Metal-ion Batteries Research Articles

Recent advances in porous multimetallic alloy-based anodes for rechargeable alkali metal-ion batteries

Recent advances in porous multimetallic alloy-based anodes for rechargeable alkali metal-ion batteries

Dual-Steric Hindrance Modulation of Interface Electrochemistry for Potassium-Ion Batteries.

Electrolyte chemistry regulation is a feasible and effective approach to achieving a stable electrode-electrolyte interface. How to realize such regulation and establish the relationship between the liquid-phase electrolyte environment and solid-phase electrode remains a significant challenge, especially in solid electrolyte interphase (SEI) for metal-ion batteries. In this work, solvent/anion steric hindrance is regarded as an essential factor in exploring the electrolyte chemistry regulation on forming ether-based K+-dominated SEI interface through the cross-combination strategy. Theoretical calculation and experimental evidence have successfully indicated a general principle that the combination of increasing solvent steric hindrance with decreasing anion steric hindrance indeed prompts the construction of an ideal anion-rich sheath solvation structure and guarantees the cycling stability of antimony-based alloy electrode (Sb@3DC, Sb nanoparticles anchored in three-dimensional carbon). These confirm the critical role of electrolyte modulation based on molecular design in the formation of stable solid-liquid interfaces, particularly in electrochemical energy storage systems.

Cu-doped graphene Cu/N2OG: A high-performance alkaline metal ion battery anode with record-theoretical capacity

Anode materials are paramount in dictating the performance of ion batteries. Therefore, the judicious design of novel anode materials boasting superior capacity is crucial to further enhancing the energy density of ion batteries. This study employs first-principles computational methods to systematically investigate the performance of Cu-doped graphene 2D material (Cu/N2OG) as an Li-ion batteries (LIBs), Na-ion batteries (NIBs), or K-ion batteries (KIBs) anode. Simulation results indicate that the structural asymmetry introduced by Cu doping significantly increases the active sites of the material, enhancing its theoretical specific capacity for Li/Na/K. Notably, the sodium storage theoretical capacity of Cu/N2OG reaches an impressive 3303.7 mAh/g, surpassing the capacity of all currently employed NIBs anode materials. Furthermore, Cu/N2OG also boasts high theoretical capacities, yielding capacities of 1651.8 mAh/g for LIBs and 1263.2 mAh/g for KIBs, respectively. The material retains excellent conductivity both prior to and following the adsorption of Li, Na, and K. Furthermore, Cu/N2OG demonstrates a low diffusion barrier and minimal lattice changes (<1 %), suggesting its potential as a high-performance anode for LIBs/NIBs/KIBs.

Two-dimensional Zr2C monolayer as anode material for Li, Na and K ion batteries

In this paper, the electronic properties and storage capacity of Zr2C after adsorption of Li, Na, and K metal ions are systematically investigated with density-functional theory (DFT) based on first-principles calculations. For Li, Na, and K ion adsorption, the negative adsorption energy indicates a strong interaction between the metal ions and the two-dimensional (2D) Zr2C monolayer, which prevents the formation of dendrites, and the adsorbed system has good metallic properties with low diffusion barriers, suitable open-circuit voltages, and high theoretical storage capacities. Our study shows that Zr2C monolayer is a promising anode material for metal-ion batteries.

Recent Advances in High-Entropy Layered Oxide Cathode Materials for Alkali Metal-Ion Batteries.

Since the electrochemical de/intercalation behavior is first detected in 1980, layered oxides have become the most promising cathode material for alkali metal-ion batteries (Li+/Na+/K+; AMIBs) owing to their facile synthesis and excellent theoretical capacities. However, the inherent drawbacks of unstable structural evolution and sluggish diffusion kinetics deteriorate their electrochemical performance, limiting further large-scale applications. To solve these issues, the novel and promising strategy of high entropy has been widely applied to layered oxide cathodes for AMIBs in recent years. Through multielement synergy and entropy stabilization effects, high-entropy layered oxides (HELOs) can achieve adjustable activity and enhanced stability. Herein, the basic concepts, design principles, and synthesis methods of HELO cathodes are introduced systematically. Notably, it explores in detail the improvements of the high-entropy strategy on the limitations of layered oxides, highlighting the latest advances in high-entropy layered cathode materials in the field of AMIBs. In addition, it introduces advanced characterization and theoretical calculations for HELOs and proposes potential future research directions and optimization strategies, providing inspiration for researchers to develop advanced HELO cathode materials in the areas of energy storage and conversion.

