Advancements in Asymmetric Supercapacitors: From Historical Milestones to Challenges and Future Directions.

Numerous challenges, like the uninterrupted supply of electricity, stable and reliable power, and energy storage during non-operational hours, arise across various industries due to the absence of advanced energy storage technologies. With the continual technological advancements in portable electronics, green energy, and transportation, there are inherent limitations in their innovative production. Thus, ongoing research is focused on pursuing sustainable energy storage technologies. An emerging solution lies in the development of asymmetric supercapacitors (ASCs), which offer the potential to extend their operational voltage limit beyond the thermodynamic breakdown voltage range of electrolytes. This is achieved by employing two distinct electrode materials, presenting an effective solution to the energy storage limitations faced by ASCs. The current review concentrates on the progression of working materials to develop authentic pseudocapacitive energy storage systems (ESS). Also, evaluates their ability to exceed energy storage constraints. It provides insights into fundamental energy storage mechanisms, performance evaluation methodologies, and recent advancements in electrode material strategies. The review approaches developing high-performance electrode materials and achieving efficient ASC types. It delves into critical aspects for enhancing the energy density of ASCs, presenting debates and prospects, thereby offering a comprehensive understanding and design principles for next-generation ASCs in diverse applications.

Electronic Properties and Mechanical Stability of Multi-Ion-Co-Intercalated Bilayered V2O5.

Incorporating metal cations into V2O5 has been proven to be an effective method for solving the poor long-term cycling performance of vanadium-based oxides as electrodes for mono- or multivalent aqueous rechargeable batteries. This is due to the existence of a bilayer structure with a large interlayer space in the V2O5 electrode and to the fact that the intercalated ions act as pillars to support the layered structure and facilitate the diffusion of charged carriers. However, a fundamental understanding of the mechanical stability of multi-ion-co-intercalated bilayered V2O5 is still lacking. In this paper, a variety of pillared vanadium pentoxides with two types of co-intercalated ions were studied. The root-mean-square deviation of the V-O bonds and the elastic constants calculated by density functional theory were used as references to evaluate the stability of the intercalated compounds. The d-band center and electronic band structures are also discussed. Our theoretical results show that the structural characteristics and stability of the system are quite strongly influenced by the intercalating strategy.

[Research Progress of Functional Materials for Conversion of Agricultural Biomass Wastes].

Excess agricultural biomass waste is increasing rapidly, leading to many environmental and governance issues. Therefore, increased attention has been paid to the recycling and value-added application of agricultural biomass waste. In recent years, the research of agricultural biomass waste utilization and derived functional materials has mainly included the following two aspects： ① the extraction of natural polymers and value-added applications and ② the direct preparation of new carbon-based materials, including adsorption, catalysis, energy storage electrode, and composite functional materials. The conversion of agricultural biomass waste into functional materials has been gradually realized and widely used. To enable industrial-scale production and the quality and safety of agricultural biomass waste derivatives and to develop highly feasible and cost-effective biomass waste conversion methods should be the focus of future studies.

Ferrocene-Based Polymer Organic Cathode for Extreme Fast Charging Lithium-Ion Batteries with Ultralong Lifespans.

To meet the growing demand for energy storage, lithium-ion batteries (LIBs) with fast charging capabilities has emerged as a critical technology. The electrode materials affect the rate performance significantly. Organic electrodes with structural flexibility support fast lithium-ion transport and are considered promising candidates for fast-charging LIBs. However, it is a challenge to create organic electrodes that can cycle steadily and reach high energy density in a few minutes. To solve this issue, accelerating the transport of electrons and lithium ions in the electrode is the key. Here, it is demonstrated that a ferrocene-based polymer electrode (Fc-SO3Li) can be used as a fast-charging organic electrode for LIBs. Thanks to its molecular architecture, LIBs with Fc-SO3Li show exceptional cycling stability (99.99% capacity retention after 10 000 cycles) and reach an energy density of 183 Wh kg-1 in 72 seconds. Moreover, the composite material through in situ polymerization with Fc-SO3Li and 50 wt % carbon nanotube (denoted as Fc-SO3Li-CNT50) achieved optimized electron and ion transport pathways. After 10 000 cycles at a high current density of 50C, it delivered a high energy density of 304 Wh kg-1. This study provides valuable insights into designing cathode materials for LIBs that combine high power and ultralong cycle life.

