Anode For Sodium-ion Batteries Research Articles

"Lasagna"-Structured SnS-TaS2 Misfit Layered Sulfide for Capacitive and Robust Sodium-Ion Storage.

Stannous sulfide (SnS), a conversion-alloying type anode for sodium-ion batteries, is strong Na+ storage activity, a low voltage platform, and high theoretical capacity. However, grain pulverization induced by intolerable volume change and phase aggregation causes quick capacity degradation and unsatisfactory rate capability. Herein, a novel "lasagna" strategy is developed by embedding a SnS layer into the interlayer of an electrochemically robust and electron-active TaS2 to form a misfit layered (SnS)1.15TaS2 superlattice. For Na+ storage, the rationally designed (SnS)1.15TaS2 anode exhibits high specific capacity, excellent rate capability, and robust cycling stability (729 mAh cm-3 at 15 C after 2000 cycles). Moreover, the as-assembled (SnS)1.15TaS2 || Na3V2(PO4)3 full cells achieve robust and fast Na+ storage performance with ≈100% capacity retention after 650 cycles at 15 C, which also demonstrates good low-temperature performance at -20°C with a capacity retention of 75% and 2 C high-rate charge/discharge ability.

Vacancies-Induced Delocalized States Cobalt Phosphide for Binder-Free Anode Toward Stable and High-Rate Sodium-Ion Batteries.

Metal phosphides with easy synthesis, controllable morphology, and high capacity are considered as potential anodes for sodium-ion batteries (SIBs). However, the inherent shortcomings of metal phosphating materials, such as conductivity, kinetics, volume strain, etc are not satisfactory, which hinders their large-scale application. Here, a CoP@carbon nanofibers-composite containing rich Co─N─C heterointerface and phosphorus vacancies grown on carbon cloth (CoP1-x@MEC) is synthesized as SIB anode to accomplish extraordinary capacity and ultra-long cycle life. The hybrid composite nanoreactor effectively impregnates defective CoP as active reaction center while offering Co─N─C layer to buffer the volume expansion during charge-discharge process. These vast active interfaces, favored electrolyte infiltration, and a well-structured ion-electron transport network synergistically improve Na+ storage and electrode kinetics. By virtue of these superiorities, CoP1-x@MEC binder-free anode delivers superb SIBs performance including a high areal capacity (2.47 mAh cm-2@0.2mA cm-2), high rate capability (0.443 mAh cm-2@6mA cm-2), and long cycling stability (300 cycles without decay), thus holding great promise for inexpensive binder-free anode-based SIBs for practical applications.

Steric Hindrance Engineering to Modulate the Closed Pores Formation of Polymer-Derived Hard Carbon for High-Performance Sodium-Ion Batteries.

The closed pores play a critical role in improving the sodium storage capacity of hard carbon (HC) anode, however, their formation mechanism as well as the efficient modulation strategy at molecular level in the polymer-derived HCs is still lacking. In this work, the steric hindrance effect has been proposed to create closed pores in the polymer-derived HCs for the first time through grafting the aromatic rings within and between the main chains in the precursor. The experimental data and theoretical calculation demonstrate that steric-hindrance effect from the aromatic ring side group can increase backbone rigidity and the internal free volumes in the polymer precursor, which can prevent the over graphitization and facilitate the formation of closed pores during the carbonization process. As a result, the as-prepared HC anode exhibits a remarkably enhanced discharge capacity of 340.3 mAh/g at 0.1 C, improved rate performance (210.7 mAh/g at 5 C) as well as boosted cycling stability (86.4% over 1000 cycles at 2C). This work provides a new insight into the formation mechanisms of closed pores via steric hindrance engineering, which can shed light on the development of high-performance polymer-derived HC anode for sodium-ion batteries.

