Anode Material For Sodium-ion Batteries Research Articles

Cu@MOF based composite materials: High performance anode electrodes for lithium-ion and sodium-ion batteries

In order to satisfy the increasing demand for energy, it is essential to improve the efficiency of lithium-ion batteries (LIBs) and sodium-ion batteries (SIBs) batteries. Metal selenides (MSes) have a high theoretical specific capacity, can be designed in a variety of ways, conduct electricity well, can change morphology easily, and have a multi-electron reaction mechanism. These characteristics make them very competitive as anode materials for LIBs and SIBs. Herein, we synthesise Cu@MOF and Cu@NH2-MOF as the precursor to prepare Cu1.95Se embedded into porous carbon matrix (Cu1.95Se@PC) and porous-N-doped carbon matrix (Cu1.95Se@NPC) via pyrolysis process of Cu@MOF and Cu@NH2-MOF, respectively. Cu1.95Se@PC and Cu1.95Se@NPC electrodes for half-cell LIBs and SIBs exhibit a high reversible capacity of 313.1, 480.9 (for LIBs), 216.3 and 303.8 (for SIBs) mAhg−1after 1000 cycles at 2 A g−1, respectively. We assess the electrochemical performance of the Cu1.95Se@PC and Cu1.95Se@NPC anodes by integrating them with commercially available LiFePO4 (LFP) into full-cell LIBs. The LFP//Cu1.95Se@PC and LFP//Cu1.95Se@NPC full-cells have discharge capacities of approximately 330 and 293 mAh g−1 at 0.3 A g−1 at the initial cycle. In order to explore the sodium storage mechanism of the Cu1.95Se composites, we conducted an in situ XRD test during the first charge/discharge cycle, considering their favourable cycling and rate performance. Our work provides a promising anode electrode material for both half-cell LIBs and SIBs with high volume utilization and superior electrochemical performances.

Sn@Zn/Co-NPC as Anode Materials for Sodium-Ion Batteries via the Solvothermal Method

Sn@Zn/Co-NPC as Anode Materials for Sodium-Ion Batteries via the Solvothermal Method

Facile synthesis of in situ carbon-coated CoS2 micro/nano-spheres as high-performance anode materials for sodium-ion batteries.

In situ carbon-coated CoS2 micro/nano-spheres were successfully prepared by sulfuric calcination using the solvothermal method with glycerol as the carbon source without introducing extraneous carbon. This method prevents carbon agglomeration and avoids the cumbersome steps of the current technology. The composite demonstrates excellent sodium storage capacity as an anode material for sodium-ion batteries. The initial charge and discharge capacities were 1027 and 1224 mA h g-1 at 50 mA g-1, respectively, with an initial coulombic efficiency of 83.9%. The capacity of CoS2@C at 350 °C was maintained at 937 mA h g-1 after 140 cycles at a current density of 2 A g-1. The outstanding electrochemical performance is mainly attributed to the nanostructure design and the presence of in situ carbon. As revealed by the kinetic analysis, the pseudo-capacitive behaviour also contributed to the excellent electrochemical performance.

Surface-dominated sodium storage enabled by TiO2 nanosheets with 84 % exposure of (0 0 1) facets for high-performance Na-ion battery anodes

Anatase titanium dioxide (TiO2) has garnered enormous attention as a promising anode material for sodium-ion batteries (SIBs), owing to its non-toxicity, superior structural stability, and cost-effectiveness. Nevertheless, its intrinsic low electrical conductivity poses a substantial challenge to its practical applications. Here, the ultrathin TiO2 nanosheets were obtained. The TiO2 nanosheets with a thickness of ∼8 nm and exposed 84 % (001) facet. The exposed (001) crystal facets and ultrathin nanosheet structure provide abundant active sites for Na-ion adsorption, shortens ion diffusion pathways, enhances reaction kinetics, and significantly boosts the pseudocapacitive effect. This synergistic strategy of exposed (001) facet with nanosheets structure leads to an exceptional capacity of 177.1 mAh/g at 0.1 A/g, and 59 % capacity retention at 5 A/g. This work will contribute to the understanding of facet-dependent electrochemical behavior anode materials for high-performance SIBs.

