Materials For Rechargeable Batteries Research Articles

Influence of iron phosphate on the performance of lithium iron phosphate as cathodic materials in rechargeable lithium batteries

Influence of iron phosphate on the performance of lithium iron phosphate as cathodic materials in rechargeable lithium batteries

Rational Regulation of High-Voltage Stability in Potassium Layered Oxide Cathodes.

Layered oxide cathode materials may undergo irreversible oxygen loss and severe phase transitions during high voltage cycling and may be susceptible to transition metal dissolution, adversely affecting their electrochemical performance. Here, to address these challenges, we propose synergistic doping of nonmetallic elements and in situ electrochemical diffusion as potential solution strategies. Among them, the distribution of the nonmetallic element fluorine within the material can be regulated by doping boron, thereby suppressing manganese dissolution through surface enrichment of fluorine. Furthermore, in situ electrochemical diffusion of fluorine from the surface into the bulk of the materials after charging reduces the energy barrier of potassium ion diffusion while effectively inhibiting irreversible oxygen loss under high voltage. The modified K0.5Mn0.83Mg0.1Ti0.05B0.02F0.1O1.9 layered oxide cathode exhibits a high capacity of 147 mAh g-1 at 50 mA g-1 and a long cycle life of 2200 cycles at 500 mA g-1. This work demonstrates the efficacy of synergistic doping and in situ electrochemical diffusion of nonmetallic elements and provides valuable insights for optimizing rechargeable battery materials.

Organic Electrode Materials for Energy Storage and Conversion: Mechanism, Characteristics, and Applications.

ConspectusLithium ion batteries (LIBs) with inorganic intercalation compounds as electrode active materials have become an indispensable part of human life. However, the rapid increase in their annual production raises concerns about limited mineral reserves and related environmental issues. Therefore, organic electrode materials (OEMs) for rechargeable batteries have once again come into the focus of researchers because of their design flexibility, sustainability, and environmental compatibility. Compared with conventional inorganic cathode materials for Li ion batteries, OEMs possess some unique characteristics including flexible molecular structure, weak intermolecular interaction, being highly soluble in electrolytes, and moderate electrochemical potentials. These unique characteristics make OEMs suitable for applications in multivalent ion batteries, low-temperature batteries, redox flow batteries, and decoupled water electrolysis. Specifically, the flexible molecular structure and weak intermolecular interaction of OEMs make multivalent ions easily accessible to the redox sites of OEMs and facilitate the desolvation process on the redox site, thus improving the low-temperature performance, while the highly soluble nature enables OEMs as redox couples for aqueous redox flow batteries. Finally, the moderate electrochemical potential and reversible proton storage and release of OEMs make them suitable as redox mediators for water electrolysis. Over the past ten years, although various new OEMs have been developed for Li-organic batteries, Na-organic batteries, Zn-organic batteries, and other battery systems, batteries with OEMs still face many challenges, such as poor cycle stability, inferior energy density, and limited rate capability. Therefore, previous reviews of OEMs mainly focused on organic molecular design for organic batteries or strategies to improve the electrochemical performance of OEMs. A comprehensive review to explore the characteristics of OEMs and establish the correlation between these characteristics and their specific application in energy storage and conversion is still lacking.In this Account, we initially provide an overview of the sustainability and environmental friendliness of OEMs for energy storage and conversion. Subsequently, we summarize the charge storage mechanisms of the different types of OEMs. Thereafter, we explore the characteristics of OEMs in comparison with conventional inorganic intercalation compounds including their structural flexibility, high solubility in the electrolyte, and appropriate electrochemical potential in order to establish the correlations between their characteristics and potential applications. Unlike previous reviews that mainly introduce the electrochemical performance progress of different organic batteries, this Account specifically focuses on some exceptional applications of OEMs corresponding to the characteristics of organic electrode materials in energy storage and conversion, as previously published by our groups. These applications include monovalent ion batteries, multivalent ion batteries, low-temperature batteries, redox flow batteries with soluble OEMs, and decoupled water electrolysis employing organic electrodes as redox mediators. We hope that this Account will make an invaluable contribution to the development of organic electrode materials for next-generation batteries and help to unlock a world of potential energy storage applications.