ZIF-derived "cocoon"-like in-situ Zn/N-doped carbon as high-capacity anodes for Li/Na-ion batteries

Owing to the unique structure and physicochemical properties, including high specific surface area, self-doped N atoms, open pore structure and good chemical stability, zeolitic imidazolate frameworks (ZIFs) and their derivatives have been widely used in the field of energy storage. Here, a new type of "cocoon"-like Zn/N doped ZIF-derived porous carbon (Zn@N-C-800) is synthesized as an anode for lithium-ion batteries (LIBs) and sodium ion batteries (SIBs) through a one-step carbonization process using a novel Zn-ZIF as the precursor. In Zn@N-C-800, the "cocoon"-like disordered carbon skeleton is conducive to electrolyte infiltration, while the Zn/N doping can provide additional active sites for ion storage. Benefiting from these unique structural characteristics, Zn@N-C-800 achieves excellent electrochemical performances as anode for both LIBs and SIBs: an ultrahigh rate capability of 352 mAh g-1 can be delivered at 12.8Ag-1 for LIBs; an outstanding long-term cycling stability (312 mAh g-1 at 1Ag-1 after 2000 cycles) can be achieved for SIBs. This paper provides new ideas for the design and preparation of high-performance anodes for LIBs and SIBs.

Properties of Ti2CO2 and Ti2CO2/G heterostructures as anodes of sodium-ion batteries by first-principles study

Properties of Ti2CO2 and Ti2CO2/G heterostructures as anodes of sodium-ion batteries by first-principles study

Prussian blue analogue derived porous hollow nanocages comprising polydopamine-derived N-doped C coated CoSe2/FeSe2 nanoparticles composited with N-doped graphitic C as an anode for high-rate Na-ion batteries

CoFe-Prussian blue analogue (CoFe-PBA) templated N-doped graphitic carbon (NGC) and polydopamine-derived carbon (PDA-20) double-coated CoSe2/FeSe2 nanoparticles are introduced as anodes for highly efficient sodium-ion batteries (SIBs). These nanoparticles are encapsulated within porous hollow nanocages, which exhibit remarkable stability in cyclic performance. The synthesis method involved co-precipitation, followed by PDA coating at varying concentrations and a subsequent selenization process. This resulted in the creation of (Co,Fe)Se-NGC nanocages, (Co,Fe)Se-NGC@PDA-20 hollow nanocages, and (Co,Fe)Se-NGC@PDA-100 filled nanocages. This strategic preparation approach leverages the synergistic effects of dual carbon coating, resulting in highly conductive and porous nanostructures. These structures facilitate rapid charge species diffusion, efficient electrolyte infiltration, and effective management of volumetric changes. When used as anodes for SIBs, the (Co,Fe)Se-NGC@PDA-20 hollow nanocages demonstrate impressive structural robustness and high-rate performance. They exhibit remarkable structural integrity, maintaining stable cycling performance for up to 200 cycles at 0.5 and 1.0 A g−1. In terms of rate capability, the hollow nanocages exhibit a high discharge capacity of 126 mA h g−1 at 10 A g−1. This clearly highlights the structural advantages of the prepared hollow nanocages.

Biomass-Derived Hard Carbon for Sodium-Ion Batteries: Basic Research and Industrial Application.

Sodium-ion batteries (SIBs) have significant potential for applications in portable electric vehicles and intermittent renewable energy storage due to their relatively low cost. Currently, hard carbon (HC) materials are considered commercially viable anode materials for SIBs due to their advantages, including larger capacity, low cost, low operating voltage, and inimitable microstructure. Among these materials, renewable biomass-derived hard carbon anodes are commonly used in SIBs. However, the reports about biomass hard carbon from basic research to industrial applications are very rare. In this paper, we focus on the research progress of biomass-derived hard carbon materials from the following perspectives: (1) sodium storage mechanisms in hard carbon; (2) optimization strategies for hard carbon materials encompassing design, synthesis, heteroatom doping, material compounding, electrolyte modulation, and presodiation; (3) classification of different biomass-derived hard carbon materials based on precursor source, a comparison of their properties, and a discussion on the effects of different biomass sources on hard carbon material properties; (4) challenges and strategies for practical of biomass-derived hard carbon anode in SIBs; and (5) an overview of the current industrialization of biomass-derived hard carbon anodes. Finally, we present the challenges, strategies, and prospects for the future development of biomass-derived hard carbon materials.

