Metal-ion Batteries Research Articles

Theoretical prediction of the potential of using two-dimensional V2S2 as an effective anode for alkali metal ion batteries

This study investigates proper anode of alkali metal-ion batteries (MIBs) in response of urgent demand for effective devices for storing energy. The 2D V2S2 system can be a potential material as a MIB anode. We have employed the density functional formalism to examine the energetical, dynamic, mechanical, and thermal stability of pristine V2S2 monolayer. The pristine monolayer has inherent metallicity, which satisfies one of the criteria for being an electrode material. The electrical and structural characteristics of the V2S2 systems with the adsorbates of alkali metals and the charge transfer within the system are explored. The barriers of Li, Na, and K migration are computed as 0.42 eV, 0.12 eV, and 0.14 eV, respectively. In addition, our predicted systems demonstrate a significant theoretical capacity of 968.9 mAh/g of the lithium and sodium atoms. The computed open-circuit voltages support that this monolayer can be a practical 2D anode.

A Review of Ionic Liquids and Their Composites with Nanoparticles for Electrochemical Applications

The current study focuses on reviewing the actual progress of the use of ionic liquids and derivatives in several electrochemical application. Ionic liquids can be prepared at room temperature conditions and by including a solution that can be a salt in water, or a base or acid, and are composed of organic cations and many charge-delocalized organic or inorganic anions. The electrochemical properties, including the ionic and electronic conductivities of these innovative fluids and hybrids, are addressed in depth, together with their key influencing parameters including type, fraction, functionalization of the nanoparticles, and operating temperature, as well as the incorporation of surfactants or additives. Also, the present review assesses the recent applications of ionic liquids and corresponding hybrids with the addition of nanoparticles in diverse electrochemical equipment and processes, together with a critical evaluation of the related feasibility concerns in different applications. Those ranging from the metal-ion batteries, in which ionic liquids possess a prominent role as electrolytes and reference electrodes passing through the dye of sensitized solar cells and fuel cells, to finishing processes like the ones related with low-grade heat harvesting and supercapacitors. Moreover, the overview of the scientific articles on the theme resulted in the comparatively brief examination of the benefits closely linked with the use of ionic fluids and corresponding hybrids, such as improved ionic conductivity, thermal and electrochemical stabilities, and tunability, in comparison with the traditional solvents, electrolytes, and electrodes. Finally, this work analyzes the fundamental limitations of such novel fluids such as their corrosivity potential, elevated dynamic viscosity, and leakage risk, and highlights the essential prospects for the research and exploration of ionic liquids and derivatives in various electrochemical devices and procedures.

Augmenting specific capacitance of ammonium vanadate cathode in aqueous zinc-ion batteries via barium doping directed by glutamic acid

Aqueous Zinc-Ion Batteries (AZIB), as a promising class of multivalent metal-ion batteries, have garnered attention for their exceptional safety and extremely high theoretical capacity. Despite these advantages, their adoption has been impeded by a notable capacity shortfall relative to Lithium-Ion Batteries (LIB). Addressing this challenge, our research leverages glutamic acid as a chelating agent to craft barium-doped ammonium vanadate nanoflowers through a hydrothermal approach, serving as an innovative AZIB cathode material. The incorporation of barium ions has notably expanded the doping distance from 9.817 Å to 12.900 Å, markedly diminishing the diffusion resistance of Zn2+ ions and unveiling a plethora of active sites. These structural enhancements have fostered accelerated ion transport and bolstered redox kinetics. Our fabricated cathode material exhibits exceptional reversibility during the redox transitions between V5+/V4+ and V3+ and the zinc ion doping process. Utilizing BNVO-3 as the cathode, which presents an ideal crystal configuration, the AZIB achieved near-perfect Coulombic efficiency. Impressively, at a current density of 0.1 A g-1, it achieved a remarkable peak discharge capacity of 384.91 mAh g-1. Furthermore, after 1500 cycles at 5A g−1, it maintained an impressive 92.9 % capacity retention. This study heralds a new era for barium-doped vanadium-based AZIB cathodes, characterized by their high stability, reversibility, and capacity.

