Anode Materials For Metal-ion Batteries Research Articles

Investigation of hexagonal boron nitride monolayer with pores as an anode material for sodium-ion batteries

The hexagonal boron nitride monolayer (h-BNML) used as an anode material for metal-ion batteries was assumed pristine form. However, inspired by the imperfections in natural materials, this study investigates the effect of defects on the electrochemical properties of h-BNML. Within the current piece of research, h-BNML with pores is introduced to develop an anode material for sodium ion battery (SIBs) by undertaking density-functional theory (DFT) computations. During the diffusion and storage process of Na ions, the pores effect was thoroughly investigated. The boron atoms were removed from the structure of the pure h-BNML in order to form the h-BNML with pores, which mimicked the pore formation. Based on the DFT results, after the pore formation, the h-BNML retained its planarity. Following the introduction of vacancies, significant alterations occurred in the electronic structure characteristics of h-BNML within the pores, facilitating the effective adsorption of Na ions within the pore. The results of quantum theory of atoms in molecules indicated that there were interactions between the pores and Na ions through an electrostatic-type attraction. The h-BNML with pores was capable of retaining a large number of Na ions at its surface without any change in its planar structure. This led to an increase in its theoretical specific capacity, which increased with porosity. Hence, unlike the pure h-BNML, the pore formation improved the diffusion of Na ions. This can be promising to designing highly efficient anodes for SIBs. The methodological approach in this study can be used for tailoring porous BN materials for SIBs.

Pyrazinoquinoxaline graphdiyne: A novel high-capacity anode material for metal-ion batteries

The rapid expansion of the electronics industry and the growing need for advanced energy storage solutions have driven the quest for rechargeable batteries with improved capacity and prolonged lifetimes. In this context, significant attention has been directed towards the exploration of two-dimensional (2D) materials, particularly carbon nanosheets such as Graphdiyne, owing to their compelling electrical, optical, mechanical, and chemical properties. The recent achievement in producing pyrazinoquinoxaline graphdiyne (PQ-GDY) nanosheets, distinguished by their remarkable stability and exceptional physical properties, has ignited our research curiosity, prompting an exploration of their potential suitability as anode materials for lithium (Li), sodium (Na), calcium (Ca), and magnesium (Mg) ion batteries. This investigation is conducted using first-principle electronic structure simulations. Drawing from our rigorous theoretical analysis, pyrazinoquinoxaline graphdiyne (PQ-GDY) has demonstrated favorable electrode properties, positioning it as a promising candidate for potential utilization in Li, Na, and Ca ion batteries. Notably, the pyrazinoquinoxaline graphdiyne rectangular (PQ-GDY-Rec) material demonstrates remarkable storage capacities for Li, Na, and Ca ions, reaching values of 1938 mAh/g, 1716 mAh/g, and 830.60 mAh/g, respectively. These findings position PQ-GDY-Rec as a highly promising material for application in metal-ion batteries, suggesting new avenues for the advancement of rechargeable batteries with significantly enhanced storage capabilities.

Fall and Rise: Disentangling Cycle Life Trends in Atmospheric Plasma-Synthesized FeOOH/PANI Composite for Conversion Anodes in Lithium-Ion Batteries

Various iron oxides have been proven to be promising anode materials for metal-ion batteries due to their natural abundance, high theoretical capacity, ease of preparation, and environmental friendliness. However, the synthesis of iron oxide-based composites requires complex approaches, especially when it comes to composites with intrinsically conductive polymers. In this work, we propose a one-step microplasma synthesis of polyaniline-coated urchin-like FeOOH nanoparticles (FeOOH/PANI) for applications as anodes in lithium-ion batteries. The material shows excellent electrochemical properties, providing an initial capacity of ca. 1600 mA∙h∙g−1 at 0.05 A∙g−1 and 900 mA∙g−1 at 1.2 A∙g−1. Further cycling led to a capacity decrease to 150 mA∙h∙g−1 by the 60th cycle, followed by a recovery that maintained the capacity at 767 mA∙h∙g−1 after 2000 cycles at 1.2 A∙g−1 and restored the full initial capacity of 1600 mA∙h∙g−1 at a low current density of 0.05 A∙g−1. Electrochemical milling—the phenomenon we confirmed via a combination of physico-chemical and electrochemical techniques—caused the material to exhibit interesting behavior. The anodes also exhibited high performance in a full cell with NMC532, which provided an energy density of 224 Wh∙kg−1, comparable to the reference cell with a graphite anode (264 Wh∙kg−1).

