High-performance Anode Materials Research Articles

First-principles calculation of ZrS2 as anode material of aluminium ion battery

Developing low-cost, high-stability, and high-performance new ion battery anode materials is beneficial for the rapid development of ion batteries in fields such as rail transit, electronic products, and aerospace. In this work, the first-principles calculation method was used to study the feasibility of ZrS2 monolayer as an anode material for Al ion batteries. The Al ions adsorbed in the strain system tend to bind to the ZrS2 monolayer. In the adsorption system, the adsorption of Al increases the conductivity of the system. The theoretical specific capacity of Al under full load is 690.303 mAh/g. The average open circuit voltage (OCV) is calculated to be 0.635 V. The diffusion barrier of Al ions is 0.071 eV. ZrS2 monolayer is an attractive anode material for ion batteries.

Electrochemical Performance of MoB/Si3N4 Heterojunction as a Potential Anode Material for Li Ion Batteries.

In response to the current policy of high storage capacity, two-dimensional (2D) materials have revealed promising prospects as high-performance electrode materials. MoB, as a type of such material, is widely regarded as an anode candidate for Li-ion batteries due to its large specific surface area and abundant ion diffusion channels; the long-term cycling stability, however, is poor owing to material pulverization during the cycle. Therefore, MoB/Si3N4 heterojunction in this work is proposed as an anode material, with Si3N4 acting as a skeleton, maintaining the stability of the structure, while retaining the high energy storage properties of MoB as well. In addition, a certain built-in electric field is formed between them, which can play a role in regulating charge transfer, improving the ion transport channel, and accelerating the migration rate. Herein, the structural, electronic, and electrochemical properties are systematically investigated by first-principles calculations; the final results indicate that the heterojunction anode material does indeed have built-in electric fields, which promote the anode material to possess excellent electrical conductivity and outstanding electrochemical property. Meanwhile, the introduction of vacancy defects can bolster the diffusion kinetic performance of ion transport and greatly reduce the diffusion energy barrier of Li ions, which is conducive to the realization of rapid charge and discharge for the Li ion battery. Based on the synergistic effect of two single-component materials, the synthesized anode material displays a high theoretical capacity of 461 mAh/g, and the calculated open-circuit voltage is 0.66 V, within the range of the negative electrode criterion of 0-1 V, which can effectively play a role in preventing the formation of Li dendrites; these properties are comparable to other 2D anode materials as well. Given these intriguing properties, the MoB/Si3N4 heterojunction is an exceptional candidate for advanced LIB high-performance anode materials.

1T′-MoSP monolayer as an anode material for sodium-ion batteries with ultrahigh storage capacity and ultralow diffusion barrier

Sodium-ion batteries (SIBs) have gained significant attention due to the abundant availability and low cost of sodium. However, the search for high-performance anode materials remains a critical challenge in advancing SIB technology. Based on first-principles swarm-intelligence structure calculations, we propose a metallic 1T′-MoSP monolayer as an anode material that offers a remarkably high storage capacity of 1011 mA h g−1, an ultralow barrier energy of 0.04 eV, and an optimal open-circuit voltage of 0.29 V, ensuring high rate performance and safety. Additionally, the monolayer presents favorable wettability with commonly used SIB electrolytes. Even after adsorbing three-layer Na atoms, the 1T′-MoSP monolayer retains its metallic nature, ensuring excellent electrical conductivity during the battery cycle. These desirable properties make the 1T′-MoSP monolayer a promising anode material for SIBs.

Exploring the potential of MXene nanohybrids as high-performance anode materials for lithium-ion batteries

Lithium-ion batteries (LIBs) are an integral part of modern life, powering diverse applications from transportable devices to electric vehicles. Efficacy of LIBs depends on the performance of their components with anode material playing the pivotal role. Traditional graphite anodes have limitations in capacity and rate capability. This review comprehensively discusses utilization of MXene-based composites as anode materials in LIBs. MXene composites exhibit versatile lithium storage mechanisms, involving intercalation and/or conversion reactions. Pure MXenes offer advantages of high capacity and cycling stability having challenges due to limited conductivity and mechanical fragility, restricting their practical utility, thereby affecting their performance in solid-state polymer electrolytes (SPEs). MXene composites overcome unsystematic dispersal and accumulation issues of pure MXene. MXenes in composite form could increase LIBs performance by overcoming limitations of pure MXenes, enabling breakthroughs in energy storage. The review covers different MXene composites viz., MXene/graphene, MXene/silicon, MXene/tin, MXene/carbon, MXene/metal oxide, and MXene/conducting polymer providing a holistic overview. Their performance, cycling stability, and rate capability are discussed to cover challenges and future prospects.

