Electrochemical Properties Research Articles

Fluorinated Linkers Enable High-Voltage Pyrrolidinium-based Dicationic Ionic Liquid Electrolytes.

Novel fluorinated, pyrrolidinium-based dicationic ionic liquids (FDILs) as high-performance electrolytes in energy storage devices have been prepared, displaying unprecedented electrochemical stabilities (up to 7 V); thermal stability (up to 370 °C) and ion transport (up to 1.45 mS cm‑1). FDILs were designed with a fluorinated ether linker and paired with TFSI/FSI counterions. To comprehensively asess the impact of the fluorinated spacer on their electrochemical, thermal, and physico-chemical properties, a comparison with their non-fluorinated counterparts was conducted. With a specific focus on their application as electrolytes in next-generation high-voltage lithium-ion batteries, the impact of the Li-salt on the characteristics of dicationic ILs was systematically evaluated. The incorporation of a fluorinated linker demonstrates significantly superior properties compared to their non-fluorinated counterparts, presenting a promising alternative towards next-generation high-voltage energy storage systems.

Magnetic, Electrochemical and Antimicrobial Properties of Li Ions Substituted by MnFe2O4 Nanoparticles

Magnetic, Electrochemical and Antimicrobial Properties of Li Ions Substituted by MnFe2O4 Nanoparticles

Complex Hydride-Based Gel Polymer Electrolytes for Rechargeable Ca-Metal Batteries.

Rechargeable Ca batteries offer the advantages of high energy density, low cost, and earth-abundant constituents, presenting a viable alternative to lithium-ion batteries. However, using polymer electrolytes in practical Ca batteries is not often reported, despite its potential to prevent leakage and preserve battery flexibility. Herein, a Ca(BH4)2-based gel-polymer electrolyte (GPE) is prepared from Ca(BH4)2 and poly(tetrahydrofuran) (pTHF) and tested its performance in Ca batteries. The electrolyte demonstrates excellent stability against Ca-metal anodes and high ionic conductivity. The results of infrared spectroscopy and 1H and 11B NMR indicate that the terminal ─OH groups of pTHF reacted with BH4 - anions to form B─H─(pTHF)3 moieties, achieving cross-linking and solidification. Cyclic voltammetry measurements indicate the occurrence of reversible Ca plating/stripping. To improve the performance at high current densities, the GPE is supplemented with LiBH4 to achieve a lower overpotential in the Ca plating/stripping process. An all-solid-state Ca-metal battery with a dual-cation (Ca2+ and Li+) GPE, a Ca-metal anode, and a Li4Ti5O12 cathode sustained >200 cycles, confirming their feasibility. The results pave the way for further developing lithium salt-free Ca batteries by developing electrolyte salts with high oxidation stability and optimal electrochemical properties.

Controlling Structure and Morphology of MoS2 via Sulfur Precursor for Optimized Pseudocapacitive Lithium Intercalation Hosts

Molybdenum disulfide (MoS2)‐based electrode materials can exhibit a pseudocapacitive charge storage mechanism induced by nanosized dimension of the crystalline domains, which is why control over material structure via synthesis conditions is of significance. In this study, we investigate how the use of different sulfide precursors, specifically thiourea (TU), thioacetamide (TAA), and L‐cysteine (LC), during the hydrothermal synthesis of MoS2, affects its physicochemical, and consequently, electrochemical properties. The three materials obtained exhibit distinct morphologies, ranging from micron‐sized architectures (MoS2 TU), to nanosized flakes (MoS2 TAA and LC). While all three synthesized samples exhibit pseudocapacitive Li+ intercalation properties, the capacity retention of the latter two consisting of nanosized flakes is further improved at high cycling rates. The individual charge storage properties are analyzed by operando X‐ray diffraction, dilatometry, and 3D Bode analysis, revealing a correlation between the morphology, porosity, and the electrochemical intercalation behavior of the obtained electrode materials. The results demonstrate a facile strategy to control MoS2 structure and related functionality by choice of hydrothermal synthesis precursors.

Versatile Activated Carbon Fibers Derived from the Cotton Fibers Used as CO2 Solid-State Adsorbents and Electrode Materials.

