Electrode Materials Research Articles

Pd-Doped RuO2: A Promising Electrode Material with Battery–Supercapacitor Hybrid Characteristics

Pd-Doped RuO₂: A Promising Electrode Material with Battery–Supercapacitor Hybrid Characteristics

In-situ growth of Ni, Co-Prussian blue nanocubes on molten salt etched lamellar Ti3C2Tx/Ni for enhanced hybrid capacitive deionization

The design and development of high-performance electrode materials are crucial for improving the desalination efficiency of hybrid capacitive deionization (HCDI). In this study, a Ti3C2Tx/Ni/NiCo-PBA composite is synthesized by in-situ growing NiCo Prussian blue (PB) nanocubes on Ti3C2Tx/Ni sheets, serving as an electrode for HCDI. The Ti3C2Tx sheets provide excellent conductivity and a suitable substrate for the growth of NiCo-PBA nanocubes. The Ni nanoparticles help prevent the oxidation of Ti3C2Tx sheets, and provide a source of Ni for NiCo-PBA synthesis. Additionally, the NiCo-PBA nanocubes effectively inhibit re-stacking of Ti3C2Tx sheets, enlarge crystal lattice spacing, and facilitate diffusion and storage of salt ions. Consequently, the AC||Ti3C2Tx/Ni/NiCo-PBA HCDI device exhibits a high salt removal capacity of 36.62 mg g−1, low energy consumption of 11.14 Wh m−3, and water recovery of 61.86 %. Importantly, the AC||Ti3C2Tx/Ni/NiCo-PBA device achieves a good salt removal capacity of 53.22 mg g−1 in a high concentration NaCl solution (2000 μS cm−1). After 20 cycles, the desalination capacity remains stable, and the structure of Ti3C2Tx/Ni/NiCo-PBA is intact, indicating excellent cycling stability. Additionally, the desalination mechanism of Ti3C2Tx/Ni/NiCo-PBA electrode is thoroughly investigated.

Microporous tungsten oxide spheres coupled with Ti3C2Txnanosheets for high-volumetric capacitance supercapacitors.

In the contemporary landscape of technological advancements, the burgeoning demand for portable electronics and flexible wearable devices has necessitated the development of energy storage systems with superior volumetric performance. Tungsten oxide (WO3), known for its high density and theoretical capacitance, is a promising electrode material for supercapacitors. However, low conductivity and poor cycling stability are still the key bottlenecks for its application. Herein, a novel composite comprising hollow porous WO3 spheres (HPWS) derived by template method was electrostatic self-assembled on the surface of the Ti3C2Tx nanosheets. The resulting electrodes exhibited ultra-high volumetric capacitance of 1930 F cm-3 at 1 A g-1 and rate capability of 46% at 50 A g-1, attributed to enhanced ion accessibility from microporous structure and electron transport from conductive network of Ti3C2Tx even at a high packing density of 3.86 g cm-3. Utilizing HPWS/Ti3C2Tx as the negative electrode and porous carbon as the positive electrode, the assembled asymmetric supercapacitor achieved an energy density of 31 Wh kg-1 at a power density of 650 W kg-1 with over 107% capacitance retention after 5000 cycles. This work provides a promising approach for developing next-generation supercapacitors with ultra-high volumetric capacitance.

A Lithium‐Oxygen Battery Exploiting Carbon Nanotubes, Graphene and Gold Catalyst

AbstractLithium‐oxygen (Li‐O2) battery is considered a high‐energy alternative to Li‐ion one due its characteristic electrochemical conversion process, with the additional advantage of lower cost and environmental impact. However, this emerging battery still requires an enhancement of stability and lifespan to allow its use as a practical energy storage system. In this work we investigate an electrode material benefitting of multiwalled carbon nanotubes (MWCNTs), few layer graphene (FLG), and gold nano‐powder catalyst to improve the Li‐O2 battery performances in terms of energy efficiency, cycle life and stability. Morphological, structural, and electrochemical tests indicate that the composite electrode can actually boost the oxygen reduction reaction (ORR) and oxygen evolution reaction (OER), and enhance the Li‐O2 process reversibility, with a capacity of 1000 mAh g−1 over 70 cycles. On the other hand, the tests reveal the role of the gold in decreasing the polarization and increasing the cell life. Therefore, the results suggest the combination of carbons with various morphologies as a suitable architecture for hosting the Li‐O2 reaction products and allowing their reversible reaction. On the other hand, the results highlight the necessity for a better tuning the noble metal characteristics to further enhance the cell performances.