Doping Engineering in Electrode Material for Boosting the Performance of Sodium Ion Batteries.

In recent years, sodium ion batteries (SIBs) emerged as promising alternative candidates for lithium ion batteries (LIBs) due to the high abundance and low cost of sodium resources. However, their commercialization has been hindered by inherent limitations, such as low energy density and poor cycling stability. To address these issues, doping methodology is one of the most promising approaches to boosting the structural and electrochemical properties of SIB electrodes. This review provides a comprehensive overview of recent advancements in doping strategies, focusing on the improvement of the performance of SIBs. Various dopants including s- and p-block elements, transition metals, oxides, carbonaceous materials, and many more dopants are discussed in terms of their effects on enhancing the electrochemical properties of SIBs. Furthermore, the mechanisms responsible for the improvement in the performance of doped SIBs materials are also discussed. It also highlights the importance of doping sites in the crystal lattice, which also play a crucial role in doping in optimizing electrode structure, enhancing ion diffusion kinetics, and stabilizing electrode/electrolyte interfaces. The review ends by looking at the recent studies in simultaneous multiple heteroatom doping, offering valuable perspectives for a high performance SIB. This study provides valuable insight into the researchers and battery industries striving for advancements in energy storage technologies.

Effect of Rh Doping on Optical Absorption and Oxygen Evolution Reaction Activity on BaTiO3 (001) Surfaces.

In the present work, we investigate the potential of modified barium titanate (BaTiO3), an inexpensive perovskite oxide derived from earth-abundant precursors, for developing efficient water oxidation electrocatalysts using first-principles calculations. Based on our calculations, Rh doping is a way of making BaTiO3 absorb more light and have less overpotential needed for water to oxidize. It has been shown that a TiO2-terminated BaTiO3 (001) surface is more promising from the point of view of its use as a catalyst. Rh doping expands the spectrum of absorbed light to the entire visible range. The aqueous environment significantly affects the ability of Rh-doped BaTiO3 to absorb solar radiation. After Ti→Rh replacement, the doping ion can take over part of the electron density from neighboring oxygen ions. As a result, during the water oxidation reaction, rhodium ions can be in an intermediate oxidation state between 3+ and 4+. This affects the adsorption energy of reaction intermediates on the catalyst's surface, reducing the overpotential value.

New Engineering Science Insights into the Electrode Materials Pairing of Electrochemical Energy Storage Devices.

Pairing the positive and negative electrodes with their individual dynamic characteristics at a realistic cell level is essential to the practical optimal design of electrochemical energy storage devices. However, the complex relationship between the performance data measured for individual electrodes and the two-electrode cells used in practice often makes an optimal pairing experimentally challenging. Taking advantage of the developed tunable graphene-based electrodes with controllable structure, experiments with machine learning are successfully united to generate a large pool of capacitance data for graphene-based electrode materials with varied slit pore sizes, thicknesses, and charging rates and numerically pair them into different combinations for two-electrode cells. The results show that the optimal pairing parameters of positive and negative electrodes vary considerably with the operation rate of the cells and are even influenced by the thickness of inactive components. The best-performing individual electrode does not necessarily result in optimal cell-level performance. The machine learning-assisted pairing approach presents much higher efficiency compared with the traditional trial-and-error approach for the optimal design of supercapacitors. The new engineering science insights observed in this work enable the adoption of artificial intelligence techniques to efficiently translate well-developed high-performance individual electrode materials into real energy storage devices.

Charging the Future: Harnessing Nature's Designs for Bioinspired Molecular Electrodes.

