Capacitance Of Electrode Research Articles

Optimizing Reversible Phase‐Transformation of FeS2 Anode via Atomic‐Interface Engineering Toward Fast‐Charging Sodium Storage: Theoretical Predication and Experimental Validation

AbstractSodium‐storage performance of pyrite FeS2 is greatly improved by constructing various FeS2‐based nanostructures to optimize its ion‐transport kinetics and structural stability. However, less attention has been paid to rapid capacity degradation and electrode failure caused by the irreversible phase‐transition of intermediate NaxFeS2 to FeS2 and polysulfides dissolution upon cycling. Under the guidance of theoretical calculations, coupling FeS2 nanoparticles with honeycomb‐like nitrogen‐doped carbon (NC) nanosheet supported single‐atom manganese (SAs Mn) catalyst (FeS2/SAs Mn@NC) via atomic‐interface engineering is proposed to address above challenge. Systematic electrochemical analyses and theoretical results unveil that the functional integration of such two type components can significantly enhance ionic conductivity, accelerate charge transfer efficiency, and improve Na+‐adsorption capability. Particularly, SAs Mn@NC with Mn‐Nx coordination center can reduce the decomposition barrier of Na2S and NaxFeS2 to further accelerate reversible phase transformation of Fe/Na2S→NaFeS2→FeS2 and polysulfides decomposition. As predicted, such FeS2/SAs Mn@NC showcases outstanding rate capability and fascinating cyclic durability. A sequence of kinetic studies and ex situ characterizations provide the comprehensive understanding for ion‐transport kinetics and phase‐transformation process. Its practical use is further demonstrated in sodium‐ion full cell and capacitor with impressive electrochemical capability and excellent energy‐density output.

Interface engineering enabling thin lithium metal electrodes down to 0.78 μm for garnet-type solid-state batteries.

Controllable engineering of thin lithium (Li) metal is essential for increasing the energy density of solid-state batteries and clarifying the interfacial evolution mechanisms of a lithium metal negative electrode. However, fabricating a thin lithium electrode faces significant challenges due to the fragility and high viscosity of Li metal. Herein, through facile treatment of Ta-doped Li7La3Zr2O12 (LLZTO) with trifluoromethanesulfonic acid, its surface Li2CO3 species is converted into a lithiophilic layer with LiCF3SO3 and LiF components. It enables the thickness control of Li metal negative electrodes, ranging from 0.78 μm to 30 μm. Quasi-solid-state lithium-metal battery with an optimized 7.54 μm-thick lithium metal negative electrode, a commercial LiNi0.83Co0.11Mn0.06O2 positive electrode, and a negative/positive electrode capacity ratio of 1.1 shows a 500 cycles lifespan with a final discharge specific capacity of 99 mAh g-1 at 2.35 mA cm-2 and 25 °C. Through multi-scale characterizations of the thin lithium negative electrode, we clarify the multi-dimensional compositional evolution and failure mechanisms of lithium-deficient and -rich regions (0.78 μm and 7.54 μm), on its surface, inside it, or at the Li/LLZTO interface.

On the Origin of Capacity Increase in Rechargeable Magnesium Batteries with Manganese Oxide Cathodes and Copper Metal Current Collectors.

Rechargeable magnesium batteries (RMBs), with Cu as positive electrode current collector (CC), typically display a gradual capacity increase with cycling. Whereas the origin of this was suggested in gradual active material electro-activation, the fact that this is prevalent in many positive electrode material systems remains unexplained. Herein, we elucidate the underlying mechanism through a series of multiscale joint operando X-ray characterizations, including operando synchrotron X-ray diffraction and imaging technology. We select a series of manganese oxides as benchmark positive electrodes and find that no magnesium ions are stored within the lattices of these materials, despite an apparent cell capacity increase with cycling. The origin of capacity increase is rooted in the gradual electrochemical corrosion of metallic Cu, release of Cu(I, II) species in electrolyte, and their subsequent redox activity, resulting in apparent electrode capacity gains. Furthermore, the shuttle and redox speciation of Cu ions trigger the irreversible depletion of both the Cu CC (or any other source) and the magnesium metal, ultimately leading to cell failure. Our work suggests the need to reconsider the appropriateness of using Cu as a positive electrode CC for RMBs.