Relationship between functionalization and structural defect density of graphite for application in potassium-ion batteries

Potassium-ion batteries (PIBs) have recently gained attention as an alternative to Li-ion batteries (LIBs) because Li and K belong to the same alkali metal group and are replaceable. However, the theoretical capacity of PIBs is hindered by the larger size of potassium ions compared to lithium ions. Generally, the surface treatment of graphite, an anode material in metal-ion batteries, enhances ion diffusivity and improves electrochemical performance. In this study, a straightforward approach is introduced in which graphite is treated with an acid to widen the interlayer spacing and an alkali to create pores. Acid and alkali treatments not only improve ion diffusivity but also control the surface charge of graphite in PIBs. Consequently, acid-treated graphite (AG) displays the highest specific capacity (206.2 mAh g−1 at 0.2 A g−1 after 100 cycles) with good durability. In addition, the trade-off between the physical ion pathway derived from structural defect density and functionalization-induced surface charge improves ion diffusivity.

Rapid synthesis of two-dimensional MoB MBene anodes for high-performance sodium-ion batteries

Two-dimensional (2D) transition metal borides (MBenes) have emerged as a rising star and hold great potential promise for catalysis and metal ion batteries owing to a well-defined layered structure and excellent electrical conductivity. Unlike well-studied graphene, perovskite and MXene materials in various fields, the research about MBene is still in its infancy. The inadequate exploration of efficient etching methods impedes their further study. Herein, we put forward an efficient microwave-assisted hydrothermal alkaline solution etching strategy for exfoliating MoAlB MAB phase into 2D MoB MBenes with a well accordion-like structure, which displays a remarkable electrochemical performance in sodium ion batteries (SIBs) with a reversible specific capacity of 196.5 mAh g–1 at the current density of 50 mA g–1, and 138.6 mAh g–1 after 500 cycles at the current density of 0.5 A g–1. The underlying mechanism toward excellent electrochemical performance are revealed by comprehensive theoretical simulations. This work proves that MBene is a competitive candidate as the next generation anode of sodium ion batteries.

In-situ dynamic catalysis electrode electrolyte interphase enabling Mg2+ insertion in 2D metal–organic polymer for high-capacity and long-lifespan magnesium batteries

Rechargeable magnesium battery is regarded as the promising candidate for the next generation of high-specific-energy storage systems. Nevertheless, issues related to severe Mg-Cl dissociation at the electrolyte–electrode interface impede the insertion of Mg2+ into most materials, leading to severe polarization and low utilization of Mg-storage electrodes. In this study, a metal–organic polymer (MOP) Ni-TABQ (Ni-coordinated tetramino-benzoquinone) with superior surface catalytic activity is proposed to achieve the high-capacity Mg-MOP battery. The layered Ni-TABQ cathode, featuring a unique 2D π-d linear conjugated structure, effectively reduces the dissociation energy of MgxCly clusters at the Janus interface, thereby facilitating Mg2+ insertion. Due to the high utilization of active sites, Ni-TABQ achieves high capacities of 410 mAh/g at 200 mA g−1, attributable to a four-electron redox process involving two redox centers, benzoid carbonyls, and imines. This research highlights the importance of surface electrochemical processes in rechargeable magnesium batteries and paves the way for future development in multivalent metal-ion batteries.

First-principles study of 3D porous penta-graphene as anode materials for alkali metal-ion batteries

