Anode Material For Batteries Research Articles

Polar Molecule Intercalation to Weaken P2─S Bonding in MnPS3 Toward Ultrahigh-Capacity Sodium Storage.

Layered transition metal trithiophosphates (TMPS3, TM = Mn, Fe, Co, etc.) with high theoretical capacity (>1300 mAh g-1) are potential anode materials for sodium-ion batteries (SIBs). However, the strong bonding between P2 dimers and S atoms in TMPS3 hinders the efficient alloying reaction between P2 dimers and Na+, resulting in practical capacities much lower than theoretical values. Herein, a polar molecule diisopropylamine (DIPA) is intercalated into MnPS3 for the first time to improve the sodium storage performance effectively. Theoretical calculations show that the electron transfer between DIPA and MnPS3 induces more delocalized S p states and weaker P─S bonds, significantly enhancing the electrochemical activity and sodiation/desodiation reaction kinetics. Moreover, the expanded interlayer spacing from 6.48 to 10.75 Å enables faster Na+ diffusion and more active sites for Na+ adsorption. As expected, the DIPA-MnPS3 exhibits an ultrahigh capacity of 1,023 mAh g-1 at 0.2 A g-1 and excellent cycling performance (≈100% capacity retention after 4200 cycles at 10 A g-1), far outperforming those metal thiophosphates anodes reported for SIBs. Interestingly, in situ and ex situ characterizations reveal a quasi-topological intercalation mechanism of DIPA-MnPS3. This work provides a novel strategy for the design of high-performance anode materials for SIBs.

Grid-Like Structured Sb@DNC Anode by Self-Sacrificial Etching for Fast and Durable Sodium Storage.

Alloying-type materials are promising anodes for sodium storage due to high specific capacities and appropriate redox potentials, but their practical application is impeded by rapid capacity decay from volume change during sodium ion insertion/extraction. Hence, a dual-type N-doped carbon-confined antimony (Sb) nanoparticle (Sb@DNC, where DNC contains an outer N-doped carbon armor and an inner N-doped grid-like carbon skeleton) anode material is fabricated via a self-sacrificial etching strategy to address this challenge. Specifically, the dual-type N-doped carbon matrix can prevent the agglomeration and precipitation of Sb particles, increase a large number of reactive active sites, alleviate severe volume expansion/contraction, and construct a highly interconnected electron/ion transport network. Benefiting from the exquisite structure, the Sb@DNC electrode exhibits excellent cycling stability (2400 cycles at 1.0 A g-1) and astonishing high-rate performance (331.0 mAh g-1 at 10.0 A g-1). Additionally, the state-of-the-art in/ex situ technologies reveals the sodium storage mechanism of the "battery-capacitance dual-mode" and the origin of the ability to withstand continuous volumetric strain for the Sb@DNC electrode. Finally, the derived sodium-ion full cell presents outstanding practical potential. This work emphasizes the great significance of rational structural engineering strategies in the field of alloy-type anode materials for high-performance sodium-ion batteries.

DFT-Guided Design of Dual Dopants in Anatase TiO2 for Boosted Sodium Storage.

Anatase titanium dioxide (TiO2) has drawn great attention as an anode material in sodium ion batteries (SIBs), but it suffers from the sluggish diffusion kinetics of Na+ within TiO2 and inferior electronic conductivity. Herein, under the guidance of density functional theory (DFT), we propose a nitrogen and selenium dual-doped TiO2 system as an advanced SIB anode. Both DFT and experimental investigations reveal the cooperative effect of dopants in boosting the electrochemical performance of TiO2, finding the optimal content ratio (N/Se at 1:3) for overall improved SIB performances. As expected, experimental results exhibit excellent sodium storage behavior of the N,Se-doped TiO2, including high discharge capacity (142 mAh g-1 at 2 A g-1), good rate performance (82 mAh g-1 at 20 A g-1), and ultralong cyclability (97% retention over 5000 cycles at 2 A g-1). Our study underscores the importance of dual-heteroatom doping in the rational design of advanced electrode materials.