On the Origin of Capacity Increase in Rechargeable Magnesium Batteries with Manganese Oxide Cathodes and Copper Metal Current Collectors

Rechargeable magnesium batteries (RMBs), with Cu as positive electrode current collector (CC), typically display a gradual capacity increase with cycling. Whereas the origin of this was suggested in gradual active material electro‐activation, the fact that this is prevalent in many positive electrode material systems remains unexplained. Herein, we elucidate the underlying mechanism through a series of multiscale joint operando X‐ray characterizations, including operando synchrotron X‐ray diffraction and imaging technology. We select a series of manganese oxides as benchmark positive electrodes and find that no magnesium ions are stored within the lattices of these materials, despite an apparent cell capacity increase with cycling. The origin of capacity increase is rooted in the gradual electrochemical corrosion of metallic Cu, release of Cu(I, II) species in electrolyte, and their subsequent redox activity, resulting in apparent electrode capacity gains. Furthermore, the shuttle and redox speciation of Cu ions trigger the irreversible depletion of both the Cu CC (or any other source) and the magnesium metal, ultimately leading to cell failure. Our work suggests the need to reconsider the appropriateness of using Cu as a positive electrode CC for RMBs.

Sodium and Potassium Storage Behaviour in AgNbO3 Perovskite

AbstractIn this work, we report on the investigation the perovskite‐type AgNbO3 as a model negative electrode for sodium and potassium systems. We demonstrated that during the initial discharge, regardless of the inserted cation, the material undergoes an activation mechanism that induces a crystalline‐to‐amorphous transition. This transition, in turn, leads to an enhancement of the electrode capacity. At 5 A g−1 sodium‐ion AgNbO3 and Potassium‐ion AgNbO3 display capacities of 81 mAh g−1 and 60 mAh g−1, respectively. Furthermore, both electrodes display good cycling stability and efficiency over 350 cycles at 1 A g−1.

Recent Advances in High-Performance Carbon-Based Electrodes for Zinc-Ion Hybrid Capacitors

Aqueous zinc-ion hybrid capacitors (ZIHCs) have emerged as a promising technology, showing superior energy and power densities, as well as enhanced safety, inexpensive and eco-friendly features. Although ZIHCs possess the advantages of both batteries and supercapacitors, their energy density is still unsatisfactory. Therefore, it is extremely crucial to develop reasonably matched electrode materials. Based on this challenge, a surge of studies has been conducted on the modification of carbon-based electrode materials. Herein, we first summarize the progress of the related research and elucidate the energy storage mechanism associated with carbon-based electrodes for ZIHCs. Then, we investigate the influence of the synthesis routes and modification strategies of the electrode materials on electrochemical stability. Finally, we summarize the current research challenges facing ZIHCs and predict potential future research pathways. In addition, we suggest key scientific questions to focus on and potential directions for further exploration.

Design of Silicon-Based Anode Materials for High Energy Density Li-Ion Batteries

Compared to other types of batteries, lithium batteries have an extremely high energy density, which means they can store more energy while maintaining a smaller size and weight. The ideal electrode material must have a high lithium ion capacity to store many lithium ions. In addition, the electrode material must have good electronic conductivity to promote lithium ions' rapid entry and exit. However, traditional carbon materials have limited theoretical specific capacity, and the transmission of lithium-ion batteries in traditional materials is limited, resulting in a significant decrease in capacity. Silicon has a theoretical capacity of up to 4200mAh/g, more than ten times the capacity of commercial graphite negative electrodes. In addition, silicon and lithium can undergo alloying reactions to form Li Si alloys, which helps improve the material's specific capacity. This article first summarizes the advantages of electric vehicles and lithium-ion batteries. Then, the benefits and challenges of using silicon-based materials as negative electrodes for lithium-ion batteries were elaborated in detail, and finally, the prospects of silicon-based materials in lithium-ion battery applications were summarized. This article has reference significance in improving the energy density of lithium-ion batteries.