Double-layer carbon coated on the micrometer bismuth by photothermal effect as anode for high-rate sodium-ion batteries

Bismuth (Bi) is considered a promising anode material for high-rate sodium-ion batteries (SIBs) due to its unique layered crystal structure which can easily insert/extract sodium-ion (Na+). However, the cycle stability of micrometer Bi with great commercial potential needs to be improved. Because the large volume change occurs during alloying/dealloying of Bi and sodium (Na) resulting in the crack of Bi, which reduces the stability of the battery. Herein, we design a Bi/Bi2O3@C composite where a double-layer carbon coated commercial micrometer Bi/Bi2O3 particles. The heat generated by Bi/Bi2O3 particles under ultraviolet (UV) exposure (called photothermal effect) accelerates the decomposition rate of photoinitiator, which in turn improves the polymerization rate of the monomer on the surface of Bi/Bi2O3 particles. So that, the surface of Bi/Bi2O3 particles is coated with a dense polymer, while the polymer away from the particle is relatively loose, thus forming a dense-loose double-layer carbon during the annealing process. The dense carbon layer can effectively protect against the volume effect of Bi/Bi2O3, and the loose carbon layer can provide channels for the transport of Na+. As a result, Bi/Bi2O3@C exhibits excellent cycling stability with a capacity retention rate of 94.5 % after 1600 cycles at 10 A g−1.

Novel multiphase nano Ni3Bi2S2/NiS anchored on graphite nanosheet for high-capacity sodium-ion battery anodes

In the context of scalable electrode production via ball-milling, achieving high cycling stability and electrochemical performance in bifunctional anodes for sodium ion batteries (SIBs) is crucial yet remains a significant challenge. To address these objectives, we have developed a unique hybrid anode nanocomposite characterized by its local multiphase nature. This composite involves the incorporation of novel ternary-Ni-Bi-S/binary-Ni-S nanomaterials onto exfoliated graphite nanosheets (Ni3Bi2S2/NiS-G) through a facile ball-milling process. Our combined experimental and theoretical investigations suggest that the interactions between graphite nanosheets and the layered structure of Ni3Bi2S2/NiS, along with the discharge products of Na2S, play pivotal roles in enhancing the Na+ diffusion rate and stability of the hierarchical configuration anode. Upon testing, the novel Ni3Bi2S2/NiS-G shows overwhelmingly higher electrochemical performance compared to the Ni3Bi2S2/NiS counterpart, the Ni3Bi2S2/NiS-G delivered a reversible capacity of 489.9 mAh/g at 0.2 A/g after 400 cycles, and displayed a high capacity of 387.3 and 339.6 mAh/g after 500 cycles at 1 A/g and 2 A/g, respectively, yielding a high capacity retention ratio of 84.8 % and 82.8 % of the 1st cycle. This work provided a novel approach for developing new bifunctional anode electrodes with high capacity and rate performance as well as superior cycling stability.

Nitrogen-Doped Bioderived Mesoporous Hard Carbon as a Promising Anode for Long-Life Sodium-Ion Battery

Nitrogen-Doped Bioderived Mesoporous Hard Carbon as a Promising Anode for Long-Life Sodium-Ion Battery

Pristine and defective 2D SiCN substrates as anode materials for sodium-ion batteries

Exploring more high-performance anode materials for sodium-ion batteries (SIBs) can smoothly help to build a more sustainable, cleaner, and reliable energy system. This study systematically investigates the potential of 2D pristine SiCN (p-SiCN) and defective (d-SiCN) substrate as candidate materials for SIBs anodes using first-principles computational method. The computational results reveal that the p-SiCN possesses excellent thermal stability and structural cyclical performance, good conductivity, high theoretical specific capacity (1486 mAh·g−1), low diffusion barrier (0.177 eV), and appropriate open-circuit voltage (0.340 V), which allows the p-SiCN substrate more suitable as a potential anode material for SIBs. Furthermore, by investigating the effects of intentionally designed defects on p-SiCN, it is observed that the adsorption energy and diffusion barrier of the Na atom on the d-SiCN substrate increase. Our work demonstrates that investigating the effect of defects on p-SiCN can better explore the properties of anode materials, thus further optimizing the battery performances.

