Cathode For Rechargeable Batteries Research Articles

Ferrocene-Derived Sulfur-Rich Cathode for High-Performance Rechargeable Lithium Batteries

Ferrocene-Derived Sulfur-Rich Cathode for High-Performance Rechargeable Lithium Batteries

Copper Tetraselenophosphate Cathode for Rechargeable Magnesium Batteries: A Redox-Active Polyatomic Anion Strategy to Design the Cathode Material

Rechargeable magnesium batteries attract interest as advantageous energy-storage devices, but the application is being hampered by the deficiency of suitable cathodes. The traditional method to weaken the interaction between bivalent Mg2+ cations and the cathode material is to increase the anion radius, but excessive expansion of the anion would lead to a decrease of the theoretical capacity and offset the performance improvement. Herein, a new strategy using a redox-active polyatomic anion is developed in terms of copper tetraselenophosphate (Cu3PSe4) fabricated by the PSe43– anion. The covalent P–Se bond facilitates the negative charge delocalization of the PSe43– anion and weakens the interaction with Mg2+ cations, which result in rapid solid-phase Mg2+ diffusion kinetics. The PSe43– anion also provides extra capacities by reversible valence state change of the P element. Cu3PSe4 delivers a high Mg-storage capacity of 225 mAh g–1 at 50 mA g–1 and a superior rate performance of 62 mAh g–1 at 5000 mA g–1, as well as a stable cyclability of 500 cycles. The redox-active polyatomic anion strategy herein opens a new avenue for the exploration of magnesium battery cathodes with a comprehensive consideration of kinetic performance and theoretical capacity.

Homogeneous regulation of arranged polymorphic manganese dioxide nanocrystals as cathode materials for high-performance zinc-ion batteries

Rechargeable aqueous zinc-ion batteries have emerged as attractive energy storage devices by virtue of their low cost, high safety and eco-friendliness. However, zinc-ion cathodes are bottlenecked by their vulnerable crystal structures in the process of zinc embedding and significant capacity fading during long-term cycling. Herein, we report the rational and homogeneous regulation of polycrystalline manganese dioxide (MnO2) nanocrystals as zinc cathodes via a surfactant template-assisted strategy. Benefiting from the homogeneous regulation, MnO2 nanocrystals with an ordered crystal arrangement, including nanorod-like polyvinylpyrrolidone-manganese dioxide (PVP-MnO2), nanowire-like sodium dodecyl benzene sulfonate-manganese dioxide and nanodot-like cetyltrimethylammonium bromide-manganese dioxide, are obtained. Among these, the nanorod-like PVP-MnO2 nanocrystals exhibit stable long-life cycling of 210 mAh g−1 over 180 cycles at a high rate of 0.3 A g−1 and with a high capacity retention of 84% over 850 cycles at a high rate of 1 A g−1. The good performance of this cathode significantly results from the facile charge and mass transfer at the interface between the electrode and electrolyte, featuring the crystal stability and uniform morphology of the arranged MnO2 nanocrystals. This work provides crucial insights into the development of advanced MnO2 cathodes for low-cost and high-performance rechargeable aqueous zinc-ion batteries.

Covalent organic framework cathodes for rechargeable Mg batteries

Rechargeable magnesium batteries (RMBs) attract interests as advantageous energy-storage devices, but the application is being hampered by the deficiency of suitable cathodes. Covalent organic frameworks (COFs) are promising selections because of the flexible organic polymer chains and open matrix. Herein, a new family of COF-based polyimide cathodes is synthesized and investigated as RMB cathodes. The COF cathode exhibits a high Mg-storage capacity of 120 mAh g−1, as well as high rate capability and good cycleability, suggesting COFs would be a promising family of cathode materials for RMBs.

Utilization of the spent catalyst as a raw material for rechargeable battery production: The effect of leaching time, type, and concentration of organic acids

This study examines the potential use of the spent catalyst as a raw material for rechargeable batteries. The spent catalyst Ni/γ-Al2O3 still contains relatively high amounts of nickel. This indicates the potential use of the spent catalyst to be leached and purified for synthesizing nickel-based compounds so that it can be applied to rechargeable battery cathodes. In this study, the spent catalyst leaching process employed four types of organic acids: citric acid, lactic acid, oxalic acid, and acetic acid. The spent catalyst was leached under atmospheric conditions and room temperature. Organic acid concentrations were also varied at 0.1, 0.5, 1, and 2 M. The leaching process took place for 240 minutes, where sampling was conducted periodically at 30, 60, 120, 180, and 240 minutes. Experimental results showed that Ni (II) and Al (III) ions were successfully leached to the maximum when using 2M citric acids at a leaching time of 240 minutes. The conditions succeeded in leaching Ni (II) and Al (III) ions of 357.8 and 1,975.4 ppm, respectively. Organic acid, notably citric acid, has excellent potential for further development. Citric acid, as a solvent, has the ability to leach metal ions with high recovery. In addition, this acid is categorized as an eco-friendly and green solvent compared to inorganic acid. Thus, the leaching process can take place without harming the environment.

