Anode For Sodium-ion Batteries Research Articles

Construction of MnS nanocubes confined in N, S co-doped carbon as high-performance anodes for sodium-ion batteries

Profiting from the huge natural abundance and high theoretical capacity, manganese sulfides (MnS) have triggered abundant interest and attention, which are expected as highly prospective anodes for sodium-ion batteries (SIBs). Nevertheless, their wide utilizations are seriously impeded by the drawbacks of low electric conductivity, extensive volumetric changes, and sluggish insertion/extraction kinetics, which often result in a rapid deterioration of the capacity and cyclic lifespan for SIBs. Herein, MnS nanocubes confined in N, S co-doped carbon (NSC) matrix are manufactured through a simple hydrothermal with the following sulfurization method. The incorporation of carbon improves the electric conductivity to accelerate electron transport and guards the structural integrality of MnS in the long-term cycling process via the confinement effect. The in situ formed sulfur-bridged bonds (C-S-Mn) provide an intimate affinity between the MnS nanocubes and NSC matrix, which effectively prevents the aggregation and mitigates the volumetric variation of MnS nanocubes in the sodiation/desodiation reactions. Moreover, the hierarchically porous structures in MnS@NSC offer rapid diffusion pathways for Na+ ions that effectively enhance the diffusion kinetics. Benefiting from the admirable synergistic effects between the hierarchically porous MnS nanocubes and conductive NSC framework, the MnS@NSC anode delivers satisfied sodium storage properties.

Bamboo waste derived hard carbon as high performance anode for sodium-ion batteries

Biomass-derived hard carbon stands out as one of the most promising anode materials for advancing the commercial viability of sodium-ion batteries (SIBs). In this study, we harnessed a straightforward and eco-friendly two-step carbonization approach to fabricate high-performance hard carbon materials, ingeniously repurposing industrial bamboo waste. Concurrently, we delved into the impact of carbonization temperature on the microstructure and properties of the hard carbon derived from bamboo waste. The findings revealed that the as-prepared hard carbon at 1400 °C (HCB-1400) showcased the most desirable sodium-ion storage capabilities. The HCB-1400 material not only can deliver a substantial reversible capacity of 328.4 mAh g−1 at 30 mA g−1 in its maiden charge-discharge cycle but also display remarkable cycling stability. Moreover, the HCB-1400//Na3V2(PO4)3 full cell, when assembled, exhibited an impressive energy density of 249.25 Wh kg−1, with a capacity retention rate of 93 % after enduring 200 cycles at a current density of 1.0 C. This research underscores the potential of transforming biomass waste into high-performance hard carbon, heralding a sustainable path for SIB applications.

Understanding pillar chemistry in potassium-containing polyanion materials for long-lasting sodium-ion batteries.

K-containing polyanion compounds hold great potential as anodes for sodium-ion batteries considering their large ion transport channels and stable open frameworks; however, sodium storage behavior has rarely been studied, and the mechanism remains unclear. Here, using a noninterference KTiOPO4 thin-film model, the Na+ storage mechanism is comprehensively revealed by in situ/operando spectroscopy, aberration-corrected electron microscopy and density functional theory calculations. We find that incomplete K+/Na+ ion exchange occurs and eventually 0.15 K+ remains as a pillar to stabilize the tunnel structure. The pillar effect substantially maintains the volume change within 3.9%, much smaller than that of K+(Na+) insertion into KTiOPO4(NaTiOPO4) (9.5%; 5%), thus enabling 10,000 cycles. The powder electrode demonstrates comparable capacity and can work efficiently at commercial-level areal capacity of 2.47 mAh cm-2. The quasi-solid-state pouch cell with high safety under extreme abuse also manifests long-term cycling stability. This pillar chemistry will inspire alkali metal ion storage in hosts containing heterogeneous cations.

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

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

(Fe, Co) oxide nanowires on gold nanoparticles modified MOF-derived carbon nanoflakes for high-efficiency sodium-ion batteries and supercapacitors across electrolytes