The C-BixSnSb composite toward fast-charging and long-life sodium-ion batteries

Sodium ion batteries (SIBs) fitted with high-rate and high-capacity anodes are attractive for their higher energy density and faster charging capability. However, it is still a challenge to develop high-energy SIBs with high power and long life, due to the sluggish kinetic and limited Na+ insertion in electrode materials. The inherent crystal structure and constituent element are two important factors to resolve the critical issues faced above. Taking the merits of layer-structure and middle-entropy, herein, we proposed and designed a high ion-conductive composite combing with ternary alloy and layered BixSnSb@C nanofibers, which eliminate ion migration barriers while maintaining the structural framework for superior rate property and cycle stability. Used as anode for SIBs, the multiphase BixSnSb@C with adjustable Bi content exhibits excellent Na storage capability as compared to their single phase counterpart. Specially, up to a rate of 132C (50 A g−1), the capacity is still as high as 400 mAh g−1, meanwhile, after 5000 charge and discharge cycles at a current density of 12C, the capacity still maintains 85 % of its initial capacity, which outperform the individual Bi- or SnSb-based materials. The superior electrochemical performances originate from the middle-entropy nature and layer structure of BiSnSb alloy, which can provide more channels for fast Na+ transport, and accommodate large volume changes. Besides, the activity energy and ions transport resistance of Na+ in different composites were evaluated. Furthermore, the full-cell coupled with NaNi1/3Fe1/3Mn1/3O2 as cathode was formed and a capacity retention of ∼80 % is realized in 100 cycles. The results show that the BixSnSb@C is a potential anode for fast-charging Na-ion batteries and could be used to guide the design of multi-component alloy-base anodes.

Engineering fast diffusion channels in metal Sulfide/Selenide heterostructures via confinement effect for high-performance sodium storage

Structural modulation plays a pivotal role in enhancing the energy storage properties of electrochemical hybrids by adjusting their interfacial and electronic characteristics. Nevertheless, facile and effective strategies for tuning the structural properties of these hybrids at the nanoscale remain scarce. In this study, we propose a novel in-situ electrochemically self-driven strategy for embedding FeSe/FeS heterostructures with rich phase boundaries concurrently encapsulated into one-dimensional porous N, S-doped carbon tubes with inner void (FeSe/FeS@SNC). This approach facilitates the creation of heterogeneous interface phases via a simple electrochemical conversion from FeS0.75Se0.25. Notably, the resultant unique one-dimensional porous structure with inner void, along with a highly conductive N/S-co-doped carbon matrix, promotes charge transfer and reinforces structural stability. in-situ/ex-situ microscopic and spectroscopic characterizations, supported by theoretical simulations, validate that FeSe/FeS heterostructures offer rapid electron transport pathways, while the abundant heterojunctions with strong electric fields facilitate ion migration and Na adsorption. As an anode in sodium-ion batteries, the FeSe/FeS@SNC electrdoe exhibits exceptional rate capability (347 mAh/g at 10 A/g) and stable cycling performance (91% capacity retention after 12000 cycles).