Surface Reconstruction Enhanced Li-Rich Cathode Materials for Durable Lithium-Ion Batteries.

Regulating the distribution of surface elements in lithium-rich cathode materials can effectively change the electrochemical performance of cathode materials. Considering that the enrichment of Mn element on the surface is the main reason for the irreversible phase transition and dissolution of its surface structure, which in turn is the main reason for performance degradation. Based on the molten salt-assisted sintering method, a lithium rich cathode material with surface rich Ni and Co is designed and prepared. The surface enrichment of Ni and Co effectively reduces the dissolution of Mn, promotes the occurrence of irreversible collapse of surface structure from layered phase to rock salt phase on the material surface, improves the stability of surface crystal phase structure, and improves the cycling stability of positive electrode materials. Notably, after 500 cycles at 1 C current density, the discharge-specific capacity attained 189.8 mAh g -1, with a capacity retention rate of 88.9%, indicating a 42.1% improvement in capacity retention. Molten salt treatment is widely used in the modification of positive electrode materials. The research work will provide new ideas for improving the stability of lithium rich materials and promoting their commercial applications.

One‐Step Laser Synthesis of Copper Nanoparticles and Laser‐Induced Graphene in a Paper Substrate for Non‐Enzymatic Glucose Sensing

AbstractThe synergy resulting from the high conductivity of graphene and catalytic properties of metal nanoparticle has been a resource to improve the activity and functionality of electrochemical sensors. This work focuses on the simultaneous synthesis of copper nanoparticles (CuNPs) and laser‐induced graphene (LIG) derived from paper, through a one‐step laser processing approach. A chromatography paper substrate with drop‐casted copper sulfate is used for the fabrication of this hybrid material, characterized in terms of its morphological, chemical, and conductive properties. Appealing conductive properties are achieved, with sheet resistance of 170 Ω sq−1 being reached, while chemical characterization confirms the simultaneous synthesis of the conductive carbon electrode material and metallic copper nanostructures. Using optimized laser synthesis and patterning conditions, LIG/CuNPs‐based working electrodes are fabricated within a three‐electrode planar cell, and their electrochemical performance is assessed against pristine LIG electrodes, demonstrating good electron transfer kinetics appropriate for electrochemical sensing. The sensor's ability to detect glucose through a non‐enzymatic route is optimized, to assure good sensing performance in standard samples and in artificial sweat complex matrix.

In Vacuo Scratching Yields Undisturbed Insight into the Bulk of Lithium-Ion Battery Positive Electrode Materials

In Vacuo Scratching Yields Undisturbed Insight into the Bulk of Lithium-Ion Battery Positive Electrode Materials

Study of dielectric measurements of Bi4Ti3O12/polystyrene composites as electrode materials for supercapacitors

Eco-friendly, nontoxic and high-energy storage materials are very important for flexible electrode materials. Bi4Ti3[Formula: see text] lead-free, perovskite phase may prove suitable as filler in composites for electrode materials because of its large spontaneous polarization. We have synthesized Bi4Ti3[Formula: see text]/polystyrene (BTO/PS) composites and carried out their structural, morphological and bonding studies with the help of X-ray diffraction (XRD), scanning electron microscopy (SEM) and Fourier transform infrared spectroscopy (FTIR), in that order. Dielectric measurements in the broad frequency range of synthesized composites determined by Impedance analyzer. We observed that the dielectric constant of composites increased with filler concentration and decreased with applied field frequency. Bi4Ti3[Formula: see text]/PS composites can be good electrode materials.

