High-performance Anode For Sodium-ion Batteries Research Articles

Co3O4/nitrogen-doped graphene promise high-performance sodium-ion battery anode

Co3O4 has been diffusely researched for high theoretical capacities and superior security. However, its poor intrinsic conductivity and serious volume effects during Na-ion insertion/extraction restrict its actual applications. Herein, graphene oxide coated Co3O4 nanoparticle are integrated through a straightforward hydrothermal method and freeze-drying treatment followed by annealing process. The characterization results indicate that the Co3O4 nanoparticles (∼20 nm) were loaded onto N-GO (∼75 nm), and nitrogen element was successfully introduced through urea. The unique Co3O4/N-GO structure suffices competent stress relaxation and fast Na+ and electron transfer during discharge/charge cycles. Consequently, the Co3O4/N-GO electrode displays a high discharge capacity of 323 mA h g−1 at 0.1 A g−1. When coupled with Na3V2(PO4)3 (NVP) cathode), the NVP//Co3O4/N-GO battery exhibits significant energy density (249.9 Wh kg−1) and power density (163.3 W kg−1).

Soft-Rigid Heterostructures with Functional Cation Vacancies for Fast-Charging And High-Capacity Sodium Storage.

Optimizing charge transfer and alleviating volume expansion in electrode materials are critical to maximize electrochemical performance for energy storage systems. Herein, an atomically thin soft-rigid Co9 S8 @MoS2 core-shell heterostructure with dual cation vacancies at the atomic interface is constructed as a promising anode for high-performance sodium-ion batteries. The dual cation vacancies involving VCo and VMo in the heterostructure and the soft MoS2 shell afford ionic pathways for rapid charge transfer, as well as the rigid Co9 S8 core acts as the dominant active component and resists structural deformation during charge/discharge. Electrochemical testing and theoretical calculations demonstrate both excellent Na+ transfer kinetics and pseudocapacitive behavior. Consequently, the soft-rigid heterostructure delivers extraordinary sodium storage performance (389.7mA h g-1 after 500 cycles at 5.0 A g-1 ), superior to those of the single-phase counterparts; and the assembled Na3 V2 (PO4 )3 ||d-Co9 S8 @MoS2 /S-Gr full cell achieves an energy density of 235.5Wh kg-1 at 0.5 C. Our finding opens up a new strategy of soft-rigid heterostructure and broadens the horizons of material design in energy storage and conversion. This article is protected by copyright. All rights reserved.

High-Energy Ball Milling Promoted Sulfur Immobilization for Constructing High-Performance Na-Storage Carbon Anodes.

Sulfur (S) doping is an effective method for constructing high-performance carbon anodes for sodium-ion batteries. However, traditional designs of S-doped carbon often exhibit low initial Coulombic efficiency (ICE), poor rate capability, and impoverished cycle performance, limiting their practical applications. This study proposes an innovative design strategy to fabricate S-doped carbon using sulfonated sugar molecules as precursors via high-energy ball milling. The results show that the high-energy ball milling can immobilize S for sulfonated sugar molecules by modulating the chemical state of S atoms, thereby creating a S-rich carbon framework with a doping level of 15.5 wt %. In addition, the S atoms are present mainly in the form of C-S bonds, facilitating a stable electrochemical reaction; meanwhile, S atoms expand the spacing between carbon layers and contribute sufficient capacitance-type Na-storage sites. Consequently, the S-doped carbon exhibits a large capacity (>600 mAh g-1), a high ICE (>90%), superior cycling stability (490 mAh g-1 after 1100 cycles at 5 A g-1), and outstanding rate performance (420 mAh g-1 at a high current density of 50 A g-1). Such excellent Na-storage properties of S-doped carbon have rarely been reported in the literatures before.

Facile and Scalable Development of High-Performance Carbon-Free Tin-Based Anodes for Sodium-Ion Batteries.

