemical stability, corrosivity, and moisture sensitivity of these ionic liquids. Here, a solid polymer electrolyte based on 1-ethyl-3-methylimidazolium chloride-aluminum chloride, polyethylene oxide, and fumed silica is developed, exhibiting increased electrochemical stability over the ionic liquid while maintaining a high ionic conductivity of ≈13 mS cm⁻¹. In aluminum–graphite cells, the solid polymer electrolytes enable charging to 2.8 V, achieving a maximum specific capacity of 194 mA h g⁻¹ at 66 mA g⁻¹. Long-term cycling at 2.7 V showed a reversible capacity of 123 mA h g⁻¹ at 360 mA g⁻¹ and 98.4% coulombic efficiency after 1000 cycles. Solid-state nuclear magnetic resonance spectroscopy measurements reveal the formation of five-coordinate aluminum species that crosslink the polymer network to enable a high ionic liquid loading in the solid electrolyte. This study provides new insights into the molecular-level design and understanding of polymer electrolytes for high-capacity aluminum batteries with extended potential limits.     

All‐Solid‐State Fiber Supercapacitors with Ultrahigh Volumetric Energy Density and Outstanding Flexibility

Fiber supercapacitors (FSCs) represent a promising class of energy storage devices that can complement or even replace microbatteries in miniaturized portable and wearable electronics. One of their main limitations, however, is the low volumetric energy density when compared with those of rechargeable batteries. Considering the energy density of FSC is proportional to CV² (E = 1/2 CV², where C is the capacitance and V is the operating voltage), one would explore high operating voltage as an effective strategy to promote the volumetric energy density. In the present work, an all‐solid‐state asymmetric FSC (AFSC) with a maximum operating voltage of 3.5 V is successfully achieved, by employing an ionic liquid (IL) incorporated gel‐polymer as the electrolyte (EMIMTFSI/PVDF‐HFP). The optimized AFSC is based on MnO_x@TiN nanowires@carbon nanotube (NWs@CNT) fiber as the positive electrode and C@TiN NWs@CNT fiber as the negative electrode, which gives rise to an ultrahigh stack volumetric energy density of 61.2 mW h cm^?3, being even comparable to those of commercially planar lead‐acid batteries (50–90 mW h cm^?3), and an excellent flexibility of 92.7% retention after 1000 blending cycles at 90°. The demonstration of employing the ILs‐based electrolyte opens up new opportunities to fabricate high‐performance flexible AFSC for future portable and wearable electronic devices.     

Fabrication and characterization of non-enzymatic glucose sensor based on ternary NiO/CuO/polyaniline nanocomposite

Novel nickel and copper oxide nanoparticle modified polyaniline (PANI) nanofibers (NiO/CuO/PANI) were fabricated and used as a non-enzymatic sensor for detecting glucose. PANI nanofibers were prepared through electrodeposition, whereas nickel and copper oxide nanoparticles were deposited on PANI nanofibers by electrodeposition and electrochemical oxidation in situ. The morphology and structure of NiO/CuO/PANI nanocomposites were characterized by field emission scanning electron microscopy (FE–SEM), X-ray diffraction (XRD), Raman spectroscopy, and Fourier transform infrared (FT–IR). The as-prepared NiO/CuO/PANI electrode was employed for non-enzymatic glucose detection in alkaline electrolyte and showed better electrocatalytic activity compared with the PANI, CuO/PANI, and NiO/PANI electrodes. Consequently, an amperometric electrode of glucose was achieved under 0.6 V versus Ag/AgCl with a wide linear range from 20 to 2500 μM (R² = 0.9978) and a low detection limit of 2.0 μM (signal/noise [S/N] = 3). This electrode can effectively analyze glucose concentration in human serum samples, avoiding interference, and is a promising non-enzymatic glucose sensor due to its low overpotential, high sensitivity, good selectivity and stability, fast response, and low cost.     

Hierarchically Multiscale Vertically Oriented NiFeCo Nanoflakes for Efficient Electrochemical Oxygen Evolution at High Current Densities

Crucial advancements in versatile catalyst systems capable of achieving high current densities under industrial conditions, bridging the gap between fundamental understanding and practical applications, are pivotal to propel the hydrogen economy forward. In this study, vertically oriented hierarchically multiscale nanoflakes of NiFeCo electrocatalysts are presented, developed by surface modification of a porous substrate with nano-structured nickel. The resulting electrodes achieve remarkably low overpotentials of 139 mV at 10 mAcm⁻² and 248 mV at 500 mAcm⁻². Further, scaled-up electrodes are implemented in a water-splitting electrolyser device exhibiting a stable voltage of 1.82 V to deliver a constant current density of 500 mA cm⁻² for over 17 days. Moreover, the role of the unique structures on electrochemical activity is systematically investigated by fractal analysis, involving computation of structure factors such as Minkowski connectivity, fractal dimension, and porosity using scanning electron microscope images. It is found that such structures offer higher surface area than typical layered double hydroxide structures due to morphological coherence that results in a superhydrophilic surface, while the base Ni layer boosts the charge transfer. This study demonstrates a Ni/NiFeCo(OH)_x heterostructure with highly porous morphology, a key to unlocking extremely efficient oxygen evolution reaction activity with exceptional stability. Moreover, fractal analysis is presented as a valuable tool to evaluate the electrochemical performance of catalysts for their structured morphology.     