Chromium Oxide Nanoparticles Anchored in Hydrogel-Derived Three-Dimensional N-Doped Porous Carbon Anode Materials as Lithium-Ion Batteries.

Transition metal oxides (TMOs) have been identified as the most promising anode materials for lithium-ion batteries (LIBs). However, these materials tend to undergo volumetric expansion during battery operation, which disrupts their internal structure and ultimately leads to a degradation of battery performance. Cr2O3/N-doped porous carbon (Cr2O3@NC) composites were successfully synthesized through high-temperature calcination using Cr2O3-containing hydrogels as precursors. The results show that the carbon material not only improves the electron transfer ability of Cr2O3 but also effectively prevents its agglomeration. The Cr2O3@CN composite as a novel anode material for LIBs exhibits a reversible capacity of 936 mAh g-1 after 200 cycles at a current density of 1 A g-1, showcasing excellent cycling and structural stability during cycling. Scanning electron microscopy analysis reveals that the Cr2O3@NC composite remains structurally intact throughout cycling. The innovative approach proposed in this study provides a new direction for the advancement of electrode materials for energy storage technologies.

Waxberry-like TiO2 with Synergistic Surface Modification of Pyrolytic Carbon Coating and Carbon Nanotubes as an Anode for Li-Ion Battery.

Titanium dioxide (TiO2) as an anode material for lithium-ion batteries (LIBs) has the advantages of tiny volume expansion, high operating voltage, and outstanding safety performance. However, due to the low conductivity of TiO2 and the slow diffusion rate of lithium ions (Li+), it is limited in the application of LIBs. Therefore, waxberry-like TiO2 comodified by pyrolytic carbon coating and carbon nanotubes was prepared in this work. The waxberry-like TiO2 with nanorods on its surface shortens the diffusion distance of Li+. Carbon nanotubes and waxberry-like TiO2 are tightly combined through electrostatic assembly and form a cross-linked conductive network to provide more electron transmission paths. A thin layer of pyrolytic carbon wraps carbon nanotubes and waxberry-like TiO2, which enhance the conductivity of the composites and ensure the structural integrity of the materials throughout the cycling process. The experimental data revealed that the discharge-specific capacity of TiO2@CNT@C is 170.5 mAh g-1 after 3000 cycles at a large current density of 5 A g-1, and the discharge-specific capacity is still 143 mAh g-1 at the superhigh rate of 10 A g-1, which provides excellent rate performance and cyclic stability. The efficient dual-carbon modification strategy could potentially be extended to other materials.

A High‐capacity Benzoquinone Derivative Anode for All‐organic Long‐cycle Aqueous Proton Batteries

AbstractQuinone compounds, with the ability to uptake protons, are promising electrodes for aqueous batteries. However, their applications are limited by the mediocre working potential range and inferior rate performance. Herein, we examined quinones bearing different substituents, and for the first time introduce tetraamino‐1,4‐benzoquinone (TABQ) as anode material for proton batteries. The strong electron‐donating amino groups can effectively narrow the band gap and lower the redox potentials of quinone materials. The protonation of amino groups and the amorphization of structure result in the formation of an intermolecular hydrogen‐bond network, supporting Grotthuss‐type proton conduction in the electrode with a low activation energy of 192.7 meV. The energy storage mechanism revealed by operando FT‐IR and ex situ XPS features a reversible quinone‐hydroquinone conversion during cycling. TABQ demonstrates a remarkable specific capacity of 307 mAh g−1 at 1 A g−1, which is one of the highest among organic proton electrodes. An all‐organic proton battery of TABQ//TCBQ has also been developed, achieving exceptional stability of 3500 cycles at room temperature and excellent performance at sub‐zero temperature.

