Charge Discharge Research Articles

Novel Ball-Type Phthalocyanines with Eight Benzotriazole Groups: Synthesis, Computational DFT Studies, and Supercapacitor Properties

Abstract Novel four MBTOB-bridged ball-type metallophthalocyanines were obtained from 4, 4'-((methylenebis(6-(2H-benzo[d][1, 2, 3]triazol-2-yl)-4-(2, 4, 4-trimethylpentan-2-yl)-2, 1-phenylene))bis(oxy))diphthalonitrile by means of transition metal (II) acetate salts in 2-dimethylaminoethanol. The new starting bisphthalonitrile compound was accomplished from 2,2'-methylenebis[6-(benzotriazol-2-yl)-4-tert-octylphenol] and 4-nitrophthalonitrile in dimethylformamide under the catalysis of potassium carbonate at 50○C. The structural characterization of the compounds was accomplished by infrared, proton-nuclear magnetic resonance, matrix-assisted laser desorption/ionisation time-of-flight mass, and ultraviolet–visible spectroscopic methods. The supercapacitor performances of the electrodes were examined by cyclic voltammetry, galvanostatic charge discharge, and electrochemical impedance spectroscopy analyses. The specific capacitances obtained from the GCD measurements were calculated as 320.4 ± 15.1 F/g for ball-type zinc (II) phthalocyanine in three electrode systems. The highest specific capacitance value was found in the electrode containing ball-type nickel (II) phthalocyanine as 929.8 ± 32.8 F/g at a scan rate of 100 mV/s. In symmetric supercapacitor measurements, the capacitance retention value was 100.7% after 5000 cycles.

Enhanced pseudocapacitive Li+ charge storage on lithium-rich disordered rock salt vanadium oxide nanocrystalline

Cation disordered rock-salt (DRS) metal compounds, featuring a three-dimensional percolation network for Li+ transportation, have attracted extensive attention as novel anode candidates for high-power lithium-ion batteries (LIBs) and capacitors (LICs). However, their low capacity and poor conductivity remain bottlenecks for their wide-scale usage, especially for high-energy applications. Here, we report a nanocrystal DRS Li3V2O5 (a-DRS-LVO) achieved by an electrochemically induced transformation on amorphous V2O5. The nanocrystalline phase of a-DRS-LVO can provide large active sites for Li+, leading to a surface-controlled solid-state Li+ diffusion behavior. In particular, the specific capacity for a-DRS-LVO reaches 716.8mAh g−1 at 0.1 A/g, exceeding that of DRS-LVO achieved by electrochemically induced transformation on well-crystallized V2O5. Further, a-DRS-LVO can work stably over 1,200 charge–discharge cycles with negligible capacity decay, due to the highly structural integrity stability, no phase change and limited volume change (∼8.2 %). A LIC with this a-DRS-LVO anode yields both high energy density (183 Wh kg−1) and power density (50,000 W kg−1), which are much higher than that of the state-of-art LICs based on graphite and other pseudocapacitive anodes, such as niobium and titanium oxides.

Zinc cobalt sulfide with carbon (graphene oxide and CNT) based nanocomposite as positive electrode for asymmetric coin cell supercapacitors

Abstract The world dependence on portable electronic devices has increased the demand for high-performance energy storage devices. The use of transition metal sulfides as faradaic electrode materials for electrochemical energy storage is rapidly increasing due to their high energy density. Herein Zinc Cobalt Sulfide (ZCS) with graphene oxide (GO) and carbon nanotubes (CNT) were used to create an interconnected ZCS composite network using a solvothermal technique. The materials were characterized by utilizing XRD, FT-Raman, TGA, FESEM/EDX, XPS, and BET. The electrochemical performance of the materials was examined using cyclic voltammetry (CV), galvanostatic charge–discharge (GCD), and electrochemical impedance spectroscopy (EIS). The prepared electrodes exhibited both pseudocapacitor behavior and double-layer capacitor behavior, indicating the hybrid nature. Furthermore, All the electrode ZCS, ZCS/GO, ZCS/CNT, and ZCS/GO/CNT electrodes demonstrated higher capacitance behavior, with values of 420, 551, 585 and 811 F g−1 at 1 A/g. Among these ZCS/GO/CNT electrode exhibits outstanding electrochemical properties, with a notable retention of 81.08% at 10 Ag−1 because Combining ZCS nanoparticles with interconnected GO and CNT provides excellent electronic conductivity and stability. The assembled ZCS/GO/CNT//graphene oxide asymmetric coin cell (ACC) supercapacitor showed a high energy density of 33.3 Wh kg–1 at a power density of 624 W kg–1. The 3D nanostructure of ZCS/GO/CNT/Graphene oxide has great potential for developing foldable energy storage devices.