Metallic CoSb and Janus Co2AsSb monolayers as promising anode materials for metal-ion batteries.

Structural symmetry breaking plays a pivotal role in fine-tuning the properties of nano-layered materials. Here, based on the first-principles approaches we propose a Janus monolayer of metallic CoSb by breaking the out-of-plane structural symmetry. Specifically, within the CoSb monolayer by replacing the top-layer 'Sb' with 'As' atoms entirely, the Janus Co2AsSb monolayer can be formed, whose structure is confirmed via structural optimization and ab initio molecular dynamics simulations. Notably, the Janus Co2AsSb monolayer demonstrates stability at an elevated temperature of 1200 K, surpassing the stability of the CoSb monolayer, which remains stable only up to 900 K. We propose that both the CoSb and Janus Co2AsSb monolayers could serve as capable anode materials for power-driven metal-ion batteries, owing to their substantial theoretical capacity and robust binding strength. The theoretical specific capacities for Li/Na reach up to 1038.28/1186.60 mA h g-1 for CoSb, while Janus Co2AsSb demonstrates a marked improvement in electrochemical storage capacity of 3578.69/2215.38 mA h g-1 for Li/Na, representing a significant leap forward in this domain. The symmetry-breaking effect upgrades the CoSb monolayer, as a more viable contender for power-driven metal-ion batteries. Furthermore, electronic structure calculations indicate a notable charge transfer that augments the metallic nature, which would boost electrical conductivity. These simulations demonstrate that the CoSb and Janus Co2AsSb monolayers have immense potential for application in the design of metal-ion battery technologies.

Can P3S and C3S monolayers be used as anode materials in metal-ion batteries? An answer from first-principles study.

With the urgent need for efficient energy storage devices, significant attention has been directed to researching and developing promising anode materials for metal-ion batteries. Through density functional study, we successfully predicted the electrochemical performance of P3S and C3S monolayers for the first time, which could be used in alkali metal (Li, Na, and K)-ion batteries. Our study examines the energetic, dynamic, and thermal stabilities of pristine monolayers. The electronic structures of the pristine nanosheets are wide-gap semiconductors. After single metalation on the monolayers, the composite systems become metallic. Charge-density difference (CDD) analysis indicates that charge transfer occurs from alkali metal atoms to the P3S and C3S monolayers, and Bader charge analysis quantifies the amount of charge transfer. We analyzed how readily a single adatom diffuses within the 2D structures. One example is the diffusion of K on C3S, which has a low barrier value of 0.06 eV and seems practically barrierless. Our predicted composite systems report considerable theoretical storage capacity (C); for example, hexalayer K-adsorbed C3S shows a storage capacity of 1182.79 mA h g-1. The estimated open-circuit voltage (OCV) values suggest that the C3S monolayer is a promising anode material for Li-, Na-, and K-ion batteries, whereas the P3S monolayer is suitable as a cathode material for Li-, Na-, and K-ion batteries.

Borophene as an anode material for metal-ion batteries

Borophene as an anode material for metal-ion batteries

On two-dimensional metal borides (MBenes) as anode materials for metal-ion batteries: A first-principles study

To find excellent materials for metal-ion batteries, we investigated the possibility of two-dimensional (2D) monolayer MBenes (CrB, FeB, MnB) as anode materials for Li, Na, K, Mg, and Ca ion batteries based on density-functional theory. The results show that the monolayer MBenes have small diffusion energy barriers, can maintain a stable average open-circuit voltage, and a theoretical storage capacity of up to 853 mA h g−1 in Li-ion batteries, superior to other ordinary anode materials. These properties suggest that monolayer CrB, FeB, and MnB are promising anode materials for metal ion batteries with good rate capacity.