The three-dimensional conductive porous carbon nanosheets (CPCN) are from the bimetallic metal-organic framework (MOFs) consisting of organic ligating groups that incorporate zinc and cobalt ions deposited onto a flexible carbon cloth (CC). Utilizing a hydrothermal approach, iron-cobalt oxide (FCO) nanowires are intricately embedded onto CPCN modified with gold (Au), forming a flexible FCO/Au/CPCN@CC electrode. The electrochemical characteristics of electrodes are evaluated in 1 M Na2SO4, supercapacitor's storage capacity is tested at 4 V using 1 M NaPF6 electrolyte. Among its remarkable attributes are a peak energy density of 291.5 W h kg−1 achieved at a power density of 153.85 W kg−1, and even at the maximum power density of 1749.9 W kg−1, it maintains 144.78 W h kg−1. Undergoing 10,000 rounds of GCD, the equipment sustains a capacitance retention of 84.27 %. Moreover, the performance of the FCO/Au/CPCN@CC anode in sodium-ion batteries (SIBs) is assessed. At 0.1C, the discharge capacity reaches 958 mAh g−1, and there is almost no loss after the rate cycle. The Coulomb efficiency surpasses 98 % during 500 cycles at a large C-rate. The integration of Au nanoparticles onto the CPNC surface enhances the energy storage characteristic of the FCO/Au/CPCN@CC composite material in both battery and supercapacitor applications.

Electrolyte Reconfiguration by Cation/Anion Cross-coordination for Highly Reversible and Facile Sodium Storage.

Hard carbon (HC) materials are promising anodes for sodium-ion batteries (SIBs) owing to low cost, high specific capacity and low working potential. However, the poor compatibility of the electrolyte with HC leads to low initial coulombic efficiency (ICE) and sluggish Na+ transport kinetics. Here, we propose an electrolyte reconfiguration strategy based on the hard and soft acid and base (HSAB) theory by introducing methyltriphenylphosphonium bromide (MTPPB). MTPPB can realize a spontaneous cross-coordination solvation structure with NaPF6 by selective affinity, synchronously optimizing the interfacial chemistry and sodium storage process. The advantages of the chemical π-π bridging of MTPP+-HC and interaction of MTPP+-PF6- contribute to preferential and oriented reduction of PF6-, forming a low-resistance supramolecular SEI. Additionally, Na+-Br- coordination weakens the Na+-solvent interactions, facilitating Na+ de-solvation kinetics. Consequently, the HC||Na cell achieves a superior ICE of 96.6%, desirable rate capability under 25 °C and invisible capacity decay after 500 cycles at 1 C under -20 °C. The Na4Fe3(PO4)2P2O7||HC pouch battery displays a high ICE of 90.3% and a 15% increment of energy density under 25 °C. This work provides a guidance through electrolyte reconfiguration engineering for designing practical HC-based SIBs with high energy/power density and long-life span in the extended operating-temperature range.

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.

Conversion of waste denim fabrics into high-performance carbon fiber anodes for sodium-ion batteries

Conversion of waste denim fabrics into high-performance carbon fiber anodes for sodium-ion batteries

Evidence of Quasi-Na Metallic Clusters in Sodium Ion Batteries through In Situ X-Ray Diffraction.

Carbonaceous materials have been considered the most promising anode in sodium-ion batteries (SIBs) due to their low cost, good electrical conductivity, and structural stability. The main challenge of carbonaceous anodes prior to their commercialization is low initial coulomb efficiencies, derived from a lack of an efficient technique to reveal a fundamental comprehension of sodium storage mechanisms. Here, the direct observation of quasi-Na metallic clusters in carbonaceous anodes during cycling through in situ XRD is reported. By means of such a technique, a strong self-adsorption behavior forming quasi-Na metallic clusters is detected within a rationally designed highly defective ultrathin carbon nanosheets (HDCS) anode. Such a self-adsorption and crystalline system transformation mechanism in HDCS brings capacity retention about 100% after 1000 cycles at 1 A g-1. This work provides a new principle for designing high-performance carbon anodes for SIBs.

CO2-converted carbon nanotubes produced from molten salt electrolytes process for application of eco-friendly sustainable anode for sodium ion batteries

CO2-converted carbon nanotubes produced from molten salt electrolytes process for application of eco-friendly sustainable anode for sodium ion batteries

External ligand-free nickel-catalyzed synthesis of polypyrazines towards stable, high-capacity and low-potential sodium ion storage