Structural regulation of 1T-MoS2/Graphene composite materials for high-performance lithium-ion capacitors

Heterogeneous composite structures are considered an effective strategy by utilizing the advantages of heterogeneous components. However, the relationship between structural modifications and electrochemical performance remains inadequately understood. In this study, we leveraged DFT calculations to elucidate the key advantages of the 1T-MoS2/Gr heterostructure, including its exceptional electrical conductivity, enhanced Li+ adsorption capabilities, and improved Li+ diffusion kinetics. To synthesize the 1T-MoS2/Gr composite, we developed a facile, one-step hydrothermal method using glucose as a reducing agent, achieving an optimal heterostructure that maximized the synergistic properties of the components. By comparing different levels of graphene content, the relationship between structural regulation and electrochemical performance has been studied, and a remarkably significant heterostructure composite material (1T-MoS2/Gr-0.8) was identified. As the anode material for lithium-ion batteries (LIBs), 1T-MoS2/Gr-0.8 presents excellent cycle performance with 467 mAh g−1 under the condition (0.5 A g−1, 600 cycles). Simultaneously, when assembling the lithium-ion capacitor (LIC) device with an activated carbon (AC) cathode, even at a high power density of 11.7 kW kg−1, the energy density of the 1T-MoS2/Gr-0.8//AC LIC is as high as 137.0 Wh kg−1. Moreover, the capacity retention rate remains at 89.9 % even after 2000 cycles at 2 A g−1, demonstrating its candidacy as a high-performance anode material for LICs.

First-principles study on the lithiation process of amorphous SiO anode for Li-ion batteries with Bayesian optimization.

Amorphous silicon monoxide (a-SiO), which contains Si atoms with various valence states, has attracted much attention as a high-performance anode material for lithium (Li) ion batteries (LIBs). Although current experiments have provided some information during charge/discharge cycles, further investigation of structural changes at the atomic scale is needed. To investigate the lithiation process of a-SiO using first-principles simulations and machine learning techniques, we developed a computational code employing Bayesian optimization to efficiently identify stable sites for Li insertion in the large search-space of amorphous models to reproduce the actual lithiation process and compared this approach to the conventional random scheme by applying it to an a-SiO model previously generated with neural network potentials. The lithiation process based on Bayesian optimization resulted in lower formation energies compared to the conventional random scheme, indicating a more stable structure. During lithiation, Li atoms tended to enter the silicon (Si) phase after the SiO2 phase, in agreement with experimental results. We analyzed the structural changes and observed significant differences in the structural evolution between the conventional and new schemes. Our study highlights the significant influence of the lithiation process on the structural transformation of a-SiO materials, which in turn affects the reversible capacity of the material. These findings will provide a framework for improving the performance and lifetime of a-SiO materials.

Biomass-derived hard carbon material for high-capacity sodium-ion battery anode through structure regulation

Economical and environmentally friendly hard carbon materials are attractive options for high-performance sodium-ion battery anode materials. Biomass-derived hard carbon materials have good economic benefits and environmentally friendliness as anode materials for sodium-ion batteries. In this work, we propose a new hard carbon material prepared from agricultural waste olive shells through a simple and environmentally friendly process. The effects of high-temperature treatments and pre-carbonization strategies on the pore structure and graphitization degree of the hard carbon materials were investigated. Combined with electrochemical performance tests, the influence of structural changes on the sodium storage properties of the olive shell-derived hard carbon was revealed. Under the optimized conditions of carbonization temperature and pre-carbonization strategy, the OSHC-Air electrode exhibits excellent sodium storage capacity with 87 % capacity remaining after 1000 cycles at 1000 mA g−1. The assembled PB//OSHC-Air sodium-ion full cell exhibits a high capacity of 216 mAh g−1. Our research provides a potential candidate for commercial anode materials for high-capacity sodium-ion batteries.

