Anode Material For Sodium-ion Batteries Research Articles

Progress and Prospect of Bimetallic Oxides for Sodium-Ion Batteries: Synthesis, Mechanism, and Optimization Strategy.

Sodium-ion batteries (SIBs) are considered as an alternative to and even replacement of lithium-ion batteries in the near future in order to address the energy crisis and scarcity of lithium resources due to the wide distribution and abundance of sodium resources on the earth. The exploration and development of high-performance anode materials are critical to the practical applications of advanced SIBs. Among various anode materials, bimetallic oxides (BMOs) have attracted special research attention because of their abundance, easy access, rich redox reactions, enhanced capacity and satisfactory cycling stability. Although many BMO anode materials have been reported as anode materials in SIBs, very limited studies summarized the progress and prospect of BMOs in practical applications of SIBs. In this review, recent progress and challenges of BMO anode materials for SIBs have been comprehensively summarized and discussed. First, the preparation methods and sodium storage mechanisms of BMOs are discussed. Then, the challenges, optimization strategies, and sodium storage performance of BMO anode materials have been reviewed and summarized. Finally, the prospects and future research directions of BMOs in SIBs have been proposed. This review aims to provide insight into the efficient design and optimization of BMO anode materials for high-performance SIBs.

A Review on the Upgradation of Biomass-derived Hard Carbon Materials

Abstract: Sodium-ion battery is a promising alternative to lithium-ion battery because of its abundant raw material resources, low price, and high specific capacity. Amorphous carbon materials (hard carbon) have micropores and impurities, facilitating the intercalation of sodium ions to form "quasi-metallic sodium," resulting in a high sodium storage capacity and a low sodium storage potential. Consequently, hard carbon is one of the most widely studied negative electrode materials. It can be prepared from biomass by thermochemical conversion and has the advantages of large specific capacity, low cost, good cycling stability, and renewability. This review focuses on the recent advances in biomass-based hard carbon materials. Firstly, the preparation methods of hard carbon, including precursor selection, pretreatment, drying methods, and carbonization processes, are summarized. Secondly, the effects of precursor composition and heteroatom doping structure and properties of hard carbon are examined, and the changes in carbon material pores during the activation process, as well as the selection of optimal drying method, pyrolysis temperature, carbonization temperature, activator dosage, and additive, are discussed. Thirdly, the impact of preparation methods on hard carbon's cost, efficiency, and stability is briefly summarized, and the relevant improvement measures and prospects are proposed. Finally, some insights are provided into preparing highperformance biomass-based anode materials for sodium-ion batteries.

Strongly coupled C@MoSe2@OMWCNT heterostructure as an anode for sodium-ion batteries

MoSe2, with its extraordinary theoretical capacity, has emerged as a profoundly auspicious anode material for Sodium-ion Batteries (SIBs). However, the actual realization of SIBs encounters hurdles arising from insufficient electron and ion transportation capabilities, along with the irreversible transformation of Mo/Na2Se into MoSe2, eventually substituted by Mo/Se. In this investigation, By employing Mo-based complexes, we have achieved a triumphant synthesis of C@MoSe2@OMWCNT (oxidized multiwall carbon nanotubes) materials, wherein OMWCNTs serve as the fundamental substrate. Theoretical analysis has revealed that the utilization of OMWCNTs not only enhances the structural stability of the anode materials but also improves the electrical conductivity and Na+ ion mobility (the Na+ diffusion barrier: (MoSe2) 0.91 eV vs (C@MoSe2@OMWCNT) 0.41 eV) of the C@MoSe2@OMWCNT. These properties make C@MoSe2@OMWCNT a promising candidate for the development of high-performance SIBs. Furthermore, the Ex-situ Transmission Electron Microscopy (TEM) examination, unveils the emergence of Se and MoSe2 within the C@MoSe2@OMWCNT. The findings indicate that the outer carbon coating layer efficiently prevents contact between Se and the electrolyte, thereby impeding the formation of polyselenides. When C@MoSe2@OMWCNT is employed as the anode for the SIB, it exhibits exceptional cycle stability, with a capacity of 303 mA h g−1 and 189 mA h g−1 after 500 and 3000 cycles, respectively, under a current density of 5 A g−1. Overall, this investigation provides valuable insights into the design and synthesis of advanced anode materials for SIBs, which could have significant implications for the development of next-generation energy storage devices.