Rational design of Two-Dimensional Buckled-Hexagonal Nb2S2 monolayer as an efficient anode material for Ca-ion Batteries: A First-Principles study

Presently, great attention is being paid to the search for promising anode materials for metal-ion batteries (MIBs) due to the rapid evolution of numerous modern electronic gadgets. In this investigation, we have predicted for the first time that the buckled-hexagonal Nb2S2 monolayer which may be an efficient anode material for calcium-ion batteries (CIBs). To that objective, we have explored the pristine monolayer system’s energetical, dynamical, and thermal stability. The inherent metallicity of the pristine monolayer facilitates its electrical conductivity as an electrode material. Our study also reveals the structural and electrical properties of the Ca-adsorbed Nb2S2 monolayer. It is observed that Ca-atoms prefer to get intercalated on top of the buckled hexagon of the pristine monolayer, and the metallicity of the 2D nanosheet remains preserved. In the adsorption process, Bader charge analysis is used to determine the amount of charge transfer from the Ca atom to the Nb2S2 monolayer. Furthermore, this system exhibits a high storage capacity of 1288.86 mAh/g and a moderately low diffusion energy barrier of 0.76 eV. The calculated open-circuit voltage of 0.49 V and the other results suggest that the Nb2S2 monolayer may be a potential candidate for anode material for rechargeable Ca-ion batteries.

Electrochemical properties of endohedral halide (F−, Cl− and Br−) encapsulated Mg12O12 nanocage for metal-ion batteries

Metal-ion batteries (MIBs) offer great potential for energy storage applications due to their advantageous features such as high energy density and environmental friendliness. Nevertheless, there is a need to investigate electrode materials that possess attributes like substantial capacity, rapid charge and discharge capabilities, stable performance over numerous cycles, and cost-effectiveness. In this context, the effectiveness of pristine and halide (F−, Cl− and Br−) encapsulated Mg12O12 nanocages are systematically examined and employed as anode materials for metal-ion batteries. Using dispersion corrected density functional theory (DFT-D3), the electrochemical performance of the nanocages in the presence and absence of halide were investigated. The oxygen atom of Mg12O12 nanocages prefers to adsorb on M/M+ (M = Li, Na, and K). The results show that, on comparison to neutral metal, cationic metal have stronger interaction for both pristine and halide encapsulated nanocages. The computed Gibbs free energy of the cell (ΔGcell) and cell voltage (Vcell) of pristine Mg12O12 adsorption of alkali metals for MIBs are found to be in the range of −13.18 to −38.91 kcal/mol and 0.57 to 1.69 V respectively. Endohedral encapsulation of the halide into the nanocages significantly increased the Gibbs free energy, which subsequently enhanced the cell voltage of the nanocages. The findings imply that Mg12O12 nanocage with halide encapsulation acts as an effective anode material for MIBs with profound performance. The outcomes of this investigation pave the way for the development of novel approaches in designing both pristine and halide (F−, Cl−, and Br−) encapsulated Mg12O12 nanocages as anodes, thereby facilitating their practical utilization in metal-ion batteries.

Two dimensional holey graphyne: An excellent anode and anchoring material for metal–ion and metal–sulfur batteries

Based on first-principles calculations, the potential of holey graphyne is investigated for battery applications in terms of the storage capacity, volume expansion, diffusion barrier, and metal polysulfides binding. We found substantially higher storage capacities of Li (873 mAh/g) and Na (558 mAh/g) than typical graphite anodes (372 mAh/g for Li and <35 mAh/g for Na) and other carbonaceous materials (450–750 mAh/g for Li and 200–500 mAh/g for Na). The migration barriers of Li and Na turn out to be 0.28 eV and 0.32 eV, respectively, lower than those theoretically reported for commercial anodes TiO2 (0.4–1.0 eV) and silicon (0.6–0.8 eV). Holey graphyne with maximum Li adsorption expands only 0.5%, in contrast to the 10% volume growth in graphite. The lithium and sodium polysulfides and S8 cluster adsorb with moderate binding energies ranging from −0.73 eV to −2.08 eV, which is sufficient to prevent the unintended decomposition of polysulfides. Our findings demonstrate that holey graphyne is a promising anode material for metal-ion batteries and an anchoring material for metal-sulfur batteries to mitigate the shuttle effect.

Aluminene as a Low-Cost Anode Material for Li- and Na-Ion Batteries.