Structure Regulation and Energy Storage Mechanisms of Bismuth‐Based Anodes for Sodium Ion Batteries

The increasing demand for eco‐friendly energy storage solutions has driven significant interest in sodium‐ion batteries (SIBs) as an alternative to lithium‐ion batteries, primarily due to sodium's abundant availability. Among various anode materials, bismuth (Bi) has emerged as a promising candidate due to its high theoretical volumetric capacity and excellent electrical conductivity. This review presents a comprehensive analysis of structural characteristics and failure mechanisms inherent to Bi‐based anode materials for SIBs, providing valuable insights into the significance of material modification methods. Structure regulation strategies for Bi‐based SIB anodes are reviewed, focusing on the challenges associated with volumetric expansion and strategies to enhance their electrochemical performance. Typically, nanostructure optimization, surface engineering, morphology modification, and composition regulation are highlighted. Furthermore, this review will discuss the underlying mechanisms that improve sodium storage capabilities and the role of bismuth in advancing the efficiency and stability of SIBs. Lastly, the prospects and imminent challenges associated with bismuth‐based materials will be presented, providing insights for future research and development in energy storage technologies.

Novel Q-Carbon Anodes for Sodium-Ion Batteries

The lack of a standard anode for sodium-ion batteries (SIBs) has greatly hindered their applications. Herein, we show that a novel phase of carbon, namely Q-carbon, is an effective anode material for sodium-ion batteries. The Q-carbon, which is a metastable phase of carbon consisting of about 80% sp3- and 20% sp2-bonded carbon, is synthesized by nonequilibrium pulsed laser annealing and arc-discharge methods. Two types of Q-carbons, Q1 and Q2, were evaluated as anode material for SIBs. Q1 had a slow quench and was used as the control, whereas Q2 was Q-carbon with a rapid quenching. Q1 exhibits a high initial columbic efficiency of 81% and a low-capacity retention of less than 60%, whereas Q2 has a low initial columbic efficiency of 58% and a high-capacity retention of 81%. Q2 exhibits a stable capacity of 168 mAh·g−1 at a cycling rate of C/3 (124 mA·g−1), which is comparable to other hard carbon anodes reported in the literature. This unique synthesis method opens a pathway for the further tuning of Q-carbon with higher trapping/charging of Na+ ions in improved SIBs.

Amorphous germanium encapsulated in flexible nitrogen-doped carbon nanofiber for sodium storage with ultra-long cycling stability

Germanium (Ge), as a viable candidate anode material for future sodium-ion batteries, has attracted much attention. However, such material is usually troubled by huge volume changes during charge/discharge process, leading to the rapid degradation of electrochemical performance. Notably, construction of carbon coating layers is a practical strategy to alleviate the volumetric effect of Ge. Moreover, rational design of nanosized Ge with amorphous structure can also significantly enhance its sodium-ion storage performance. Herein, amorphous Ge (a-Ge) encapsulated by nitrogen-doped carbon nanofiber (Ge@NC) was successfully prepared by facile electrostatic spinning technique and annealing treatment. Impressively, the a-Ge nanoparticles are effectively protected by the flexible nitrogen-doped carbon nanofiber (NC), contributing to faster reaction kinetics and improved cycling stability since the high electrical conductivity and buffering effect of the NC layers. In addition, the nanosized Ge with amorphous structure can offer more open framework and higher structural stability. Therefore, the integrated Ge@NC electrode displays a high capacity of 404 mAh g−1 after 300 cycles at 0.1 A g−1. More excited, the synergistic effect of amorphous structure of Ge and nitrogen-doped carbon layers endow Ge@NC with remarkable long cycle life up to 15,000 cycles at 5 A g−1.

Irida-graphene as a high-performance anode for sodium batteries

Clean energy storage is in the spotlight of the scientific community, as is the development of alternatives to the negative impact of conventional lithium-based batteries; therefore, sodium-ion batteries (SIBs) have emerged due to the abundant Na resources. In this sense, the performance of irida-graphene (IG), a 2D carbon allotrope with metallic character, and geometrically formed by 3-, 6- and 8- carbon rings, is computationally investigated for Na storage by density functional theory (DFT) simulations. The maximum Na capacity in the IG is 24 atoms, a ratio of 1 Na to 2C (1:2), with adsorption energies from −1.42 eV (single Na) to −0.38 eV (24 Na), demonstrating its electrochemical stability. The Na mobility was analyzed, indicating a high diffusion rate (3.11 × 10−5 cm2/s at 300 K) associated with a very small diffusion barrier (0.09 eV). The operating open circuit voltage (OCV) ranges from 0.32 to 1.42 V, which is suitable for a safety battery application. Finally, the Na storage capacity is 1022 mAhg−1, surpassing many commercial anodes and competitive with other structures. The results highlight the IG potential as an effective and safe anode material for SIBs.