Unveiling BaTiO3-SrTiO3 as Anodes for Highly Efficient and Stable Lithium-Ion Batteries.

Amidst the swift expansion of the electric vehicle industry, the imperative for alternative battery technologies that balance economic feasibility with sustainability has reached unprecedented importance. Herein, we utilized Perovskite-based oxide compounds barium titanate (BaTiO3) and strontium titanate (SrTiO3) nanoparticles as anode materials for lithium-ion batteries from straightforward and standard carbonate-based electrolyte with 10% fluoroethylene carbonate (FEC) additive [1M LiPF6 (1:1 EC: DEC) + 10% FEC]. SrTiO3 and BaTiO3 electrodes can deliver a high specific capacity of 80 mA h g-1 at a safe and low average working potential of ≈0.6 V vs. Li/Li+ with excellent high-rate performance with specific capacity of ~90 mA h g-1 at low current density of 20 mA g-1 and specific capacity of ~80 mA h g-1 for over 500 cycles at high current density of 100 mA g-1. Our findings pave the way for the direct utilization of perovskite-type materials as anode materials in Li-ion batteries due to their promising potential for Li+ ion storage. This investigation addresses the escalating market demands in a sustainable manner and opens avenues for the investigation of diverse perovskite oxides as advanced anodes for next-generation metal-ion batteries.

Sodium Vanadates for Metal-Ion Batteries: Recent Advances and Perspectives.

Rechargeable metal-ion batteries (MIBs) play a pivotal role in advancing the stable supply of renewable energy by efficiently storing and discharging electrical energy. In recent years, to propel the continuous advancement of MIB technology, numerous studies have concentrated on exploring and innovating electrode materials, aiming to engineer commercial batteries with high energy density, superior power density, and extended cycle life. Notably, sodium vanadates have garnered significant attention in the realm of MIBs owing to their distinctive crystal structures, abundant resource reservoirs, and exceptional electrochemical properties. This paper provides a prompt and comprehensive review of the research landscape for various sodium vanadates (such as NaxV2O5, Na1+ xV3O8, Na2V6O16·xH2O, etc.) in the domain of MIBs over the past five years. It delves into the structural characteristics, electrochemical performances, and energy storage mechanisms of these materials, while also proposing some effective strategies to augment their electrochemical capabilities. Building upon these insights and prevailing research outcomes, this review envisions the future developmental pathways of sodium vanadates for MIBs and aims to reveal the vast potential of sodium vanadates in the emerging energy storage field and provide researchers with clear insights and perspectives for developing optimal sodium vanadate electrodes.

The Development and Prospect of Stable Polyanion Compound Cathodes in LIBs and Promising Complementers.

Cathode materials are usually the key to determining battery capacity, suitable cathode materials are an important prerequisite to meet the needs of large-scale energy storage systems in the future. Polyanionic compounds have significant advantages in metal ion storage, such as high operating voltage, excellent structural stability, safety, low cost, and environmental friendliness, and can be excellent cathode options for rechargeable metal-ion batteries. Although some polyanionic compounds have been commercialized, there are still some shortcomings in electronic conductivity, reversible specific capacity, and rate performance, which obviously limits the development of polyanionic compound cathodes in large-scale energy storage systems. Up to now, many strategies including structural design, ion doping, surface coating, and electrolyte optimization have been explored to improve the above defects. Based on the above contents, this paper briefly reviews the research progress and optimization strategies of typical polyanionic compound cathodes in the fields of lithium-ion batteries (LIBs) and other promising metal ion batteries (sodium ion batteries (SIBs), potassium ion batteries (PIBs), magnesium ion batteries (MIBs), calcium ion batteries (CIBs), zinc ion batteries (ZIBs), aluminum ion batteries (AIBs), etc.), aiming to provide a valuable reference for accelerating the commercial application of polyanionic compound cathodes in rechargeable battery systems.