A Defective Disc-Like Cu1.96S Anode Material with the Efficient Cu Vacancies for High-Performance Sodium-Ion Storage.

Due to their significant capacity and reliable reversibility, transition metal sulphides (TMSs) have received attention as potential anode materials for sodium-ion batteries (SIBs). Nonetheless, a prevalent challenge with TMSs lies in their significant volume expansion and sluggish kinetics, impeding their capacity for rapid and enduring Na+ storage. Herein, a Cu1.96S@NC nanodisc material enriched with copper vacancies is synthesised via a hydrothermal and annealing procedure. Density functional theory (DFT) calculations reveal that the incorporation of copper vacancies significantly boosts electrical conductivity by reducing the energy barrier for ion diffusion, thereby promoting efficient electron/ion transport. Moreover, the presence of copper vacancies creates ample active sites for the integration of sodium ions, streamlines charge transfer, boosts electronic conductivity, and, ultimately, significantly enhances the overall performance of SIBs. This novel anode material, Cu1.96S@NC, demonstrates a reversible capacity of 339mAhg-1 after 2000 cycles at a rate of 5Ag-1. In addition, it maintains a noteworthy reversible capacity of 314mAhg-1 with an exceptional capacity retention of 96% even after 2000 cycles at 20Ag-1. The results demonstrate that creating cationic vacancies is a highly effective strategy for engineering anode materials with high capacity and rapid reactivity.

Interface engineering of metal sulfides-based composites enables high-performance anode materials for sodium-ion batteries

Metal sulfides (MSs) have attracted much attention as anode materials for sodium-ion batteries (SIBs) due to their high sodium storage capacity. However, the unsatisfactory electrochemical performance induced by the huge volume change and sluggish kinetics hampered the practical application of SIBs. Herein, guided by the heterostructure interface engineering, novel multicomponent metal sulfide-based anodes, including SnS, FeS, and Fe3N embedded in N-doped carbon nanosheets (SnS/FeS/Fe3N/NC NSs), have been synthesized for high-performance SIBs. The as-prepared SnS/FeS/Fe3N/NC NSs with abundant heterointerfaces and high conductivity of N-doped carbon nanosheet matrix can shorten the Na+ diffusion path and promote reaction kinetics during the sodiation/desodiation process. Moreover, the presence of Fe3N can promote the reversible conversion of SnS and FeS during the cycling process. As a consequence, when evaluated as anode materials for SIBs, the SnS/FeS/Fe3N/NC NSs can maintain a high sodium storage capacity of 473.6 mAh g-1 after 600 cycles at 2.0 A g-1 and can still provide a high reversible capacity of 537.4 mAh g-1 even at 5.0 A g-1 This discovery offers a novel strategy for constructing metal sulfide-based anode materials for high-performance SIBs.

Superior initial Coulombic efficiency and areal capacity of hard carbon anode enabled by graphite-assisted carbonization for sodium-ion battery

Hard carbons are perceived as promising anode materials in sodium-ion batteries, while their practical implementation is largely impeded by the insufficient initial Coulombic efficiency (ICE). Hard carbons with self-supporting architecture are intriguing to enhance ICE owing to the omission of binder and conductive agent; whereas elaborate architecture and microstructure design are still required to further raise the ICE to the level of commercial graphite in lithium-ion batteries, especially under high areal capacity. Herein, we propose a graphite-assisted pressurization strategy during carbonization to achieve remarkable ICE and high areal capacity in resulting self-supporting cellulose tissue derived hard carbon anode. The intimate contact of graphite plate enables suitable local ordering of pseudo-graphitic nanodomains with low intrinsic defects, responsible for enhanced ICE. While the pressure-reinforced dense yet self-interwoven fibrous networks render high areal capacity. Consequently, the as-prepared self-supporting hard carbon anode displays remarkable ICE to 95% and areal capacity of 2.4 mAh cm−2, far exceeding the reported value of less than 0.8 mAh cm−2. Meanwhile, the rate and durability are not scarified under such superior ICE due to the well-manipulated pseudo-graphitic nanodomains and porous fibrous networks. The practicality is further demonstrated in coin-type and pouch-type full cells delivering high capacity and long-term stability. Our finding offers an impetus for the development of high ICE and areal capacity for sodium-ion battery anode.