Tin (Sn)-based anodes for sodium (Na)-ion batteries possess higher Na-storage capacity and better safety aspects compared to hard carbon -based anodes but suffer from poor cyclic stability due to volume expansion/contraction and concomitant loss in mechanical integrity during sodiation/desodiation. To address this, the usage of nanoscaled electrode-active particles and nanoscaled-carbon-based buffers has been explored, but with compromises with the tap density, accrued irreversible surface reactions, overall capacity (for "inactive" carbon), and adoption of non-scalable/complex preparation routes. Against this backdrop, anode-active "layered" bismuth (Bi) has been incorporated with Sn via a facile-cum-scalable mechanical-milling approach, leading to individual electrode-active particles being composed of well-dispersed Sn and Bi phases. The optimized carbon-free Sn-Bi compositions, benefiting from the combined effects of "buffering" action and faster Na transport of Bi, to go with the greater Na-storage capacity and lower operating potential of Sn, exhibit excellent cyclic stability (viz., ∼83-92% capacity retention after 200 cycles at 1C) and rate capability (viz., no capacity drop from C/5 to 2C, with only ∼25% drop at 5C), despite having fairly coarse particles (∼5-10 μm). As proven by operando synchrotron X-ray diffraction and stress measurements, the sequential sodiation/desodiation of the components and, concomitantly, stress build-ups at different potentials provide "buffering" action even for such "active-active" Sn-Bi compositions. Furthermore, the overall stress development upon sodiation of Bi has been found to be significantly lower than that of Sn (by a factor of ∼3.8), which renders Bi promising as a "buffer" material, in general. Dissemination of such complex interplay between electrode-active components during electrochemical cycling also paves the way for the development of high-performance, safe, and scalable "alloying-reaction"-based anode materials for Na-ion batteries and beyond, sans the need for ultrafine/nanoscaled electrode particles or "inactive" nanoscaled-carbon-based "buffer" materials.

Novel Bismuth Nanoflowers Encapsulated in N-Doped Carbon Frameworks as Superb Composite Anodes for High-Performance Sodium-Ion Batteries.

Bismuth (Bi) has attracted attention as a promising anode for sodium-ion batteries (SIBs) owing to its suitable potential and high theoretical capacity. However, the large volumetric changes during cycling leads to severe degradation of electrochemical performance and limits its practical application. Herein, Bi nanoflowers are encapsulated in N-doped carbon frameworks to construct a novel Bi@NC composite via a facile solvothermal method and carbonization strategy. The well-designed composite structure endows the Bi@NC with uniformly dispersed Bi nanoflowers to alleviate the attenuation while the N-doped carbon frameworks improve the conductivity and ion transport of the whole electrode. As for sodium-ion half-cell, the electrode exhibits a high specific capacity (384.8mAhg-1 at 0.1Ag-1 ) and excellent rate performance (341.5mAhg-1 at 10Ag-1 ), and the capacityretention rate still remains at 94.9% after 5000 cycles at 10Ag-1 . Furthermore, the assembled full-cell with Na3 V2 (PO4 )3 cathode and Bi@NC anode can deliver a high capacity of 251.5mAhg-1 at 0.1Ag-1 , and its capacity attenuates only 0.009% in each cycle after 2000 times at 5.0Ag-1 . This work offers a convenient, low-cost, and eco-friendliness approach for high-performance electrodes in the field of sodium ion electrochemical storage technology.

Short rod-like NiCoSe2 binary-metal selenide nanomaterials of carbon-coated as high-performance anode for sodium-ion batteries

Short rod-like NiCoSe2 binary-metal selenide nanomaterials of carbon-coated as high-performance anode for sodium-ion batteries

Few layers 2D MoS2/tubular sisal fiber-derived carbon composite: Enhanced cycling performance as anode material for sodium-ion batteries

Biomass carbon for sodium ion anode material has advantages of wide source, low cost, and renewable resources, but poor electrochemical performance limits its commercial application. In this work, we propose a hybrid composite based on few-layer MoS2 2D nano-structures and tubular sisal fiber carbon (TSFC) micro-structures as anode materials for SIBs, where the in situ vertical growth of MoS2 nanosheets uniformly on TSFC was successfully obtained by a simple hydrothermal method. It is found that the synthesis conditions play an important role in the formation of MoS2 nanosheets and provide tunable structure, morphology, and electrochemical property for the proposed composites. The unique cross-linked network micro-nano-structures of the MoS2/TSFC can effectively improve the electrochemical performance of the anode materials, which shows a reversible specific capacity up to 243 mAh g−1 after 500 long-term cycles at a current density of 0.1 A g−1, with a capacity retention of 97 % from 200 to 500 cycles, and a high initial coulombic efficiency of 64 %. This work can provide a new way of resource utilization for natural sisal cellulose, and obtain a new low-cost high-performance sodium ion battery anode material.