Dual zinco-phobic/-philic ferroelectric nanorods coated mesh for stable Zn anode

Aqueous Zn-ion batteries are emerging as a promising option for energy storage systems due to their safety and environmental benefits. However, their stability and reversibility are often hindered by dendrite growth and interfacial side reactions. In this study, we introduce an innovative strategy to address these issues by engineering an artificial interfacial layer (AIL) on Zn anode surface. This AIL is composed of a dual zinco-phobic/-philic ferroelectric nanorods (FE NRs) mesh, which contrasts with the traditional BaTiO3 nanoparticles. The BTO NRs, particularly those with exposed P4/mmm (100) and (211) facets enriched with oxygen vacancy, facilitate a partial phase transition from the FE tetragonal P4mm phase to the paraelectric tetragonal P4/mmm phase, thereby creating dual zinco-phobic/-philic sites. Additionally, the integration of microchannels within the FE BTO NRs mesh can efficiently modulate the electric field distribution and Zn2+ concentration, leading to a more uniform Zn deposition, as conformed by electrochemical simulations. The Zn anode coated with the FE BTO NRs mesh exhibits impressive performance, achieving an ultralong cycle life of 3050 h at 1 mA cm−2 and 1mAh cm−2. It sustains a Coulombic efficiency exceeding 99.8 % over 2000 cycles, highlighting its exceptional reversibility. These findings underscore the potential of the dual zinco-phobic/-philic FE NRs mesh in overcoming the challenges faced in aqueous metal-ion batteries, showcasing its versatility and the significant performance enhancements it can offer.

Very High-Capacity Li/Na-Ion battery anodes Enabled by Blue phosphorene and boron phosphide vdW heterostructure

The fascinating features of van der Waals heterostructure (vdWH) based electrodes and their potential to overcome the limiting properties of single-material systems have sparked a great deal of scientific attention. In this study, we investigate the potential of a blue phosphorene/boron phosphide (Blue-P/BP) vdWH as an anode material for both lithium-ion (Li-ion) and sodium-ion (Na-ion) batteries using first-principles calculations. We suggest that this vdWH could act as an effective anode material for metal-ion batteries, due to their high theoretical capacity and strong binding strength. Intriguingly, the theoretical specific capacity exhibits remarkable values, notably reaching 4510 mAhg−1 for Li and 3849 mAhg−1 for Na, which surpasses all capacities reported in the existing literature. Additionally, electronic structure calculations reveal a significant charge transfer that enhances the metallic characteristics, thereby increasing electrical conductivity. As we delve deeper into the electronic structure and calculate diffusion barriers and pathways, we observe that ionic diffusion (∼0.12/0.11 eV) is notably rapid compared to graphitic anodes (∼0.2 eV). We also found that intercalating Li/Na atoms in the Blue-P/BP vdWH results in low operating potentials of 0.38 V for Li and 0.34 V for Na. This research highlights the substantial enhancement of electrochemical performance of Blue-P/BP vdWH and holds great promise as high-power-density anode materials for Li/Na-ion batteries, facilitating rapid charge and discharge rates.

Effective CuO/Cu7S4 nanospheres heterostructures for advanced “rocking-chair” zinc-ion battery

Rechargeable aqueous zinc-ion batteries (ZIBs) have attracted considerable attention for energy storage owing to their environmental friendliness and high safety. However, the adverse side reactions and unsatisfactory cycle life brought by Zn-metal anodes limit their large applications. Herein, CuO/Cu7S4 (CSO) heterostructured hollow nanospheres is proposed as an attractive conversion-type Zn-metal-free anode for “rocking-chair” ZIBs. The CSO/graphite self-supporting electrode delivers a high capacity of 271 mAh/g at current density of 0.1 A/g and a superior cyclic stability of 1200 cycles. Based on the excellent electrochemical performance of CSO/graphite electrode, we have constructed a self-powered pressure sensor integrated system using the “rocking-chair” zinc ion battery as the power source, demonstrating significant practicality. This work provides a high-performance conversion type anode material for aqueous multivalent metal ion batteries.