Low‐Temperature Sodium‐Ion Batteries: Challenges and Progress

AbstractAs an ideal candidate for the next generation of large‐scale energy storage devices, sodium‐ion batteries (SIBs) have received great attention due to their low cost. However, the practical utility of SIBs faces constraints imposed by geographical and environmental factors, particularly in high‐altitude and cold regions. In these areas, the low‐temperature (LT) performance of SIBs presents a pressing technological challenge that requires significant breakthroughs. In LT environments, the electrochemical reaction kinetics of SIBs are sluggish, the electrode/electrolyte interface is unstable, and the diffusion of sodium ions in electrode materials is slow, leading to a decrease in battery performance. Therefore, the reasonable design of electrolyte and electrode materials is of great significance for optimizing the LT performance of SIBs. In this review, the research progress of LT SIBs electrolytes, cathode, and anode materials, as well as sodium metal batteries and solid‐state electrolytes is systematically summarized in recent years, aiming to understand the design principles of LT SIBs, clarify the basic research and development of high‐performance SIBs in practical applications, and promote the development of SIBs technology in the full temperature range.

Flexible Self-Supporting MOF-Based Bean Pod Cube Hollow Nanofibers for Ultralong Cycling and High Rate Na Storage.

Sodium-ion batteries (SIBs) have garnered significant attention due to their potential as an emerging energy storage solution. Tin sulfide (SnS) has emerged as a promising anode material for SIBs due to its impressive theoretical specific capacity of 1022 mA h g-1 and excellent electrical conductivity. However, its practical application has been hindered by issues such as large volume expansion, which adversely affects cycling stability and rate performance during the charge/discharge processes. In this study, a novel approach to address these issues by synthesizing the bean pod cube hollow metal-organic framework (MOF)-SnSx/NC@N-doped carbon nanofibers through a process involving electrospinning, PDA coating, and calcination. The Sn-MOF serves as a self-sacrificing template, facilitating the simultaneous dissociation of MOF and polymerization of dopamine, leading to the creation of hollow intermediates that retain tin components. Subsequent sulfidation results in the integration of the hollow MOF-SnSx/NC nanoparticles within 3D nitrogen-doped carbon nanofibers, forming the distinctive bean pod cube composite structure. This unique configuration effectively shortens the diffusion path and mitigates volume expansion for sodium ions, ultimately yielding an exceptional high rate performance of 130 mA h g-1 (10 A g-1) and an ultralong cycling performance of 328 mA h g-1 even after 3500 cycles (2 A g-1) as the anode for SIBs.

Microporous Sulfur-Carbon Materials with Extended Sodium Storage Window.

Developing high-performance carbonaceous anode materials for sodium-ion batteries (SIBs) is still a grand quest for a more sustainable future of energy storage. Introducing sulfur within a carbon framework is one of the most promising attempts toward the development of highly efficient anode materials. Herein, a microporous sulfur-rich carbon anode obtained from a liquid sulfur-containing oligomer is introduced. The sodium storage mechanism shifts from surface-controlled to diffusion-controlled at higher synthesis temperatures. The different storage mechanisms and electrode performances are found to be independent of the bare electrode material's interplanar spacing. Therefore, these differences are attributed to an increased microporosity and a thiophene-rich chemical environment. The combination of these properties enables extending the plateau region to higher potential and achieving reversible overpotential sodium storage. Moreover, in-operando small-angle X-ray scattering (SAXS) reveals reversible electron density variations within the pore structure, in good agreement with the pore-filling sodium storage mechanism occurring in hard carbons (HCs). Eventually, the depicted framework will enable the design of high-performance anode materials for sodium-ion batteries with competitive energy density.

Zn/Co-ZIF-Derived Composites as High-Performance Anode Materials for Sodium-Ion Batteries

Zn/Co-ZIF-Derived Composites as High-Performance Anode Materials for Sodium-Ion Batteries

Unleashing the Power of Sn2S3 Quantum Dots: Advancing Ultrafast and Ultrastable Sodium/Potassium-Ion Batteries with N, S Co-Doped Carbon Fiber Network.