Two-dimensional (2D) materials are promising candidates for next-generation battery technologies owing to their high surface area, excellent electrical conductivity, and lower diffusion energy barriers. In this work, we use first-principles density functional theory to explore the potential for using a 2D honeycomb lattice of aluminum, referred to as aluminene, as an anode material for metal-ion batteries. The metallic monolayer shows strong adsorption for a range of metal atoms, i.e., Li, Na, K, and Ca. We observe surface diffusion barriers as low as 0.03 eV, which correlate with the size of the adatom. The relatively low average open-circuit voltages of 0.27 V for Li and 0.42 V for Na are beneficial to the overall voltage of the cell. The estimated theoretical specific capacity has been found to be 994 mA h/g for Li and 870 mA h/g for Na. Our research highlights the promise of aluminene sheets in the development of low-cost, high-capacity, and lightweight advanced rechargeable ion batteries.

Firmly interlocked Janus-type metallic Ni3Sn2S2-carbon nanotube heterostructure suppresses polysulfide dissolution and Sn aggregation

Ternary transition-metal tin chalcogenides, with their diverse compositions, abundant constituents, high theoretical capacities, acceptable working potentials, excellent conductivities, and synergistic active/inactive multi-components, hold promise as anode materials for metal-ion batteries. However, abnormal aggregation of Sn nanocrystals and the shuttling of intermediate polysulfides during electrochemical tests detrimentally affect the reversibility of redox reactions and lead to rapid capacity fading within a limited number of cycles. In this study, we present the development of a robust Janus-type metallic Ni3Sn2S2-carbon nanotube (NSSC) heterostructured anode for Li-ion batteries (LIBs). The synergistic effects of Ni3Sn2S2 nanoparticles and a carbon network successfully generate abundant heterointerfaces with steady chemical bridges, thereby enhancing ion and electron transport, preventing the aggregation of Ni and Sn nanoparticles, mitigating the oxidation and shuttling of polysulfides, facilitating the reforming of Ni3Sn2S2 nanocrystals during delithiation, creating a uniform solid-electrolyte interphase (SEI) layer, protecting the mechanical integrity of electrode materials, and ultimately enabling highly reversible lithium storage. Consequently, the NSSC hybrid exhibits an excellent initial Coulombic efficiency (ICE > 83 %) and superb cyclic performance (1218 mAh/g after 500 cycles at 0.2 A/g and 752 mAh/g after 1050 cycles at 1 A/g). This research provides practical solutions for the intrinsic challenges associated with multi-component alloying and conversion-type electrode materials in next-generation metal-ion batteries.

Theoretical prediction and characterization of novel two-dimensional ternary tetradymite compounds La2X2Y (X = I, Br, Cl; Y = Ge, Te) as anode materials for metal-ion batteries.

Tetradymite compounds, such as Bi2Te3, crystallizing in rhombohedral structures have triggered tremendous research interest from the scientific community because of their intriguing properties. Herein, using the state-of-the-art first-principles calculations, we identify that La2X2Y (X = I, Br, Cl; Y = Ge, Te) nanosheets exhibit a ternary tetradymite-type structure with extraordinary electrical and electrochemical properties. It is first demonstrated that the layered La2X2Y compounds exhibit weak interlayer coupling with cleavage energies in the range of ∼0.28-0.38 J m-2, allowing the ready separation of monolayers that can be synthesized by mechanical exfoliation from their bulk counterparts. Next, we predict that La2X2Ge nanosheets exhibit a semiconducting nature, and upon physical realistic strain, a Dirac cone can be realized. These findings can be exploited in the transport properties. Furthermore, we comprehensively investigated the electrochemical properties of the predicted systems to evaluate their potential use in metal-ion (Li/Na) batteries. Our detailed analyses reveal that the Li (Na) adatoms are sufficiently mobile on the surface of the studied systems. For instance, the binding energy for the Li (Na) adatom on La2I2Ge is -2.24(-1.79) eV with a diffusion barrier of as small as ∼0.31(0.20) eV. Subsequently, the maximum theoretical specific capacity for Li (Na) reaches as high as 887(1064) mA h g-1, which can be attributed to a much higher storage capacity compared to previously identified 2D anode materials. These findings substantiate that the predicted nanosheets could be synthesized to explore their potential applications in future metal-ion batteries.