Development of Biomass‐Derived Hard Carbon for Sodium‐Ion Batteries: Optimizing Microstructure and Electrochemical Performance

The development of sodium‐ion batteries (SIBs) as a sustainable alternative to lithium‐ion batteries (LIBs) has garnered considerable attention, mainly due to the abundant supply and economic viability of sodium sources. In this study, we present the synthesis and characterization of hard carbon (HC) derived from biomass coconut shells, with the objective of optimizing its performance as an anode material for SIBs. A series of hard carbon samples (denoted as YHC‐T) were prepared via carbonization at 1000°C, 1100°C, 1200°C, 1300°C and 1400°C. The YHC‐1200 sample, exhibiting an expanded interlayer spacing of approximately 0.384 nm, demonstrated superior sodium storage properties, achieving a high reversible specific capacity of 350 mA h g <sup>‐1</sup> and an initial Coulombic efficiency (ICE) of 92.9% at a current density of 0.1 A g <sup>‐1</sup>. Moreover, YHC‐1200 exhibited excellent cycling stability, retaining a capacity of 198 mA h g <sup>‐1</sup> after 1000 cycles at 1 A g <sup>‐1</sup>.

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.

Constructing a Functional Fast‐Ion Conductor Interface for Vertically Aligned Titanium Boride Nanosheets to Achieve Superior Sodium‐Ion Storage Performances

AbstractDesigning excellent anode materials to enhance the sluggish interfacial kinetics of Na+ is a key challenge in improving the electrochemical performance of sodium‐ion batteries (SIBs). Herein, an ultra‐thin fast‐ionic conductor NaB5C coating TiB2 nanoflowers with vertically aligned nanosheet arrays to form yolk–shell TiB2@NaB5C (TBNBC) nanospheres as an anode material for SIBs. The unique structure creates direct and short ion/electron transfer pathways and reserves enough space to prevent the uneven electrochemical reactions from TiB2 nanosheets aggregation and stacking, thus ensuring the long‐term cycling stability of SIBs. Additionally, the NaB5C coating with fast‐ionic conductor functional interphase provides rapid Na+ transport channels and effectively reduces the Na+ de‐solvation barrier, accelerating Na+ reaction kinetics. Furthermore, a homogeneous and robust solid electrolyte interphase (SEI) film including inorganic boron species and fluorine‐rich inner layer is constructed on the TBNBC electrode to delocalize stress and induce a uniform Na+ flux, further promoting fast Na+ interphase reaction kinetics. Consequently, the optimized composites achieve ultrastable cycling performances of 173 mAh g−1 over 5000 cycles at 10 A g−1. More importantly, they also exhibit an outstanding capacity of 182.2 mAh g−1 at −20 °C. This work offers opportunities for the energy storage use of transition metal borides under extreme conditions.

Construction of an Anode Material for Sodium-Ion Batteries with an Ultrastable Structure.

The reserves of sodium resources are much larger than those of lithium resources, and they are widely distributed and easy to produce and can be widely used in photovoltaic energy storage and other industries on the premise of this advantage. However, how to produce hard carbon anodes at a low cost for the preparation of energy storage materials requires continuous exploration and experimentation to find the optimal solution. Here, we used waste sour date shell biomass as a precursor for a hard carbon anode obtained by simple acid treatment and two pyrolyses. It is shown that acid washing after prepyrolysis has a significant effect on the electrochemical performance of the sour date shell-derived hard carbon (ZJ), constructing a stable structure that makes it easier for sodium ions to be embedded and dislodged, and the carbon particles are homogeneous and free of bonding and electrode cracking. The ZJ-1500-HCl pyrolyzed at 1500 °C has a high reversible capacity of 329.1 mAh g-1, 94.1% initial Coulombic efficiency (ICE), 90.54% capacity retention efficiency cycling 300 cycles at a current density of 300 mA g-1, and a resistivity below 10 Ω. It has good cycle stability and a good multiplier performance. It is expected to be used in practical production and photovoltaic energy storage in the future.

The Research About Anode Material for Sodium-Ion Batteries

Sodium-ion batteries are replacing lithium-ion batteries due to their lower cost and more abundant resources. The sodium-ion battery anode, including carbon-based materials, alloy materials, and organic materials, plays a key role in improving battery performance but also faces problems such as poor conductivity, which limits sodium storage capacity attenuation and irreversible volume expansion. To solve these problems, researchers have proposed a variety of solutions, such as chemical activation, element doping, micro-nanostructure design, composite material preparation, surface coating application, and buffer medium introduction. This article summarizes these strategies and points out the direction of future research, including the development of innovative anode materials with better conductivity and sodium storage capacity, and improved manufacturing processes. Further research and development of sodium-ion batteries anode is expected to make important contributions to the new energy field.