Rapid synthesis of two-dimensional MoB MBene anodes for high-performance sodium-ion batteries

Two-dimensional (2D) transition metal borides (MBenes) have emerged as a rising star and hold great potential promise for catalysis and metal ion batteries owing to a well-defined layered structure and excellent electrical conductivity. Unlike well-studied graphene, perovskite and MXene materials in various fields, the research about MBene is still in its infancy. The inadequate exploration of efficient etching methods impedes their further study. Herein, we put forward an efficient microwave-assisted hydrothermal alkaline solution etching strategy for exfoliating MoAlB MAB phase into 2D MoB MBenes with a well accordion-like structure, which displays a remarkable electrochemical performance in sodium ion batteries (SIBs) with a reversible specific capacity of 196.5 mAh g–1 at the current density of 50 mA g–1, and 138.6 mAh g–1 after 500 cycles at the current density of 0.5 A g–1. The underlying mechanism toward excellent electrochemical performance are revealed by comprehensive theoretical simulations. This work proves that MBene is a competitive candidate as the next generation anode of sodium ion batteries.

Demineralization activating highly-disordered lignite-derived hard carbon for fast sodium storage

Lignite, as one of the coal materials, has been considered a promising precursor for hard carbon anodes in sodium-ion batteries (SIBs) owing to its low cost and high carbon yield. Nevertheless, hard carbon directly derived from lignite pyrolysis typically exhibits highly ordered microstructure with narrow interlayer spacing and relatively unreactive interfacial properties, owing to the abundance of polycyclic aromatic hydrocarbons and inert aromatic rings within its molecular composition. Herein, an innovative demineralization activating strategy is established to simultaneously modulate the interfacial properties and the microstructure of lignite-derived carbon for the development of high-performance SIBs. Demineralization process not only creates numerous void spaces in the matrix of lignite precursor to assist aromatic hydrocarbon rearrangement, thereby reducing the ordering and expanding interlayer spacing, but also exposes more interfacial oxygen-containing functional groups to effectively increasing the sodium storage active sites. As a result, the optimal demineralized lignite-derived hard carbon (DLHC 1300) delivers a high reversible capacity of 335.6 mAh/g at 30 mA g−1, superior rate performance of 246.3 mAh/g at 6 A/g and nearly 100 % capacity retention after 1100 cycles at 1A/g. Furthermore, the optimized DLHC 1300 material functions as an outstanding anode in sodium ion full cells. This work significantly advances the development of low-cost, high-performance commercial hard carbon anodes for SIBs.

Review and Recent Advances in Metal Compounds as Potential High-Performance Anodes for Sodium Ion Batteries

Review and Recent Advances in Metal Compounds as Potential High-Performance Anodes for Sodium Ion Batteries

Mo4/3B2Tx induced hierarchical structure and rapid reaction dynamics in MoS2 anode for superior sodium storage

Molybdenum sulfide (MoS2) with large layer distance and high theoretical capacity has been identified as one of the most promising anodes for sodium ion batteries, but the poor intrinsic conductivity and severe structural agglomeration restricted its diffusion kinetic and specific capacity. In this work, the synergistic effect of heterogeneous interface and Na2S adsorption/conversion active sites was employed to construct Mo4/3B2Tx-MoS2@C composites using a self-assembly and calcination strategy. Theoretical calculation and experimental results demonstrated that the charge transfer and interface between Mo4/3B2Tx and MoS2 along with the 3D hydrangea-like structure improved the intrinsic conductivity and provided fast ion diffusion channels, boosting the electrochemical kinetics; while the favorable adsorption of Na2S and weakened Na-S bond at Mo4/3B2Tx-Mo interface optimized the recombination energies of Mo-S bond, accelerating the ion diffusion and enhancing the electrochemical reversibility. In addition, the copious sulfur vacancies provided additional active sites for ion storage, ameliorating the electrochemical capacity. As expected, the novel Mo4/3B2Tx-MoS2@C electrode delivered a satisfactory rate capacity (340.6 mAh g−1 at 1 A g−1) and durable cyclic performance (267.2 mAh g−1 after 600 cycles at 2 A g−1). When paring with Na3V2(PO4)3, the Mo4/3B2Tx-MoS2@C||Na3V2(PO4)3 full cell exhibited high energy densities of 234.0 and 131.7 Wh kg−1 at 215.7 W kg−1 and 4.4 kW kg−1, respectively. The proposed synergistic strategy of heterogeneous interface and Na2S adsorption/conversion active sites provided a new guidance for the rational design of transitional metal sulfide anodes for sodium ion batteries.