Defect-Healing Induced Monoclinic Iron-Based Prussian Blue Analogs as High-Performance Cathode Materials for Sodium-Ion Batteries.

Prussian blue analogs (PBAs) have attracted wide interest as a class of ideal cathodes for rechargeable sodium-ion batteries due to their low cost, high theoretical capacity, and facile synthesis. Herein, a series of highly crystalline Fe-based PBAs (FeHCF) cubes, where HCF stands for the hexacyanoferrate, is synthesized via a one-step pyrophosphate-assisted co-precipitation method. By applying this proposed facile crystallization-controlled method to slow down the crystallization process and suppress the defect content of the crystal framework of the PBAs, the as-prepared materials demonstrate high crystallization and a sodium-rich induced rhombohedral phase. As a result, the as prepared FeHCF can deliver a high specific capacity of up to 152.0mAhg-1 (achieving ≈90% of its theoretical value) and an excellent rate capability with a high-capacity retention ratio of 88% at 10C, which makes it one of the most competitive candidates among the cathodes reported regarding both capacity and rate performance. A highly reversible three-phase-transition sodium-ion storage mechanism has been revealed via multiple in situ techniques. Furthermore, the full cells fabricated with as-prepared cathode and commercial hard carbon anode exhibit excellent compatibility which shows great prospects for application in the large-scale energy storage systems.

Integrated Combinatorial Synthesis, Characterization, and Test Platform for Lithium-Ion Battery Cathode Materials

An integrated combinatorial synthesis, characterization, and testing methodology and platform is proposed and developed for high-throughput exploration of Li-ion rechargeable battery cathode chemistries. This article describes the design of the platform’s combinatorial synthesis part and its prototype performance. A key design element is a multi-gear powertrain with a unique milling-force adjustable pestle that ensures high compatibility with varying types of electrode materials. To demonstrate the prototype, LiNiO2 was prepared via a solid-state route under various operating conditions. We evaluated the effects of processing parameters, including milling force and mixing speed, on the synthesized electrode’s physical properties and electrochemical behavior. The synthesized LiNiO2 materials show excellent electrochemical performance comparable to manually synthesized LiNiO2.

Enabling rechargeable Li‐MnO2 batteries using ether electrolytes

AbstractA low‐carbon future demands more affordable batteries utilizing abundant elements with sustainable end‐of‐life battery management. Despite the economic and environmental advantages of Li‐MnO2 batteries, their application so far has been largely constrained to primary batteries. Here, we demonstrate that one of the major limiting factors preventing the stable cycling of Li‐MnO2 batteries, Mn dissolution, can be effectively mitigated by employing a common ether electrolyte, 1 mol/L lithium bis(trifluoromethanesulfonyl)imide (LiTFSI) in 1,3‐dioxane (DOL)/1,2‐dimethoxyethane (DME). We discover that the suppression of this dissolution enables highly reversible cycling of the MnO2 cathode regardless of the synthesized phase and morphology. Moreover, we find that both the LiPF6 salt and carbonate solvents present in conventional electrolytes are responsible for previous cycling challenges. The ether electrolyte, paired with MnO2 cathodes is able to demonstrate stable cycling performance at various rates, even at elevated temperature such as 60°C. Our discovery not only represents a defining step in Li‐MnO2 batteries with extended life but provides design criteria of electrolytes for vast manganese‐based cathodes in rechargeable batteries.

Recent advances of Na3V2(PO4)3 as cathode for rechargeable zinc-based batteries

Recent advances of Na3V2(PO4)3 as cathode for rechargeable zinc-based batteries

Enhanced electrochemical performance of ammonium vanadate (NH4V4O10) cathode for rechargeable aqueous zinc-ion batteries by altering pH regulators

Ammonium vanadate (NH4V4O10: NVO) as cathode for rechargeable aqueous zinc-ion batteries (AZIBs) have drawn extensive concern due to its high specific capacity and long cycle life. The controllable synthesis of high-performance NH4V4O10 is greatly desirable for the development of AZIBs but still remains a significant challenge. In this work, sulfuric acid, hydrochloric acid, and nitric acid were used as pH regulators to prepare NVO via a simple one-step hydrothermal route. The resulting NVO product (NVO-1) based on sulfuric acid pH regulator has the optimal overall performance for its favorable structure stability originated from the high crystallinity and wonderful 3D cross-linked nanowire morphology, contributing to fast electron transfer in the (de)intercalation process of Zn2+. Consequently, NVO-1 electrode exhibits excellent rate capability and cyclic stability, delivering high reversible capacities of 418.9 and 257.1 mAh g−1 at current densities of 0.1 and 2 A g−1, respectively, and demonstrating a discharge capacity of 105.7 mAh g−1 as well as superior long-term durability with an ultra-high capacity retention of 119.7 % at a large current density of 5 A g−1 after 2000 cycles. Investigation on the electrochemical kinetics reveals that surface capacitive behavior plays a significant role in the highly reversible Zn2+ storage in NVO electrode.