Tin sulfide (Sn2S3) has been recognized as a potential anode material for sodium-ion batteries (SIBs) and potassium-ion batteries (PIBs) due to its high theoretical capacities. However, the sluggish ion diffusion kinetics, low conductivity, and severe volume changes during cycling have limited its practical application. In this study, Sn2S3 quantum dots (QDs) (≈1.6nm) homogeneously embedded in an N, S co-doped carbon fiber network (Sn2S3-CFN) are successfully fabricated by sequential freeze-drying, carbonization, and sulfidation strategies. As anode materials, the Sn2S3-CFN delivers high reversible capacities and excellent rate capability (300.0 mAh g-1 at 10 A g-1 and 250.0 mAh g-1 at 20 A g-1 for SIBs; 165.3 mAh g-1 at 5 A g-1 and 100.0 mAh g-1 at 10 A g-1 for PIBs) and superior long-life cycling capability (279.6 mAh g-1 after 10 000 cycles at 5 A g-1 for SIBs; 166.3 mAh g-1 after 5 000 cycles at 2 A g-1 for PIBs). According to experimental analysis and theoretical calculations, the exceptional performance of the Sn2S3-CFN composite can be attributed to the synergistic effect of the conductive carbon fiber network and the Sn2S3 quantum dots, which contribute to the structural stability, reversible electrochemical reactions, and superior electron transportation and ions diffusion.

A superior sodium-ion anode material from PAN/lignin-derived carbon nanofibers with inter-connected structure prepared through phosphoric acid induced cross-linking

A feasible route to fabricate phosphorus-doped carbon nanofibers (P-CNFs) with an inter-connected structure has been demonstrated through electrospinning, stabilization, and subsequent phosphoric acid impregnation and carbonization processes using polyacrylonitrile and lignin as carbon sources. The results illustrate that the phosphoric acid induced cross-linking could be beneficial to acquire the closed-pore structure and the heteroatom-doped surface chemistry of nanofibers. As a result, the P-CNFs exhibit higher interlayer spacing of graphite and lower BET specific surface area compared to the pristine CNFs. The P-CNFs as an anode material for sodium-ion batteries (SIBs) present a high reversible capacity 278 mA h g−1 at 0.2 A g−1 and a superior initial Coulomb efficiency (ICE) of 78.86 %. Moreover, the reversible capacity of P-CNFs can be stably maintained near the initial capacity after 5000 cycles at 1 A g−1, showing exceptional structural stability and cycling durability. Meanwhile, the sodium storage mechanism of P-CNFs was investigated using in-situ Raman and ex-situ XRD analysis to understand the exceptional structural stability and Na+ adsorption capacity of P-CNFs. This work provides valuable insights for the design of carbon nanofibers with an inter-connected structure as anode materials for SIBs, exhibiting outstanding electrochemical properties.

Cotton Stalk-Derived Porous Carbon as Anode Material for Sodium-Ion Batteries

Cotton Stalk-Derived Porous Carbon as Anode Material for Sodium-Ion Batteries

Optimizing Synthesis Temperature for Lignin-Derived Hard Carbon Anode for High Cycling Capacity in Sodium-Ion Batteries

This comprehensive study sheds light on the promising potential of lignin-derived carbonaceous materials as sustainable and cost-effective anode materials for sodium-ion batteries, contributing to the development of eco-friendly energy storage technologies. Lignin, a complex and abundant biopolymer, undergoes a facile pyrolysis process to produce carbonaceous materials. The unique microstructure of lignin-derived carbon, characterized by a relatively high surface area and interconnected porous network, facilitates efficient sodium ion diffusion and accommodates volume changes during cycling. The effects of pre-treatment methods, carbonization conditions, and structural modifications of lignin on the electrochemical performance are systematically investigated. Furthermore, the electrochemical mechanisms underlying the sodiation/desodiation processes in lignin-derived carbon (LDC) based anodes are elucidated through advanced characterization techniques, including in situ spectroscopy and microscopy. Among the different hard carbon materials, pre-pyrolyzed lignin-derived carbon LDC-300–1400 (300 shows which pre-treatment pyrolysis temperature was used and 1400 is the post-pyrolysis temperature in °C) shows the most favourable outcomes, demonstrating a reversible capacity of 359 mAh g−1, 1st cycle coulombic efficiency of 81%, and good rate capabilities. Hydrothermally pre-treated LDCs show a slightly lower specific capacity value reaching up to 337 mAh g−1.