Enhancing lithium storage performance of Carbon/SiOx composite via coating edge-nitrogen-enriched carbon

Silicon oxide (SiOx) exhibits promising potential as a lithium-ion battery anode. However, its practical application is impeded by low electrical conductivity and significant volumetric expansion. To overcome these limitations, we developed a novel co-precipitation and selectively etching approach that leveraged the nitrogen-retaining effect of ZnNCN to prepare an edge-nitrogen-enriched carbon/SiOx composite (NEC@LC-SiOx). This NEC@LC-SiOx showed enhanced electrical conductivity and reduced volumetric expansion. Our innovative approach effectively prevented excessive decomposition of nitrogen species, resulting in a high nitrogen doping content of 21.67 at.% while maintaining a stable structure and mitigated volume expansion during charging and discharging. Consequently, the prepared NEC@LC-SiOx exhibited excellent performance as an anode material for lithium-ion batteries, demonstrating a high reversible specific capacity of 802 mAh/g and outstanding rate capability. This work presents a novel strategy for designing high-performance SiOx anode materials.

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.

Tuning Crystalline Preferred Orientation of SnSe2 Anode by Co-doping to Enhance Pseudocapacitive Behaviors for High-Performance Sodium Storage.

SnSe2 has attracted great attention due to its unique 2D-layered structure, which makes it capable of sodium ion storage and higher theoretical capacities compared to traditional anode materials like hard carbon for sodium ion batteries (SIBs). However, SnSe2-based materials will cause structural damage due to volume expansion during ion storage, leading to poor cycle stability and rate capacity. In this work, Co-doped SnSe2 (Co-SnSe2) with preferred crystal orientation was fabricated by a one-step solvothermal method. It has been found that after doping Co, the lower (001) crystal plane located at 14.4° replaced the higher (101) plane at 30.7° as the dominant crystal plane in Co-SnSe2, which significantly promoted ion diffusion and enhanced the pseudocapacitance behavior. Therefore, this Co-SnSe2 anode achieves a high capacity of 504 mAh g-1 at 1 A g-1, and a high-rate cycle stability, delivering a reversible capacity of 302 mAh g-1 at 5 A g-1 after 1800 cycles with a retained capacity rate of 94%. Moreover, the Na3V2(PO4)3||Co-SnSe2 full cell exhibits a stable cycle performance of over 300 cycles at 1 A g-1, demonstrating great promise for practical applications. This work provides an effective reference for the exploration of high-performance sodium storage anode materials.

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.

Unveiling the Microscopic Origin of Ultrahigh Initial Coulombic Efficiency of High-Entropy Metal-Organic Frameworks for Sodium Storage.

The initial irreversible capacity loss during the first charging process largely reduces the affordable energy and power density of sodium storage devices, and developing advanced materials is the efficient way to solve this problem, which is fraught with challenges. Herein, inspired by theoretical calculations and the high-entropy concept, a series of fewer layers of high-entropy metal-organic frameworks (FLHE-MOFs) are successfully fabricated, delivering an ultrahigh initial Coulombic efficiency (ICE) of 86.1% and excellent cycling performance, which is far more than that of the other electrode materials (generally <70%). Greatly, the storage behavior of high-, medium-, and low-entropy MOFs is clarified by theoretical calculations and in-/ex-situ characterization, revealing that Co and Fe species can provide substantial sodium storage sites and largely enhance the charge transfer rate, whereas high-entropy effect can enable structural reversibility. Sodium ion capacitors constructed with FLHE-MOFs as the anode can provide an ultrahigh energy density of 121.8 W h kg-1 (200 W kg-1) and an extremely long-term cycle lifespan. This work not only breaks the limitation of MOF materials with poor performance for sodium storage but also provides an effective strategy for the fabrication and application of high-performance MOF-based anode materials with high ICE, in which this idea may also be applied in other fields.

Carbon matrix NiFeP/C nanoparticles anchored on Ti3C2Tx nanosheets as heterostructure high-performance anode for lithium-ion batteries