PHP-graphene nanoribbon-assembled porous metallic carbon for sodium-ion battery anode with high specific capacity

In recent years, a number of three-dimensional (3D) porous metallic carbon allotropes have been proposed to be used as anode materials for metal-ion batteries by assembling graphene or penta-graphene nanoribbons. Here, based on density functional theory and tight-binding model, we design a new 3D porous metallic carbon monolith (termed Hex-C568) consisting of PHP-graphene nanoribbons which contain pentagonal, hexagonal and octagonal rings. It is thermally, dynamically and mechanically stable. We find that its metallicity is attributed to the delocalized electrons in the p-orbitals of the sp2 hybridized carbon atoms, and Hex-C568 is a promising anode material for Na-ion batteries with high performance. Its reversible gravimetric and volumetric capacities are 787.53 mAhg−1 and 718.10 mAhcm−3, respectively, with low diffusion energy barrier (0.04–0.30 eV), low average open-circuit voltage (0.26 V), and small volume change during the charging/discharging process (3.71%). These electrochemical properties are superior to those of most recently reported anode materials, suggesting that PHP-graphene nanoribbon is a promising building unit for the design of novel carbon anode materials going beyond graphene and penta-graphene.

First-principles calculations study of TiS2/Ti2CS2 heterostructure as an anode material for Li/Na/K-ion batteries

TiS2 and Ti2CS2 are two potential candidates as anode materials for rechargeable ion batteries. However, the issues of semiconductor property and re-stacking prevent their development. In this work, we assembled a van der Waals heterostructure of TiS2/Ti2CS2 and investigated its possibility as an anode material for Li/Na/K-ion batteries (LIBs/NIBs/KIBs) by first-principles calculations. The results show that the TiS2/Ti2CS2 has excellent stability and metallic nature. The Li, Na and K ions exhibit extremely low diffusion barriers (below 0.4 eV) in the TiS2/Ti2CS2 interlayer, which predicts that it has remarkable rate performance. For NIBs and KIBs, the average open circuit voltages (0.626 V and 0.995 V) of TiS2/Ti2CS2 are in the range of 0–1 V and the theoretical specific capacities (566 mA·h/g and 283 mA·h/g) are higher than those (35 mA·h/g and 279 mA·h/g) of graphite anode for the corresponding batteries. All of this indicate that the TiS2/Ti2CS2 is well suited as an anode material for NIBs and KIBs. Our study may provide guidance and new ideas for the theoretical and experimental design of new anode materials for metal-ion batteries.

Monolayer Ge2S: An auxetic semiconductor with high carrier mobility for metal (Na, K, Mg)-ion battery anodes

Using first-principles calculations, we propose a new two-dimensional Ge2S (space group P21212) with unique mechanical and electronic properties. Monolayer Ge2S has excellent thermal, mechanical, and dynamic stabilities, exhibiting a semiconducting behavior with an indirect bandgap and anisotropic carrier mobility. The uniaxial strain along the zigzag direction can induce an indirect-to-direct bandgap transition. Remarkably, Ge2S possesses large in-plane negative Poisson's ratios, comparable with that of well-known penta-graphene. Moreover, we identify Ge2S as a high-performance anode material for metal-ion batteries. It shows metallic features after adsorbing Na, K, and Mg, providing good electrical conductivity during the charge/discharge process. The diffusion of metal ions on Ge2S is anisotropic with modest energy barriers in the armchair direction of 0.12, 0.39, and 0.76 eV for Na, K, and Mg, respectively. Ge2S can adsorb metal atoms up to a stoichiometric ratio of 1:1, which yields storage capacities of 151.17, 151.17, and 302.35 mA h g−1 for Na, K, and Mg, respectively. The volume of Ge2S shrinks slightly upon the adsorption of metal ions even at high concentrations, ensuring a good cyclic stability. Besides, the average open circuit voltage (0.30–0.70 V) falls within the acceptable range (0.1–1.0 V) of the anode materials. These results make Ge2S a promising anode material for the design of future metal-ion batteries.

Biphenylene monolayer: a novel nonbenzenoid carbon allotrope with potential application as an anode material for high-performance sodium-ion batteries.

Allotrope metal structures composed of carbon as anode materials for metal-ion batteries are a current research hotspot. In this work, the recently synthesized graphene allotrope, two-dimensional (2D) biphenylene, consisting of tetragonal, hexagonal and octagonal carbon rings, was explored theoretically. Our first-principles calculations verified that 2D biphenylene has dynamical, mechanical and thermal stability and exhibits metallic features. Its novel structure can provide multiple adsorption sites for Na ions, a fast charge-discharge rate (low Na migration barriers of <0.2 eV) and high theoretical capacity (1075.37 mA h g-1). These superior properties, combined with its carbon abundance and light mass, make the biphenylene monolayer a promising high-performance anode for sodium-ion batteries (SIBs).