A High Voltage Aqueous Zinc–Organic Hybrid Flow Battery

Water‐soluble redox‐active organic molecules have attracted extensive attention as electrical energy storage alternatives to redox‐active metals that are low in abundance and high in cost. Here an aqueous zinc–organic hybrid redox flow battery (RFB) is reported with a positive electrolyte comprising a functionalized 1,4‐hydroquinone bearing four (dimethylamino)methyl groups dissolved in sulfuric acid. By utilizing a three‐electrolyte, two‐membrane configuration this acidic positive electrolyte is effectively paired with an alkaline negative electrolyte comprising a Zn/[Zn(OH)₄]^2? redox couple and a hybrid RFB is operated at a high operating voltage of 2.0 V. It is shown that the electrochemical reversibility and kinetics of the organic redox species can be enhanced by an electrocatalyst, leading to a cyclic voltammetry peak separation as low as 35 mV and enabling an enhanced rate capability.     

Electrogenerated chemiluminescence of ruthenium complex immobilized in a highly cross‐linked polymer and its analytical applications

Electrogenerated chemiluminescence (ECL) of a ruthenium complex polymer modified carbon paste electrode and its analytical applications were investigated. The ruthenium complex polymer was prepared using bis(2,2‐bipyridine) (4,4‐dicarboxy‐2,2‐bipyridine) ruthenium(II). The ECL behaviours of ruthenium complex polymer modified carbon paste electrode were investigated in the absence and presence of tripropylamine (TPA). The modified carbon paste electrode exhibited long‐term stability and fine reproducibility. The ECL intensity of the modified carbon paste electrode was linear with the concentration of TPA in the range 2.0 × 10^–6–3.8 × 10^–3 mol/L, with a detection limit (S:N = 3) of 6 × 10^–7 mol/L. It was also found that raceanisodamine could enhance the ECL intensity of the modified electrode. The ECL intensity of the modified carbon paste electrode was linear with the concentration of raceanisodamine in the range 1.1 × 10^–5–6.0 × 10^–4 mol/L, with a detection limit (S:N = 3) of 6 × 10^–6 mol/L. This work demonstrates that the entrapment of ruthenium complex in a highly cross‐linked polymer is a promising approach to construct an ECL modified electrode with long‐term stability and fine reproducibility. The modified electrode designed has a potential application in the ECL detector. Copyright © 2008 John Wiley & Sons, Ltd.     

Influence of cytosolic conditions on the reaction equilibrium and the reaction enthalpy of the enolase reaction accessed by calorimetry and van ‘t HOFF

BackgroundThermodynamic methods are finding more and more applications in systems biology, which attempts to understand cell functions mechanistically. Unfortunately, the state variables used (reaction enthalpy and Gibbs energy) do not take sufficient account of the conditions inside of cells, especially the crowding with macromolecules.MethodsFor this reason, the influence of crowding agents and various other parameters such as salt concentrations, pH and temperature on equilibrium position and reaction enthalpy of the glycolytic example reaction 9 (2-Phospoglycerate - > Phosphoenolpyruvate + H₂O) was investigated. The conditions were chosen to be as close as possible to the cytosolic conditions. Poly(ethylene glycol) MW = 20,000 g mol⁻¹ (PEG 20,000) was used to analyze the influence of crowding with macromolecules. The equation of state electrolyte Perturbed-Chain Statistical Associating Fluid Theory (ePC-SAFT) was applied to consider the influence of crowding agents on the reaction equilibria.Results and conclusionsFor the reaction enthalpies and for the equilibria, it was found that the influence of salts and temperature is not pronounced while that of pH and PEG 20,000 concentration is considerable. Furthermore, it could be shown that under identical measurement conditions there are no differences between the van ‘t Hoff and the calorimetrically determined reaction enthalpy.General significanceThe results show how important it is to consider the special cytosolic conditions when applying thermodynamic data in systems biology.     

Integrated Conductive Hybrid Architecture of Metal–Organic Framework Nanowire Array on Polypyrrole Membrane for All‐Solid‐State Flexible Supercapacitors

Metal–organic frameworks (MOFs) with intrinsically porous structures are promising candidates for energy storage, however, their low electrical conductivity limits their electrochemical energy storage applications. Herein, the hybrid architecture of intrinsically conductive Cu‐MOF nanowire arrays on self‐supported polypyrrole (PPy) membrane is reported for integrated flexible supercapacitor (SC) electrodes without any inactive additives, binders, or substrates involved. The conductive Cu‐MOFs nanowire arrays afford high conductivity and a sufficiently active surface area for the accessibility of electrolyte, whereas the PPy membrane provides decent mechanical flexibility, efficient charge transfer skeleton, and extra capacitance. The all‐solid‐state flexible SC using integrated hybrid electrode demonstrates an exceptional areal capacitance of 252.1 mF cm^?2, an energy density of 22.4 µWh cm^?2, and a power density of 1.1 mW cm^?2, accompanied by an excellent cycle capability and mechanical flexibility over a wide range of working temperatures. This work not only presents a robust and flexible electrode for wide temperature range operating SC but also offers valuable concepts with regards to designing MOF‐based hybrid materials for energy storage and conversion systems.