Improved rate and cycling capability of V2O5@MoS2 nanocomposites as an advanced cathode material for rechargeable aqueous zinc-ion batteries

Owing to the benefits of higher energy density, reliable safety, and eco-friendliness, rechargeable aqueous zinc (Zn)-ion batteries (RAZIBs) are employed in energy storage applications. Nevertheless, the enhancement of potential cathodes is hindered by low reversibility and sluggish Zn-ion diffusion kinetics, causing deficient rate capability and modest cycling performance. Vanadic anhydride (V2O5) provides a potential in RAZIBs from its layered structure and superior capacity. Herein, molybdenum disulfide (MoS2) was combined into the V2O5 to form V2O5@MoS2 nanocomposites (NCs) via a simple hydrothermal method. The V2O5@MoS2 NCs enable Zn ions to migrate effectively between layers and stabilize volume changes during the insertion/extraction process. Moreover, the presence of MoS2 as a mediator in the framework produces additional defects, which leads to an enhanced storage area for Zn ions. The optimized V2O5@MoS2–2 NCs exhibited a cycling capacity of 230.74 mA h g−1 at 0.5 A g−1, superior rate performance (73.59 mA h g−1 at 30 A g−1), and excellent long-term cycling stability (108.16 mA h g−1 at 10 A g−1 over 6000 cycles), surpassing those of V2O5@MoS2–1, V2O5@MoS2–3, V2O5, and MoS2 counterparts. Such fascinating properties reveal that the proposed composite materials as a progressive cathode for RAZIBs.

Bimetallic Selenide CuFeSe2 as Mg‐Storage Material for Rechargeable Magnesium Batteries

AbstractRechargeable magnesium batteries (RMBs) are appealing alternatives for energy storage systems based on the high theoretical capacity, low price and high security of the Mg metal anode. Nevertheless, the shortage of high‐performance cathode materials severely obstructs its development. As an important conversion material, transition metal selenides, with desirable theoretical capacity and weak bond energy (Mg−Se), have attracted more attention in recent years. In this study, CuFeSe2 (CFS) nanoparticles were produced by a hydrothermal approach and its feasibility as a cathode material for RMBs was further investigated. Given the synergistic effect between Cu and Fe, the optimized CFS shows a reversible capacity of 120 mAh g−1 at 100 mA g−1, outstanding long‐term cyclability (86 mAh g−1 at 1 A g−1 after 600 cycles), and prominent rate capability (85 mAh g−1 at 1 A g−1). Density functional theory (DFT) computations conclude CFS exhibits a suitable migration barrier for Mg2+ along the tunnel of 0.92 eV. An in‐depth investigation of the mechanism demonstrates that the Mg storage process can be divided into solid solution reaction and the conversion processes by ex‐situ techniques. This work contributes to further investigate the Mg2+ storage mechanism of cathode materials for RMBs.

Heavily vanadium-doped LiFePO4 olivine as electrode material for Li-ion aqueous rechargeable batteries

Since LiFePO4 batteries play a major role in the transition to safe, more affordable and sustainable energy production, numerous strategies have been applied to modify LFP cathode, with the aim of improving its electrochemistry. In this contribution, a highly vanadium-doped LiFe0.9V0.1PO4/C composite (LFP/C-10V) is synthesized using the glycine combustion method and characterized by x-ray diffraction (XRD), X-ray photoelectron spectroscopy (XPS), Thermogravimetry Differential Thermal Analysis (TGDTA) and Cyclic Voltammetry (CV). It is shown that 10wt.% of vanadium can substitute Fe positions, thus decreasing unit cell volume, which is followed by generation of Li3V2PO4 traces, as detected by CV. High vanadium doping does not change the carbon content in the composite (≈13 wt%) but improves its electronic conductivity and electrochemical performance in both aqueous and organic electrolytes. The reversibility and current response are increasing following the trend: LFP/C, LFP/C -3mol%V, LFP/C - 5 mol % and LFP/C-10 mol %. The best specific capacity is obtained for the most highly doped olivine, which exhibits a reversible process at 1 mV s−1 in an aqueous electrolyte, thus showing a peak-to-peak distance of 56 mV. The high capacity of LFPC-10V is measured in both LiNO3 and NaNO3 electrolytes amounting to around 100 mAh g−1 at 20 mV s−1. Still, the material is only stable in LiNO3 electrolyte, making it more suitable for Li than Na-ion aqueous rechargeable batteries.