Unravelling the effect of crystal lattice compression on the supercapacitive performance of hydrothermally grown nanostructured hollandite α-MnO2 induced by incremental growth time

Manganese oxide (α-MnO2) nanoparticles are highly recognised for their use in supercapacitor applications. This study demonstrates the successful synthesis of flower-like and nanorods hollandite α-MnO2 by a simple one-pot hydrothermal technique at various reaction times. The synthesised nanoparticles were characterised by various physicochemical and electrochemical characterisation techniques. The influence of the various reaction times on the structural and morphological properties was evaluated by X-ray diffraction (XRD) and scanning electron microscope. XRD patterns revealed that the synthesized MnO2 nanoparticles are tetragonal structures with crystallite sizes ranging from 13.69 to 20.37 nm estimated from the Williamson–Hall method. Moreover, the functional groups and surface area were examined by Fourier transform infrared spectroscopy and Bruner–Emmert–Teller, respectively. Furthermore, the compositional elements were studied by X-ray photoemission spectroscopy and energy-dispersive X-ray spectroscopy. Finally, the electrochemical performances were studied using cyclic voltammetry, galvanostatic charge–discharge and electrochemical impedance spectroscopy (EIS). The GCD characteristics revealed that the optimised α-MnO2 has a good capacitive behaviour, which predicts the potential application in energy storage. Electrochemical studies revealed that the 3 h-MnO2 sample exhibited a superior electrochemical behaviour and demonstrated a high specific capacitance of 132 F/g at a current density of 1A/g.

Flexible Supercapacitor Device Based on Laser‐Synthesized Nanographene for Low‐Power Applications

Laser‐induced graphene (LIG) and laser‐induced reduced graphene oxide (LIrGO) are two relatively recent graphene‐based nanoscale materials suitable for miniaturized flexible supercapacitors. This study employs direct laser engraving techniques to generate patterns on flexible substrates, such as paper and polyamide (PI). This methodology allows fine control over the formed nanographene structures to fabricated LIG and LIrGO supercapacitors. The LIG on PI exhibits a distinctive porous structure and high surface area, adsorption, and transportation of ions. Furthermore, paper‐based LIrGO electrodes are recyclable and are formed in a single step. The morphological study is done using scanning electron microscopy, Raman spectroscopy, X‐ray photoelectron spectroscopy, and X‐ray diffraction. Galvanostatic charge–discharge studies at 0.05 mA cm−2 current density show an areal capacitance of 3.69 mF cm−2 for LIG and 1.61 mF cm−2 for LIrGO. The comparable energy densities for LIG and LIrGO are 0.32 and 0.16 μWh cm−2, respectively. From the calculative analysis of both types, the variation in specific areal capacitance enabling effective is 56.3% from GCD, indicating that the LIG device performs better. Finally, a portable potentiostat is employed to investigate the viability of utilizing supercapacitors to operate self‐powered sensors in a portable and integrable fashion.

LiTFSI salt concentration effect for well‐balanced ion transport and physical properties in nanocellulose‐reinforced PEO#600 solid electrolytes

AbstractPoly(ethylene oxide) (PEO) with an oxygen group serves as a reactive site for the pathway of lithium‐ion transport. Reducing the PEO crystal domain in solid electrolytes is an extremely efficient approach for enhancing the mobility of ions. The present study applied various EO/Li molar ratios to modify the physical and electrochemical properties of PEO nanocomposite reinforced by nanocellulose. An elevated lithium salt concentration causes a gradual decline in crystallinity and mechanical strength. The electrochemical performance of the 13 EO/Li molar ratio voltammogram and charge–discharge shows efficient Li‐ion transport with 5.6 × 10−4 S/cm conductivity at room temperature and 131 mA h g−1 initial discharge capacity. The shifting glass transition and melting point at lower temperatures (−40.5 to −44.5°C and 45.3–43.8°C) suggest greater ion mobility throughout the large non‐crystalline structure. Lithium ions are limited by membrane weakening and re‐crystallization caused by high lithium salt (EM_11) concentrations. EM_13 has the highest specific capacity, operating voltage, and lithium transfer number depends on balanced electrochemical performance and physical features. XPS surface chemistry analysis explains LiF, Li2CO3, and Li2O solid electrolyte interfaces (SEI) in EM samples. A lower Li2O (11.62 at.%) than LiF (38.4 at.%) after cycling enhances Li‐ion diffusion and cell reversibility.