Assessment of simultaneous removal of salt and dye by utilizing capacitive deionization and UV-electro oxidation hybrid process in saline wastewater treatment

In this research, the goal was simultaneous elimination of salt (NaCl) and dye (C·I Acid Orange 7 or AO7) through integration of capacitive deionization (CDI) technique with UV-based electrochemical advanced oxidation process (UV-EAOP). To optimize salt adsorption capacity (SAC) of MnO2 electrode, Taguchi's experimental design methodology was employed to fine-tune synthesis parameters, including bath temperature, current density, and precursor concentrations. BiOCl was synthesized and implemented as an anode to bolster AOP's effectiveness. Several experiments were conducted to analyze the effects of applying the combined AOP and CDI. The findings revealed that parameter optimization improved SAC, and the application of UV irradiation decreased electrode's SAC. Furthermore, it was observed that AO7 could enhance SAC while lowering salt adsorption rate (SAR). More importantly, the combined application of CDI and AOP resulted in superior pollutant removal efficiency and improved SAC, despite reduced SAR. Finally, color was entirely eliminated after 90 min, and the generated species were recognized by GC–MS. Additionally, a possible pathway for AO7 degradation was suggested based on the generated species.

Optimizing Sodium Ion Adsorption Through Robust d–d Orbital Modulation for Efficient Capacitive Deionization

AbstractUnraveling the fundamental mechanisms of sodium ion adsorption behavior is crucial for guiding the design of electrode materials and enhancing the performance of capacitive deionization systems. Herein, the optimization of sodium ion adsorption is systematically investigated through the robust d–d orbital interactions within zinc‐doped iron carbide, facilitated by a novel liquid nitrogen quenching treatment. Liquid nitrogen quenching treatment can enhance the coordination number, strengthen d–d orbital interactions, promote electron transfer, and shift the d‐band center of Fe closer to the Fermi level, thereby enhancing sodium ions adsorption energy. Consequently, the obtained electrode material achieves a superior gravimetric adsorption capacity of 121.1 mg g−1 and attractive cyclic durability. The adsorption capacity is highly competitive compared to the vast majority of related research works in the field of capacitive deionization. Furthermore, sodium ion adsorption/desorption mechanisms are substantiated through ex situ techniques, revealing dynamic atomic and electronic structure evolutions under operational conditions. This work demonstrates that optimizing sodium ion adsorption via robust d–d orbital modulation enabled by liquid nitrogen quenching treatment is an effective approach for developing efficient capacitive deionization electrode materials.

High-energy Mn2V2O7//C asymmetric supercapacitors in aqueous/organic hybrid electrolytes

The demand for advanced energy storage devices, such as high-energy density supercapacitors, has spurred efforts to develop new environmentally friendly and efficient electrode materials and electrolyte solutions for sustainable development. A prominent strategy is the fabrication of high-voltage and energy-density asymmetric supercapacitors (AS). In this study, dimanganese divanadate (Mn2V2O7, MVO) particles were synthesized via a hydrothermal process and used as pseudocapacitive electrodes for AS. The pseudocapacitive MVO electrode offered synergistic advantages of reversible surface or near-surface Faradaic reactions for charge storage. Another approach to address the challenges of limited energy density in supercapacitors was modifying the electrolyte solution to widen the operating voltage window and increase energy density. A hybrid electrolyte solution of 5 M sodium perchlorate (NaClO4) in a mixture of (2:1) volume ratio of acetonitrile (AN) and water (H2O) was introduced to expand the voltage window in the AS. The fabricated AS with MVO as a pseudocapacitive electrode and activated carbon as a double-layer capacitive electrode operated in a voltage window > 2.0 V with the hybrid electrolyte. The AS device exhibited a capacitance of 156.9 F g−1 at 0.1 A g−1 and a high energy density of 87.2 Wh kg−1, surpassing the carbon-based symmetric supercapacitor (58.9 Wh kg−1). Furthermore, the pseudocapacitive supercapacitor showed exceptional long-term stability over 50,000 cycles. Structural and surface characterization of the MVO electrode after CV testing validated that the charge storage mechanism in Mn2V2O7//C was a surface-controlled process. The performance of the AS pouch cell revealed the great promise of the pseudocapacitive electrode in practical applications.