Porous structure with larger specific surface area is more conducive to ion diffusion for the anode materials of metal-ion batteries. In this work, some 3D porous structures with larger and more pores in three directions were designed based on 2D penta-graphene (PG) nanoribbons. By systematically calculations, it was found two of them (h-PG40 and o-PG36) are both thermally and mechanically stable, even at such high temperatures of 1000 K. The alkali metal-ions of Li, Na, and K can be absorbed and diffuse in the pores of h-PG40/o-PG36, and all the porous structures remain metallic regardless of adsorbed ions. Using ab initio molecular dynamics (AIMD) simulation, the diffusion coefficients of Li, Na, and K at different temperatures were calculated. It is found that Li ions can rapidly diffuse in h-PG40 along three directions, but alkali metal-ions of Na and K with larger radii can rapidly diffuse along larger pores in both structures, and have good rate performance. Based on the diffusion coefficients, the obtained diffusion barriers of Li, Na, and K in the h-PG40/o-PG36 structures were 0.19/0.27, 0.26/0.17, 0.41/0.27 eV, which are considerably smaller compared to the minimum diffusion barrier observed in graphite. As the anode of LIB/SIB/PIB, the theoretical specific capacities of h-PG40 and o-PG36 are above 1451.67/781.67/781.67 and 1116.67/868.52/496.30 mAh·g−1, respectively, and the calculated OCV of both structures are smaller than 1.5 V. This reflects their good specific capacity and cycling performance. This theoretical exploration may open a new frontier in searching more practical 3D porous structures as anode materials for alkali metal-ion batteries.

Alleviated mechanical structure decay and accelerated transport kinetics via KNCHCF@NiHCF core–shell structure for aqueous potassium-ion batteries

The sluggish ion transport and mechanical decay caused by K+ intercalation can hinder the K+ storage ability of Prussian blue analogs (PBAs), potential cathode materials for potassium-ion batteries (PIBs). The construction of composite materials using adjustable chemical components of PB is an effective method to improve cycling stability. In this study, a core–shell structure of KNiCoFe(CN)6@NiFe(CN)6 (KNCHCF@NiHCF) was prepared to utilize the inertness of Ni2+ and the stability of Fe–CN–Ni bonds and enhance the performance of PBAs. Different concentrations of NiHCF coating (Ni-0, Ni-2, Ni-5, and Ni-60) were introduced into the outer layer of KNCHCF using a simple solution precipitation method. The aforementioned core–shell structure and the corresponding built-in electric field enhanced the structural stability and K+/e− transport kinetics of the fabricated materials. And Ni-5 exhibited the best electrochemical performance with excellent durable cycling stability and rate performance. Furthermore, the reversible single-phase insertion and extraction reaction of K+ storage mechanism within the Ni-5 cathode was revealed using ex-/in-situ characterization techniques. This strategy may facilitate the development of other cathode materials for rechargeable metal ion batteries.

Possibility of defective monolayer graphene as potential anode material of metal-ion batteries

The necessitates exploration in the field of rechargeable metal ion batteries demands safe, cost-efficient, and face significant challenges in their development. Defect engineering may be helpful for the ion storage and diffusion in the battery anodes. In this paper, we use density functional theory to investigate the adsorption and diffusion behavior of Li, Mg, and Al atom on single vacancy (SV), Stone-Wales vacancy (SWV), double vacancy (DV) and quadruple vacancy (QV) defective monolayer graphene. It is evident that metal exhibits the strongest adsorption strengthen at the defect center. The DV and QV defective graphene shows the ideal diffusion energy barrier for three metals. Importantly, the QV structure exhibit maximum storage capacities of the 775 mAh/g for Li, 911 mAh/g for Mg, and 1543.4 mAh/g for Al respectively. Additionally, their open-circuit voltages are all in a very safe range. This study can support a strong basis for the experimental research for metal-ion battery anodes.

Prediction of S-functionalized double-metal TiNbC MXene monolayer as a promising anode material for superior high-capacity mono- and multivalent ion batteries

In search of new electrode materials that improve rechargeable metal-ion batteries’ performance, S-functionalized double-metal TiNbC MXene monolayer (TiNbCS2) is designed, and its properties as an anode material for Li-, Na-, K-, Mg-, Ca-, and Al-ion batteries are investigated employing density functional theory. Due to technical issues during the preparation process, the surface of MXenes is mostly terminated by –O, –OH, and –F functional groups. It is possible to modify the surface by other terminal groups to improve MXenes’ energy storage performance. According to our findings, the TiNbCS2 monolayer, thanks to its metallic behavior, high chemical stability, low diffusion energy barriers, and low open-circuit voltages of these metal cations, is a promising anode material for rechargeable metal-ion batteries. Notably, the adsorption of multilayers of Na+ and Mg2+ cations on the surface of TiNbCS2 provides excellent capacities of 494 mA h g−1 and 988 mA h g−1 for Na- and Mg-ion batteries, respectively. Although the trivalent Al ion may offer a higher energy density, our calculations show that Al3+ ions are not adsorbed onto the surface of the TiNbCS2 monolayer effectively.