Performance optimization for magnetoelectric antennas based on a multi-field coupling analysis model

This paper presents a multi-field coupling model for magnetoelectric (ME) antennas, encompassing a ME film, electrode layers, and a substrate featuring a cavity structure. This model accounts for the nonlinear magnetoelastic coupling within the radiation layer and employs a combined DC and AC simulation methodology to capture the antenna's radiation mechanism. Leveraging this multi-field coupling model, performance differences between the ME antenna and an ideal ME composite film are analyzed. By exploring optimization schemes based on multi-physics fields, electrode materials, and structural design, the ME antenna's radiation performance is significantly enhanced. The findings demonstrate that the complete antenna structure, with its increased thickness and cavity design, exhibits a lower resonance frequency and a higher converse ME (CME) coefficient compared to the ideal ME film. The optimal CME effect is achieved under proper external stimuli, leading to a broader 3 dB bandwidth. Expanding the cavity dimensions enhances the CME coefficient by 42% and reduces the resonance frequency due to decreased acoustic wave loss. Adopting electrode materials with higher acoustic impedance elevates the CME coefficient, yet narrows the bandwidth. Conversely, using silver (Ag) electrodes promotes a broader bandwidth. Additionally, ME antenna arrays are designed to broaden the bandwidth by 300%.

Free-Standing Poly(vinyl benzoquinone)/Reduced Graphene Oxide Composite Films as a Cathode for Lithium-Ion Batteries.

Quinones with a rapid reduction-oxidation rate are promising high-capacity cathodes for lithium-ion batteries. However, the high solubility of quinone molecules in polar organic electrolytes results in low cycle stability, while their low electric conductivity causes low utilization of electrode materials. In this article, a new p-benzoquinone derivative, poly(vinyl benzoquinone) (PVBQ), is designed and synthesized, and a solution-based method of preparing free-standing PVBQ/reduced graphene oxide (RGO) composite films is developed. PVBQ has a high theoretical specific capacity (400 mA h g-1) because of its low dead moiety mass. In the produced composite films, PVBQ nanoparticles are uniformly dispersed on RGO sheets, which endows the composite films with high electric conductivity and inhibits the dissolution of PVBQ through strong adsorption. As a result, the composite films show a high active material utilization, high practical specific capacity, and excellent cycling stability. PVBQ in the composite membrane containing 60.2 wt % RGO deliver 244 mA h g-1 capacity after 200 charge-discharge cycles at a current density of 300 mA g-1. At a current density of 1500 mA g-1, the reversible specific capacity is still 170 mA h g-1. This work provides a high-performance cathode material for lithium-ion batteries, and the molecular structure and electrode structure design ideas are also instructive for developing other organic electrode materials.

Fermi level limitation in Na1/2Bi1/2TiO3–BaTiO3 piezoceramics by electrochemical reduction of Bi

The (electro)chemical stability of undoped and Zn-doped 0.94Na1/2Bi1/2TiO3–0.06BaTiO3 lead-free piezoceramics (NBT–6BT) was studied. For this purpose, the Fermi level at the interface between NBT–6BT and Sn-doped In2O3 (ITO) electrode is varied by gradually reducing the ITO film either by annealing in vacuum or by applying a voltage across a Pt/NBT–6BT/ITO. The chemical and electronic changes are monitored in situ by x-ray photoelectron spectroscopy. The experiments reveal the formation of metallic Bi when the Fermi level is reaching a value of 2.23 ± 0.10 eV above the valence band maximum, while no reduction of Ti is observed. The electrochemical reduction of Bi constitutes an upper limit of the Fermi level at ≈1 eV below the conduction band minimum. High electron concentrations in the conduction band and a contribution of free electrons to the electrical conductivity of NBT–6BT can, therefore, be excluded. The reduction occurs for an ITO work function of 4.2–4.3 eV. As typical electrode materials such as Ag, Cu, Ni, or Pt have higher work functions, an electrochemical instability of the electrode interfaces in ceramic capacitors is not expected. Under the given experimental conditions (350 °C, electric fields <40 V/mm), no degradation of resistance and no enrichment of Na at the interface are observed.