Activated carbon has an excellent porous structure and is considered a promising adsorbent and electrode material. In this study, activated carbon fibers (ACFs) with abundant microporous structures, derived from natural cotton fibers, were successfully synthesized at a certain temperature in an Ar atmosphere and then activated with KOH. The obtained ACFs were characterized by field emission scanning electron microscopy (FESEM), transmission electron microscopy (TEM), elemental analysis, nitrogen and carbon dioxide adsorption-desorption analysis, X-ray diffraction (XRD), X-ray photoelectron spectroscopy (XPS) and N2 adsorption-desorption measurement. The obtained ACFs showed high porous qualities and had a surface area from 673 to 1597 m2/g and a pore volume from 0.33 to 0.79 cm3/g. The CO2 capture capacities of prepared ACFs were measured and the maximum capture capacity for CO2 up to 6.9 mmol/g or 4.6 mmol/g could be achieved at 0 °C or 25 °C and 1 standard atmospheric pressure (1 atm). Furthermore, the electrochemical capacitive properties of as-prepared ACFs in KOH aqueous electrolyte were also studied. It is important to note that the pore volume of the pores below 0.90 nm plays key roles to determine both the CO2 capture ability and the electrochemical capacitance. This study provides guidance for designing porous carbon materials with high CO2 capture capacity or excellent capacitance performance.

Effect of AlN on the Mechanical and Electrochemical Properties of Aluminum Metal Matrix Composites.

In the present investigation, aluminum metal matrix composites (AMMs) reinforced with aluminum nitride (AlN) nanoparticulates at different volumetric ratios of (0, 0.5, 1, 1.5, and 2 vol.%) were manufactured via a microwave-assisted powder metallurgy technique. The morphological, physical, mechanical, and electrochemical properties of the produced billets were examined to reflect the impact of the successive addition of AlN into the aluminum (Al) matrix. The morphological analysis revealed the high crystalline patterns of the formation of the Al-AlN composites. The microstructural analysis confirmed the presence of the elemental constituents of Al and AlN particles in the fabricated composites, showing an enhanced degree of agglomeration in conjunction with the additional amount of AlN. Positive behavior exhibited by the micro- and nanohardness was noticeable in the Al-AlN composites, especially at the ultimate concentration of AlN in the Al matrix of a 2 vol.%, where it reached 669.4 ± 28.1 MPa and 659.1 ± 11 MPa compared to the pure Al metal at 441.2 ± 20 MPa and 437.5 ± 11 MPa, respectively. A declining trend in the compressive strength was recorded in the reinforced Al samples. The corrosion resistance of the AlN-reinforced Al metal matrix was estimated at 3.5 wt.% NaCl using electrochemical impedance spectroscopy and potentiodynamic polarization. The results reveal that the inclusion of 2.0 vol.%AlN led to the lowest corrosion rate.

Phosphorous - Containing Activated Carbon Derived From Natural Honeydew Peel Powers Aqueous Supercapacitors.

The introduction of phosphorous (P), and oxygen (O) heteroatoms in the natural honeydew chemical structure is one of the most effective, and practical approaches to synthesizing activated carbon for possible high-performance energy storage applications. The performance metrics of supercapacitors depend on surface functional groups and high-surface-area electrodes that can play a dominant role in areas that require high-power applications. Here, we report a phosphorous and oxygen co-doped honeydew peel-derived activated carbon (HDP-AC) electrode with low surface area for supercapacitor via H3PO4 activation. This activator form phosphorylation with cellulose fibers in the HDP. The formation of heteroatoms stabilizes the cellulose structure by preventing the formation of levoglucosan (C6H10O5), a cellulose combustion product, which would otherwise offer a pathway for a substantial degradation of cellulose into volatile products. Therefore, heteroatom doping has proved effective, in improving the electrochemical properties. The improved performance is attributed to the high phosphorous doping with a hierarchical porous structure, which enables the transportation of ions at higher current rates. The high specific capacitance of 486, and 478 F/g at 0.6, and 1.3 A/g in 1M H2SO4 electrolyte with a prominent retention of 98% is observed for 2M H3PO4 having an impregnation ratio of 1:4.