Sodium ion batteries (SIBs) have been regarded as a promising alternative to lithium-ion battery owing to low cost and good sustainability, but its competitiveness in energy storage is still limited largely by the development of suitable electrode materials. Traditional inorganic anode materials for SIBs face the problems of sluggish electrochemical kinetics and large volume strain due to the insertion/extraction of large size Na+. By comparison, organic anodes have the advantages of abundance resources, renewability, and designability, but suffer from the lack of stable electrode materials with both high specific capacity and low redox potential. Here, a class of pyrazine rings-rich organic polymers (polypyrazines) were designed and synthesized through external ligand-free nickel-catalyzed carbon–carbon coupling reactions. Among them, poly(2,6-pyrazine) shows the lowest synthetic cost, the highest porosity and the best conductivity. Consequently, as the anode of SIBs, poly(2,6-pyrazine) delivers a low redox potential (about 1 V, vs Na+/Na), high-specific-capacity (617.2 mA h/g at 0.1 A/g), excellent rate-capability (300 mA h/g at 10 A/g) and long-term cycling stability (81 % after 1000 cycles at 1.0 A/g). The low preparation cost and outstanding electrochemical performance of poly(2,6-pyrazine) make it a promising anode candidate for further boosting the energy density of SIBs.

Construction of Microporous Structure in Hard Carbon via Adjustable Zn Salt Templates for High-Performance Sodium-Ion Batteries

Template method is an effective strategy for the construction of microporous structure in hard carbons. However, the introduction of templates will inevitably affect the original structure of hard carbon, making it necessary to develop an adjustable template for the high sodium storage property of Sodium-ion battery anodes. Herein, we propose an effective strategy of developing size-controlled ZnO microcrystal in precursor carbon by zinc salts templates and promoting the formation of numerous closed pores during subsequent pyrolysis. All of the obtained hard carbons exhibit high specific capacities of over 340 mAh/g, and initial Coulomb efficiencies of over 90%. Besides, the information of closed pore structure in hard carbon, accompanying with the diffusive behavior of Na+ and the in-situ Raman spectroscopy reveal a strong link between the increased plateau and the closed pore volume, providing a compelling insight for the mechanism of Na+ storage in hard carbon. The optimal sample exhibits the highest closed pore volume, which performs a remarkable specific capacity of 374 mAh/g and a high initial Coulombic efficiency of 92.4%. Furthermore, all zinc salt-derived hard carbon exhibit analogous microstructures and electrochemical behaviors, demonstrating the universality of utilizing both inorganic and organic zinc salts as templates for adjusting the microporous structure of hard carbon. These findings provide a systematic approach to enhance the reversible capacity and maintain high initial Coulombic efficiency for sodium-ion battery anodes.

Bimetallic Sulfide Hollow Nanocubes Heterostructure Promotes Dual Coupling of Conversion and Alloying/Dealloying Reactions to Achieve Durable Potassium-Ion Battery Anode.

Conversion and alloying-type transitional metal sulfides have attracted significant interests as anodes for Potassium-ion batteries (PIBs) and Sodium-ion batteries (SIBs) due to their high theoretical capacities and low cost. However, the poor conductivity, structural pulverization, and high-volume expansions greatly limit the performance. Herein, Co1-xS/ZnS hollow nanocube-like heterostructure decorated on reduced graphene oxide (Co1-xS/ZnS@rGO) composite is fabricated through convenient hydrothermal and post-heat vulcanization techniques. This unique composite can provide a more stable conductive network and shorten the diffusion length of ions, which exhibits a remarkable initial charge capacity of 638.5mA h g-1 at 0.1 A g-1 for SIBs and 606mA h g-1 at 0.1 A g-1 for PIBs, respectively; It is worth noting that the composite presents remarkable long stable cycle performance in PIBs, which initially delivered 274mA h g-1 and sustained the charge capacity up to 245mA h g-1 at high current density of 1 A g-1 after 2000 cycles. A series of in situ/ex situ detections and first principle calculations further validate the high potassium ions adsorption ability of Co1-xS/ZnS anode materials with high diffusion kinetics. This work will accelerate the fundamental construction of bimetallic sulfide hollow nanocubes heterostructure electrodes for energy storage applications.

Analysis of interlayer dependency of MoS2/g-C3N4 heterostructure as an anode material for sodium-ion batteries

In this present work, we explore the effectiveness of layered molybdenum disulfide (2H-MoS2) and graphitic carbon nitride (g-C3N4) heterostructure as anode for Sodium-Ion Batteries (SIBs) by using first principles analysis. To study the anode properties, we varied the interlayer distance between 2H-MoS2/g-C3N4 as 3Å, 6Å, 9Å,12 Å, and 14 Å between MoS2 as substrate and g-C3N4 as top layer. The fundamental properties, such as structural stability and electronic structure were analysed for the respective systems. The adsorption kinetics of Na ion on the g-C3N4 layer were analysed by performing molecular dynamics (MD) simulations to understand the adsorption mechanism better. Our results showed that the interlayer distance of 6 Å with formation energy of −4.31 eV, the theoretical specific capacity value of 765.32 mAhg−1, the average electrode potential is between 0.8 and 1.3 V and the adsorption energy of −2.16 eV is suitable for MoS2/g-C3N4 based anodes for Na ion batteries.