Electrochemical Hydrogenation of N‐Heterocycles and Related Substrates: A Mini‐Review

ABSTRACTCatalytic hydrogenation refers to the (often) metal‐mediated addition of dihydrogen (H2) equivalents to unsaturated compounds to form new element‐hydrogen bonds. This conceptually simple reaction is ubiquitous in the production of a vast number of essential chemicals. Despite a growing recognition of the importance of sustainability in manufacturing, the use of fossil‐derived hydrogen gas and precious metal catalysts in hydrogenation remains widespread. Electrochemical variants of these processes are an appealing alternative, especially those that can make use of sustainable Brønsted acids, more abundant electrode materials and renewable electricity. In this mini‐review, we give a selective overview of electrochemical hydrogenation methodologies for N‐heterocycles and some related substrates from the specific perspective of the synthetic chemistry made possible by this increasingly popular approach.

Biosensor Based on ZIF-67-HRP and MWCNTs Nanocomposite Modified Glass Carbon Electrode for the Detection of Luteolin in Vegetables.

Luteolin has various pharmacological properties, including anti-inflammatory, antioxidant, and antitumor characteristics. Due to its potential value in drugs and functional foods, it is important to develop an efficient method for detecting luteolin. In this work, the poor selectivity of existing luteolin nonenzymatic sensors was solved by translating the enzyme-catalyzed reaction from bulk solution to the surface of a horseradish peroxidase (HRP) modified electrode through an electrocatalytic oxidation process. Here, we modified the surface of a glassy carbon electrode (GCE) with metal-organic frameworks (MOFs; ZIF-67 here, abbreviated as ZIF), functional nanomaterials, and HRP and finally covered it with Nafion (NF). In this case, luteolin acts as a hydrogen donor, and the electrode acts as a hydrogen acceptor; the oxidation reaction occurs on the electrode surface. The use of ZIF-67 ensured the conformational stability of HRP to ensure the selectivity and anti-interference property, and SDS-dispersed multiwalled carbon nanotubes (MWCNTs) enhanced the electrode conductivity. The use of NF avoids shedding of the electrode material during the testing process. A UV-vis spectrophotometer was used to study the selectivity of luteolin by HRP and the compatibility between HRP and ZIF. The materials were characterized and analyzed by scanning electron microscopy and transmission electron microscopy. Due to the synergistic effect of these nanomaterials, the linear range of NF/ZIF-HRP/MWCNTs-SDS/GCE was 1.0 × 10-2 to 6.0 μM, with detection limits of 25.3 nM (S/N = 3). The biosensor showed long-term stability and reproducibility, with a relative standard deviation of 4.2% for the peak current (n = 5). Finally, the biosensor was successfully used to detect luteolin in carrots, celery, and cauliflower.

Role of Graphene in Next-Generation Electrochemical Energy Storage Systems: Insights and Innovations

Abstract There is a rising demand for energy storage systems (ESS) that are both environmentally sustainable and high-performing. To meet the prerequisites of diverse energy-consuming applications, developing novel, better-quality and highly-performing electrode materials for ESS is vital. In this quest, graphene emerges as a wonder material, ascribed to its unmatched mechanical, electrical and thermal behaviour. Different ESS can be significantly developed with enhanced energy storage capacity with the application of graphene. Herein, a brief discussion of the structure and synthesis techniques for graphene and its derivatives is presented. In addition to this, the study also offers a comprehensive summary on the latest developments in lithium-ion batteries, double-layer supercapacitors, pseudo capacitors and hybrid supercapacitors using graphene as the dominant material for anode/cathode electrodes in the form of composites and hybrids. The effect of the graphene on the performance metrics of the EESS has also been imparted. Despite the promising advancements, the key challenges and limitations in the development of graphene-based high-performing energy storage devices are described in detail. The article concludes with the potential prospects of energy storage using graphene are also discussed.

