Anode For Sodium-ion Batteries Research Articles

(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.

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.

Enhanced Sodium Storage in MXene Transition Metal Chalcogenides Anode through Dual Molten Salt Etching

Referred to as potential options for anodes in sodium-ion batteries, transition metal chalcogenides (TMCs) exhibit unique electronic and structural characteristics. However, the limited electrical conductivity inherent in them poses a hindrance to electron transport, while their tendency to undergo volumetric expansion during cycling exacerbates structural instability, thereby imposing constraints on practical applications. Herein, a dual molten salt etching strategy followed by a sulfidation-selenidation process was employed to anchor multi-component sulfides FeS2/NiS and FeSe/NiSe onto conductive Ti3C2Tx MXene, achieving superior sodium storage performance. Owing to the enhanced Na⁺ and faster kinetics of electronic transport, mechanical strain is effectively reduced, and strong covalent interactions are formed at the interface, significant enhancement in the cycling stability is observed for the anodes of Ti3C2Tx@FeS2/NiS and Ti3C2Tx@FeSe/NiSe (with specific capacities of 309.4 and 162.6 mAh g−1, respectively, after 1000 cycles at 5 A g−1, with a former retention capacity rate that can reach as high as 87.8%) and exceptional rate performance (252.1 and 207.8 mAh g−1, respectively, at 8 A g−1). Furthermore, full cells assembled by pairing Ti3C2Tx@FeS2/NiS and Ti3C2Tx@FeSe/NiSe with Na3V2(PO4)3 cathodes also demonstrate excellent cycling performance, with both configurations achieving up to 500 cycles. The suggested approach enables efficient utilization of byproducts from Lewis acidic etching, expanding possibilities for synthesizing high-performance anodes in sodium-ion batteries consisting of MXene and TMCs.

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.

Elimination of hydrogen bonds in cellulose enables high-performance disordered carbon anode in sodium-ion batteries

Pre-oxidation remains an advantageous method to regulate the cross-linking structure of cellulose to prepare an increasingly disordered hard carbon applied in sodium-ion batteries. However, it is ambiguous how the introduction of oxygen affects the changes in the molecular structure of cellulose as well as the micro-structure of hard carbon. We herein systematically investigate the effect of air pre-oxidation on the crystallinity and cross-linking structure of cellulose macro-molecules by controlling the degree of oxidation. The findings indicate that the introduction of air can break the hydrogen bonding network of cellulose in advance and release a large number of reactive hydroxyl groups on the surface to be oxidized to form ether and ester cross-linking bonds. Ether bonds can transversely cross-link and extend the carbon layer and the bent carbon layers enclose a well-developed connective pore structure. Additionally, the breakage of oxygen-containing functional groups leads to the escape of large amounts of oxygen-containing gases to etch out more open pore structures with large pore sizes. Benefiting from these advantages, the prepared hard carbon possesses a specific capacity of 335 mAh·g‒1 and 89% of initial coulombic efficiency at 30 mA·g‒1 by pre-oxidating at 300°C for 12 h.

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.

Sulfuric acid treatment to control the microcrystalline structure of starch-based hard carbon for sodium storage

By treating starch with different concentrations of sulfuric acid, we investigated the effect of cross-linked starch-based hard carbon on the performance of sodium-ion batteries (SIBs) at various concentrations. After treatment, the optimal sample exhibits a spherical microstructure, which can provide effective active sites and enhance structural stability, thereby achieving high capacity and long cycle life for SIB electrodes. In subsequent electrochemical tests, after 100 cycles at low current density of 0.1 A g−1, the capacity of H40 remains of 306 mA h g−1. And under the high current density of 1 A g−1, the capacity of H40 can still maintain of 228 mA h g−1, exhibiting a high capacity retention rate of 89 %, which is higher than other samples. This study provides a promising approach for the large-scale production of biomass-derived carbonaceous SIBs anodes.

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.

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.

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.

Innovative Multielement Modification of Pitch-Derived Two-Dimensional Carbon Nanosheets as Anodes for Superior Performance Sodium-Ion Batteries.