Chemo-mechanical instabilities in lithium cobalt oxide at higher state-of-charge in Li-Ion batteries

Transition metal oxide cathodes are widely used in commercial Li-ion batteries. However, their practical charge capacity is limited due to severe chemo-mechanical instabilities at higher charge voltage, and state-of-charge condition. Here, in situ stress and strain measurements were synchronized to probe mechanical deformations in the lithium cobalt oxide (LCO) cathode via a multi-beam stress sensor and digital image correlation, respectively. In situ mechanical measurements revealed how Li removal from the electrode structure induces deformations on the LCO composite cathodes during cycling. The structure and morphology of the LCO cathodes were further investigated by X-ray diffraction (XRD) and scanning electron microscopy (SEM) studies. Two distinct electrochemical and mechanical behaviors were identified when the LCO was charged up to 4.65 V. The LCO undergoes a compressive stress generation when charged up to 4.2 V and surface fractures on the LCO particles were detected by SEM. LCO cathode experienced significantly large contractions (negative strains) when charged up to 4.65 V, where intergranular crack formation and phase transformation were detected on the LCO particles via SEM and XRD, respectively. Overall, the study bridges complicated structural deformations with in situ analysis of mechanical degradations in LCO cathodes charged at higher voltages. The correlation is vital to understanding instability mechanisms in transition metal oxides at high voltages for alkali metal ion batteries.

Covalent Organic Frameworks (COFs): A New Class of Materials for Multivalent Metal‐Ion Energy Storage Systems

The rise of electronic societies is driving a surge in the demand for energy storage solutions, particularly in the realm of renewable energy technologies like batteries, which rely heavily on efficient electrode materials and separators. As an answer to this necessity, Covalent Organic Frameworks (COFs) are emerging and a highly intriguing class of materials, garnering increased attention in recent years for their extensive properties and possible applications. This review addresses the remarkable versatility and boundless potential of COFs in scientific fields, mainly focusing on multivalent metal ion batteries (MMIBs), which include AIB (Aluminium‐ion batteries), MIB (Magnesium‐ion battery), CIB (Calcium‐ion battery), and ZIB (Zinc‐ion battery), as both electrode materials and separators across a spectrum of battery technology. Inclusive of their approaches, merits, and reaction mechanisms, this review offers an extensive summary of COFs concerning multivalent ion batteries. By providing a rigorous analysis of COF attributes, electrochemical behaviour, and methodologies, our explanation contributes to a deeper understanding of their potential in advancing battery technology.

Exploring the potential of two-dimensional MB4 (M=Cr, Mo, and W) monolayer as a high-capacity negative electrode material for Al-ion batteries

Rechargeable metal-ion batteries can employ two-dimensional transition metal tetraboride monolayers because of their numerous accommodating sites, high specific surface area, and layered structure. Li-ion batteries (LIBs) can be efficiently replaced by aluminum ion batteries (AIBs) because aluminum is a cheap and abundant resource. In this work, the density functional theory approach has been used for Al-ion batteries to predict MB4(M= Cr, Mo, W) monolayers performance as anode material. We analyze these monolayers' structures, which are mechanically, thermally, and dynamically stable. Utilizing the energy-efficient adsorption of six Al-atom layers and their lightweight properties, with large storage capacities of 5066 mA h g−1, 3466 mA h g−1, and 2124 mA h g−1, with relatively low average open circuit voltages of 0.18 V, 0.15 V, and 0.11 V for CrB4, MoB4, and WB4, respectively, these monolayers show significant superiority over other 2D anode materials. Likewise, MB4 monolayer showed faster Al ion mobility as seen by the low activation barriers of 0.95 eV, 0.83 eV, and 0.49 eV for CrB4, MoB4, and WB4, respectively. Additionally, even after the full content of Al ions was adsorbed, the metallic characteristics of the materials were mostly retained. These traits suggest that monolayer CrB4, MoB4, and WB4 are promising anode materials for AIBs, with impressive rate capacities.

Strain Engineering of ScYCCl2 MXene Monolayer and Intercalation of Metal-ions on MXene Surface: A DFT Study

The present work theoretically examines the influence of bi-axial strain on functionalized ScYCCl2 monolayer. The indirect to direct band gap transition on tensile conditions and the phase transition from semiconductor to metal on compressive strain have been studied. The analysis of extreme conditions of 10% compressive and 10% tensile strain through phonon and AIMD simulations underscore the kinetic and thermal stability, respectively of the monolayer under strain. These findings assure the possibility of experimental synthesis of the ScYCCl2 monolayer. After metallization, ScYCCl2 MXene is used as an anode of metal-ion (−Na, −K, −Li, −Mg) batteries as it has high theoretical storage capacity and low open circuit voltage. Work function engineering and the strain-dependent optical behavior of the ScYCCl2 monolayer have been examined. The work function of the ScYCCl2 monolayer has been raised under compressive strain and decreased under tensile strain. The Crystal Orbital Hamiltonian Population has been simulated under tensile and compressive strain to check the bond- strengths. Hence, the ScYCCl2 monolayer has the capability to alter its characteristics under strain. The improved optical characteristics recommend its applications in low-dimensional photonic devices and metallization after compressive strain recommends its energy storage applications in metal-ion batteries.