Cobalt-Mediated Defect Engineering Endows High Reversible Amorphous VS4 Anode for Advanced Sodium-Ion Storage.

Metal sulfides are promising anode materials for sodium-ion batteries (SIBs) due to their structural diversity and high theoretical capacity, but the severe capacity decay and inferior rate capability caused by poor structural stability and sluggish kinetics impede their practical applications. Herein, a cobalt-doped amorphous VS4 wrapped by reduced graphene oxide (i.e., Co0.5-VS4/rGO) is developed through a Co-induced defect engineering strategy to boost the kinetics performances. The as-prepared Co0.5-VS4/rGO demonstrates excellent rate capacities over 10Ag-1 and superior cycling stability at 5Ag-1 over 1600 cycles, which is attributed to the defects formed by Co doping, the formed amorphous structure and the robust rGO substrate. The great features of Co0.5-VS4/rGO anode are further confirmed in sodium-ion capacitors when the active carbon cathode is used. Additionally, the relationships between metal doping, the derived defects, the amorphous structure, and the sodium storage of VS4 are uncovered. This work provides deep insights into preparing amorphous functional materials and also probes the potential applications of metal sulfide-based electrode materials for advanced batteries.

Non-graphitic carbon as sodium-ion battery anode materials with improved ratio of plateau to sloping capacities prepared from lignite-based organic maceral

Herein, huminite concentrate is obtained from lignite with high yield of 68.9 % by density gradient separation, subsequently converted to non-graphitic carbon (HM-H) by carbonization at 1400 °C for 2 h. Huminite concentrate possesses relatively high oxygen content and considerable amount of aromatic component, with modest yield of volatile matter during pyrolysis, resulting in optimized carbon phase distribution and enhanced electrical conductivity of HM-H. Compared with HM prepared by direct carbonization of lignite, HM-H has slightly higher contents of pseudo-graphitic and graphite-like carbons, and lower content of highly disordered one. Notably, HM-H exhibits remarkably improved electrical conductivity (1773 S m−1) than HM (1406 S m−1). Compared with HM anode for SIBs, HM-H one delivers higher plateau capacity (170.1 mAh g−1) meanwhile lower sloping capacity (91.8 mAh g−1), with significantly improved rate and cycling performances. Full cell assorted with NaFe1/3Ni1/3Mn1/3O2 cathode and HM-H anode demonstrates higher energy density of 210.5 Wh kg−1 than its counterpart (193.8 Wh kg−1) at 20 mA g−1, with superior rate performance (208.6 mAh g−1 at 200 mA g−1) and a capacity retention ratio of 89.7 % after 100 cycles. This work provides a facile and effective strategy for preparing non-graphitic carbon as high-performance anode materials for SIBs.

Facile processing of red phosphorous-carbon composites as high-performance anode materials for sodium-ion batteries

Sodium-ion batteries (SIBs) are being consideredas potentially useful alternatives for the storage of energy owing to the limited availability of lithium resources. However, high-performance electrode materials with facile design are essential for successful and sustainable deployments. Herein, red phosphorous is processed using a facile balling with super P (P@C), carbon nanotubes (P@CNT), and graphene oxide P@GO, and their electrochemical performances are evaluated as anodes in SIBs. The P@CNT and P@GO anodes have approved excellent cyclabilities, at 0.1 C, of 497 and 458 mAh/g, respectively at the 200th cycle compared to 235 mAh/g of P@C. The rate capability test shows relatively low capacity of 122 mAh/g for P@C while the P@CNT and P@GO electrodes exhibit 284 and 211 mAh/g capacities, respectively, at a high rate of 3.0 C. The charge transfer resistance values obtained for P@C, P@CNT, and P@GO anodes were 711, 478, and 486, respectively, corroborating the results of the rate capability. Further, ex-situ transmission electron microscopy measurements conform properly maintained surface morphology of the P particles even after 200 cycles, indicating the better stability of the P@GO electrode.