Fine nanostructure design of metal chalcogenide conversion-based cathode materials for rechargeable magnesium batteries

Fine nanostructure design of metal chalcogenide conversion-based cathode materials for rechargeable magnesium batteries

High mass loading potassium ion stabilized manganese dioxide nanowire forests for rechargeable Zn batteries

Manganese dioxide (MnO2) represents an ideal cathode material for rechargeable aqueous Zn batteries due to its high theoretical capacity (308 mAh g−1), suitable potential (1.4 V vs. Zn2+/Zn), natural abundance, and negligible toxicity. However, the capacity and rate capability of MnO2 deteriorate significantly in thick electrodes owing to its low electrical and ionic conductivities. Herein, we report the design of high mass loading potassium ion stabilized α-MnO2 (K0.133MnO2) nanowire forests on carbon cloth through a seed-assisted hydrothermal method for Zn batteries. The vertically aligned K0.133MnO2 nanowire forests with uninterrupted charge transport afford a high area capacity of 3.54 mAh cm−2 and a capacity retention of 79.2% over 1000 cycles in aqueous electrolyte. Moreover, the high area capacity and cyclability can be readily transferred to quasi-solid-state devices.

Lithiophilic ZnCu alloy sites on copper current collector for high performance Li metal anode

Lithium (Li) metal has been widely regarded as the optimal anode material for the high-energy density rechargeable batteries, due to its ultrahigh theoretical specific capacity and lowest electrochemical potential. However, the formation of Li dendrites presents a significant safety concern, which limits its practical application. In this paper, to address this issue, an efficient and cost-effective strategy was proposed to prepare a zinc-copper composite collector (ZCC) with outstanding electrochemical performance, which can effectively suppress the formation of lithium dendrites. The lithophilic surface with ZnCu alloy nanoparticles was achieved through physical vapor deposition followed by annealing treatment. The ZCC collector enables dendrite-free deposition of Li due to its negligible nucleation overpotential. Even at high area capacity of 3 mAh cm−2 at 1 mA cm−2 in half-cells, the ZCC exhibits exceptional cycling performance and high coulomb efficiency. Preloaded with Li, the composite electrode (Li/ZCC) delivers an enhanced lifespan with low overpotential evidently. Matched with LiFePO4 (LFP) cathode, LFP||Li/ZCC full cells reveal a superior cycling stability with enhanced capacity retention of 85 % (after 1000 cycles at 1 C) and 87 % (after 800 cycles at 3 C) respectively.

Phytic Acid Customized Hydrogel Polymer Electrolyte and Prussian Blue Analogue Cathode Material for Rechargeable Zinc Metal Hydrogel Batteries.

Zinc anode deterioration in aqueous electrolytes, and Zn dendrite growth is a major concern in the operation of aqueous rechargeable Zn metal batteries (AZMBs). To tackle this,the replacement of aqueous electrolytes with a zinc hydrogel polymer electrolyte (ZHPE) is presented in this study. This method involves structural modifications of the ZHPE by phytic acid through an ultraviolet (UV) light-induced photopolymerization process. The high membrane flexibility, high ionic conductivity (0.085Scm-1), improved zinc corrosion overpotential, and enhanced electrochemical stability value of ≈2.3V versus Zn|Zn2+ show the great potential of ZHPE as an ideal gel electrolyte for rechargeable zinc metal hydrogel batteries (ZMHBs). This is the first time that the dominating effect of chelation of phytic acid with M2+ center over H-bonding with water is described to tune the gel electrolyte properties for battery applications. The ZHPE shows ultra-high stability over 360h with a capacity of 0.50mAhcm-2 with dendrite-free plating/stripping in Zn||Zn symmetric cell. The fabrication of the ZMHB with a high-voltage zinc hexacyanoferrate (ZHF) cathode shows a high-average voltage of ≈1.6V and a comparable capacity output of 63mAhg-1 at 0.10Ag-1 of the current rate validating the potential application of ZHPE.