The transition toward electric-powered devices is anticipated to play a pivotal role in advancing the global net-zero carbon emission agenda aimed at mitigating greenhouse effects. This shift necessitates a parallel focus on the development of energy storage materials capable of supporting intermittent renewable energy sources. While lithium-ion batteries, featuring inorganic electrode materials, exhibit desirable electrochemical characteristics for energy storage and transport, concerns about the toxicity and ethical implications associated with mining transition metals in their electrodes have prompted a search for environmentally safe alternatives. Organic electrodes have emerged as promising and sustainable alternatives for batteries. This review paper will delve into the recent advancements in nature-inspired electrode design aimed at addressing critical challenges such as capacity degradation due to dissolution, low operating voltages, and the intricate molecular-level processes governing macroscopic electrochemical properties.

Comprehensive study on the selection and performance of the best electrode pair for electrocoagulation of textile wastewater using multi-criteria decision-making methods (TOPSIS, VIKOR and PROMETHEE II).

The accelerating environmental impact of the textile industry, especially in water management, requires efficient wastewater treatment strategies. This study examines the effectiveness of various electrode pairs in the Electrocoagulation (EC) process for treating textile wastewater, focusing on removing of Total Suspended Solids (TSS), turbidity, Chemical Oxygen Demand (COD), and Total Organic Carbon (TOC). A comprehensive analysis was conducted using thirty-six electrode pair combinations, consisting of six materials: Aluminium (Al), Zinc (Zn), Carbon (C), Copper (Cu), Mild Steel (MS), and Stainless Steel (SS). The results demonstrated that different electrode pairs yielded varying removal efficiencies for various pollutants, with the highest efficiencies being 92.09% for COD (Al-C pair), 99.66% for TSS (Al-Cu pair), 99.17% for turbidity (Al-MS pair), and 70.99% for TOC (SS-SS pair). However, no single electrode pair excelled in removing all pollutant categories. To address this, three Multi-Criteria Decision Making (MCDM) methods such as TOPSIS, VIKOR, and PROMETHEE II were used to assess the most effective electrode pair. The results indicated that the Al-Zn combination was the most efficient, exhibiting high removal efficiencies for various pollutants (99.32% for TSS, 98.88% for turbidity, 68.62% for COD, and 57.96% for TOC). This study demonstrates that the EC process can effectively treat textile effluent and emphasizes the importance of selecting suitable electrode materials. Furthermore, pollutant removal was optimal with the Al-Zn electrode pair, offering a balanced and efficient approach to textile wastewater treatment. Thus, MCDM methods offer a robust framework for assessing and optimizing electrode selection, providing valuable insights for sustainable environmental management practices.

Tetrathiafulvalene Carboxylate-Based Anode Material for High-Performance Sodium-Ion Batteries.

Organic electrode materials are promising to be applied in sodium ion batteries (SIBs) due to their low cost and easily modified molecular structures. Nevertheless, low conductivity and high solubility in electrolytes still limit the development of organic electrodes. In this work, a carboxylate small molecule (BDTTS) based on tetrathiafulvalene is developed as anode material for SIBs. BDTTS has a large rigid π-conjugated planar structure, which may reduce solubility in the electrolyte, meanwhile facilitating charge transporting. Experimental results and theoretical calculations both support that apart from the four carbonyl groups, the sulfur atoms on tetrathiafulvalene also provide additional active sites during the discharge/charge process. Therefore, the additional active sites can well compensate for the capacity loss caused by the large molecular weight. The as-synthesized BDTTS electrode renders an excellent capacity of 230 mAh g-1 at a current density of 50 mA g-1 and an excellent long-life performance of 128 mAh g-1 at 2 C after 500 cycles. This work enriches the study on organic electrodes for high-performance SIBs and paves the way for further development and utilization of organic electrodes.

Phase Evolution of Multi-Metal Dichalcogenides With Conversion-Alloying Hybrid Mechanism for Superior Lithium Storage.