Spectral properties and photophysical processes of triphenylamine-porphyrin-pyrimidine triads

Porphyrins have attracted considerable attention as an important family of photosensitizers used for dye-sensitized solar cells (DSSCs). In this work, a novel triphenylamine-porphyrin-pyrimidine triad with a triple bond linkage was synthesized and characterized. The sensitizer presents broad absorption in solution and on TiO2 films across the UV-Vis region benefiting from the extended conjugation. The acetenyl π-conjugated bridge stimulates the photoinduced electron transfer (PET) process and brings a charge-separated state lifetime of around 4 μs. DSSC devices based on the sensitizer achieve a power conversion efficiency (PCE) of 3.77% thanks to the prolonged charge-separated state lifetime and suppressed charge recombination. The understanding of the structural, optical, and electrochemical properties of triphenylamine-porphyrin-pyrimidine triads provides new insights into the rational design of porphyrin sensitizers for various applications.

Manipulating disorder within cathodes of alkali-ion batteries.

The fact that ordered materials are rarely perfectly crystalline is widely acknowledged among materials scientists, but its impact is often overlooked or underestimated when studying how structure relates to properties. Various investigations demonstrate that intrinsic and extrinsic defects, and disorder generated by physicochemical reactions, are responsible for unexpectedly detrimental or beneficial functionalities. The task remains to modulate the disorder to produce desired properties in materials. As disorder is often correlated with local interactions, it is controllable. In this Review, we explore the structural disorder in cathode materials as a novel approach for improving their electrochemical performance. We revisit cathode materials for alkali-ion batteries and outline the origins and beneficial consequences of disorder. Focusing on layered, cubic rocksalt and other metal oxides, we discuss how disorder improves electrochemical properties of cathode materials and which interactions generate the disorder. We also present the potential pitfalls of disorder that must be considered. We conclude with perspectives for enhancing the electrochemical performance of cathode materials by using disorder.

Electrochemical Detection of Acetaminophen in Pharmaceuticals Using Rod-Shaped α-Bi2O3 Prepared via Reverse Co-Precipitation

This study employed a novel synthetic approach involving a modified reverse co-precipitation method utilizing glacial acetic acid to synthesize α-Bi2O3. X-ray powder diffraction and scanning and transmission electron microscopy analyses revealed the formation of a rod-like α-Bi2O3 microstructure. The prepared material was utilized to modify a glassy carbon paste (GCP) electrode for the development of an electrochemical sensor for acetaminophen (APAP) detection using differential pulse voltammetry (DPV). Cyclic voltammetry studies revealed that the GCP@Bi2O3 electrode exhibited enhanced electrochemical properties compared to the bare GCP. The designed GCP@Bi2O3 sensor detected APAP in the linear concentration range from 0.05 to 12.00 µM, with LOQ and LOD of 36 nM and 10 nM, respectively. Additionally, the developed sensor demonstrated sufficient precision, repeatability, and selectivity toward APAP detection. The recovery values between the declared and found APAP content in a pharmaceutical formulation (Caffetin®) displayed the advantageous accuracy, precision, and applicability of the GCP@Bi2O3 sensor and the developed DPV method for real-time APAP detection in pharmaceuticals, with minimal interference from the matrix effect.

First-Principles Calculations of TiB4 and TiB5 as Anodes with High Capacity for Na-Ion Batteries.

The electrochemical properties of TiB4 and TiB5 monolayers in Na-ion batteries (NIBs) were studied by using the first-principles calculation method based on density functional theory. The TiB4/TiB5 monolayer showed excellent Na storage capacity, capable of adsorbing two layers of Na with theoretical capacities of 1176.77 and 1052.05 mA g-1, respectively. The average operating voltages of the TiB4 and TiB5 monolayers are 0.073 and 0.042 eV, respectively, indicating that they can be used as anode materials for NIBs. More interestingly, the exposed B surface not only brings a high theoretical capacity but also provides a relatively small diffusion barrier of 0.16 (for TiB4) and 0.33 eV (for TiB5), enhancing their rate capability in NIBs.