Enhancing Vanadium Redox Flow Battery Performance with ZIF-67-Derived Cobalt-Based Electrode Materials

Vanadium redox flow batteries (VRFBs) have emerged as a promising energy storage solution for stabilizing power grids integrated with renewable energy sources. In this study, we synthesized and evaluated a series of zeolitic imidazolate framework-67 (ZIF-67) derivatives as electrode materials for VRFBs, aiming to enhance electrochemical performance. Four materials—Co/NC-700, Co/NC-800, Co3O4-350, and Co3O4-450—were prepared through thermal decomposition under different conditions and coated onto graphite felt (GF) electrodes. X-ray diffraction (XRD), scanning electron microscopy (SEM), and transmission electron microscopy (TEM) analyses confirmed the structural integrity and distribution of the active materials. Electrochemical evaluations revealed that electrodes with ZIF-67-derived coatings exhibited significantly lower charge transfer resistance (Rct) and higher energy efficiency (EE) compared to uncoated GF electrodes. Co/NC-800//GF delivered the highest energy efficiency and discharge capacity among the tested configurations, maintaining stable performance over 100 charge–discharge cycles. These results indicate that Co/NC-800 holds great potential for use in VRFBs due to its superior electrochemical activity, stability, and scalability.

Recent Progress in Liquid Electrolytes for High‐Energy Lithium–Metal Batteries: From Molecular Engineering to Applications

AbstractLithium–metal batteries (LMBs) have garnered significant interests for their promising high gravimetric energy density (Eg) ∼ 750 Wh kg−1. However, the practical application of the LMBs is plagued by the high reactivity and large volume change during charging–discharging of the lithium–metal anode (LMA), seriously deteriorating the battery safety and cycle life. Great efforts have been devoted to tailoring the electrolytes to favor the Li–metal electroplating by uniformizing the deposition morphology and by suppressing the side reactions between electrolytes and LMA. The aggressive chemistries of both the LMA and its high‐voltage counterpart give new electrolyte components more opportunities, especially designing via molecular engineering. Here, a comprehensive and in‐depth overview of the scientific challenges, fundamental mechanisms, and particularly historical strategies of designing new molecules for electrolyte components including solvents, salts, and additives. Their important roles in tuning the Li+ solvation structure, interface composition, decomposition pathways, and the resultant electrochemical performance of LMBs are also presented. Finally, novel insights and promising research directions from the practical application viewpoints are proposed for future electrolyte designs for high‐voltage LMBs.

Constructing Co3O4 Nanowire@NiCo2O4 Nanosheet Hierarchical Array as Electrode Material for High-Performance Supercapacitor

The Co3O4 nanowire@NiCo2O4 nanosheet hierarchical array was constructed on Ni foam using hydrothermal and annealing approaches in turn, from which a NiCo2O4 nanosheet could self-assemble on the Co3O4 nanowire. The structure and morphology of the Co3O4 nanowire@NiCo2O4 nanosheet hierarchical array were characterized via XRD, EDS, SEM, and FESEM, respectively. The electrochemical performance of the composite array was measured via a cyclic voltammetry curve, galvanostatic current charge–discharge, charge–discharge cycle, and electrochemical impedance and then compared with the Co3O4 nanowire. The results show that the Co3O4 nanowire@NiCo2O4 nanosheet hierarchical array could reach a high value of 2034 F g−1 at a current density of 2.5 A g−1. After 5000 galvanostatic charge–discharge cycles, the specific capacitance of the Co3O4 nanowire@NiCo2O4 nanosheet hierarchical array could still maintain 94.7% of the original value. Therefore, the Co3O4 nanowire@NiCo2O4 nanosheet hierarchical array would be a desirable electrode material for a high-performance supercapacitor.