Traditional lithium-ion battery (LIB) anodes, whether intercalation-type like graphite or alloying-type like silicon, employing a single lithium storage mechanism, are often limited by modest capacity or substantial volume changes. Here, the kesterite multi-metal dichalcogenide (CZTSSe) is introduced as an anode material that harnesses a conversion-alloying hybrid lithium storage mechanism. Results unveil that during the charge-discharge processes, the CZTSSe undergoes a comprehensive phase evolution, transitioning from kesterite structure to multiple dominant phases of sulfides, selenides, metals, and alloys. The involvement of multi-components facilitates electron transport and mitigates swelling stress; meanwhile, it results in formation of abundant defects and heterojunctions, allowing for increased lithium storage active sites and reduced lithium diffusion barrier. The CZTSSe delivers a high specific capacity of up to 2266 mA h g-1 at 0.1 A g-1; while, maintaining a stable output of 116 mA h g-1 after 10 000 cycles at 20 A g-1. It also demonstrates remarkable low-temperature performance, retaining 987 mA h g-1 even after 600 cycles at -40 °C. When employed in full cells, a high specific energy of 562 Wh kg-1 is achieved, rivalling many state-of-the-art LIBs. This research offers valuable insights into the design of LIB electrodes leveraging multiple lithium storage mechanisms.

Revealing Hydrogen Bond Effect in Rechargeable Aqueous Zinc-Organic Batteries.

The surrounding hydrogen bond (H-bond) interaction around the active sites plays indispensable functions in enabling the organic electrode materials (OEMs) to fulfill their roles as ion reservoirs in aqueous zinc-organic batteries (ZOBs). Despite important, there are still no works could fully shed its real effects light on. Herein, quinone-based small molecules with a H-bond evolution model has been rationally selected to disclose the regulation and equilibration of H-bond interaction between OEMs, and OEM and the electrolyte. It has been found that only a suitable H-bond interaction could make the OEMs fully liberate their potential performance. Accordingly, the 2,5-diaminocyclohexa-2,5-diene-1,4-dione (DABQ) with elaborately designed H-bond structure exhibits a capacity of 193.3 mAh g-1 at a record-high mass loading of 66.2 mg cm-2 and 100 % capacity retention after 1500 cycles at 5 A g-1. In addition, the DABQ//Zn battery also possesses air-rechargeable ability by utilizing the chemistry redox of proton. Our results put forward a specific pathway to precise utilization of H-bond to liberate the performance of OEMs.

Bibliometric analysis and systematic review of electrochemical methods for environmental remediation.

Electrochemical methods are increasingly favored for remediating polluted environments due to their environmental compatibility and reagent-saving features. However, a comprehensive understanding of recent progress, mechanisms, and trends in these methods is currently lacking. Web of Science (WoS) databases were utilized for searching the primary data to understand the knowledge structure and research trends of publications on electrochemical methods and to unveil certain hotspots and future trends of electrochemical methods research. The original data were sampled from 9080 publications in those databases with the search deadline of June 1st, 2022. CiteSpace and VOSviewer software facilitated data visualization and analysis of document quantities, source journals, institutions, authors, and keywords. We discussed principles, influencing factors, and progress related to seven major electrochemical methods. Notably, publications on this subject have experienced significant growth since 2007. The most frequently-investigated areas in electrochemical methods included novel materials development, heavy metal remediation, organic pollutant degradation, and removal mechanism identification. "Advanced oxidation process" and "Nanocomposite" are currently trending topics. The major remediation mechanisms are adsorption, oxidation, and reduction. The efficiency of electrochemical systems is influenced by material properties, system configuration, electron transfer efficiency, and power density. Electro-Fenton exhibits significant advantages in achieving synergistic effects of anodic oxidation and electro-adsorption among the seven techniques. Future research should prioritize the improvement of electron transfer efficiency, the optimization of electrode materials, the exploration of emerging technology coupling, and the reduction in system operation and maintenance costs.