Predicting corrosion current density in magnesium alloy battery anodes: machine learning approach using rapid miner

ABSTRACT Magnesium (Mg) alloys are increasingly recognised for their potential as anode materials in batteries due to their high specific capacity and cost-effectiveness. However, their susceptibility to corrosion poses a significant challenge to practical applications. This study explores the effectiveness of various machine learning models – local polynomial regression, Decision Trees, Random Forest, Gradient Boost, and Extreme Gradient Boost – in predicting the corrosion behaviour of Mg alloy battery anodes in a 3.5 wt.% NaCl electrolyte. Experimental data on the corrosion current density of Mg alloys are collected and analysed using the RapidMiner tool for model training and evaluation. The findings highlight that the Extreme Gradient Boost (XGBoost) model excels among other machine learning techniques in accurately forecasting the corrosion rates of Mg alloys. XGBoost achieves an exceptional R2 value of 0.9931 in Tafel plots, indicating a robust fit to the data as evidenced by scatter plots. Furthermore, the XGBoost model demonstrates strong positive monotonic and ordinal relationships between actual and predicted corrosion current densities, as indicated by a Spearman correlation coefficient of 1 and a Kendall tau coefficient of 0.99. These outcomes underscore XGBoost's potential as a powerful tool for enhancing the understanding and management of corrosion in Mg alloy battery applications.

Molten salt assisted synthesis of Si/C nanocomposite derived from palygorskite and sodium alginate for electrochemical lithium storage.

Silicon/carbon (Si/C) nanocomposites are considered as one of the most promising anode materials for lithium-ion batteries due to their high capacity and suitable lithiation potential. However, the complex and time-consuming preparation processes of silicon-based nanocomposites and the unexpected silicon carbide generated during high treatment make it difficult to achieve high-performance Si/C nanocomposites for practical applications. Herein, a silicon/carbon nanocomposite is successfully prepared through a facile and eco-friendly molten salt assisted precarbonization-reduction method using palygorskite (PAL) and sodium alginate as raw materials. Based on physical characterizations, it is demonstrated that the sodium alginate plays a key role in the successful preparation of Si/C nanocomposite, which not only boosts uniform embedding of PAL nanoparticles in the carbon matrix but also releases molten sodium salt to suppress the formation of unexpected SiC. When used as an alternative anode material for lithium-ion battery applications, the as-obtained Si/C composite delivers a high reversible specific capacity of 1362.7 mA h g-1 with an initial Coulombic efficiency of 70.3% at a current density of 200 mA g-1 and excellent long-term cycling stability. The findings here provide a facile and eco-friendly molten salt assisted precarbonization-reduction method for high-performance silicon/carbon anode materials.

Design of Silicon-Based Anode Materials for High Energy Density Li-Ion Batteries

Compared to other types of batteries, lithium batteries have an extremely high energy density, which means they can store more energy while maintaining a smaller size and weight. The ideal electrode material must have a high lithium ion capacity to store many lithium ions. In addition, the electrode material must have good electronic conductivity to promote lithium ions' rapid entry and exit. However, traditional carbon materials have limited theoretical specific capacity, and the transmission of lithium-ion batteries in traditional materials is limited, resulting in a significant decrease in capacity. Silicon has a theoretical capacity of up to 4200mAh/g, more than ten times the capacity of commercial graphite negative electrodes. In addition, silicon and lithium can undergo alloying reactions to form Li Si alloys, which helps improve the material's specific capacity. This article first summarizes the advantages of electric vehicles and lithium-ion batteries. Then, the benefits and challenges of using silicon-based materials as negative electrodes for lithium-ion batteries were elaborated in detail, and finally, the prospects of silicon-based materials in lithium-ion battery applications were summarized. This article has reference significance in improving the energy density of lithium-ion batteries.

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.

A DFT Study of Band-Gap Tuning in 2D Black Phosphorus via Li+, Na+, Mg2+, and Ca2+ Ions.