Hierarchical core-shelled CoMo layered double hydroxide@CuCo2S4 nanowire arrays/nickel foam for advanced hybrid supercapacitors

The development of core-shelled heterostructures with the unique morphology can improve the electrochemical properties of hybrid supercapacitors (HSC). Here, CuCo2S4 nanowire arrays (NWAs) are vertically grown on nickel foam (NF) utilizing hydrothermal synthesis. Then, CoMo-LDH nanosheets are uniformly deposited on the CuCo2S4 NWAs by electrodeposition to obtain the CoMo-LDH@CuCo2S4 NWAs/NF electrode. Due to the superior conductivity of CuCo2S4 (core) and good redox activity of CoMo-LDH (shell), the electrode shows excellent electrochemical properties. The electrode’s specific capacity is 1271.4C g−1 at 1 A g−1, and after 10, 000 cycles, its capacity retention ratio is 92.2 % at 10 A g−1. At a power density of 983.9 W kg−1, the CoMo-LDH@CuCo2S4 NWAs/NF//AC/NF device has an energy density of 52.2 Wh kg−1. This indicates that CoMo-LDH@CuCo2S4/NF has a great potential for supercapacitors.

Efficient Synthesis and Electrochemical Profiling of Nickel Tungstate for Supercapacitor Application

The Nickel Tungstate nanomaterial was synthesized by the green synthesis method. The powder x-ray diffraction analysis was carried out for Nickel Tungstate and its crystalline nature was identified. The optical properties of the Nickel Tungstate were studied. The surface morphology of the Nickel Tungstate was tested using a scanning electron microscope (SEM). The surface area analysis was obtained by BET analysis. X-ray photoelectron Spectroscopy was used to identify the Binding energy of the materials. The electrochemical properties were investigated using Cyclic Voltammetry (CV), Electrochemical Impedance Spectroscopy (EIS), and Charge-Discharge (GCD). The highest cyclic stability for 10000 charge and discharge cycle was reported in this paper with good retention at 98%. NiWO4 NPs electrode material shows high specific capacitance values of 425 F/g−1, 300 F/g−1 and 605 F/g−1 at a scan rate of 3 mA/g for pH5, pH6 and pH7 respectively.

Hollow-structured cobalt sulfoselenide as cathode host to enhance the kinetics and improve the energy density of lithium-sulfur batteries

Lithium-sulfur batteries are a promising next-generation battery system due to their high energy density, low cost, and environmental friendliness. However, the shuttle effect and resulting low redox kinetics are significant issues that currently hinder their development. The addition of catalysts to accelerate the redox process is a common strategy. Metal sulfide catalysts, in particular, have been widely studied due to their good affinity for sulfur and sulfides. Although metal sulfide show good adsorption performance for lithium polysulfides, their low conductivity does not significantly improve the kinetic performance of the battery. Additionally, the high molecular weight of the inactive sulfide leads to the low actual energy density of the battery. Thus, this study constructed the hollow structural cobalt sulfoselenide by replacing partial elemental sulfur in cobalt sulfide (Co3S4) with the higher metallicity element selenium (Se). This was done to increase catalytic activity and reduce the amount of inactive substances, ultimately leading to an increase in actual energy density. This strategy systematically investigated the electrical conductivity, catalytic activity, and inhibition of the shuttle effect of Co3S2Se2. It was found that cobalt sulfoselenide with a 1:1 ratio of sulfur to selenium exhibited higher catalytic activity than pure cobalt sulfide. Additionally, the hollow structure of cobalt sulfoselenide showed greater performance enhancement than bulk cobalt sulfoselenide. In the assembled lithium-sulfur battery, the initial specific capacity of 1294.7 mAh/g at 0.1C was obtained, and the capacity retention was 77.5 % after 100 cycles. On this basis, the structure–activity relationship between selenium-sulfur ratio and electrochemical properties will provide ideas for the design of microscopic cathode structures.