Exploring Mo2B MBene as a high-capacity anode material for multi-valent metal-ion batteries: Insights from first-principles calculations

A novel class of 2-dimensional (2D) materials, known as MBenes, has recently been proposed as a promising candidate for electrode applications in metal-ion batteries due to their high conductivity and rich chemistry. In this study, we present a computational investigation into the potential of Mo2B MBene as an anode material for Na-, Mg-, and Al-ion batteries. Using density functional theory (DFT) calculations, we examine the structural, electronic, and electrochemical properties of both H- and T-type configurations of Mo2B. Our findings reveal that Mo2B exhibits metallic behavior and excellent metal adsorption characteristics, with Al exhibiting the strongest binding affinity, followed by Mg and Na. This strong binding, especially with Al, although results in higher diffusion barriers, it enhances layer adsorption leading to increased theoretical capacity. The calculated maximum capacities are significant, with Al (1323 mAh g−1) showing the highest capacity, followed by Mg (923 mAh g−1) and Na (216 mAh g−1). Additionally, the open-circuit voltage (OCV) for all metals ranges between 0.1 and 1.0 V, suggesting the suitability of Mo2B MBene as an anode material that minimizes dendrite formation risks. These results indicate the potential of Mo2B for high-performance multi-valence ion batteries, with particular promise for Al-ion batteries due to their superior capacity. Furthermore, we propose that strain engineering could optimize Mo2B for enhanced performance in Na-ion batteries. Overall, this study suggests Mo2B MBene as a highly promising anode material for next-generation metal-ion batteries, offering significant advantages in terms of capacity, voltage, and safety. Our findings provide insights that could be used for further experimental design of Mo2B-based anodes for energy storage technologies.

AB–stacked bilayer β12–borophene as a promising anode material for alkali metal-ion batteries

As the lightest 2D material, monolayer borophene exhibits a specific charge capacity of 1860 mA h g−1 for Li-ion batteries, which is four times higher than that of graphite and is one of the highest specific charge capacities ever reported for 2D anode materials. Additionally, it showed high mechanical strength and a low diffusion barrier. However, monolayer borophene suffers from stability issues in its free-standing form, which restricts its real-life applications. Inspired by the recent experimental investigations, which proved the higher stability of bilayer borophene polymorphs (BBPs) over their monolayer counterparts, in this work, we investigated the dynamical and thermodynamical stabilities of both AA– and AB–stacked BBPs in their β12 phase using first-principles calculations. Between the two stacking patterns, we found that only the AB–stacked β12–BBP is both energetically and dynamically stable, and we further investigated its potential as a high-performance anode material for alkali metal-ion batteries. Our investigations show that AB–stacked β12–BBP exhibits good electrical conductivity before and after metal atom (Li/Na/K) adsorption onto it. Further, AB–stacked β12–BBP adsorbs the metal atoms strongly with adsorption energies ranging between −0.89 to −1.44 eV, indicating that there is a lesser possibility of forming dendrites on this anode. Similarly, it has a low diffusion energy barrier (~ 0.13–0.49 eV) for metal atoms, meeting the fast charge/discharge rate requirements. Moreover, it exhibits a reasonably low average metal-insertion voltage (0.43 to 0.65 V) and a specific charge capacity of 330–413 mA h g−1 that is comparable to graphite. All the above findings suggest that the AB–stacked bilayer β12– borophene can be a potentially favorable anode material.