Electrochemical boost via thermally reduced graphene oxide for tailoring composite paste electrodes

Carbon-based composite materials are employed in diverse electrochemical applications, such as in catalysis, (bio)molecular sensing, and energy storage. In practice, electrode material needs to be highly conductive to allow high-speed electron transference to electrolyte species and possess high-surface area to obtain greater measured signals and power capabilities, as well as long useful life and stability. In this sense, graphene derivatives emerge as interesting candidates, even more so if they constitute part of practical, economical and versatile paste electrodes.This work presents a detailed analysis of the electrochemical performance of paste electrodes fabricated with multilayer partially reduced graphene oxide (rGO). The rGO was strategically produced via thermal treatment as a key factor that minimizes both mass loss and energy consumption. The results obtained through diffraction, microscopy and spectroscopy techniques show an effective partial reduction in the range of 100 to 400 °C. Furthermore, the enhanced electrochemical performance of rGO was determined by exploring the specific capacitance from cyclic voltammetry (CV) and galvanostatic charge–discharge measurements (GCD) as well as charge transfer resistance via electrochemical impedance spectroscopy (EIS). Our results evidence how an integral performance with suitable chemical, structural and morphological properties achieved for GO heat-treated at 200 °C leads to an improved electronic conductivity when a small part is combined with graphite in paste electrodes. This latter combination provides higher versatility compared to other alternatives since it arises as an economical and effective carbonaceous matrix for (bio)electrochemical sensors, hybrid supercapacitors or other desired nanotechnological applications.

Tailoring eco-friendly siloxane-based electrolytes for high-performance lithium–sulfur batteries

Lithium–sulfur batteries (LSBs), with their ultra-high theoretical energy density (2600 Wh kg−1), are considered one of the most attractive high-energy batteries. However, the “shuttling effect” of polysulfides and the uncontrolled growth of lithium (Li) dendrites pose significant challenges to the practical implementation of LSBs. Herein, a lightweight and eco-friendly diethoxydimethylsilane (DEMS) is chosen as a multi-functional solvent for LSBs. The low polarity of DEMS promotes the “solid–solid” conversion of sulfurized polyacrylonitrile (SPAN) during charge–discharge processes, eliminating the shuttle effect of polysulfides. Moreover, the DEMS-based electrolyte enables highly reversible Li plating/stripping processes across a wide temperature range spanning from −20 to 60 °C. As a result, the Li/SPAN batteries using the DEMS electrolyte exhibit excellent cyclic stability at 0.2 C with retainable capacities of 524.4 mAh/g after 200 cycles, 598.8 mAh/g after 100 cycles, and 318.6 mAh/g after 50 cycles at 26, 60 and −20 °C, respectively. This study aims to identify low-cost and highly stable electrolytes through solvent screening to enhance the electrochemical performance of LSBs.

Data-Driven Clustering Analysis for Representative Electric Vehicle Charging Profile in South Korea

As the penetration of electric vehicles (EVs) increases, an understanding of EV operation characteristics becomes crucial in various aspects, e.g., grid stability and battery degradation. This can be achieved through analyzing large amounts of EV operation data; however, the variability in EV data according to the user complicates unified data analysis and identification of representative patterns. In this research, a framework that captures EV charging characteristics in terms of charge–discharge area is proposed using actual field data. In order to illustrate EV operation characteristics in a unified format, an individual EV operation profile is modeled by the probability distribution of the charging start and end states of charge (SoCs).Then, hierarchical clustering analysis is employed to derive representative charging profiles. Using large amounts of real-world, vehicle-specific EV data in South Korea, the analysis results reveal that EV charging characteristics in terms of the battery charge–discharge area can be summarized into seven representative profiles.

Lignin-Based N-Carbon Dots Anchoring NiCo2S4/Graphene Hydrogel Exhibits Excellent Performance as Anodes for Hybrid Supercapacitor

A NiCo2S4/N-CDs/RGO ternary composite hydrogel was prepared via a one-step hydrothermal method, utilizing lignin-based nitrogen-doped carbon dots as a bridge connecting NiCo2S4 and graphene. The specific capacitance of NiCo2S4/N-CDs/RGO significantly outperforms that of the GH and NiCo2S4/RGO electrodes, achieving 1050 F g−1. The 3D mesh porous hydrogel structure mitigates NiCo2S4 nanoparticle aggregation, providing a larger specific surface area for enhanced charge storage. The abundant functional groups of N-CDs interact with Ni (II) and Co (III) cations, favoring NiCo2S4 particle synthesis. Additionally, an assembled solid-state asymmetric supercapacitor employing NiCo2S4/N-CDs/RGO as the positive electrode exhibited excellent energy density (68.4 Wh kg−1) and cycle stability (82% capacitance retention after 10,000 constant current charge–discharge cycles).