Integrating Multiple Redox‐Active Units into Conductive Covalent Organic Frameworks for High‐Performance Sodium‐Ion Batteries

AbstractThe rational design of porous covalent organic frameworks (COFs) with high conductivity and reversible redox activity is the key to improving their performance in sodium‐ion batteries (SIBs). Herein, we report a series of COFs (FPDC‐TPA‐COF, FPDC‐TPB‐COF, and FPDC‐TPT‐COF) based on an organosulfur linker, (trioxocyclohexane‐triylidene)tris(dithiole‐diylylidene))hexabenzaldehyde (FPDC). These COFs feature two‐dimensional crystalline structures, high porosity, good conductivity, and densely packed redox‐active sites, making them suitable for energy storage devices. Among them, FPDC‐TPT‐COF demonstrates a remarkably high specific capacity of 420 mAh g−1 (0.2 A g−1), excellent cycling stability (~87 % capacity retention after 3000 cycles, 1.0 A g−1) and high rate performance (339 mAh g−1 at 2.0 A g−1) as an anode for SIBs, surpassing most reported COF‐based electrodes. The superior performance is attributed to the dithiole moieties enhancing the conductivity and the presence of redox‐active carbonyl, imine, and triazine sites facilitating Na storage. Furthermore, the sodiation mechanism was elucidated through in situ experiments and density functional theory (DFT) calculations. This work highlights the advantages of integrating multiple functional groups into redox‐active COFs for the rational design of efficient and stable SIBs.

Integrating Multiple Redox-Active Units into Conductive Covalent Organic Frameworks for High-Performance Sodium-Ion Batteries.

The rational design of porous covalent organic frameworks (COFs) with high conductivity and reversible redox activity is the key to improving their performance in sodium-ion batteries (SIBs). Herein, we report a series of COFs (FPDC-TPA-COF, FPDC-TPB-COF, and FPDC-TPT-COF) based on an organosulfur linker, (trioxocyclohexane-triylidene)tris(dithiole-diylylidene))hexabenzaldehyde (FPDC). These COFs feature two-dimensional crystalline structures, high porosity, good conductivity, and densely packed redox-active sites, making them suitable for energy storage devices. Among them, FPDC-TPT-COF demonstrates a remarkably high specific capacity of 420 mAh g-1 (0.2 A g-1), excellent cycling stability (~87 % capacity retention after 3000 cycles, 1.0 A g-1) and high rate performance (339 mAh g-1 at 2.0 A g-1) as an anode for SIBs, surpassing most reported COF-based electrodes. The superior performance is attributed to the dithiole moieties enhancing the conductivity and the presence of redox-active carbonyl, imine, and triazine sites facilitating Na storage. Furthermore, the sodiation mechanism was elucidated through in situ experiments and density functional theory (DFT) calculations. This work highlights the advantages of integrating multiple functional groups into redox-active COFs for the rational design of efficient and stable SIBs.

Ball-Milling-Assisted N/O Codoping for Enhanced Sodium Storage Performance of Coconut-Shell-Derived Hard Carbon Anodes in Sodium-Ion Batteries.

Sodium-ion batteries (SIBs) are regarded as cost-effective alternatives or competitors to lithium-ion batteries for large-scale electric energy storage applications. However, their development has been hindered by the high cost of hard carbon (HC) anodes and poor electrochemical performance. To enhance the sodium storage capacity and rate performance of HC, this study accelerated the electrochemical performance of coconut-shell-derived HC anodes for SIBs through N/O codoping using ball milling and pyrolysis. Experimental results demonstrate that the simultaneous introduction of N and O generates a synergistic effect, increasing the surface oxygen-containing functional groups, defects, and interlayer spacing of coconut-shell-derived HC through the codoping of light elements. The excellent strategy has increased the slope capacity and platform capacity of HC, and the synergistic modification of N/O has increased its reversible specific capacity from 272 to 343 mA h g-1 (30 mA g-1), with a retention rate of approximately 92.1% after 100 cycles. In addition, it also exhibits an excellent rate performance, reaching 178 mA h g-1 at 1500 mA g-1. In summary, this study presents an effective strategy for modifying biomass-derived HC.