Sulfuric acid treatment to control the microcrystalline structure of starch-based hard carbon for sodium storage

By treating starch with different concentrations of sulfuric acid, we investigated the effect of cross-linked starch-based hard carbon on the performance of sodium-ion batteries (SIBs) at various concentrations. After treatment, the optimal sample exhibits a spherical microstructure, which can provide effective active sites and enhance structural stability, thereby achieving high capacity and long cycle life for SIB electrodes. In subsequent electrochemical tests, after 100 cycles at low current density of 0.1 A g−1, the capacity of H40 remains of 306 mA h g−1. And under the high current density of 1 A g−1, the capacity of H40 can still maintain of 228 mA h g−1, exhibiting a high capacity retention rate of 89 %, which is higher than other samples. This study provides a promising approach for the large-scale production of biomass-derived carbonaceous SIBs anodes.

Selective ammonia recovery from wastewater by SDS-AC based microfiltration membrane flow electrode capacitor deionization

Selective ammonia recovery from wastewater by SDS-AC based microfiltration membrane flow electrode capacitor deionization

Initial Study of Reduced Graphene Oxide Foams Modified by Mn and Bi as Capacitive Electrode Materials

In a view of application of porous materials in wearable electronics and self-powered systems, reduced graphene oxide (rGO) foams modified by Mn or/and Bi were produced in this study to be used as electrodes for supercapacitors. The hydrothermal method and the freeze-drying processes were used for the preparation of the materials further morphologically, elementally and structurally analyzed. Based on the electrochemical characterization, Bi-modified rGO foam was found to be more a promising material for capacitive electrodes in comparison to the other prepared materials.

Synergistic Bimetallic Effects of BiSb Anodes Enable Long‐Stable Sodium Storage

AbstractAlloy‐type anodes are of interest for their resource‐rich and high theoretical capacity performance in sodium‐ion batteries (SIBs). However, severe volume expansion may lead to rapid capacity decay and electrode pulverization. In this work, metallic Bi with better structure stability is rationally selected as a skeleton to form a 2D BiSb alloy to alleviate the volume expansion. Interestingly, by combining in‐situ XRD and ex‐situ TEM characterizations, a reversible multi‐step alloying sodium storage mechanism of BiSb ↔ Na(Bi, Sb) ↔ Na3(Bi, Sb) in Bi0.4Sb0.6 anode is elucidated, and the partial amorphization and expanded interlayer spacing of BiSb alloy is also revealed, which greatly alleviate volume expansion thereby enhancing electrochemical stability. Furthermore, density functional theory and kinetic calculations demonstrate that Bi0.4Sb0.6 demonstrates lower Na+ adsorption energy and Na+ diffusion energy barriers, ensuring fast electron and ion transportation during sodium storage. Benefiting from the synergistic effects of binary alloy, Bi0.4Sb0.6 exhibits a high reversible capacity and cycling stability of 446 mAh g−1 at 0.1 A g−1, and 70% high capacity after 1100 cycles at 0.5 A g−1. This work provides new insights and opportunities to develop advanced precise alloy‐type anode materials for SIBs.

Li-ion solvation structure at electrified solid-liquid interface: Understanding solvation structure dynamics and its role in electrochemical energy storage through binary ethylene carbonate and dimethyl carbonate solvent.