Achieving Highly Stable Zn Metal Anodes at Low Temperature via Regulating Electrolyte Solvation Structure.

Zinc metal is an attractive anode material for rechargeable aqueous Zn-ion batteries (ZIBs). However, the dendrite growth, water-induced parasitic reactions and freezing problem of aqueous electrolyte at low temperatures are the major roadblocks that hinder the widely commercialization of ZIBs with Zn anodes. Herein, tetrahydrofuran (THF) is proposed as the electrolyte additive to improve the reversibility and stability of Zn anode. Theoretical calculation and experimental results reveal that the introduction of THF into the aqueous electrolyte can optimize the solvation structure and preferentially form solvated clusters with Zn2+, which can effectively alleviate the H2O-induced side reactions and protect Zn anode from being corrosion. While, THF molecules have stronger affinity for Zn2+ compared to H2O, which can greatly enhance the reversibility of Zn plating/stripping and suppress the formation of Zn dendrite. Moreover, THF can act as hydrogen bond acceptor to interact with H2O, which can greatly reduce the activity of free H2O in electrolyte and improve the low-temperature electrochemical performance of Zn anode. As a result, the Zn anodes demonstrate a high cyclic stability for 2800h at 27°C and over 4000h at -10°C at 1mA cm-2 with an areal capacity of 1 mAh cm-2. The full cell with NaV3O8∙1.5H2O cathode and Zn anode exhibits an excellent cyclic stability and rate capability at 27 and -10°C. This work is expected to provide a new approach to regulate the aqueous electrolyte and Zn anode interface chemistry for highly stable and reversible Zn anodes. This article is protected by copyright. All rights reserved.

Triazacoronene‐Based 2D Conductive Metal–Organic Framework for High‐Capacity Lithium Storage

Abstract2D conductive metal–organic frameworks (2D c‐MOFs) have attracted increasing attention as promising electrode materials for rechargeable batteries due to their designable periodic motifs, large specific surface areas, and prominent electrical conductivity. However, the development of 2D c‐MOF electrode materials with functionality remains a significant challenge because of the limited electroactive ligand motifs available. Herein, a hexahydroxy‐substituted triazacoronene ligand (6OH‐TAC) is deliberately designed and synthesized, which coordinates with Cu2+ ions to form an unprecedented 2D c‐MOF (Cu‐TAC) with functionality sites of efficient lithium storage. The synergistic effect of TAC and CuO4 enables Cu‐TAC as an anode for lithium‐ion batteries with a superior reversible capacity of 772.4 mAh g−1 at 300 mA g−1, remarkable rate performance, and outstanding long‐term cyclability (83% capacity retention at 300 mA g−1 for 600 cycles). These metrics outperform almost all 2D c‐MOF‐based electrodes, shedding light on new opportunities for energy storage devices.

Recent Progress on Cathode Materials for Rechargeable Zinc Ion Batteries

Due to their low cost, high capacity, mild assembly and testing conditions, as well as environmentally friendly characteristics, rechargeable zinc ion batteries (RZIBs) have attracted more and more attention. RZIBs have a broad development prospect and may partly replace the traditional batteries in the near future. Tremendous efforts have been devoted to developing various of high‐efficient cathode materials for improving comprehensive performances of RZIBs. However, many problems such as poor electron/ion conductivity, weak structural stability and complex energy storage mechanisms still exist in current cathode materials which hinder the practical application of RZIBs. This paper presents a timely review on recent progresses and challenges in cathode materials for rechargeable zinc ion batteries (RZIBs). Various types of reported cathode materials for RZIBs are summarized, their electrochemical performances were compared and their probable working mechanisms are investigated with the association of computational chemistry. Moreover, the existing problems and expected development directions of these materials were further discussed.