Cell-Shearing Chemistry Directed Closed-Pore Regeneration in Biomass-Derived Hard Carbons for Ultrafast Sodium Storage.

The closed-pore structure of hard carbons holds the key to high plateau capacity and rapid diffusion kinetics when applied as sodium-ion battery (SIB) anodes. However, understanding and establishing the structure-electrochemistry relationship still remains a significant challenge. This work, for the first time, introduces an innovative deep eutectic solvent (DES) cell-shearing strategy to precisely tailor the cell structure of natural bamboo and consequently the closed-pore in its derived hard carbons. The DES shearing force effectively modifies the pore architecture by simultaneously shearing and dissolving amorphous components to form closed pore cores with adjustable sizes, as well as disintegrating crystalline cellulose through generation of competing hydrogen bonds to elaborately tune the pore wall thickness and ordering. The optimized closed-pore structure featuring appropriate pore size (∼2 nm) and ultra-thin (1-3 layers) disordered pore walls, exhibits abundant active sites and delivers rapid ion diffusion kinetics and high reaction reversibility. Consequently, a high reversible capacity of 422 mAh g-1 at 30 mA g-1 along with an exceptional rate capability (318.6 mAh g-1 at 6 A g-1) are achieved, outperforming almost all previous reported hard carbons. The new concept of cell-shearing chemistry for closed-pore regeneration significantly advances the applications of biomass materials for energy storage.

Unravelling the electrochemical characteristics and sodium storage mechanism of pistachio shell derived hard carbon as high plateau capacity anodes by operando Raman spectroscopy and full cell demonstration

Hard carbon has emerged as a highly promising material for negative electrode in sodium-ion batteries (SIBs). This study focuses on the synthesis of an anode material through the pyrolysis of Pistachio shells, a commonly available nut waste, at different temperatures ranging from 900° to 1400°C. The material pyrolyzed at 1400 °C exhibits a remarkable reversible discharge capacity of 302 mAhg−1 and plateau capacity of 223 mAhg−1 at a current rate of 10 mAg−1, displaying stable cyclic performance and an impressive 80% capacity retention after 500 cycles at 200 mAg−1. The morphological, structural, and surface chemical characteristics of the cycled hard carbon anode materials were examined through ex-situ FE-SEM, XRD, and XPS analyses. Furthermore, the sodiation and desodiation mechanisms of the synthesized hard carbon were investigated using operando Raman Spectroscopy. The diffusion kinetics parameters were determined by Electrochemical Impedance Spectroscopy (EIS) and CV analyses. This study underscores the potential of Pistachio shells as a promising precursor for the synthesis of carbonaceous anode for SIBs, employing a straightforward one-step pyrolysis process. The excellent electrochemical performance, along with the ease of material sourcing and synthesis, places this nutty waste as a promising, sustainable and clean energy resource option for advancing sodium-ion battery technology.

Self-Standing vanadium oxide pillared carbon microfiber film as an excellent anode for lithium & sodium ion batteries

Insertion of substances (such as atoms/molecules/ions) into the interlayer spaces of graphite to increase its layer separation is found to be extremely useful for sodium-ion batteries (SIBs). Therefore, expanded graphitic systems are the obvious choice as anode material for both lithium/sodium-ion batteries (LIBs/SIBs). Hard carbon-based materials altogether give a decent electrochemical performance, as well as allow structural integrity for long-term use. Herein, we report a facile route to prepare free-standing vanadium oxide doped carbon microfibers (V@CMFs) films. The V@CMFs show ∼ 200 % expansion in the graphitic interlayer distances while accommodating minute deformations in the final compound which is further theoretically verified as the stage-1 type dilute graphite intercalation compound (GICs) with pillar-like structures. Best battery performance was obtained for the 1 % doped (V1@CMFs) sample, with an initial discharge capacity of 1501.8 and 703.4 mAhg−1, reversible capacities of 1253.8 and 288.7 mAhg−1 at 20 mAg−1, and rate capabilities i.e., 362.4 and 108.1 mAhg−1 at 1600 mAg−1, for LIBs and SIBs, respectively. The results revealed that the rate capability and the reversible specific capacity of the 1 % vanadium oxide doped carbon microfibers (V1@CMFs) are significantly superior compared to the pristine and previous reports. Here, the incorporation of just 1 % vanadium oxide acts as a pillar, enhancing the stability and conductivity of the carbon. Thus, the present work highlights the utility of molecularly doped GICs as potential anode materials for LIBs/SIBs.