Rubik’s cube PBA frameworks for optimizing the electrochemical performance in alkali metal-ion batteries

PBA frameworks have stood out among metal–organic frameworks because of their easy preparation, excellent stability, porous structures, and rich redox properties. Unfortunately, their non-ideal conductivity and significant volume expansion during cycling prevent more widespread application in alkali-metal-ion (Li+, Na+, and K+) batteries. By changing the type and molar ratio of metal ions, Rubik’s PBA frameworks with infinite structural variations were obtained in this study, just like the Rubik’s cube undergoes infinite changes during the rotation. X-ray adsorption fine structure measurements have documented the existence and determined the coordination environment of the metal ions in the Rubik’s PBA framework. Benefiting from the more stable Rubik’s cube structures with diverse composition, enhanced conductivity, and greater adsorption capacity, the obtained Rubik’s cubes CoM-PBA anodes, especially CoZn-PBA deliver the enhanced cycling and rate performance in all the alkali-metal-ion batteries. The findings are supported by density functional theory calculations. Ex-situ X-ray photoelectron spectroscopy, and in-situ X-ray diffraction measurements were undertaken to explore the storage mechanism of CoZn-PBA anodes. Our results further demonstrate that the Rubik’s cube PBA framework-based materials could be widely applied in the field of alkali-metal-ion batteries.

Prussian blue/reduced graphene oxide composites cathode material via one-pot precipitation synthesis for enhancing capacity sodium metal pouch cell batteries

The popularity of sodium metal-ion batteries (SMBs) is increasingly displacing lithium-ion batteries (LIBs). Iron-based Prussian blue (Fe4[Fe(CN)6]3) analogs promise low-cost and easily prepared cathode materials for sodium metal-ion batteries. However, the effectiveness of these materials has consistently been attributed to their inadequate electrical conductivity. In this study, we employed a one-pot synthesis technique to prepare composites of Prussian blue (PB) and reduced graphene oxide (PB/rGO) with varying rGO concentrations. Ascorbic acid was utilized as a reducing agent to convert graphene oxide (GO) into reduced graphene oxide (rGO). Following optimization, the SMB coin cell with PB/rGO(5 %) electrode exhibited an initial specific discharge capacity of 91 mAh/g at a current density of 0.3C. This electrode had exceptional rate performance and remarkable capacity retention, with 75.3 % remaining after 2000 cycles. Furthermore, the pouch cell SMB using PB/rGO(5 %) showed a high capacity of 87 mAh/g at 0.05C with an energy density of 34 Wh kg−1 and good cycle ability over 500 cycles. Notably, the performance of the SMBs surpasses that of the PB cathode, making it highly advantageous for efficient sodium ion storage in SMBs.

Nanoflake Ni-MOF anchored octahedral nickel-porphyrins as a high-performance anode for lithium-ion batteries

Metal-organic framework materials (MOFs) have great potential as organic electrode materials for lithium-ion batteries due to their amiable porous structure and property tunability. However, the structure instability and poor electrochemical durability of MOFs hinders their application. An interesting metal–organic composite composed of Ni-MOF and Nickel (II)meso-Tetraphenylporphyin (NiTPP) is strategically proposed and configured in this study. The synergic integration of Ni-MOF and NiTPP presents a stable electrochemical cycling performance with a high retention capacity up to 840 mAh/g after 200 cycles, ascribed to the facilitation of the charge transfer capability and the diffusion kinetics. The configured metal–organic composites provide an explorative approach for organic alternatives for nonaqueous metal-ion batteries.