Unraveling the enhanced sodium-storage mechanism in a strongly bonded 2D honeycomb borophene/boron phosphide heterostructure

The growing modern demand for battery capacity is driving the development of high-capacity metal-ion battery anodes for future energy storage. Two-dimensional (2D) material-based heterostructures have shown advantages as alternative anodes due to their enhanced adsorption capacity. The lightweight nature of honeycomb borophene (HB) is beneficial for serving as a high-capacity anode but is constrained by structural instability arising from electron deficiency. In this study, using first-principles calculations, we propose a HB/boron phosphide (BP) heterostructure as an anode for both lithium-ion batteries and sodium-ion batteries (SIBs). The heterostructure engineering not only stabilizes the HB structure but also leads to a bonding heterostructure instead of common van der Walls type. The HB/BP demonstrates robust structural stability and reversibility when multiple ions are stored. In addition, the HB/BP offers stable storage sites and low diffusion barriers for lithium (0.31 eV) and sodium (0.28 eV), indicating rapid charging–discharging performance. Notably, the predicted maximum sodium storage capacity reaches 2402 mAh/g, surpassing that of the constituent monolayers and most 2D heterostructures. The underlying mechanism for high storage capacity is elucidated through detailed charge image model analysis, offering atomistic-scale insights for constructing high-capacity anodes. All results suggest that the presented HB/BP is a promising anode candidate for SIBs and opens an avenue for stabilizing HB in energy storage.

Functionalized MBene, Ti[formula omitted]BX[formula omitted] (X=Si, Ge, P, As) as potential excellent anode materials for lithium and sodium-ion batteries: A first-principles study

In the search for next-generation energy storage devices, superior-performance alternative electrode materials based on two-dimensional materials for rechargeable metal-ion batteries are essential. Here, we explored group III and IV functionalization of 2D Ti2B, Ti2BX2 (X=Si, Ge, P, As) as anode materials for Li and Na ion batteries using first-principles calculations. The structures had excellent metallic properties and demonstrated energetically favorable adsorptions for metal ions. Analyzing charge transfer and electronic band structures, silicon and phosphorous-functionalized Ti2B (Ti2BSi2 and Ti2BP2) showed the most potential. The energy band diagrams showed that both Ti2BSi2 and Ti2BP2 had metallic characteristics after Li and Na-ion adsorption, which offered considerable advantage for rechargeable-ion batteries. The structures exhibited low energy barriers for Li and Na-ion migration. The minimum energy barriers calculated for Na were 0.08 eV for Ti2BSi2 and 0.24 eV for Ti2BP2. Theoretical specific capacity and open circuit voltage were calculated using maximum layer adsorption. For both Li and Na, high values of specific capacity and low values of open circuit voltage (¡ 1 V) were found. Ti2BSi2 had the best performance, with a theoretical specific capacity of 1647.10 and 1317.68 mA h/g for Li and Na, respectively. Its open circuit voltages for Li and Na were 0.65 and 0.38 V. The insights of this study will be beneficial in fabricating high-performing Ti2BX2-based anodes for rechargeable Li and Na ion batteries.

High performance potassium/sodium-ion storage enabled by anchoring cobalt atoms on sulfur vacancies in WS2 nanosheets

Transition metal dichalcogenides (TMDs) as anodes have presented significant potential in alkali-ion batteries. Nevertheless, they are generally vulnerable to low conductivity and sluggish ion diffusion as well as severe volume variation. Here, a strategy of filling metal atoms into anion vacancies is proposed and applied to the example of WS2. More specifically, sulfur vacancies are produced and partially filled by Co atoms simultaneously in WS2 (denoted as Co@WS2-SV), creating a highly reactive micro-structure composed of Co-W-S, which can not only effectively provide more active sites, but also boost the charge transfer and reaction kinetics. Consequently, the as-prepared Co@WS2-SV exhibits superior K+ storage performance, which includes an ultrahigh reversible capacity of 382.9 mAh g−1 at 0.05 A g−1. Besides, Co@WS2-SV still maintain a capacity of 112.6 mAh g−1 after 1100 cycles at 2 A g−1 while the capacity fades to ∼0 mAh g−1 after only 800 cycles for WS2. Simultaneously, Co@WS2-SV also displays outstanding rate capability (338.7 mA h g−1 at 2 A g−1) and acceptable cycling performance (264.2 mA h g−1 at 1 A g−1 after 100 cycles) for sodium storage. The strategy in our study provides new way of precisely designing the other TMDs anodes for metal-ion batteries.