Metallic penta-Graphene/penta-BN2 heterostructure with high specific capacity: A novel application platform for Li/Na-ion batteries

Considerable efforts have been devoted to design effective anode material for metal-ion batteries. Heterostructures obtained by vertically stacking two-dimensional (2D) monolayers are being considered as alternatives. Here, a hybrid Van der Waals heterostructure with penta-graphene and penta-BN2 (PG/P-BN2) has been investigated for application as an anode material. First-principles calculations indicate that the PG/P-BN2 heterostructure is energetically and thermally stable. The electronic structures of the pristine and ionized heterostructures suggest their metallic properties, which presages good electrical conductivity for the anode material. The metal ions (Li and Na) are found to have low diffusion barriers and low average open-circuit voltages on the PG/P-BN2 heterostructure. The theoretical specific capacities of the PG/P-BN2 heterostructure for the both metal ions reach up to 1054.35 mA·h·g−1, being superior to those of the previously reported 2D anode materials. These results provide innovative advantages at the complex 2D heterostructures and will propel further development of efficient anode materials for superior alkali metal-ion batteries.

A Dirac nodal surface semi-metallic carbon-based structure as a universal anode material for metal-ion batteries with high performance.

The rapid development of electronic devices requires high power storage batteries. However, reported 3D carbon-based materials are semiconductors or metals and are used in Li- or Na-ion batteries with low capacities. Thus, it is of interest to discover whether there is a universal semi-metallic material for use in high performance Li-, Na-, and K-ion batteries. Inspired by the recent synthesis of 3D carbon-based materials, in the research reported here, a 3D regular porous structure (bct-C56) is designed using graphene sheets. The porous carbon-based material has mechanical, dynamic, thermal, and mechanical stabilities. Interestingly, bct-C56 exhibits semi-metallic features with two Dirac nodal surfaces with mirror symmetry, as well as high Fermi velocities, indicating high electron-transport abilities. More excitingly, its theoretical capacities are 743.8, 478.2, and 425.0 mA h g-1, with diffusion barriers of 0.05-0.12, 0.07-0.12, and 0.03-0.05 eV, average OCVs of 0.31, 0.45, and 0.59 V, and volume expansion levels of 1.2%, 0.02%, and 3.1%, in Li-, Na-, and K-ion batteries, respectively. All these excellent characteristics suggest that semi-metallic bct-C56 is a universal anode material for use in metal-ion batteries with a fast charge-discharge rate. In this research, not only was a new material with a Dirac nodal surface feature designed, but it also offers an approach for the creation of high performance and universal metal-ion battery anodes with 3D porous carbon materials.

Theoretical investigation of the intercalation mechanism of VS2/MXene heterostructures as anode materials for metal-ion batteries

Ti2CO2 is one of the lightest MXenes, which is beneficial for achieving higher capacity as electrode material for batteries. However, its semiconductor conductivity has a negative effect on its charging/discharging rate and cyclability performance as electrode materials for batteries. Integrating two different two-dimensional materials to form heterostructures is an effective strategy to optimize the properties of materials. In this work, two heterostructures VS2/Ti2CT2 (T = O and S) are constructed and their electrochemical performances as anode materials for Li, Na and Mg-ion batteries are explored based on first-principles calculations. First of all, the lattice mismatch of these two heterostructures are relatively small, particularly, the lattice mismatch of VS2/Ti2CS2 is as low as 0.63%. Besides, compared with common graphene/Ti2CO2 and MoS2/Ti2CO2 heterostructures, VS2/Ti2CT2 simultaneously exhibit superior metal conductivities and stronger adsorption properties towards Li, Na and Mg atoms, thus achieving higher capacities. Considering the strong adsorption properties, suitable diffusion energy barriers, low open circuit voltages and high capacities, VS2/Ti2CO2 and VS2/Ti2CS2 are proposed to be promising high-performance anode materials for Mg-ion batteries, and VS2/Ti2CS2 is a preferable anode material for Na-ion batteries.