Revealing Na+‐coordination induced Failure Mechanism of Metal Sulfide Anode for Sodium Ion Batteries

AbstractMetal sulfide (MS) is regarded as a promising candidate of the anode materials for sodium‐ion battery (SIB) with ideal capacity and low cost, yet still suffers from the inferior cycling stability and voltage degradation. Herein, the coordination relationship between the discharge product Na2S with the Na+ (NaPF6) in the electrolyte, is revealed as the root cause for the cycling failure of MS. Na+‐coordination effect assistants the dissolution of Na2S, further delocalizing Na2S from the reaction interface under the function of electric field, which leads to the solo oxidation of the discharge product element metal without the participation of Na2S. Besides, the higher highest occupied molecular orbital of Na2S suggest the facilitated Na2S solo oxidation to produce sodium polysulfides (NaPSs). Based on these, lowering the Na+ concentration of the electrolyte is proposed as a potential improvement strategy to change the coordination environment of Na2S, suppressing the side reactions of the solo‐oxidation of element metal and Na2S. Consequently, the enhanced conversion reaction reversibility and prolonged cycle life are achieved. This work renders in‐depth perception of failure mechanism and inspiration for realizing advanced conversion‐type anode.

Revealing Na+-coordination induced Failure Mechanism of Metal Sulfide Anode for Sodium Ion Batteries.

Metal sulfide (MS) is regarded as a promising candidate of the anode materials for sodium-ion battery (SIB) with ideal capacity and low cost, yet still suffers from the inferior cycling stability and voltage degradation. Herein, the coordination relationship between the discharge product Na2S with the Na+ (NaPF6) in the electrolyte, is revealed as the root cause for the cycling failure of MS. Na+-coordination effect assistants the dissolution of Na2S, further delocalizing Na2S from the reaction interface under the function of electric field, which leads to the solo oxidation of the discharge product element metal without the participation of Na2S. Besides, the higher highest occupied molecular orbital of Na2S suggest the facilitated Na2S solo oxidation to produce sodium polysulfides (NaPSs). Based on these, lowering the Na+ concentration of the electrolyte is proposed as a potential improvement strategy to change the coordination environment of Na2S, suppressing the side reactions of the solo-oxidation of element metal and Na2S. Consequently, the enhanced conversion reaction reversibility and prolonged cycle life are achieved. This work renders in-depth perception of failure mechanism and inspiration for realizing advanced conversion-type anode.

Heterostructure CoSe2/Sb2Se3 nanocrystals embedded into nanocage-in-nanofiber carbon framework for ultralong-life sodium-ion batteries

Transition metal selenides are considered as one of the most promising anode materials for sodium-ion batteries (SIBs) on account of their high theoretical specific capacity. However, the poor conductivity, sluggish kinetics and volume expansion during the (de)sodiation process hinder its application. Herein, a novel heterostructure of CoSe2/Sb2Se3 nanocrystals embedded into nanocage-in-nanofiber carbon framework is designed and constructed via electrospinning, carbonization, ion exchange and selenization processes. In this structure, bimetallic selenide heterostructure accelerates electron/ion transfer kinetics and Na+ adsorption capacity, carbon nanocages structure alleviates the volume expansion and maintains structural integrity during the (de)sodiation process, and carbon nanofibers connect the nanocages in series to shorten the electron transmission path and enhance electrical conductivity. As a self-supporting anode for SIBs, as-synthesized CoSe2/Sb2Se3@C@CNF shows a high reversible capacity of 406 mAh g-1 at 0.2 A g-1 after 200 cycles and displays excellent rate capability. More remarkably, the CoSe2/Sb2Se3@C@CNF anode manifests an outstanding cycling stability for over 2000 and 12,000 cycles at 1 and 5 A g-1, with the capacity retention being 97 % and 103 % respectively. Meanwhile, the excellent sodium storage performance is revealed by kinetic analysis, energy level analysis and density functional theory calculations.