The development of advanced anode materials for sodium-ion batteries (SIBs) using pitch-based carbon materials has the advantages of low cost, high electrical conductivity and easy structural modification. In this research, various well-established modification techniques for petroleum pitch are integrated, including the use of recrystallized NaCl as molten salt template, pretreatment and high-temperature carbonization under a pure oxygen atmosphere, and the introduction of heteroatoms (N and S) by hydrothermal methods. The resulting two-dimensional carbon nanosheets with multielement modification exhibit enhanced Na+ storage properties, thereby bringing higher cycling stability and superior rate performance. Due to its specific structure and chemical composition, NS-P-OPDC exhibited a high reversible capacity of 406.77 mAh g-1 at a current density of 100 mA g-1 and a superior rate performance of 193.20 mAh g-1 at a current density of 3 A g-1 after being applied to the anode of SIB half-cell. Especially, a capacity retention of 97.7% was still achieved after 4000 cycles. Meanwhile, the full-cell assembled by Na3V2(PO4)3 (NVP) cathode and NS-P-OPDC anode could provide a reversible capacity of 235.30 mAh g-1 at a current density of 300 mA g-1. This application proves to advance petroleum pitch-based high-performance electrodes toward greater efficiency in electrochemical energy storage.

Biomass-derived hard carbon material for high-capacity sodium-ion battery anode through structure regulation

Economical and environmentally friendly hard carbon materials are attractive options for high-performance sodium-ion battery anode materials. Biomass-derived hard carbon materials have good economic benefits and environmentally friendliness as anode materials for sodium-ion batteries. In this work, we propose a new hard carbon material prepared from agricultural waste olive shells through a simple and environmentally friendly process. The effects of high-temperature treatments and pre-carbonization strategies on the pore structure and graphitization degree of the hard carbon materials were investigated. Combined with electrochemical performance tests, the influence of structural changes on the sodium storage properties of the olive shell-derived hard carbon was revealed. Under the optimized conditions of carbonization temperature and pre-carbonization strategy, the OSHC-Air electrode exhibits excellent sodium storage capacity with 87 % capacity remaining after 1000 cycles at 1000 mA g−1. The assembled PB//OSHC-Air sodium-ion full cell exhibits a high capacity of 216 mAh g−1. Our research provides a potential candidate for commercial anode materials for high-capacity sodium-ion batteries.

Free-standing medium-entropy porous needle-like FeCoCuNi phosphide nanowires-formed flower clusters/carbon fiber anode with high capacity and long durability for sodium-ion batteries

The drastic volume expansion and slow sodium-ion kinetics hinder the practical application of phosphides with high specific capacity and low discharge voltage in sodium-ion batteries (SIBs). Herein, we introduced entropy configuration into nanostructures and prepared a novel free-standing, three-dimensional, porous needle-like medium-entropy Fe, Co, Cu, Ni phosphide (ME-FCCNP) nanowires-formed flower clusters/carbon fiber cloth (CFC) anode (ME-FCCNP@CFC) for SIBs. The distorted lattices caused by medium-entropy configuration provide abundant sites for sodium-ion reactions and improve the electron transfer rate. The medium-entropy effects improve the mechanical stability, while the three-dimensional networks and porous needle-like nanowires provide sufficient space for the volume expansion. These combined properties enable the ME-FCCNP@CFC electrode to exhibit a high-rate capability of 170.8 mAh g−1 at 5.0 A g−1 and deliver a specific capacity of 325.8 mAh g−1 after 2000 cycles at 2.0 A g−1, far surpassing most of reported transition-metal phosphides. Moreover, the Na3V2(PO4)3 || ME-FCCNP@CFC full cell showcases a high-energy density of 256.8 Wh kg−1 and a long cycling life (267.8 mAh g−1 at 2.0 A g−1 with a capacity retention of 83.2 % after 1000 cycles). These results provide significantly promising implications for the anode design of SIBs by employing self-supporting and medium-entropy structures.