Intercalation Reaction of Molybdenum Trioxide Cathode for Rechargeable Ion Batteries

AbstractBased on the intercalation reaction, molybdenum trioxide has become an attractive cathode material for rechargeable ion batteries owing to its high theoretical capacity and layered structure. This review summarizes the recent research progress of molybdenum trioxide‐based cathode in non‐aqueous lithium, magnesium, calcium‐ion batteries, aqueous zinc, hydrogen, and aluminum‐ion batteries, focusing on the energy storage mechanism, existing problems, and optimization strategies in rechargeable ion batteries. Finally, the perspectives about challenges and future further development directions of molybdenum trioxide cathode in electrochemical energy storage are proposed. This review will comprehensively summarize molybdenum trioxide as a cathode in rechargeable ion batteries and clarify its practical application prospects for sustainable development.

Three-dimensionally ordered Co3O4@WO3 composite arrays as a binder-free air cathode for high-performance Zn-air batteries

The development of low-cost, stable, and highly-active bifunctional catalysts is an important step to realize high-performance rechargeable Zn-air batteries. Herein, we report an innovative air cathode of three-dimensionally (3D) ordered macroporous Co3O4@WO3 composite arrays on a flexible carbon cloth substrate prepared by the decoration of Co3O4 nanosheets on electrodeposited macroporous WO3 inverse opals. Benefiting from a high specific surface area, rich active sites, and a facilitated charge/mass transfer process provided by the 3D ordered macroporous structure, the as-prepared Co3O4@WO3 composite exhibits excellent bifunctional catalytic activity with a half-wave potential of 0.75 V for oxygen reduction reaction and an overpotential of 339 mV at 10 mA/cm2 for oxygen evolution reaction, contributing to a low oxygen potential gap (ΔE) of 0.81 V. Furthermore, Co3O4@WO3 composite arrays are directly used as a binder-free air cathode for rechargeable Zn-air batteries, ensuring excellent mechanical and electrochemical stability. The aqueous Zn-air batteries based on 3D Co3O4@WO3 air cathodes exhibit excellent performance, in terms of a high specific capacity of 828.6 mAh/gZn1 at 5 mA/cm2 and long-term cycling stability of over 646 h.

Nitrogen-doped NiCo2O4 nanowires on carbon paper as a self-supported air cathode for rechargeable Zn-air batteries

A noble-metal-free bifunctional electrocatalyst with outstanding activity and stability is of great importance for the development of rechargeable zinc-air batteries (ZABs). Herein, we employed a facile strategy to fabricate nitrogen-doped NiCo2O4 nanostructures on carbon paper as a binder-free air cathode for rechargeable ZABs. An optimized process of nitrogen plasma treatment has enhanced the electrical conductivity of the metal oxide and induced abundant active sites into the crystal structures, resulting in enhanced electrocatalytic activities toward oxygen evolution reaction (OER) and oxygen reduction reaction (ORR). Notably, mild plasma treatment leads to efficient N doping while the morphology and specific surface area of the catalyst both remain unchanged. The air cathode with NiCo2O4 doped with nitrogen in 2 min plasma treatment and integrated into a zinc-air battery with liquid electrolyte provided a small charge-discharge voltage gap and distinguished cycling stability superior to the air cathode with noble-metal catalyst counterparts. Furthermore, the solid-state zinc-air battery with this material displays excellent stability with just a small increase of the charge-discharge voltage gap over 20 h of operation. This work illustrates the promising potential of plasma treatment in the fabrication of high-performance catalysts.

Metal organic frameworks derived NiSe2 microspheres wrapped with graphene as a high-performance cathode for rechargeable magnesium batteries

Rechargeable magnesium batteries (RMBs) are suitable for large-scale energy storage, but the cathode materials are deficient. Herein, NiSe2 microspheres derived from Ni-metal organic frameworks (Ni-MOFs) and wrapped with reduced graphene oxide (NiSe2/rGO) are fabricated and used as RMB cathodes. The NiSe2 microspheres are composed of tiny nanoparticles and interweaved with conductive graphene network. The NiSe2/rGO cathode exhibits a capacity of 215.5 mAh g−1 at 50 mA g−1, a good rate capability of 66.8 mAh g−1 at 2.0 A g−1 and a stable cycling for 300 cycles. Further kinetic investigation indicates the graphene improves the activity of the tiny NiSe2 nanoparticles, enhancing the interphase charge transfer and the magnesium storage performance.