Study on the hard carbon anode from different precursors for sodium ion batteries

Sodium-ion batteries (SIBs) are commonly utilized in power storage applications. It can be used as alternatives to lithium-ion batteries. Nevertheless, the development of SIBs is restricted by anode materials due to the high redox potential and large irreversible capacity. As a common anode material of SIBs, hard carbon exhibits a substantial interlayer spacing and a excellent reversible specific capacity, while the properties and costs are affected by its precursors. This article mainly describes the sodium storage principle of hard carbon and compares the performances as well as modification methods of hard carbon produced from various precursors. The hard carbon basing on coal has the advantages of low cost due to the abundant reserves of coal precursors and low redox potential. Biomass-based hard carbon has natural pores which can assist the sodium ions transport in carbon materials. We further explain the effects of modification strategies such as heteroatom doping, activation treatment and mechanical ball milling on electrochemical properties of hard carbon. Finally, this paper recognizes the existing problems and corresponding solutions of materials made of hard carbon and looks forward to the future research focus on hard carbon materials.

Designing Tin and Hard Carbon Architecture for Stable Sodium‐Ion Battery Anode

The lack of anodes stability is one among key barriers to the widespread commercialization of sodium‐ion batteries (SIBs). This is attributed to graphite, a well‐known common anode material for a range of commercial batteries including lithium‐ion batteries (LIBs), which limits the insertion of sodium (Na) ions due to their large ionic size. Tin (Sn) has shown its potential as a suitable anode material because it exhibits high capacities in conversion and alloying reactions. However, it endures significant volumetric expansion and slower reaction rates during sodiation. To overcome these challenges, this work presents a novel anode material for SIBs where a 2D layered architecture of Sn with a hard carbon (HC) buffer layer is engineered using physical vapor deposition technique. This novel anode (SnHT/HC) exhibits a high initial capacity of 470 mAhg−1 and an exceptional retention of 438 mAhg−1 after 3000 cycles at 0.2C, with 99 % Coulombic efficiency. SnHT/HC testing at varying fast charge and discharge C‐rate of 5C, 10C, 15C, and 50C has shown promising results. Better electron transport and reduced volumetric changes are perceived to enhance the overall performance of SnHT/HC electrodes.

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.

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.

Fabrication of a Stable and Highly Effective Anode Material for Li-Ion/Na-Ion Batteries Utilizing ZIF-12.

Transition metal selenides (TMSs) are receiving considerable interest as improved anode materials for sodium-ion batteries (SIBs) and lithium-ion batteries (LIBs) due to their considerable theoretical capacity and excellent redox reversibility. Herein, ZIF-12 (zeolitic imidazolate framework) structure is used for the synthesis of Cu2Se/Co3Se4@NPC anode material by pyrolysis of ZIF-12/Se mixture. When Cu2Se/Co3Se4@NPC composite is utilized as an anode electrode material in LIB and SIB half cells, the material demonstrates excellent electrochemical performance and remarkable cycle stability with retaining high capacities. In LIB and SIB half cells, the Cu2Se/Co3Se4@NPC anode material shows the ultralong lifespan at 2000 mAg-1, retaining a capacity of 543 mAhg-1 after 750 cycles, and retaining a capacity of 251 mAhg-1 after 200 cycles at 100 mAg-1, respectively. The porous structure of the Cu2Se/Co3Se4@NPC anode material can not only effectively tolerate the volume expansion of the electrode during discharging and charging, but also facilitate the penetration of electrolyte and efficiently prevents the clustering of active particles. In situ X-ray difraction (XRD) analysis results reveal the high potential of Cu2Se/Co3Se4@NPC composite in building efficient LIBs and SIBs due to reversible conversion reactions of Cu2Se/Co3Se4@NPC for lithium-ion and sodium-ion storage.

SnO2–SnS2/graphene heterojunction composite promotes high-performance sodium ion storage

The design of electrode material nanostructures including reducing material sizes and designing appropriate heterostructures, has great potential in improving charge storage dynamics and enhancing practical performance. In this study, we present the innovative synthesis of SnO2-SnS2/graphene heterojunction composite materials via a controlled vulcanization reaction process. The unique structure endows the composite with high electronic conductivity, rapid ion diffusion rates, elevated electrochemical activity, excellent structural stability, and abundant reaction sites, making it a highly efficient anode material for sodium-ion batteries (SIBs). Half-cell tests demonstrate that the SnO2–SnS2/r–G composite achieves a first Coulombic efficiency of 77.3% at a high current density of 5 A/g, showing remarkable cycling stability. Remarkably, the composite retains a reversible capacity of 330 mA·h/g after 1000 cycles, with a capacity retention rate of 77.5%. Moreover, we elucidate the specific sodium storage mechanisms of the heterojunction composite electrode via in-situ and ex-situ characterization methods. Furthermore, a full battery utilizing Na0.53MnO2 as the cathode and SnO2–SnS2/r–G composite as the anode exhibits outstanding rate performance and long-term cycling stability. This method of heterostructure design and fabrication, coupled with the exceptional performance metrics, suggests that the SnO2–SnS2/r–G heterostructure is a promising candidate for advanced anode materials in SIBs applications.