Electrochemical performance of cobalt-doped NiO thin films synthesized by spray pyrolysis

ABSTRACT In this work, various cobalt-doped NiO thin films have been synthesized via the spray pyrolysis. The cobalt-doped NiO thin films show a cubic phase with preferred orientation along the (111) plane. The scanning electron microscopy images of the cobalt-doped NiO thin films show interconnected flakes with small agglomerated particles. The optical bandgap decreases from 3.30 eV for the undoped NiO thin film to 2.90 eV for 20 mol% cobalt doping, with an increase in cobalt doping concentration in NiO. The electrochemical activities have been tested in 2M KOH electrolyte with cyclic voltammetry, galvanostatic charge–discharge and electrochemical impedance spectroscopy. The highest specific capacitance observed for the 10 mol% cobalt-doped NiO thin film electrode is 760 Fg−1 at a scan rate of 5 mVs−1. The 10 mol% cobalt-doped NiO thin film electrode shows 92% retention in capacitance after 1000 cycles and a low charge transfer resistance of 10 Ωcm2.

NiCo-MOFs derived carbon matrix composites: A promising electrode construction for high-performance supercapacitors

Metal-organic frameworks (MOFs) are great precursors and templates for preparing adsorbents, catalysts and electrodes due to the porous structure and high specific surface area. We report a promising approach to prepare nanocrystalline Co, Ni sulfides (CNS) embedded and N self-doped porous carbon (NPC) matrix composites derived from NiCo-MOFs. The CNS@NPC composite was investigated as electrodes for hybrid supercapacitors (HSCs). The prepared electrode achieved specific capacitance of 2789 F g−1 at 1 A/g, and high capacitance retention of 88.93% after 6000 galvanostatic charge–discharge (GCD) cycles under 10 A/g. The HSC structured with CNS@NPC//AC achieved an energy density of 46.79 Wh kg−1 at power density of 800 W kg−1. Meanwhile, specific capacitance of 131.56 F g−1 at 1 A/g and capacitance retention of 99.17% over 6000 GCD cycles under 3 A/g were obtained. Space confinement by the carbon skeleton effectively prevents the aggregation of the redox active nanocrystalline and improves the durability of the electrode. Meanwhile, the carbon skeleton provides abundant charge transfer channels to enhance the redox reaction. In other words, synergistic effect of the carbon skeleton and the active redox nanocrystalline significantly improves the electrochemical properties of the composite.

Environmentally Friendly Biological Activated Carbon Derived from Sugarcane Waste as a Promising Carbon Source for Efficient and Robust Rechargeable Zinc–Air Battery

China is one of the largest sugarcane industrial countries in the world, and the annual output of bagasse waste is abundant. Classical incineration, landfill, and other treatment methods are inefficient and seriously harmful to the environment, so it is urgent to develop a new comprehensive utilization of agricultural waste. In this work, the sugarcane waste residue is converted to biological activated carbon (BAC) through a simple pre-carbonization and KOH activation process, which is then mixed with perovskite oxide BaCo0.5Fe0.5O3−δ (BCF) to form BAC/BCF composite air electrode. BAC/BCF assembled rechargeable zinc–air battery (ZAB) exhibits a relatively good output maximum power density of 96 mW·cm−2 and considerable long-term charge–discharge cycle stability over 250 h operation. These results indicate that the BAC derived from sugarcane waste is a promising potential carbon material candidate for ZAB application, which can realize the high-value utilization of agricultural waste in the field of efficient and durable energy storage and conversion devices.

Synergistic effects of MXene and Co3O4 in composite electrodes: High-performance energy storage solutions

The development of high-performance electrode materials is crucial for advancing supercapacitor technology. The two-dimensional layered structure of MXene (Ti3C2Tx) presents high conductivity, abundant surface functional groups and accessible ion interaction between layers. However, the MXene suffers from the layer aggregation. To overcome this issue, we synthesized a composite material combining MXene with cobalt oxide (Co3O4) to enhance electrochemical performance in supercapacitors. MXene’s two-dimensional layered structure, high conductivity, and abundant surface functional groups allow for efficient ion intercalation, while Co3O4 contributes high theoretical capacitance and rich oxidation states. The resulted MXene/Co3O4 composite exhibits an impressive areal capacitance of 6.456F/cm2 at a current density of 3 mA/cm2, maintaining 90.52 % capacitance retention at 30 mA/cm2, and 81.37 % capacity after 5000 charge–discharge cycles. Additionally, the asymmetric supercapacitor (ASC) device fabricated using the MXene/Co3O4 composite achieves a power density of 6.41 mW/cm2 at an energy density of 0.37 mWh/cm2, with 82.3 % capacitance retention after 5000 cycles. These results demonstrate that the MXene/Co3O4 composite material is a promising candidate for high-performance supercapacitors, offering significant improvements in rate capability and long-term cycling stability.