Extended Conjugation Acceptors Increase Specific Energy Densities in π-Conjugated Redox Polymers

Organic materials are a sustainable alternative to replace inorganic transition metal-based cathodes in rechargeable intercalation batteries. Among the possible redox active organic materials, conjugated polymers with multiple redox sites per repeat unit are expected to afford high energy and power densities while being resistant to dissolution when in contact with battery electrolytes. However, accessing the full capacity of polymeric electrodes while ensuring electrochemical reversibility has been challenging. Using diketopyrrolopyrrole (DPP)-based donor–acceptor (D–A) polymers as model systems and complementary electrochemical experiments and first-principles calculations, we show that conjugated backbone moieties that minimize charge localization on the electron accepting repeat units lead to near theoretical discharge capacities. Further, the capacity enhancement is associated with better rate performance and improved electrochemical stability of the polymer over prolonged cycling. Our work suggests that charge density on the electron accepting moiety is a potential descriptor for rationally designing redox-active polymer electrodes that afford high discharge capacities along with a long cycle life.

In Situ TEM Studies on Electrochemical Mechanisms of Rechargeable Ion Battery Cathodes

Due to recent developments in secondary ion batteries for high‐energy‐density applications, a thorough understanding of the underlying mechanism of advanced cathode materials is of vital importance. In situ transmission electron microscopy (TEM) techniques capable of high spatial and temporal resolution in operando analysis of dynamic battery systems have attracted significant interest. However, the complex electrochemical reaction mechanisms of cathode materials have not been extensively investigated using in situ TEM due to technical difficulties in implementation. This perspective provides an overview on the recent development of in situ TEM for studying representative layered and olivine‐type cathode materials in secondary ion batteries; it further discusses the critical challenges and possible breakthroughs of this technique in deepening fundamental understandings in the near future.

Structure and reactions mechanism of sulfurized polyacrylonitrile as cathodes for rechargeable Li-S batteries

Structure and reactions mechanism of sulfurized polyacrylonitrile as cathodes for rechargeable Li-S batteries

Layered buserite Mg-Mn oxide cathode for aqueous rechargeable Mg-ion battery

Layered buserite Mg-Mn oxide cathode for aqueous rechargeable Mg-ion battery

Octylamine‐Supporting Interlayer Expanded Molybdenum Diselenide as a High‐Power Cathode for Rechargeable Mg Batteries

Rechargeable Mg batteries (RMBs) are a promising large‐scale energy‐storage technology with low cost and high safety, but the performance is limited by the inferior kinetics of Mg‐intercalation cathodes. In the present study, an octylamine‐supporting interlayer expanded molybdenum diselenide (e‐MoSe2) is synthesized and used as cathode for RMBs, in comparison with ordinary crystalline MoSe2. The octylamine molecules introduced show a strong interaction with the MoSe2 layers and increase the layer spacing significantly from 6.46 to 11.5 Å. e‐MoSe2 shows a high Mg‐storage capacity of 238 mAh g−1 at 50 mA g−1 and a superior rate performance of 39 mAh g−1 at 10 A g−1, far advantageous over crystalline MoSe2. e‐MoSe2 also shows a considerably high structure stability during repeated magnesiation/demagnesiation, providing an outstanding cycling stability for 1000 cycles. Further electrochemical tests demonstrate the high Mg2+ diffusion coefficients in e‐MoSe2. Theoretical computation indicates the interlayer expansion changes the Mg2+ diffusion paths from “hollow site → hollow site” to “hollow site → Se atom site → hollow site”, largely decreasing the energy barrier and improving the Mg2+ diffusion kinetics. The present work highlights an efficient strategy for the improvement of Mg‐storage performance for RMB cathodes.

Synergistic Transition-Metal Selenide Heterostructure as a High-Performance Cathode for Rechargeable Aluminum Batteries.

We synthesize and characterize a rechargeable aluminum battery cathode material composed of heterostructured Co3Se4/ZnSe embedded in a hollow carbon matrix. This heterostructure is synthesized from a metal-organic framework composite, in which ZIF-8 is grown on the surface of ZIF-67 cube. Both experimental and theoretical studies indicate that the internal electric field across the heterostructure interface between Co3Se4 and ZnSe promotes the fast transport of electron and Al-ion diffusion. As a result, the heterostructured Co3Se4/ZnSe demonstrates superior specific capacity and cycle stability compared to the single-phase Co3Se4 and ZnSe cathode materials.