Engineered micro-nano heterogeneous architectures for transition metal phosphide (TMPs) anode materials in lithium-ion batteries (LIBs) provide multifunctional active components. These components synergistically interact to address pivotal challenges of pronounced volume expansion and sluggish reaction kinetics within the electrode. Consequently, this engineering design approach significantly enhances the overall battery performance. In this study, a self-assembled approach is employed to integrate hybridized NiFe-PBA nanocubes with two-dimensional (2D) monolayer MXene (Ti3C2Tx), producing a heterostructured NiFeP/C@Ti3C2Tx composite. In this meticulously engineered architecture, the interface between the outer MXene layer and NiFeP embedded within the carbon matrix exhibits several distinct superiorities, such as rapid interfacial ion migration, multidirectional migration pathways, and strong spatial adaptability. The resulting non-uniform phase structure effectively mitigates electrode expansion and enhances electronic conductivity. Consequently, the NiFeP/C@Ti3C2Tx-15 composite demonstrates distinct performance advantages over NiFeP/C without MXene. The composite achieves a specific capacity of 689.4 mAh g⁻¹ at 200 mA g⁻¹ over 300 cycles, double that of NiFeP/C. Furthermore, density functional theory (DFT) calculations validate the electronic conductivity facilitated by the heterointerface between MXene and NiFeP, substantiating the strategic significance of the heterostructure in advancing high-performance anode materials for lithium-ion batteries.

Two-dimensional vanadium carbide (V2C) MXene derived heterostructures for high-performance lithium storage

Li3VO4 is notable for its high theoretical capacity and favorable lithium-ion insertion potential, making it a promising candidate for lithium storage applications. However, its practical use is limited by low electronic conductivity, which results in reduced electrochemical performance and significant resistance polarization during lithium storage. Herein, we developed a Li3VO4/V2CTx heterostructure using a MXene-derived approach, where Li3VO4 is anchored onto a conductive V2CTx MXene substrate. Theoretical calculations suggest that the heterostructure exhibits enhanced lithium adsorption capabilities compared to V2CTx, indicating improved interactions with lithium ions. The synthesized Li3VO4/V2CTx heterostructure demonstrates excellent rate performance and cycling stability. Additionally, a lithium-ion capacitor utilizing this heterostructure as the anode and activated carbon as the cathode achieves impressive power density and energy density. This study underscores the potential of this heterostructure as a high-performance anode material and offers valuable insights for the design of other advanced electrode materials.

Effective stress dissipation by multi-dimensional architecture engineering for ultrafast and ultralong sodium storage

Stress accumulation is a key factor leading to sodium storage performance deterioration for NiSe2-based anodes. Therefore, inhibiting the concentrated local stress during the sodiataion/desodiation process is crucial for acquiring stable NiSe2-based materials for sodium-ion batteries (SIBs). Herein, a stress dissipation strategy driven by architecture engineering is proposed, which can achieve ultrafast and ultralong sodium storage properties. Different from the conventional sphere-like or rod-like architecture, the three-dimensional (3D) flower-like NiSe2@C composite is delicately designed and assembled with one-dimensional nanorods and carbon framework. More importantly, the fundamental mechanism of improved structure stability is unveiled by simulations and experimental results simultaneously. It demonstrates that this designed multidimensional flower-like architecture with dispersed nanorods can balance the structural mismatch, avoid concentrated local strain, and relax the internal stress, mainly induced by the unavoidable volume variation during the repeated conversion processes. Moreover, it can provide more Na+-storage sites and multi-directional migration pathways, leading to a fast Na+-migration channel with boosted reaction kinetic. As expected, it delivers superior rate performance (441 mA h g−1 at 5.0 A g−1) and long cycling stability (563 mA h g−1 at 1.0 A g−1 over 1000 cycles) for SIBs. This work provides useful insights for designing high-performance conversion-based anode materials for SIBs.

VBO3/V2O3@C heterogeneous anode material with high-specific-capacity and high-stability for lithium-ion batteries

The design and synthesis of high-performance anode materials is the key to further improve the performance of lithium-ion batteries. In this study, VBO3/V2O3 heterogeneous material with high crystallinity was prepared in vacuum quartz tubes by a facile high-temperature solid-phase method, and the electron transport capacity of VBO3/V2O3 was further improved by ball-milling with conductive carbon. As a result, the obtained VBO3/V2O3@C heterogeneous anode material delivers an initial discharge specific capacity of 927 mAh·g−1 and good cycling stability. Even at −20 °C, VBO3/V2O3@C still presents a discharge specific capacity of 432 mAh·g−1. In addition, ex-situ XRD and ex-situ XPS measurements reveal the conversion reaction and (de)intercalation reaction mechanism during charge/discharge. This work deepens the understanding of the structure-activity relationship of borate/oxide heterogeneous anode materials.