Construction of MXene interlayer conductive ion transport channel by polypyrrole-coated cellulose nanofibers for ultralow voltage high-performance ionic soft actuators

Ionic soft actuators are extensively utilized in soft robotics and intelligent flexible devices due to their low-voltage actuation capability. MXene(Ti3C2Tx) has potential value as an electrode material for ionic soft actuators owing to its high conductivity and large specific surface area. However, the actuation performance of its ionic soft actuator is limited by poor extensibility and low capacitance caused by the stacking effect. Here, a high-performance ionic soft actuator with MXene\\polypyrrole-coated cellulose nanofibers (CNF@PPy) is reported. While gaining high flexibility of the electrode due to the great mechanical property of CNF, the fast conductive transport channel is constructed by doping CNF@PPy between MXene layers, which not only effectively reduces the loss of conductive properties and drastically improves the ion migration rate, but also prevents MXene from stacking and has additional chemical active sites, significantly increasing its ion storage capacity. Consequently, the actuator exhibits excellent actuation performance at the 0.5 V ultralow voltage: 0.79 % bending strain, 6 s rapid response, and 91.03 % high durability after 5 hours. Additionally, the potential for the actuating core of advanced flexible electronic devices is demonstrated by the application of flexible forceps and the flexible electronic eye.

Tuning the Electronic Structures of Mo-Based Sulfides/Selenides with Biomass-Derived Carbon for Hydrogen Evolution Reaction and Sodium-Ion Batteries

A key research focus at present is the exploration and innovation of electrode materials suitable for energy storage and conversion. Molybdenum-based sulfides/selenides (primarily MoS2 and MoSe2) have garnered attention in recent years due to their intrinsic two-dimensional structures, which are conducive to ion/electron transfer or insertion/extraction, making them promising candidates in electrocatalytic hydrogen production and sodium-ion battery applications. However, their inherently poor electronic structures have led most research efforts to concentrate on modifications aimed at enhancing their performance in hydrogen evolution reactions (HERs) and sodium-ion batteries (SIBs). Owing to their remarkable chemical inertness, expansive specific surface areas, and tunable pore architectures, carbon-based materials have garnered significant attention in research. The utilization of biomass as a renewable and environmentally sustainable precursor offers considerable benefits, including abundant availability, ecological compatibility, and cost-effectiveness. Consequently, recent scholarly endeavors have concentrated intensively on the synthesis of valuable carbon materials derived from renewable biomass sources. This review addresses the scientific challenges related to the development of electrode materials for HERs and SIBs in electrochemical energy storage and conversion. It delves into the recent focus on the two-dimensional transition-metal chalcogenides, particularly MoS2 and MoSe2, and the difficulties encountered in modulating their electronic structures when applied to HERs and SIBs. The review proposes the use of eco-friendly and widely sourced biomass-derived carbon (BMC) as a supporting matrix combined with MoS2 and MoSe2 to regulate their structures and enhance their electrocatalytic activity and sodium storage performance. Additionally, it highlights the existing challenges faced by these BMC/MoS2 and BMC/MoSe2 composites and offers insights into future developments.

Enhanced Lithium Extraction from Brines: Prelithiation Effect of FePO4 with Size and Morphology Control.

Extracting lithium resources from seawater and brine can promote the development of the new energy materials industry. The electrochemical method is green and efficient. Iron phosphate (FePO4) crystal, with its 1D ion channel, holds significant potential as a primary lithium extraction electrode material. Li+ encounters a substantial concentration disadvantage in brines, and the co-intercalation of Na+ diminishes Li+ selectivity. To address this issue, this work enhances the energy barrier for Na+ insertion through prelithiation strategies applied to the 1D channels of FePO4 crystal, thereby improving Li+ selectivity, and further investigating the prelithiation effect with particle size and morphology control. The results indicate that the Li(4C-40%)FePO4// Activated carbon(AC) system enhances selectivity of lithium. The Li(4C-40%)FePO4 with size diameter of 2500nm demonstrates an energy consumption of 0.79Whmol-1 and a purity of 97.94% for lithium extraction at a unit lithium extraction of 5.93mmolg-1 in simulated brine. Li(4C-40%)FePO4-nanoplates demonstrate the most optimal lithium extraction performance among the three morphologies due to their lamellar structure's short ion diffusion path in the [010] channel, favoring Li+ diffusion. The diffusion energy barriers of Li+ and Na+ are calculated using Density Functional Theory (DFT) before and after prelithiation, showing good agreement with experimental results.