Advances In Borophene: Synthesis, Tunable Properties, and Energy Storage Applications.

Monolayer boron nanosheet, commonly known as borophene, has garnered significant attention in recent years due to its unique structural, electronic, mechanical, and thermal properties. This review paper provides a comprehensive overview of the advancements in the synthetic strategies, tunable properties, and prospective applications of borophene, specifically focusing on its potential in energy storage devices. The review begins by discussing the various synthesis techniques for borophene, including molecular beam epitaxy (MBE), chemical vapor deposition (CVD), and chemical methods, such as ultrasonic exfoliation and thermal decomposition of boron-containing precursors. The tunable properties of borophene, including its electronic, mechanical, and thermal characteristics, are extensively reviewed, with discussions on its bandgap engineering, plasmonic behavior, and thermal conductivity. Moreover, the potential applications of borophene in energy storage devices, particularly as anode materials in metal-ion batteries and supercapacitors, along with its prospects in other energy storage systems, such as sodium-oxygen batteries, are succinctly, discussed. Hence, this review provides valuable insights into the synthesis, properties, and applications of borophene, offering much-desired guidance for further research and development in this promising area of nanomaterials science.

How Thick Aqueous Alkali Should be Better for Aluminum-Air Batteries at Sub-Zero Temperatures: A Critical Anti-Freezing Concentration.

The application of portable aluminum-air batteries (AABs) in extreme environments is an inevitable demand for future development. Aqueous electrolytefreezing is a major challenge for low-temperature operations. Conventionally, enlightened by the organic system in metal ion batteries, blindly increasing the concentration is regarded as an efficient technique to reduce the freezing point (FP). However, the underlying contradiction between the adjusting mechanism of the FP and OH- transportation is ignored. Herein, the aqueous alkali solution of CsOH is researched as a prototype to disclose the intrinsic conductive behavior and related solvent structure evolution. Different from these inorganic electrolyte systems, the concept of a critical anti-freezing concentration (CFC) is proposed based on a specific temperature. The relationship between hydrogen bond reconstruction and de-solvation behavior is analyzed. A high conductivity is obtained at -30°C, which is also a recorded value in an intrinsic aqueous AAB. The homogenous dissolution of the Al anode is also observed. As a general rule, the CFC concept is also applied in both the KOH and NaOH systems.

Biomimetic Superstructured Interphase for Aqueous Zinc-Ion Batteries.

The practical application of aqueous zinc-ion batteries (AZIBs) is greatly challenged by rampant dendrites and pestilent side reactions resulting from an unstable Zn-electrolyte interphase. Herein, we report the construction of a reliable superstructured solid electrolyte interphase for stable Zn anodes by using mesoporous polydopamine (2D-mPDA) platelets as building blocks. The interphase shows a biomimetic nacre's "brick-and-mortar" structure and artificial transmembrane channels of hexagonally ordered mesopores in the plane, overcoming the mechanical robustness and ionic conductivity trade-off. Experimental results and simulations reveal that the -OH and -NH groups on the surface of artificial ion channels can promote rapid desolvation kinetics and serve as an ion sieve to homogenize the Zn2+ flux, thus inhibiting side reactions and ensuring uniform Zn deposition without dendrites. The 2D-mPDA@Zn electrode achieves an ultralow nucleation potential of 35 mV and maintains a Coulombic efficiency of 99.8% over 1500 cycles at 5 mA cm-2. Moreover, the symmetric battery exhibits a prolonged lifespan of over 580 h at a high current density of 20 mA cm-2. This biomimetic superstructured interphase also demonstrates the high feasibility in Zn//VO2 full cells and paves a new route for rechargeable aqueous metal-ion batteries.