First-principles study of slag impurity doped Na2Ti3O7 as anode material for Na-ion batteries

Na2Ti3O7 (NTO) has attracted significant attention as a promising anode material for sodium-ion batteries (SIBs). However, its practical electrochemical performance is hindered by its inherently low electronic conductivity. To address this limitation, researchers have turned to elemental doping as an effective strategy to enhance the conductivity of NTO electrodes. Interestingly, the process of purifying titanium for NTO synthesis often yields Al and Ca impurities, which can be harnessed as cost-effective dopants. In this study, we employ first-principles calculations to conduct a comprehensive investigation into the structural, electronic, and sodium ion diffusion properties of NTO when doped with Al and Ca, either individually or in combination. Doping system structure has good stability. Our findings reveal that both Al or Ca single-doping Our findings reveal that all the Al and Ca single-doping, and AlCa co-doping transform NTO from semiconducting into metallicity. Notably, the sodium ion migration barriers for Ca single-doping greatly decrease (0.13 eV) compared with that of pristine NTO (0.23 eV), indicating fast ion transport. The insights gained from our research hold promise for the development of cost-effective multi-component anode materials for SIBs.

Synergistic effects of confined substitution and architecture engineering in CoTe2/Sb2Te3 heterostructures towards durable and fast sodium storage

Metal tellurides (MTes) with high volume-specific capacity are promising anode materials for sodium-ion batteries (SIBs), but they constantly suffer from capacity degradation and slow dynamics. Herein, we propose a hierarchical porous structure to address the aforementioned challenges by incorporating electrospinning and in-situ ion-substitution, in which ultrafine CoTe2/Sb2Te3 heterojunction particles are confined by dual-carbon layers (CoTe2/Sb2Te3@NCNFs). Specifically, the porous nanofiber network enhances electrolyte infiltration and constitutes a highway for electron transport. Interestingly, high-capacity Sb replaces part of the Co through an asymmetric ion-substitution reaction, which not only obtains more pores to alleviate volume stress and particle agglomeration during cycling, but also improves the reversible capacity by constructing heterostructures. Impressively, the CoTe2/Sb2Te3@NCNFs anode exhibits outstanding specific capacity (301.77 mAh g−1 after 500 cycles at 0.2 A g−1) and excellent rate performance (144.52 mAh g−1 at 5.0 A g−1) for sodium storage. Systematic in-situ testing reveals the highly reversible “conversion-alloy” storage mechanism, and the “battery-capacitor dual-mode” reaction process. Finally, a Na-ion full cell (P2-NaNMMT//CoTe2/Sb2Te3@NCNFs) is assembled and achieves excellent cycling performance and rate capability. This unique nanostructure design approach provides new insights into the design of advanced electrode materials for sodium-ion batteries.

Cobalt-vanadium sulfide yolk-shell nanocages from surface etching and ion-exchange of ZIF-67 for ultra-high rate-capability sodium ion battery

Development of high-performance metal sulfides anode materials is a great challenge for sodium-ion batteries (SIBs). In this work, a cobalt-based imidazolate framework (ZIF-67) were firstly synthesized and applied as precursor. After the successive surface etching, ion exchange and sulfidation processes, the final cobalt-vanadium sulfide yolk-shell nanocages were obtained (CoS2/VS4@NC) with VS4 shell and CoS2 yolk encapsulated into nitrogen doped carbon frameworks. This yolk-shell nanocage structure effectively increases the specific surface area and provides enough space for inhibiting the volume change during charge/discharge processes. Besides, the nitrogen doped carbon skeleton greatly improves the ionic conductivity and facilitates ion transport. When used as the anode materials for SIBs, the yolk-shell nanocages of CoS2/VS4@NC electrode exhibits excellent rate capability and stable cycle performance. Notably, it displays a long-term cycling stability with excellent capacity of 417.28 mA h g−1 after 700 cycles at a high current density of 5 A/g. This developed approach here provides a new route for the design and synthesis of various yolk-shell nanocages nanomaterials from enormous MOFs with multitudinous compositions and morphologies and can be extended to the application into other secondary batteries and energy storage fields.