Recovered cobalt-nickel sulfide from spent lithium-ion batteries as an advanced anode material toward sodium-ion batteries

Explosive growth of the electric vehicle market has led to a substantial accumulation of spent lithium-ion batteries (LIBs), causing significant environmental pollution and the wastage of precious metal resources. Thus, we developed a simple hydrothermal method to convert the spent LiNi0.8Co0.1Mn0.1O2 (NMC-811) cathode into CoNi-MOF. After the subsequent sulfidation process, waxberry-like Co0.11Ni0.89S@N-doped carbon composites (Co0.11Ni0.89S@NC), as a bimetallic sulfide solid solution, can be successfully synthesized to serve as high-performance anode materials for sodium-ion batteries (SIBs). The waxberry-like structure and strong S-C bonds between the carbon matrix and transition metal sulfides ensure the structural stability of the material during the cycle. Besides, the coexistence of Co and Ni in the bimetallic sulfide solid solution generates abundant lattice defects and modifies the electronic structures that significantly improve the charge transfer ability and Na+ diffusivity. The as-prepared Co0.11Ni0.89S@NC exhibits a high specific capacity of 622 mAh g−1 at 200 mA g−1, outstanding rate capacity of 370 mAh g−1 at 5000 mA g−1 and good cycling stability (330 mAh g−1 after 1500 cycles at 5000 mA g−1). This study presents a promising approach for the recycling of spent LIBs into high-performance anodes for SIBs, thus achieving the transformation of waste into valuable resources.

Fabrication of nano-solid spherical Nb2O5/nitrogen-doped carbon composite for high-performance sodium-ion battery anodes

Fabrication of nano-solid spherical Nb2O5/nitrogen-doped carbon composite for high-performance sodium-ion battery anodes

Trash to treasure: Sulfonation-assisted transformation of waste masks into high-performance carbon anode for sodium-ion batteries

The global pandemic of COVID-19 poses significant challenge to the recycling of disposable polypropylene (PP)-based waste masks. Herein, a simple but effective sulfonation route has been proposed to transform PP-based waste masks into value-added hard carbon (CM) anode materials for advanced sodium-ion batteries. The sulfonation treatment improves the thermal stability of the PP molecule, preventing their complete decomposition and the release of massive gas molecules during the carbonization process. Meanwhile, the oxygen functional groups introduced during sulfonation effectively facilitates the cross-linking between the PP chains, hindering the rearrangement of carbon microcrystalline structures and enhancing its structural disorder. As a result, the prepared hard carbon anode (CM-180) with a high disorder degree and minimal surface defects realizes a high sodium storage capacity of 327.4 mAh g−1 with excellent cycle and rate capability. In addition, when coupled with O3–NaNi1/3Fe1/3Mn1/3O2 cathode, the fabricated sodium-ion full cell delivers a high energy density of 238 Wh kg−1 and achieves an outstanding rate capability with a retained capacity of 75 mAh g−1 even at an ultrahigh current rate of 50 C. This work offers a novel insight into transforming the waste masks to value-added hard carbons with promising prospects for sodium-ion batteries.

A Multifunctional Coating on Sulfur-Containing Carbon-Based Anode for High-Performance Sodium-Ion Batteries.

A sulfur doping strategy has been frequently used to improve the sodium storage specific capacity and rate capacity of hard carbon. However, some hard carbon materials have difficulty in preventing the shuttling effect of electrochemical products of sulfur molecules stored in the porous structure of hard carbon, resulting in the poor cycling stability of electrode materials. Here, a multifunctional coating is introduced to comprehensively improve the sodium storage performance of a sulfur-containing carbon-based anode. The physical barrier effect and chemical anchoring effect contributed by the abundant C-S/C-N polarized covalent bond of the N, S-codoped coating (NSC) combine to protect SGCS@NSC from the shuttling effect of soluble polysulfide intermediates. Additionally, the NSC layer can encapsulate the highly dispersed carbon spheres inside a cross-linked three-dimensional conductive network, improving the electrochemical kinetic of the SGCS@NSC electrode. Benefiting from the multifunctional coating, SGCS@NSC exhibits a high capacity of 609 mAh g-1 at 0.1 A g-1 and 249 mAh g-1 at 6.4 A g-1. Furthermore, the capacity retention of SGCS@NSC is 17.6% higher than that of the uncoated one after 200 cycles at 0.5 A g-1.