Theoretical study on arsenene as anode material for magnesium ion battery in rail transit

The development and regulation of high-performance anode materials contribute to the rapid development of ion batteries in rail transit. In this paper, based on the first-principles calculation method of density functional theory, the properties of two-dimensional arsenene materials are regulated by torsional deformation, and the feasibility of torsionally deformed arsenene as an electrode material for magnesium ion batteries is studied. The results show that the arsenene monolayer remains stable after being adsorbed by a single Mg ion. The properties of arsenene are indirect bandgap semiconductors with a band gap of 1.60 eV. In the current research scope, deformation does not change the semiconductor properties of intrinsic arsenene. As the torsion angle increases, the band gap gradually decreases. The Mg-adsorbed arsenene system exhibits quasi-metallic properties with a band gap of 0.07 eV. The torsional deformation transforms the adsorption system into a small band gap semiconductor. The torsion deformation makes the diffusion energy barrier of magnesium ions on the arsenene monolayer only 0.09 eV, which ensures an excellent charge–discharge rate. The research results provide a theoretical basis for the design of magnesium ion batteries in rail transit.

Carbon-encapsulated silicon ordered nanofiber membranes as high-performance anode material for lithium-ion batteries

Silicon have attracted much attention as a promising anode material for lithium-ion batteries due to the extremely high theoretical capacity. However, its practical application is limited by the huge volume expansion during the cycling process. To address this issue, carbon-encapsulated silicon ordered nanofiber membranes were designed through a modified electrospinning technology with a strong magnetic field. Compared with the conventional nanofiber membranes, the optimized M1200 Gs anode exhibited a high discharge capacity of 1603.1 mAh·g−1 at 0.1 A·g−1, a superior rate performance, and a robust cycling stability with a reversible capacity of 658.1 mAh·g−1 at 1 A·g−1 after 100 cycles. The improved electrochemical performance was confirmed to be highly correlated with the parallel structure of nanofibers, which help to facilitate the diffusion and transport of electrons and ions, realize the stress distribution and buffer the volume changes. This work provides unique insights into designing silicon-based anodes with novel structures for lithium-ion batteries.

Coal-based graphene derived from different coal ranks: exceptional sodium storage performance in sodium-ion batteries.

Coal is a premium carbon material precursor as anode materials for sodium-ion batteries (SIBs). Additionally, developing anode materials with large capacity and rapid charging performance is essential for the advancement of SIBs. Consequently, in this work, coal-based reduced graphene oxide (CrGO) was prepared as an anode materials for SIBs by a modified Hummers-high temperature thermal reduction method with different ranks of coal (coal-based graphite, CG) as a precursor. The CG prepared from higher-rank coal exhibits a higher degree of graphitization, and its graphene layers are easier to exfoliate. The unique microstructure of CrGO provides stability during the sodium storage process and exhibits fast ion capacitive adsorption behavior, enhancing reaction kinetics. CrGO, with an initial reversible capacity of up to 331 mA h g-1 at a current density of 0.03 A g-1, achieves a specific capacity of 75 mA h g-1, even at a high current density of 10 A g-1. Notably, CrGO also maintains a good specific capacity of 123 mA h g-1 after 1000 cycles at a current density of 1 A g-1, with a capacity retention rate of 91.8%. This study highlights the potential for using coal-derived materials in the development of high-performance anode materials for SIBs, promoting the green and high-value utilization of coal.

Enhancing performance of Si/C composite anode in high energy density lithium-ion batteries with CMC-CPAM-SBR binder

Abstract The utilization of polymeric binders is indispensable in the implementation of silicon/carbon anode materials in high-energy-density lithium-ion batteries (LIBs). This necessity arises from their pivotal function in upholding structural integrity. However, current water-based binders solely focus on binder adhesion, neglecting the crucial interaction with the carbon material. In this work, a composite binder (CMC-CPAM-SBR) was constructed by combining Styrene Butadiene Rubber (SBR) with cationic polyacrylamide (CPAM) network binder with self-healing carboxymethyl cellulose (CMC). This innovative binder formulation was designed to enhance the performance of Si@C/graphite composite anodes. A capacity retention rate of 92.86% was achieved after 100 cycles, which represents the improvement over the performance of electrodes utilizing the CMC-CPAM binder, which only retained a capacity of 84.53% after the same number of cycles. A full battery with a capacity of 1992.8 mAh was designed, and the battery capacity remained at 80.6% of its capacity after completing 500 cycles. This research presents an effective technique for manufacturing high-performance anode materials.