Binary solvent electrolytes can provide interpretations for designing advanced electrolytes of next generation batteries. This study investigates the adsorption mechanisms of solvated lithium ions in binary solvents near charged electrodes. Molecular dynamic simulations are performed for lithium hexafluorophosphate (LiPF6) in ethylene carbonate and dimethyl carbonate (EC:DMC) solvent sandwiched between two electrodes. Results show that lithium ions form a tetrahedral solvation structure with two EC and two DMC molecules. The solvated lithium ion shows anti-electrostatic interaction with electrodes. This can be attributed to the electrostatic attraction of the polar end of the DMC molecule, which keeps the cation anchored to the positive electrode. Meanwhile, the solvation structure adopts a fix orientation at the negative electrode, which leads to unchanged electrostatic interaction at high charge density. Finally, EC molecules are swapped by DMC molecules near the negative electrode at high charge density. This leads to a decrease in local relative permittivity and, therefore, a decrease in differential capacitance. The differential capacitance of the positive electrode continuously decreases with increasing charge density. This is caused by the partial anchoring of solvent molecules holding the cations, which cancels the adsorption of anions near the positive electrode. This study provides insights into designing better electrolytes for efficient battery performance.

Impedance Spectroscopy for Bacterial Cell Monitoring, Analysis, and Antibiotic Susceptibility Testing.

Conventional approaches for bacterial cell analysis are hindered by lengthy processing times and tedious protocols that rely on gene amplification and cell culture. Impedance spectroscopy has emerged as a promising tool for efficient real-time bacterial monitoring, owing to its simple, label-free nature and cost-effectiveness. However, its limited practical applications in real-world scenarios pose a significant challenge. In this review, we provide a comprehensive study of impedance spectroscopy and its practical utilization in bacterial system measurements. We begin by outlining the fundamentals of impedance theory and modeling, specific to bacterial systems. We then offer insights into various strategies for bacterial cell detection and discuss the role of impedance spectroscopy in antimicrobial susceptibility testing (AST) and single-cell analysis. Additionally, we explore key aspects of impedance system design, including the influence of electrodes, media, and cell enrichment techniques on the sensitivity, specificity, detection speed, concentration accuracy, and cost-effectiveness of current impedance biosensors. By combining different biosensor design parameters, impedance theory, and detection principles, we propose that impedance applications can be expanded to point-of-care diagnostics, enhancing their practical utility. This Perspective focuses exclusively on ideally polarizable (fully capacitive) electrodes, excluding any consideration of charge transfer resulting from Faradaic reactions.

Novel Binders for Aqueous Electrode Processing of Electrochemical Capacitors.

This work studies the use of epoxy and polyurethane formulations as binders for the aqueous processing of activated carbon (AC) electrodes used as positive and negative electrodes in Electrochemical Double Layer Capacitors (EDLCs). The use of amine and carbodiimide as crosslinkers is also evaluated. The mechanical properties of those different binders have been investigated, looking towards aqueous processable and flexible electrodes. Microstructural analysis of the fabricated AC electrodes has been carried out to understand the pore-blocking effect exhibited by certain polymers. Furthermore, electrochemical characterization of all the systems has been performed by cyclic voltammetry, electrochemical impedance spectroscopy, and constant current charge/discharge measurements at different current densities. The obtained results show that polyurethane outperforms in terms of energy and power density the CMC:SBR reference system. Moreover, the studied polyurethanes maintain close to 100% of their initial capacitance after 2500 cycles under a current density of 5 A g-1 and a discharge time of 20 s.

Tuning solvation behavior within electric double layer via halogenated MXene for reliable lithium metal batteries