High-performance asymmetric supercapacitors assembled with novel disc-like MnCo2O4 microstructures as advanced cathode material.

Herein, porous MnCo2O4 with disc-like (MnCo2O4-discs) and ring-like (MnCo2O4-rings) microstructures were respectively synthesized using an initial hydrothermal method at different temperatures and a calcination treatment in air. The electrochemical properties of these MnCo2O4 materials were investigated in three-electrode and two-electrode systems, and as such, MnCo2O4 presented a battery-like electrochemical response. The specific capacity of MnCo2O4-discs was determined to be 296.1C/g at 1 A/g, superior to 246.3C/g for MnCo2O4-rings. An asymmetric supercapacitor (ASC) was assembled with MnCo2O4 as the cathode and activated carbon (AC) as the anode to evaluate the potential for practical application. The MnCo2O4-discs//AC ASC exhibited an energy density (Ed) of 35.8 W h kg-1 at a power density (Pd) of 927.5 W kg-1. For the MnCo2O4-rings//AC ASC, an inferior Ed of 31.4 W h kg-1 under 890.9 W kg-1 was achieved. Furthermore, the two ASCs presented outstanding cyclic performance after 5000 cycles at 6 A/g. The exceptional properties of MnCo2O4 microstructures can be applied to the assembly of ASC devices, which can have promising potential for application in electrochemical energy storage. This synthetic method is straightforward, cost-effective, and can be extended to fabricate similar electrode materials with superior electrochemical performance.

Constructing a 3D Ion Transport Channel-Based CNF Composite Film with an Intercalated Structure for Superior Performance Flexible Supercapacitors.

The weak stiffness, huge thickness, and low specific capacitance of commonly utilized flexible supercapacitors hinder their great electrochemical performance. Learning from a biomimetic interface strategy, we design flexible film electrodes based on functional intercalated structures with excellent electrochemical properties and mechanical flexibility. A composite film with high strength and flexibility is created using graphene (reduced graphene oxide (rGO)) as the plane layer, layered double metal hydroxide (LDH) as the support layer, and cellulose nanofiber (CNF) as the connection agent and flexible agent. The interlayer height can be adjusted by the ion concentration. The highly interconnected network enables excellent electron and ion transport channels, facilitating rapid ion diffusion and redox reactions. Moreover, the high flexibility and mechanical properties of the film achieve multiple folding and bending. The CNF-rGO-NiCoLDH film electrode exhibits high capacitance performance (3620.5 mF cm-2 at 2 mA cm-2), excellent mechanical properties, and high flexibility. Notably, flexible all-solid assembled CNF-rGO-NiCoLDH//rGO has an extremely high area energy density of 53.5 mWh cm-2 at a power density of 1071.2 mW cm-2, along with cycling stability of 89.8% retention after 10 000 charge-discharge cycles. This work provides a perspective for designing high-performance energy storage materials for flexible electronics and wearable devices.

Unveiling Phenoxazine's Unique Reversible Two-Electron Transfer Process and Stable Redox Intermediates for High-Performance Aqueous Zinc-ion Batteries.

The low specific capacity determined by the limited electron transfer of p-type cathode materials is the main obstruction to their application towards high-performance aqueous zinc-ion batteries (ZIBs). To overcome this challenge, boosting multi-electron transfer is essential for improving the charge storage capacity. Here, as a typical heteroaromatic p-type material, we unveil the unique reversible two-electron redox properties of phenoxazine in the aqueous electrolytes for the first time. The second oxidation process is stabilized in the aqueous electrolytes, a notable contrast to its less reversibility in the non-aqueous electrolytes. A comprehensive investigation of the redox chemistry mechanism demonstrates remarkably stable redox intermediates, including a stable cation radical PNO⋅+ characterized by effective electron delocalization and a closed-shell state dication PNO2+. Meanwhile, the heightened aromaticity contributes to superior structural stability during the redox process, distinguishing it from phenazine, which features a non-equivalent hybridized sp2-N motif. Leveraging these synergistic advantages, the PNO electrodes deliver a high capacity of 215 mAh g-1 compared to other p-type materials, and impressive long cycling stability with 100 % capacity retention over 3500 cycles. This work marks a crucial step forward in advanced organic electrodes based on multi-electron transfer phenoxazine moieties for high-performance aqueous ZIBs.