Black phosphorus (BP) and its two-dimensional derivative (2D-BP) have garnered significant attention as promising anode materials for electrochemical energy storage devices, including next-generation fast-charging batteries. However, the interactions between BP and light metal ions, as well as how these interactions influence BP's electronic properties, remain poorly understood. Here, we employed density functional theory (DFT) to investigate the effects of monovalent (Li+ and Na+) and divalent (Mg2+ and Ca2+) ions on the valence electronic structure of 2D-BP. Molecular orbital analysis revealed that the adsorption of divalent cations can significantly reduce the band gap, suggesting an enhancement in charge transfer rates. In contrast, the adsorption of monovalent cations had minimal impact on the band gap, suggesting the preservation of 2D-BP's intrinsic electrical properties. Energetic and charge analyses indicated that the extent of charge transfer primarily governs the ability of ions to modulate 2D-BP's electronic structure, especially under high-pressure conditions where ions are in close proximity to the 2D-BP surface. Moreover, charge polarization calculations revealed that, compared with monovalent cations, divalent cations induced greater polarization, disrupting the symmetry of the pristine 2D-BP and further influencing its electronic characteristics. These findings provide a molecular-level understanding of how ion interactions influence 2D-BP's electronic properties during ion-intercalation processes, where ions are in close proximity to the 2D-BP surface. Moreover, the calculated diffusion barrier results revealed the potential of 2D-BP as an effective anode material for lithium-ion, sodium-ion, and magnesium-ion batteries, though its performance may be limited for calcium-ion batteries. By extending our understanding of interactions between ions and 2D-BP, this work contributes to the design of efficient and reliable energy storage technologies, particularly for the next-generation fast-charging 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.

Solid-Liquid-Solid Growth of Doped Silicon Nanowires for High-Performance Lithium-Ion Battery Anode

Silicon nanowires (SiNWs) have great potential in electronic devices, sensors, energy storage, and conversion devices. Despite various ways to synthesize SiNWs, however, the growth of SiNWs directly from stable, abundant, sustainable silica sources has yet to be achieved. Herein, we report a modified alumino-reduction process of the silica to produce tin (Sn)-doped SiNWs that can be initiated at low temperature (250 °C) based on a solid-liquid-solid growth mechanism in analogy to the well-known vapor-liquid-solid (VLS). In this growth process, the reduced silicon atoms migrate freely in the molten salt and alloy with pre-reduced Sn. The supersaturation of silicon in the Sn-Si alloy leads to the precipitation of single-crystal SiNWs. The prepared SiNWs are of excellent crystallinity and doped with high non-equilibrium concentration (~3.0at.%) of Sn. This process with the solid-liquid-solid mechanism can also be extended to produce other group IV elements-based nanowires such as germanium. In addition, the prepared Sn-doped SiNWs as the anode material in lithium-ion batteries exhibit excellent performance with a high initial Coulombic efficiency of 85.4%, and a substantial reversible capacity of 1133 mAh g-1 even after 500 cycles at 4Ag-1. By utilizing the solid-liquid-solid mechanism, this modified alumino-reduction process offers a novel route for synthesizing doped SiNWs, holding promise for diverse applications.

Preparation of Fe2O3 nanoparticles with ultrathin carbon covered as lithium storage anodes

This study focuses on the development of ultrathin carbon (UTC) treated with Fe2O3 nanoparticles as anode materials for lithium-ion batteries (LIBs). Here, a simple hydrothermal method has been adopted to prepare Fe2O3@C nanocomposite, followed by annealing. The obtained Fe2O3@C demonstrates Fe2O3 nanoparticles (NPs) with uniform carbon, which effectively mitigates volume expansion and enhances electrochemical performance. Encouraging, the first principal calculations ensure that carbon doping in Fe2O3 can notably reduce the band gap from 2.12 to 1.10 eV and enhance electronic conductivity.