Solid electrolyte interphase (SEI)/electrolyte interface is critical in determining the lithium (Li) plating/stripping behavior. The solvation structure of Li-ion is well understood in the bulk electrolyte. Still, the mechanism of how SEI components affect the Li-ion solvation structure and desolvation energy barrier at the SEI/electrolyte interface is still unclear. Herein, Ti3C2 Maxine with single halogenated terminations (−Cl, −Br, −I) are synthesized and used as a model system, because their surface terminations induce a double halide-rich SEI formation (LiF and LiCl/LiBr/LiI). We examine the influence of the interaction strength between different Li halides and Li-ion on coordination number of Li ions and distribution of Li ions within the inner Helmholtz plane (IHP). A solvation sheath with a low solvent coordination number forms near the IHP of the LiBr interphase, improving the kinetics of Li deposition. Accordingly, half-cells utilising Li-carbon fiber/Ti3C2Br2 electrodes exhibit a long lifespan of 12,000 h (1 mA cm−2, 1 mAh cm−2). A pouch cell comprising Li-carbon fiber/Ti3C2Br2 anode and LiFePO4 cathode displays a capacity retention rate of 97 % after 300 cycles even at a low negative to positive electrode capacity ratio of 2.26. Our research provides crucial principles for the design of SEI components in Li metal batteries.

Enhanced Oxidation Resistance and Interface Stability of Atomic-Layer-Deposited MoNx Electrodes via TiN Passivation for DRAM Cell Capacitor Applications.

The continuous miniaturization of dynamic random-access memory (DRAM) capacitors has amplified the demand for electrode materials featuring specific characteristics, such as low resistivity, high work function, chemical stability, excellent interface quality with high-k dielectrics, and superior mechanical properties. In this study, molybdenum nitride (MoNx) films were deposited using a plasma-enhanced atomic layer deposition (PEALD) employing bis(isopropylcyclopentadienyl)molybdenum(IV) dihydride and NH3 plasma for DRAM capacitor electrode applications. Depending on the deposition temperatures of the PEALD MoNx films ranging from 200 to 400 °C, the Mo/N ratio and crystal structure varied, transitioning from the cubic NaCl-B1-type MoN phase with Mo/N ratio of 1.4 to the cubic γ-Mo2N phase with Mo/N ratio of 1.9. Notably, MoNx films grown at 400 °C exhibited low resistivity (435 μΩ·cm), a high work function (5.28 eV), and superior mechanical hardness (11.3 GPa) compared to ALD TiN films. Despite these excellent properties, the PEALD MoNx electrode demonstrated insufficient chemical stability, particularly in terms of oxidation resistance and interface quality with ALD HfxZr1-xO2 (HZO) films. This resulted in poor morphology and the formation of significant oxygen-deficient HZO layers (such as HfO2-x), leading to considerable degradation in the electrical performance of metal-insulator-metal (MIM) capacitors. To mitigate this issue, a thin (2.5-14 nm) ALD TiN layer was introduced as a passivation layer between the MoNx bottom electrode and HZO dielectric. The TiN-passivated MoNx (TiN/MoNx) electrode showed substantially enhanced oxidation resistance and reduced interfacial reactions with the HZO dielectric. Consequently, MIM capacitors with TiN/MoNx bottom electrodes demonstrated outstanding electrical performance, including excellent dielectric properties, low leakage current density, and high mechanical strength. Hence, this study proposes a promising candidates for storage nodes in the next-generation DRAM capacitors.

Quasi-Homogeneous Bromine Phase in Zinc-Bromine Batteries with Advanced Energy Efficiency and Energy Density

Abstract Regarding energy density, kinetics, and reversibility, the zinc-bromine batteries (ZBBs) exhibit advantages comparable to the conventional metal hydride nickel batteries as aqueous systems. However, the development of ZBBs has been impeded by two critical challenges: the self-discharge of Br-Br species cross-over and the short circuit caused by zinc dendrites. Achieving high energy density necessitates a large areal capacity electrode and tight battery assembly, which introduces additional hurdles. Addressing these challenges, we have successfully implemented a novel quasi-homogeneous bromine phase. Our optimized approach has realized ZBBs with a remarkable energy efficiency (EE) of 92.7% based on an areal capacity of 12 mA h cm-2 in a period duration of 13 h, an energy density of whole battery (EDB) of 80 W h L-1 with average EE of 92.5% for an extended cycle life of approximately 500 cycles, and a maximum EDB of 186 W h L-1 without pre-added zinc metal. This innovative work holds practical significance for developing ZBBs and providing insights and solutions to critical challenges.