Electron paramagnetic resonance as a tool to determine the sodium charge storage mechanism of hard carbon

Hard carbon is a promising negative electrode material for rechargeable sodium-ion batteries due to the ready availability of their precursors and high reversible charge storage. The reaction mechanisms that drive the sodiation properties in hard carbons and subsequent electrochemical performance are strictly linked to the characteristic slope and plateau regions observed in the voltage profile of these materials. This work shows that electron paramagnetic resonance (EPR) spectroscopy is a powerful and fast diagnostic tool to predict the extent of the charge stored in the slope and plateau regions during galvanostatic tests in hard carbon materials. EPR lineshape simulation and temperature-dependent measurements help to separate the nature of the spins in mechanochemically modified hard carbon materials synthesised at different temperatures. This proves relationships between structure modification and electrochemical signatures in the galvanostatic curves to obtain information on their sodium storage mechanism. Furthermore, through ex situ EPR studies we study the evolution of these EPR signals at different states of charge to further elucidate the storage mechanisms in these carbons. Finally, we discuss the interrelationship between EPR spectroscopy data of the hard carbon samples studied and their corresponding charging storage mechanism.

Identifying the plateau sodium storage behavior of hard carbon through the spin state

Hard carbon has emerged as a promising anode material for rechargeable sodium-ion batteries, owing to its abundant precursor sources and remarkable reversible charge storage capacity. The key to achieving an extended sodium storage capacity lies in the plateau capacity largely associated with the closed-pore structure, yet a comprehensive understanding in this area remains incomplete. In our study, we utilized electron paramagnetic resonance (EPR) spectra to discern the spin state of unpaired electrons within hard carbon materials, enabling the identification of sodium storage plateau regions. Hard carbon anodes with plateau capacity predominantly exhibit delocalized spins, evident in the EPR spectrum by limited spin density and a linewidth exceeding 100 G. These spins originate from the extended aromatic structure within small-sized but curved nano-graphite and the closed-pore walls, which are crucial for plateau capacity. Conversely, hard carbon anodes exclusively possessing slope capacity are characterized by localized spins, presenting a typical narrow and intense Lorentzian EPR signal. These localized spins arise from the edge defects of the nano-graphite structure, serving as favourable sites for sodium adsorption. Our development of a methodology to discern hard carbon plateau capacity behavior based on EPR spectra presents a facile and rapid approach for advancing high-performance hard carbon materials.

Accessing Mg‐Ion Storage in V2PS10 via Combined Cationic‐Anionic Redox with Selective Bond Cleavage

AbstractMagnesium batteries attract interest as alternative energy‐storage devices because of elemental abundance and potential for high energy density. Development is limited by the absence of suitable cathodes, associated with poor diffusion kinetics resulting from strong interactions between Mg2+ and the host structure. V2PS10 is reported as a positive electrode material for rechargeable magnesium batteries. Cyclable capacity of 100 mAh g−1 is achieved with fast Mg2+ diffusion of 7.2 10−11–4 10−14 cm2 s−1. The fast insertion mechanism results from combined cationic redox on the V site and anionic redox on the (S2)2− site; enabled by reversible cleavage of S−S bonds, identified by X‐ray photoelectron and X‐ray absorption spectroscopy. Detailed structural characterisation with maximum entropy method analysis, supported by density functional theory and projected density of states analysis, reveals that the sulphur species involved in anion redox are not connected to the transition metal centres, spatially separating the two redox processes. This facilitates fast and reversible Mg insertion in which the nature of the redox process depends on the cation insertion site, creating a synergy between the occupancy of specific Mg sites and the location of the electrons transferred.

Accessing Mg-Ion Storage in V2PS10 via Combined Cationic-Anionic Redox with Selective Bond Cleavage.