Metal-organic frameworks and composites on their basis: structure, synthesis methods, electrochemical properties and application prospects (a review)

Various types of metal-organic frameworks (MOF) and their structural parameters have been reviewed and their classification has been presented. Most widely used synthesis methods and approaches for MOF and composites on their basis have been discussed. MOF structure is a regular 3D lattice formed by organic linkers and metallic clusters. It has been shown for an example of literary data on MOF synthesis and structural studies that the types of bonds and metals can strongly affect the spatial structure and dimensions of MOF crystals: they can have nano-, micro- and meso-dimensions, be dense or porous, bulk or layered. This variety of structural parameters determines the wide range of their properties and potential applications. Prospects and methods of controlling the shapes of the crystals, their size and spatial bonds between organic components and metal ions have been reviewed. Major attention has been paid to zeolite-like frameworks (ZIF) as the most promising ones from the viewpoint of structure, synthesis and electrochemical current source applications. Discussion has touched on possible modifications and methods of controlling the properties of those MOFs and composites on their basis and introduction of impurities, including those having magnetic properties. Possible synthesis options of complex composites through controlled MOF pyrolysis have been presented, for either small-batch or scalable processes. The effect of heat treatment conditions on the final properties and electrochemical applications of those materials has been demonstrated. ZIF-67 structured MOF doping with one more metal has been presented as variant of modifying the properties of MOF and composites on their basis. For example, the Authors have implemented cobalt MOF synthesis wherein cobalt is partially substituted for manganese at the synthesis stage. Furthermore, a simple water solution co-deposition synthesis technique has been modified with ultrasonication thus reducing the time consumption of the process. Electrochemical studies have shown that the unit electrochemical capacity of pyrolyzed MOF electrodes with partial cobalt substitution for manganese is appreciably higher as compared to the manganese-free materials. The unit capacity and energy density increase with manganese content in the MOF. MOF manganese doping delivers a considerable improvement in the electrochemical parameters of the electrode materials for hybrid supercapacitors on their basis (from 100 to 298 F/g at 0.25 A/g current density). The results suggest that cobalt substitution for manganese is an effective method of improving the electrochemical parameters of MOFs. It has been demonstrated that the development of new approaches to the design of MOF based composite materials and the study of the physicochemical regularities of their interaction with various carriers is an important task.

Electrochemical properties and corrosion induced mechanical degradation of biomedical Zn–Cu–Li alloy in simulated body fluid

The electrochemical behavior and corrosion induced mechanical degradation of biodegradable Zn–2Cu–0.03Li alloy were in detail investigated. The results indicated that the corrosion product film presented an increasing corrosion resistance, while the localized corrosion induced by microgalvanic effect was intensified. Corrosion pits, as the typical defect, acted as the crack initiation sites and accelerated the fracture process of the Zn–2Cu–0.03Li alloy. Accordingly, the fracture mode transformed from ductile to brittle failure. Significant loss in ultimate tensile strength and elongation of the alloys occurred due to strong stress concentration at corrosion pit, threatening the mechanical reliability after implantation.

Hierarchical core-shelled CoMo layered double hydroxide@CuCo2S4 nanowire arrays/nickel foam for advanced hybrid supercapacitors

The development of core-shelled heterostructures with the unique morphology can improve the electrochemical properties of hybrid supercapacitors (HSC). Here, CuCo2S4 nanowire arrays (NWAs) are vertically grown on nickel foam (NF) utilizing hydrothermal synthesis. Then, CoMo-LDH nanosheets are uniformly deposited on the CuCo2S4 NWAs by electrodeposition to obtain the CoMo-LDH@CuCo2S4 NWAs/NF electrode. Due to the superior conductivity of CuCo2S4 (core) and good redox activity of CoMo-LDH (shell), the electrode shows excellent electrochemical properties. The electrode’s specific capacity is 1271.4C g−1 at 1 A g−1, and after 10, 000 cycles, its capacity retention ratio is 92.2 % at 10 A g−1. At a power density of 983.9 W kg−1, the CoMo-LDH@CuCo2S4 NWAs/NF//AC/NF device has an energy density of 52.2 Wh kg−1. This indicates that CoMo-LDH@CuCo2S4/NF has a great potential for supercapacitors.