Carbon coated Co(PO3)2/CoSe2 heterostructure as high performance sodium storage anode

Heterostructure fabrication is believed to acquire promoted charge transfer and improved surface storage contribution, thus obtaining high-performance anodes for sodium-ion batteries. Herein, the simultaneous phosphatization and selenization of polydopamine functionalized ZIF-67 is adopted to engineer N-doped carbon coated Co(PO3)2/CoSe2 heterostructure. The hetero-interface with plenty of surface sites is activated with large surface reaction and fast sodium ion transport dynamics. The multiphase synergism and carbon coating layer assure high conductivity and structural stability. The designed sample delivers impressive anode performance, exhibiting a high sodium storage capacity of 333.4 mAh g−1 at 0.1 A g−1 and 192.7 mAh g−1 after 1000 cycles at 2 A g−1. This simple and reasonable method can be utilized to construct other transition metal based heterostructures with multiphase synergism for the application of advanced anodes.

Insights into the storage mechanism of freestanding MoTe2/C nanofibers as binder-free anodes for high-performance sodium-ion batteries

Developing flexible and binder-free electrodes with superior electrochemical performance is the critical key for flexible electronics and wearable devices. MoTe2, a typical two-dimensional (2D) layered material, has emerged as an attractive anode material for sodium ion batteries (SIBs) because its abundant active sites and rapid Na+ transfer and storage. In this work, a series of flexible MoTe2/C nanofibers (NFs) are successfully synthesized via a facile electrospinning process with tellurization treatment. As binder and current collector-free anodes, the optimized MoTe2/C-600 shows significantly enhanced Na+ storage performance, which delivers a high reversible capacity of 294 mAh g−1 after 100 cycles at 0.1 A g−1 and an ultra-long time cycling performance of 5000 cycles at 1.0 A g−1. The as-prepared MoTe2/C NFs possess double merits of well 1D conductive paths and 3D ion diffusion channels, which effectively boost the electron/Na+ transfer. Meanwhile, its excellent flexibility and mechanical strength greatly enhance the cycling stability. More importantly, in-situ X-ray diffraction and ex-situ transmission electron microscope were employed to demonstrate its structure evolution, revealing that the high capacity of MoTe2/C-600 results from the cooperation of Na+ intercalation and conversion reaction. The findings of this study provide a better understanding on the sodium storage mechanism of MoTe2-based flexible electrodes.

Sawdust-derived hard carbon as a high-performance anode for sodium-ion batteries

Sawdust-derived hard carbon as a high-performance anode for sodium-ion batteries

Design of High-Performance Defective Graphite-Type Anodes for Sodium-Ion Batteries

Intercalation of graphite with alkali metal ions, such as Li+, K+, Rb+, and Cs+ ions, has long been reported over past few decades. One exceptional candidate is Na+ ions in which they have very small solubility in graphite in the form of C70Nax (x ≤ 1), attributed to the positive formation energies. In this paper, we systematical design a series of high-defect graphite-type anodes through the ball-milling process. To our surprise, the electrochemically Na+ storage of the highly defective graphite was found to have a 3-fold increment, comparing to the pristine graphite. The hexagonal space group P63mmc was progressively converted into the rhombohedral space group R3̅m, attributed to the mechanical gliding during the ball-milling process. In additional large amount of atomic defects were found in two positions in the P63mmc space group. The average grain sizes of the particles would decrease with increasing the grinding time. The defective graphite samples disintegrated into the nanoscale flakes with enlarged interlayer spacings which could further promote the secondary formation of defects in the crystal structure. Some of the regions had highly distorted lattices in defective graphite. All these positive changes lead to a dramatic increase in the adsorption and intercalation of Na+ ions into the graphite host. The capacity of the high defect graphite was found to be 128.7 mAh g–1 at 0.1 A g–1, with a superior capacity retention over 8000 cycles at 5 A g–1. This work sheds some light on the design prospective of synthesizing defective graphite-type anodes for sodium-ion batteries.

Molten salt synthesis of carbon anode for high-performance sodium-ion batteries

Preparation of high-performance anode materials in a convenient, efficient and environment friendly way is a challenge for the commercialization of sodium-ion batteries (SIBs). Herein, a carbon material was fabricated via a facile reaction between CaC2 and CaCO3 in CaCl2NaCl molten salt. The microstructure of the carbon materials was systemically characterized and the electrochemical performance was investigated. By optimizing temperature and duration, the carbon product has porous and disordered structures. These characteristics facilitate the reversible capacity of Na storage. The optimized carbon anode exhibits excellent rate capabilities (179 and 129 mAh·g−1 at 5 and 20 A·g−1, respectively) and high reversible capacities (295 mAh·g−1 at a low current density of 0.1 A·g−1). The carbon anode also presents attractive stability with 0.0275% capacity decay per cycle at 5 A·g−1 over 1000 cycles. Furthermore, the utilization of this route to transform CO2 to high-performance carbon anode was evaluated.