Negative Joule heat effect on supercapacitor module

Joule heat as the main heat source in high-power operation of supercapacitor modules, needs to be carefully considered in thermal management. The sufficient discussion on the temperature characteristics of supercapacitor modules, especially those containing auxiliary electronic components during operation is of importance. Here we reported the Joule heat effect on a supercapacitor module integrated on a circuit board in the charge and discharge cycles by an in situ Infrared imaging method. Temperature rise of total components including wires, circuit board, welding pint, resistor and capacitor cell could be simultaneously imaged with a sensitivity of 0.2–0.3 °C. Upon charge–discharge cycles from 5C-60C, Joule heat on these electronic components was discovered. The thermal transfered from the connected wires to the circuit board and finally to the cell, which significantly increased the temperature rise (from 9.3 °C to 19.6 °C at 60C) and temperature difference (9.6 °C at 60C) of different capacitors in modules. Further simulation results indicated that Joule heat on the circuit board was 2–3 times that of the capacitors in the module. Such additional heat flow without suitable cooling system would result an accelerated capacitance decay of the module. Therefore, a suitable module structure and thermal management strategy needed to be designed to minimize the Joule heat generation of such electronic components.

Infiltration-driven performance enhancement of poly-crystalline cathodes in all-solid-state batteries

All-solid-state batteries (ASSBs) with adequately selected cathode materials exhibit a higher energy density and better safety than conventional lithium-ion batteries (LIBs). Ni-rich layered cathodes are benchmark materials for traditional LIBs owing to their high energy density. Recent studies have highlighted the advantages of using crack-free, single-crystalline cathode materials in ASSBs. In this study, a scalable infiltration sheet-type process was used to fabricate composite electrodes with different cathode-material morphologies for ASSBs. Typically, crack-free single-crystalline materials exhibit better retention performance and lower rate capability (i.e., slower kinetics in charge‒discharge processes) than polycrystalline cathode materials. Li6PS5Cl-infiltrated polycrystalline electrodes showed excellent retention performance and rate capability. Galvanostatic intermittent titration technique analysis and transmission electron microscopy of the single-crystalline electrode confirmed severe polarization and the presence of a rock-salt-structure layer in the cathode particles; these results indicated side reactions within the layered structure of the material. In contrast, composite electrodes consisting of polycrystalline cathode materials infiltrated with the solid electrolyte Li6PS5Cl showed excellent electrochemical performance owing to intimate electrode–electrolyte interfacial contact. The result from this study confirmed the critical influence of interface engineering and material morphology on the overall performance and stability of ASSBs and could facilitate the development of high-performance ASSBs in the future.

Highly Stable Alkaline All‐Iron Redox Flow Batteries Enabled by Disulfonated Ligands Chelation

AbstractAlkaline all‐iron flow batteries possess intrinsic safety and low cost, demonstrating great potential for large‐scale and long‐duration energy storage. However, their commercial application is hindered by the issue of capacity decay resulting from the decomposition of iron complexes and ligand crossovers. In this paper, an robust anolyte Fe(TEA‐2S) is reported, which is formed by chelating iron ions with the sulfonate‐enriched ligand (TEA‐2S) in alkaline environment. By skillfully designing the ligands, the binding energy of the iron complexes increases and ligand crossovers are suppressed, making the iron complexes highly stable in the charge–discharge cycles. Alkaline all‐iron flow batteries coupling with Fe(TEA‐2S) and the typical iron‐cyanide catholyte perform a minimal capacity decay rate (0.17% per day and 0.0014% per cycle), maintaining an average coulombic efficiency of close to 99.93% over 2000 cycles along with a high energy efficiency of 83.5% at a current density of 80 mA cm−2. In addition, Fe(TEA‐2S) exhibits high solubility of up to 1.85 м (with a theoretical capacity of up to 49.58 Ah L−1), even at low temperatures as extreme as −30 °C. This work demonstrates a promising pathway toward achieving long‐duration and large‐scale energy storage.