Revealing the Chemical and Structural Complexity of Electrochemical Ion Exchange in Layered Oxide Materials.

Soft chemistry techniques, such as ion exchange, hold great potential for the development of battery electrode materials that cannot be stabilized via conventional equilibrium synthesis methods. Nevertheless, the intricate mechanisms governing ion exchange remain elusive. Herein, we investigate the evolution of the long-range and local structure, as well as the ion (de)intercalation mechanism during electrochemical Li-to-Na ion exchange initiated from an O3-type lithium-layered oxide cathode. The in situ-formed mixed-cation electrolyte leads to competitive intercalation of Li and Na ions. While Li ion intercalation predominates at the beginning of initial discharge, Na ion cointercalation into a different layer results in ion redistribution and phase separation, with the emergence of a P3-Na phase alongside an O3-Li phase. Further, this study spatially resolves the heterogeneous nature of electrochemical ion exchange reactions within individual particles and provides insights into the correlations between local Ni redox processes and phase separation. Overall, electrochemical ion exchange leads to a mixed-phase cathode and alters its reaction kinetics. Those findings have important implications for the development of new metastable materials for renewable energy devices and ion separation applications.

Hierarchical porous self-supporting graphite carbon electrodes based on the biomimetic structure for supercapacitors

Regulating pore structure, improving conductivity, and reducing the influence of binders are considered important ways to improve the performance of carbon-based electrode materials for supercapacitors. This study successfully prepares a highly graphitized hierarchical porous self-supporting carbon electrode without the need for binders, conductive agents, and current collectors using low-cost and abundant pine wood as the precursor and K2FeO4 as the activator and catalyst. The self-supporting electrode inherits the biological structure of biomass and forms a large number of micro mesopores through activation, showing an excellent 3D interconnected pore structure, and achieves a high degree of graphitization with the ID/IG ratio of being only 0.47. The self-supporting electrode facilitates the effective transport of electrolyte ions and electrons, demonstrating excellent electrochemical performance. It achieves an area specific capacitance of 3.64 F cm−2 under a current density of 5 mA cm−2. Two identical self-supporting electrodes are employed to construct a symmetric supercapacitor. The supercapacitor exhibits an energy density of 148.61 μWh cm−2 at a power density of 1 mW cm−2, with a capacity retention rate of 89.26 % after 10,000 charge-discharge cycles.

Upcycling linear low-density polyethylene waste to turbostratic graphene for high mass loading supercapacitors

Linear low-density polyethylene (LLDPE) waste is difficult to upcycle into more valuable carbon materials because it tends to completely decompose into small molecules during thermal processing. In this work, LLDPE is upcycled into a high quality turbostratic graphene using a pre-treatment step to oxidatively crosslink the polymer with the assistance of solid additives (KCl and K2CO3) that improve crosslinking by increasing the effective surface area of the polymer melt during processing. After this pretreatment step, the crosslinked polymer could then be carbonized and catalytically graphenized between 400–950 °C without decomposition of the polymer feedstock. The LLDPE derived graphene (LLDPE-G) obtained from this process has a Brunauer–Emmett–Teller (BET) specific surface area, up to 1800 m2 g−1 and average Raman ID/IG and I2D/IG ratios of 0.85 and 0.57, respectively, indicating high quality graphene. When used as an electrode material in symmetric supercapacitors, LLDPE-G possesses a specific capacitance up to 175 Fg−1 at a mass loading of 20 mgcm−2, which is two times the commercial requirement, yielding an areal capacitance of 3.5 Fcm−2. Moreover, LLDPE-G exhibits exceptional cycling stability with a capacitance retention of 95.8 % after 100,000 cycles at a current density of 4.0 Ag−1. Additionally, the KCl and K2CO3 solids are recycled and reused over 3 complete reaction cycles to make new LLDPE-G with the material quality and electrocapacitive performance retained and verified after each cycle. Our approach creates new opportunities for upcycling waste LLDPE and other varieties of polyethylene into a higher value graphene used for electrochemical energy storage applications.