DFT simulations of photovoltaic parameters of dye‐sensitized solar cells with new efficient sensitizer of indolo[3, 2‐b]carbazole complexes

AbstractDeveloping economical and high‐performing sensitizers is crucial in advancing dye‐sensitized solar cells (DSSCs) and optoelectronics. This research paper explores the potential of novel red light‐absorbing organic dyes based on Indolo[3,2‐b]carbazole (ICZ) as the donor applied in co‐sensitizer‐free DSSCs for breakthroughs in photovoltaic (PV) applications. DFT and TD‐DFT based computational methods were employed to calculate the conduction band levels, electron injection capabilities, and power conversion efficiency (PCE) of metal‐free organic dyes (ICZ1–ICZ9) having D‐A‐π‐A architecture. Comprehensive analyses included NBO, DOS, FMO, ICT, MEP, binding energy, and TDM analysis. Quantum chemical calculations of the structural, photochemical, and electrochemical properties, as well as the key parameters, reveals that all the designed dyes could be an excellent candidate for high‐efficiency DSSCs due the small energy gap (2.130–1.947 eV), longer wavelength absorption (759.47–520.63 nm), longer lifetimes (15.65–6.67 ns), a lower ΔGreg (0.29–0.14 eV), a significant dipole moment changes (31.489–16.195D), LHE (0.95‐0.46), the large qCT (0.962–0.689), small DCT (7.657, 4.897 Å), and VOC (1.13–0.86 eV). This quantum simulation showed that, when compared to reference D8, the photovoltaic dyes ICZ8, ICZ2, and ICZ7 are recognized as being eye‐catching. Furthermore, dye@(TiO2)9 cluster model results demonstrate promising prospects for enhancing the photovoltaic (PV) performance of ICZ1–ICZ9 dyes by electron injection and conduction band (CB) engineering. This study will help the experimentalists for developing ICZ‐based PVs as more efficient and sustainable energy solutions.

The Role of the Anion in Concentrated Electrolytes for Lithium-Sulfur Batteries

Highly concentrated electrolytes show promise in enhancing lithium-sulfur (Li-S) battery performance by mitigating polysulfide (PS) solubility. The role of the salt anion for the performance improvement(s) is however not well understood. Here a systematic characterization using (concentrated) electrolytes based on three different salts: LiTFSI, LiTf, and LiTDI, in a common DOL:DME solvent mixture is reported for a wide range of physicochemical and electrochemical properties: ionic conductivity, density, viscosity, speciation, and PS solubility. While increased salt concentration in general improves Li-S battery performance, the role of the salt anion introduces complexity. The 2 m LiTDI-based electrolyte, with a slightly higher viscosity and lower PS solubility, outperforms the LiTFSI-based counterpart in terms of accessible reversible capacity. Conversely, the 2 m LiTf-based electrolyte exhibits subpar performance due to the formation of ionic aggregates that renders more free solvent and, therefore higher PS solubility, which, however can be improved by using a 5 m concentrated electrolyte. Hence, using electrolyte salt concentration as a rational design route demands an understanding of the local molecular structure, largely determined/affected by the choice of anion, as well as how it connects to the global properties and in the end improved Li-S battery performance.

High entropy induced lattice expansion in layered oxide cathode towards fast sodium storage

Although O3-type layered oxides have become viable cathode materials for sodium-ion batteries (SIBs) due to their high energy densities, they still suffer from narrow ion channels and serious structure degradation, severely jeopardizing their electrochemical properties. Here, a stable O3-type layered oxide NaNi0.4Mn0.4M0.2O2 (M= Fe, Cu, Mg, Ti, Sn) (HE-NaNM) was synthesized by a high-entropy doping strategy. Owing to the introduction of the metal cations with ionic radiuses in a range of 0.61-0.73 Å into the layered structure, the lattice is expanded from 15.94 to 16.03 Å in c-axis, associated with a high distortion of TMO6 octahedrons, offering broad channels for sodium-ion transport in the lattices. Moreover, such expanded lattices and highly distorted TMO6 octahedrons enable to efficiently restrain the migration of TM ions and the severe sliding of TMO2 slabs, affording one-step reversible structure evolution between O3 and P3 phase during sodium extraction/insertion without formation of harmful interphases. As a result, a good rate capability of 77.9 mAh g-1 at 10 C and a long-term cycling stability up to 400 cycles at 5 C are achieved for sodium storage.