Understanding the Relationship of Closed Pore Structure in Biomass- derived Hard Carbon with Cellulose Regulating Strategy.

Recycling waste biomass to pyrolytic carbon has become a development direction of sodium-ion batteries (SIBs)anodes. However, it remains a challenge to precisely control the composition and structure of biomass to modify the properties of derived carbon. Herein, a strategy of hydrolyzing cellulose in phellem with sulfuric acid is proposed, which can promote cellulose fracture, reduce the graphitization and increase the content of closed pores in hard carbon. Accordingly, after the regulation of closed pore structure, the reversible capacity increased from 207 to 330 mAh g-1 at 20mA g-1, realizing an increase of ≈130 mAh g-1 in the plateau region and the initial Coulombic efficiency (ICE) is enhanced from 78% to 90%. When applied in full cell with O3-Na[Ni1/3Fe1/3Mn1/3]O2, it showed an energy density of 247Wh kg-1. This strategy has certain universality, and it provides the feasibility to use low-value cellulose-containing biomass to fabricate high-performance hard carbon materials.

N, S-Codoped 3D Carbon Protected Nanoporous MnS With Record High Sodium Ion Storage Performance for Potential Industry Applications.

With a high theoretical capacity, the MnS anode, however, exhibits a rather complex sodium diffusion kinetics and poor mechanical stability that hinder its application in sodium-ion batteries (SIBs). In this work, a simple, economical, and scalable strategy is developed to inherently coat nanoporous MnS with a 3D N, S co-doped thin carbon layer by using commercially available MnCO3 as precursors. Specifically, the strategy involves a two-step annealing process, which converts the MnCO3 microparticles into nanoporous Mn2O3 and MnS step by step. The 3D N, S codoped carbon layer is in situ formed during the second annealing process by first coating the nanoporous Mn2O3 with a polyaniline layer. Due to the inherent 3D carbon protection and the strong electronic interaction between N, S dopants and MnS, the N, S codoped carbon protected MnS obtained at 900 °C (NS-C@MnS-900) anode displays a high specific capacity of 845mAhg-1 at 0.1Ag-1, which is higher than all reported MnS-based SIB anodes. It also shows an outstanding cyclability and rate performance, maintaining a stable capacity of ≈493mAhg-1 after 1300 cycles at 10Ag-1, which is also the best according to knowledge. These exceptional electrochemical performances and the scalable/simple/low-cost synthesis make the NS-C@MnS-900 attractive for industry application.

Electrolyte-Salts Regulated Hydrogen-Bonding Configuration and Interphase Formation Achieving Highly Stable Anode for Rechargeable Aqueous Sodium-Ion Batteries.

Hydrogen evolution reactions that cause the alkalization of aqueous electrolytes generally frustrate the structural stability and cycling performance of NaTi2(PO4)3/C anode material for rechargeable aqueous sodium-ion batteries (ASIBs). Herein, a novel highly concentrated electrolyte with a large hydrogen-evolution overpotential and hydroxide-capture ability is rationally established by incorporating a bifunctional Mg(Ac)2 additive into a concentrated NaAc aqueous solution. The highly concentrated electrolyte salts (4m NaAc+3m Mg(Ac)2) favor regulation on hydrogen-bonding configurations and kinetically shift the hydrogen evolution potential to a lower value of -1.37 V (vs Ag/AgCl). The Mg(Ac)2 additive plays particular roles in spontaneously capturing hydroxide ions generated during hydrogen evolution reactions on anode surfaces and simultaneously forming a protective Mg(OH)2-like interphase. As a result, the unique electrolyte significantly improves the structural stability and cycling performance of NaTi2(PO4)3/C anode (94.8% capacity retention after 100 cycles at 100 mA·g-1). The effect of salt concentration on hydrogen bonding configurations of aqueous electrolytes is investigated with Raman spectroscopy and FTIR spectroscopy. The interphase is identified by coupling EDS mapping, X-ray photoelectron spectroscopy, and X-ray diffraction. This work provides a new strategy for improving the cycling stability of aqueous sodium-ion batteries.

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.