Crab Shell-Derived SnS2/C and FeS2/C Carbon Composites as Anodes for High-Performance Sodium-Ion Batteries.

The demand for energy storage devices has increased significantly, and the sustainable development of lithium-ion batteries is limited by scarce lithium resources. Therefore, alternative sodium-ion batteries which are rich in resource may become more competitive in the future market. In this work, we synthesized low-cost SnS2/C and FeS2/C anode materials of sodium-ion batteries which used waste crab shells as biomass carbon precursor. The SnS2 nanosheet and FeS2 nanosphere structures are deposited on the crab shell-derived carbon through simple hydrothermal reaction. Due to the coexistence of transition metal dichalcogenides (TMDs) and crab-derived biomass carbon, the anode material has excellent cycle stability and rate performance. SnS2/C and FeS2/C deliver capacities of 535.4 and 479 mA h g-1 at the current density of 0.1 A g-1, respectively. This study explored an effective and economical strategy to use biomass and TMDs to construct high-performance sodium-ion batteries.

Controlled construction of three-dimensional graphene foam with FeSe2 as anode for high-performance sodium-ion batteries

Controlled construction of three-dimensional graphene foam with FeSe2 as anode for high-performance sodium-ion batteries

MoS2/CoS heterostructures grown on carbon cloth as free-standing anodes for high-performance sodium-ion batteries.

Heterostructure construction with mixed transition metal sulfides has been recognized as a promising strategy to boost the performance of sodium-ion batteries (SIBs). Herein, a carbon-decorated MoS2/CoS heterostructure on carbon cloth (MoS2/CoS@CC) as a free-standing anode for SIBs was synthesized via a facile growth-carbonization strategy. In the composite, the generated built-in electric field at MoS2 and CoS heterointerfaces is beneficial for elevating the electron conductivity, thus expediting the Na-ion transport rate. Moreover, different redox potentials between MoS2 and CoS can effectively mitigate the mechanical strain induced by repeated Na+ de-/intercalation, thus ensuring the structural integrity. In addition, the carbon skeleton derived from the carbonization of glucose can enhance the conductivity of the electrode and maintain the structural integrity. Consequently, the resulting MoS2/CoS@CC electrode delivers a reversible capacity of 605 mA h g-1 at 0.5 A g-1 after 100 cycles, and prominent rate performance (366 mA h g-1 at 8.0 A g-1). Theoretical calculations also confirm that the establishment of a MoS2/CoS heterojunction can powerfully promote the electron conductivity, thereby enhancing the Na-ion diffusion kinetics.

Sulfur-doped carbonized bacterial cellulose as a flexible binder-free 3D anode for improved sodium ion storage.

Carbon-based materials have received wide attention as electrodes for energy storage and conversion owing to their rapid mass transfer processes, outstanding electronic conductivities, and high stabilities. Here, sulfur-doped carbonized bacterial cellulose (S-CBC) was prepared as a high-performance anode for sodium-ion batteries (SIBs) by simultaneous carbonization and sulfidation using the bacterial cellulose membrane produced by microbial fermentation as the precursor. Doping sublimed sulfur powder into CBC results in a greater degree of disorder and defects, buffering the volume expansion during the cycle. Significantly, the three-dimensional (3D) network structure of bacterial cellulose endows S-CBC with flexible self-support. As an anode for sodium ion batteries, S-CBC exhibits a high specific capacity of 302.9 mA h g-1 at 100 mA g-1 after 50 cycles and 177.6 mA h g-1 at 2 A g-1 after 1000 cycles. Compared with the CBC electrode, the S-CBC electrode also exhibits enhanced rate performance in sodium storage. Moreover, theoretical simulations reveal that Na+ has good adsorption stability and a faster diffusion rate in S-CBC. The doping of the S element introduces defects that enlarge the interlayer distance, and the synergies of adsorption and bonding are the main reasons for its high performance. These results indicate the potential application prospects of S-CBC as a flexible binder-free electrode for high-performance SIBs.