Magnesium batteries attract interest as alternative energy-storage devices because of elemental abundance and potential for high energy density. Development is limited by the absence of suitable cathodes, associated with poor diffusion kinetics resulting from strong interactions between Mg2+ and the host structure. V2PS10 is reported as a positive electrode material for rechargeable magnesium batteries. Cyclable capacity of 100 mAh g-1 is achieved with fast Mg2+ diffusion of 7.2 10-11-4 10-14 cm2 s-1. The fast insertion mechanism results from combined cationic redox on the V site and anionic redox on the (S2)2- site; enabled by reversible cleavage of S-S bonds, identified by X-ray photoelectron and X-ray absorption spectroscopy. Detailed structural characterisation with maximum entropy method analysis, supported by density functional theory and projected density of states analysis, reveals that the sulphur species involved in anion redox are not connected to the transition metal centres, spatially separating the two redox processes. This facilitates fast and reversible Mg insertion in which the nature of the redox process depends on the cation insertion site, creating a synergy between the occupancy of specific Mg sites and the location of the electrons transferred.

Dynamic Molecular Interphases Regulated by Trace Dual Electrolyte Additives for Ultralong-Lifespan and Dendrite-Free Zinc Metal Anode.

Metallic zinc is a promising anode material for rechargeable aqueous multivalent metal-ion batteries due to its high capacity and low cost. However, the practical use is always beset by severe dendrite growth and parasitic side reactions occurring at anode/electrolyte interface. Here we demonstrate dynamic molecular interphases caused by trace dual electrolyte additives of D-mannose and sodium lignosulfonate for ultralong-lifespan and dendrite-free zinc anode. Triggered by plating and stripping electric fields, the D-mannose and lignosulfonate species are alternately and reversibly (de-)adsorbed on Zn metal, respectively, to accelerate Zn2+ transportation for uniform Zn nucleation and deposition and inhibit side reactions for high Coulombic efficiency. As a result, Zn anode in such dual-additive electrolyte exhibits highly reversible and dendrite-free Zn stripping/plating behaviors for >6400 hours at 1 mA cm-2, which enables long-term cycling stability of Zn||ZnxMnO2 full cell for more than 2000 cycles.

Research progress on lignin-based carbon electrode materials in rechargeable batteries

Lignin, with its carbon content of up to 60%, can be an ideal precursor for the preparation of carbon materials. Carbonaceous materials obtained from lignin can be transformed into porous and structural morphologies at different scales, providing a biomass approach to energy conversion and storage in batteries. Focusing on lignin-derived carbon materials, this paper summarizes the different morphologies and structures of lignin-based carbon obtained through different preparation methods, and the different electrochemical properties exhibited by these materials as electrode materials for rechargeable batteries (lithium-ion batteries, sodium-ion batteries, lithium-sulphur batteries, etc.). In addition, the development prospects and challenges of lignin-based carbon materials in the field of rechargeable batteries are summarized, providing ideas for the next step in the design and development of high-performance lignin-based carbon-based electrode materials.

CoNi hexacyanoferrate nanoparticles anchored on carbon nanotubes as superior cathode materials for rechargeable aqueous zinc-ion batteries

Prussian blue analogues (PBAs) have attracted growing interest as competitive cathode materials for aqueous zinc-ion batteries (AZIBs). However, their low conductivity and easy structural collapse often lead to poor reversible capacity and cyclability. Herein, cobalt‑nickel hexacyanoferrate (CoNiHCF), a CoNi-Prussian blue analogue, are designed as AZIBs cathode materials for the first time, in which highly uniform CoNiHCF nanocubes are in-situ decorated on carbon nanotubes (CNTs) via a simple co-precipitation method. The resulted CoNiHCF/CNTs composite displays superior zinc ion storage performance, with a great reversible capacity of 124.9 mAh g−1 at the current density of 50 mA g−1, and a high capacity retention of 81.8 % at 3000 mA g−1 for 1000 cycles, which are remarkably superior to those of CoHCF, NiHCF and CoNiHCF. The excellent Zn2+ storage properties of CoNiHCF/CNTs can be ascribed to the bimetallic synergistic effect of Co and Ni as well as the introduction of conductive CNTs skeleton. This study offers a straightforward and efficient method for promoting the application of PBAs-based cathodes in AZIBs.