Self‐Assembled Protection Layer Induced by Bifunctional Additive for Reversible Aqueous Zinc Metal Battery

AbstractAqueous zinc metal battery (AZMB) has received widespread attention due to the advantages of low cost and high safety. However, challenges of dendritic growth, hydrogen evolution reaction, and other side‐reaction impede the performance of the Zn anode. Herein, 4‐amino‐benzene‐sulfonic acid (ABSA) is proposed as an additive to the ZnSO4 electrolyte for improving the performance of AZMB. Combined analyses of theoretical calculations and experiment results, ABSA assumes a pivotal function in constructing an adsorptive layer, facilitating the subsequent formation of a stable sulfur‐rich solid‐electrolyte interphase (SEI). Consequently, the SEI layer modulates the pathway of Zn2+ electrodeposition/dissolution and effectively hinders the deleterious growth of dendrites and unwanted side reactions. As a result, the Zn||Zn cells stably cycles for 2500 h at 1 mAh cm−2/1 mA cm−2 and over 1000 h at 10 mAh cm−2/10 mA cm−2. Significantly, the pouch cell of Zn||VO2 can obtain the specific capacity of 151 mAh g−1 after 100 cycles. This work may provide a new perspective for designing advanced electrolytes from the prospect of interface protection for the AZMB and other metal ion batteries.

Advanced Insights on MXenes: Categories, Properties, Synthesis, and Applications in Alkali Metal Ion Batteries.

The development and optimization of promising anode material for next-generation alkali metal ion batteries are significant for clean energy evolution. 2D MXenes have drawn extensive attention in electrochemical energy storage applications, due to their multiple advantages including excellent conductivity, robust mechanical properties, hydrophilicity of its functional terminations, and outstanding electrochemical storage capability. In this review, the categories, properties, and synthesis methods of MXenes are first outlined. Furthermore, the latest research and progress of MXenes and their composites in alkali metal ion storage are also summarized comprehensively. A special emphasis is placed on MXenes and their hybrids, ranging from material design and fabrication to fundamental understanding of the alkali ion storage mechanisms to battery performance optimization strategies. Lastly, the challenges and personal perspectives of the future research of MXenes and their composites for energy storage are presented.

Investigation of N C and B C bilayers as anode materials for Li-ion batteries by first-principles calculations.

The best choice today for a realistic method of increasing the energy density of a metal-ion battery is to find novel, effective electrode materials. In this paper, we present a theoretical investigation of the properties of hitherto unreported two-dimensional B C and N C bilayer systems as potential anode materials for lithium-ion batteries. The simulation results show that N C bilayer is not suitable for anode material due to its thermal instability. On the other hand B C is stable, has good electrical conductivity, and is intrinsically metallic before and after lithium intercalation. The low diffusion barrier (0.27 eV) of Li atoms shows a good charge and discharge rate for B C bilayer. Moreover, the high theoretical specific capacity (579.57 mAh/g) connected with moderate volume expansion effect during charge/discharge processes indicates that B C is a promising anode material for Li-ion batteries.

Order-disorder structural engineering of vanadium oxide anode: Balancing ionic and electronic dynamic for fast-charging aqueous Li-ion battery

Fast-charging aqueous lithium-ion batteries (ALIBs) are considered as promising energy storage devices because of their non-flammability and environmentally friendly characteristics. However, how to balance the ionic and electronic dynamics for fast charging reactions remains a significant challenge under the current research status. Here, the order-disorder structural engineering strategy is adopted to resolve this issue, considering the difference between ion and electron transportation in the crystalline and amorphous phases, respectively. Vanadium oxide anodes were developed with optimized ionic and electronic dynamics by using an organic-inorganic hybrid material as a precursor along with refined regulation on the calcination temperature and time. This facile and large-scale extendable approach harnesses the benefits of the order-disorder structure to optimize Li+ storage efficiency and facilitate the high reversibility of Li-ion during fast charging. Consequently, the order-disorder V2O5-based full cell with LiMn2O4 as a cathode exhibits high specific capacity (262.71 mAh g−1, 89.35 % of the theoretical capacity of V2O5), high energy density (166.04 Wh kg−1), fast Li-ion diffusion coefficient (7.34×10−5 cm2 s−1) and fast-charging performance (only 6 min achieves 82.84 % of initial state-of-charge capacity). This work explores the ionic and electronic dynamic of ordered-disorder structure and offers new insights into the development of fast-charging metal ion batteries.