Optimizing Interface Chemistry with Novel Covalent Molecule for Highly Sustainable and Kinetics-Enhanced Sodium Metal Batteries

Metallic sodium has attracted increasing attention as an ideal anode material for next-generation high energy density and low-cost secondary batteries. However, it is highly desired yet remains challenging to improve their cycling stability and safety due to unstable solid electrolyte interphase and dendrite growth. Herein, a hybrid interface layer composed of Na2Se and Na3P is constructed on the surface of Na (Na@NPS) via in situ spontaneous reaction. The hybrid interface layer with merits of high sodiophilicity and high Na-ion conductivity can effectively induce homogeneous Na-ion flux distribution, accelerate the reaction kinetics and suppress decomposition of electrolyte components. Benefitting from the above advantages, the Na@NPS symmetric cell delivers a long cycle life (1000 h at 1 mA cm–2 and 1 mAh cm–2). Furthermore, the full cell coupling with Na3V2(PO4)3-based cathode provides an exceptionally long lifespan (1500 cycles) at 20 C with a capacity retention of 98.2% and high energy density (226 Wh kg–1). Therefore, the enhanced electrochemical performance illustrates the feasibility of the covalent molecule derived hybrid multifunctional interfaces in solving the irregular deposition of Na-ion and expediting reaction kinetics in Na metal batteries.

NiCo2S4 nanoparticles encapsulated within hollow mesoporous carbon spheres enabling rapid and stable sodium storage

Poor rate capability and cycling performance significantly impair the utilization of NiCo2S4 as an anode material in sodium-ion batteries. Herein, hollow mesoporous carbon spheres (HMCSs) are synthesized using a hard-template method. NiCo2S4 nanoparticles with sizes ranging from 15 to 43 nm are grown in-situ within HMCSs (NiCo2S4@HMCS) by melt adsorption, solution impregnation, and gas-phase sulfurization. Specifically, NiCo2S4 nanoparticles are uniformly distributed on the inner walls of HMCSs and within the mesoporous channels of spherical shells. In half-cells, NiCo2S4@HMCS exhibits reversible capacities of 482 mAh g−1 after 340 cycles at 1.0 A g−1, 340 mAh g−1 after 600 cycles at 5.0 A g−1, and 271 mAh g−1 after 700 cycles at 10.0 A g−1. In NiCo2S4@HMCS//Na3V2(PO4)3 full-cells, NiCo2S4@HMCS maintain reversible capacities of 203 mAh g−1 after 1200 cycles at 1.0 A g−1 and 122 mAh g−1 after 2000 cycles at 5.0 A g−1. The unique nano-encapsulated structure prevents the detachment of NiCo2S4 from HMCSs, maintaining electrochemical activity and stability of NiCo2S4. Additionally, the nano-encapsulated structure also facilitates electrolyte penetration and enhances the electronic conductivity of NiCo2S4. These effects synergistically result in rapid and stable sodium storage performance.

Pomegranate-like cobalt Phosphides@P-Doped carbon Nanostructures with controlled phase as anode materials for Lithium-Ion batteries

Transition metal phosphides (TMPs) have recently emerged as prominent energy conversion and storage materials owing to their unique physicochemical property. Nevertheless, it’s still a difficult task to obtain phase-control of TMPs owing to multiple energetically favorable stoichiometries. Herein, a phase-controllable cobalt phosphide@C with the pomegranate core–shell structure are successfully realized by employing Co-glycerate as precursors and phytic acid (PA) as P sources, etching and coordination agents. With the presence of six phosphoryl groups and the strong coordination ability, PA allows the self-phosphating of Co atoms and the P-doped carbon shell, as well as the confinement of the obtained nanoparticles Additionally, as an organic acid, PA can etch the Co-glycerate precursors with the formation of hollow structures. With different etching time, metal-rich phosphides Co2P@C and monophosphides CoP@C are successfully achieved. When applied as anode materials, CoP@C demonstrates superior lithium storage performance by delivering a prominent reversible capacity up to 1187 mAh/g at 0.1 A/g and shows no capacity loss at 1 A/g after 500 cycles. This work presents a simple protocol to obtain TMPs with tunable metal/phosphorus ratios, phase selectivity and interface engineering, which could be applied in the field of energy storage and electrocatalysis.

Synthesis of high-entropy perovskite metal fluoride anode materials for lithium-ion batteries via a one-pot solution method

Synthesis of high-entropy perovskite metal fluoride anode materials for lithium-ion batteries via a one-pot solution method