The effects of different electrode materials on the electric field-assisted co-composting system for the soil remediation of heavy metal pollution.

The electric field-assisted composting system (EACS) is an emerging technology that can enhance composting efficiency, but little attention has been given to electrode materials. Herein, an EACS was established to investigate the effects of electrode materials on humic substance formation and heavy metal speciation. Excitation-emission matrix analysis showed that carbon-felt and stainless-steel electrodes increased humic acid (HA) by 48.57 % and 47.53 %, respectively. In the EACS with the carbon-felt electrode, the bioavailability factors (BF) of Cu and Cr decreased by 18.00 % and 7.61 %, respectively. Despite that the stainless-steel electrodes decreased the BF of As by 11.26 %, the leaching of Cr, Ni, Cu, and Fe from the electrode itself is an inevitable concern. Microbial community analyses indicated that the electric field increased the abundance of Actinobacteria and stimulated the multiplication of heavy metal-tolerant bacteria. Redundancy analysis indicates that OM, pH, and current significantly affect the evolution of heavy metal speciation in the EACS. This study first evaluated the metal leaching risk of stainless-steel electrode, and confirmed that carbon-felt electrode is environment-friendly material with high performance and low risk in future research with EACS.

Engineering Faradaic Electrode Materials for High-Efficiency Water Desalination.

Water desalination technologies play a key role in addressing the global water scarcity crisis and ensuring a sustainable supply of freshwater. In contrast to conventional capacitive deionization, which suffers from limitations such as low desalination capacity, carbon anode oxidation, and co-ion expulsion effects of carbon materials, the emerging faradaic electrochemical deionization (FDI) presents a promising avenue for enhancing water desalination performance. These electrode materials employed faradaic charge-transfer processes for ion removal, achieving higher desalination capacity and energy-efficient desalination for high salinity streams. The past decade has witnessed a surge in the advancement of faradaic electrode materials and considerable efforts have been made to explore optimization strategies for improving their desalination performance. This review summarizes the recent progress on the optimization strategies and underlying mechanisms of faradaic electrode materials in pursuit of high-efficiency water desalination, including phase, doping and vacancy engineering, nanocarbon incorporation, heterostructures construction, interlayer spacing engineering, and morphology engineering. The key points of each strategy in design principle, modification method, structural analysis, and optimization mechanism of faradaic materials are discussed in detail. Finally, this work highlights the remaining challenges of faradaic electrode materials and present perspectives for future research.

Functional Electrochemistry: On-Nerve Assessment of Electrode Materials for Electrochemistry and Functional Neurostimulation.

Emerging therapies in bioelectronic medicine highlight the need for deeper understanding of electrode material performance in the context of tissue stimulation. Electrochemical properties are characterized on the benchtop, facilitating standardization across experiments. On-nerve electrochemistry differs from benchtop characterization and the relationship between electrochemical performance and nerve activation thresholds are not commonly established. This relationship is important in understanding differences between electrical stimulation requirements and electrode performance. We report functional electrochemistry as a follow-up to benchtop testing, describing a novel experimental approach for evaluating on-nerve electrochemical performance in the context of nerve activation. An ex-vivo rat sciatic nerve preparation was developed to quantify activation thresholds of fiber subtypes and electrode material charge injection limits for platinum iridium, iridium oxide, titanium nitride and PEDOT. Finally, we address experimental complexities arising in these studies, and demonstrate statistical solutions that support rigorous material performance comparisons for decision making in neural interface development.