Anode For Sodium-ion Batteries Research Articles

Joule heating for structure reconstruction of hard carbon with superior sodium ion storage performance

Hard carbon anode for sodium ion batteries still remains many challenges including insufficient cycling life and initial Coulombic efficiency (ICE), weak rate capability and poor compatibility in common ester electrolytes. Here, we propose a Joule heating post-treatment including multifield sintering method to reconstruct the structure of hard carbon from thick graphene layers to more disordered vortex layer structure composed of thin and curved graphite-like domains. The molecular dynamics simulation and differential charge density distribution demonstrate the crucial effect of electric field in strengthening the interaction between the polar molecule groups and the graphene layer, leading to the distortion and expanding of graphene layer. This is a universal and highly efficient strategy to modify various hard carbons within minutes. The optimized hard carbon anode exhibits exceptional rate capability and cycling stability with a high retention rate of 88.4% after 15,000 cycles at 10C in ether electrolyte. It also displays remarkably improved reversible capacity, initial Coulombic efficiency ICE of 89.5% and cycling stability in ester electrolyte. It is revealed by in-situ electrochemical impedance spectroscopy and atomic force microscopy that the spontaneous formation of a thin, stable and inorganic substance-rich solid electrolyte interface layer with significantly improved mechanical property is largely responsible for the outstanding sodium-ion transport kinetics and long lifespan.

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

Low cobalt single atoms loading on N-doped carbon for high Na storage performance

Cobalt single atoms on nitrogen-doped carbon (CoSAs/N-C) were successfully synthesized through the pyrolysis of metal-organic supramolecular self-template. Only 0.12 wt% metal-doped CoSAs/N-C anodes bring a rate capacity enhancement of 195 mAh g−1 compared to the blank group of nitrogen-doped carbon electrodes at 0.1 A g−1. In addition, the CoSAs/N-C anodes exhibit remarkable sodium-ion storage capacities of 285 mAh g−1 after 2000 cycles at 1.0 A g−1 and 133 mAh g−1 with an exceptional cycling stability for 10,000 cycles at an ultra-high current density of 20 A g−1, thereby showcasing excellent Na ion storage performance. Ex-situ X-ray photoelectron spectroscopic study demonstrates that some N atoms in CoSAs/N-C can reversibly store and release Na ions during discharge and charge cycles. The full cell assembled with CoSAs/N-C anode and Na3V2(PO4)3 cathode displays Coulombic efficiency of >99.7 % after 200 cycles at 0.5 A g−1. Density functional theory (DFT) calculations further reveal that the presence of single-atom Co results in a decrease in the Na binding energy surrounding pyrrolic-N and pyridinic-N structures. This moderate binding energy may be beneficial for Na ion adsorption and desorption. This study opens up new possibilities of fabricating advanced metal single atom anodes for high-performance sodium-ion batteries.

Upscaling Brønsted acid intercalation and exfoliation of graphite into graphene by polyoxometalate clusters for sodium-ion battery application

Non-oxidative intercalation of graphite avoids damage to graphene lattices and is a suitable method to produce high-quality graphene. However, the yield of exfoliated graphene is low in this process due to the poor delamination efficiency of guest species. In this study, a Brønsted acid intercalation protocol is developed involving polyoxometalate (POM) clusters (H6P2W18O62) as guests and intercalation of graphite is realized at the sub-nanometer scale. Theoretical simulation based on DFT elucidates the stepwise intercalation mechanism of Brønsted acid molecules and clusters. Unlike common molecules/ionic guests, intercalation of POM clusters induces large expansion and extensive donor–acceptor interactions among graphite interlayers. This significantly weakens the van der Waals forces and promotes exfoliation efficiency of graphene layers. The exfoliated graphene possesses outstanding features of large lateral size, thin thickness, and high purity, and shows excellent performance as the anode for high power sodium-ion batteries. This work proffers a new pathway toward non-oxidative intercalation of graphite for large-scale production of graphene.

Sub-minute carbonization of polymer/carbon nanotube films by microwave induction heating for ultrafast preparation of hard carbon anodes for sodium-ion batteries

Hard carbons (HCs) are excellent anode materials for sodium-ion batteries (SIBs). However, the carbonization and granulation of HC powders involve complex processes and require considerable energy. Here, we developed a facile method for manufacturing HC anodes for SIBs via a novel microwave induction heating (MIH) process for polymer/single-walled carbon nanotube (SWCNT) films. Numerical simulations solving electromagnetic field and heat transfer problems revealed the MIH mechanism; the electric current induced by the applied microwave enables direct Joule heating of the SWCNT networks in the composite film. Consequently, the composite films could be heated to the target temperatures (800–1400 °C) and free-standing HC/SWCNT anodes could be prepared by applying MIH for only 30 s. Comparative analyses confirmed that ultrafast MIH is a reliable technique for producing HC anodes and can replace conventional carbonization processes which require a high-temperature furnace. Moreover, the HC/SWCNT anodes prepared by the ultrafast MIH were successfully applied to the SIB full cells. Finally, the feasibility of MIH for scalable roll-to-roll production of HC anodes was verified through local heating tests using a circular sheet larger than a resonator.

Lattice-confined localized alloying of Bi0.67TaS2 anode enabling ultrafast and stable sodium storage up to 150 C

Bismuth is considered to be a promising anode for sodium-ion batteries due to its low voltage plateau and high volumetric capacity. However, the large volume variation during alloying/dealloying leads to electrode pulverization and performance degradation, especially under high current densities. Herein we propose a lattice-confined localized alloying reaction mechanism to solve the above issues. By chemically embedding Bi atoms in a rigid layered ▪ host framework, the alloying reaction of Bi is spatially and kinetically confined within the ▪ interlayer, allowing for complete recovery of the Bi0.67TaS2 crystal structure after desodiation. The as-prepared Bi0.67TaS2 anode exhibits superior rate performance, achieving capacities of 256 mAh g ▪ at 1 C and 186 mAh g ▪ at 150 C, along with remarkable long-term cycling stability for maintaining 153 mAh g ▪ after 20000 cycles at 150 C. This work demonstrates that the localized alloying mechanism enabled by lattice confinement significantly contributes to both rate and cycling performance, which is expected to provide insights into electrode design for future fast-charging batteries.

Binderless Electrodeposited NiCo2S4-MWCNT as a Potential Anode Material for Sodium-Ion Batteries

Conversion type ternary NiCo2S4, exhibiting high electrical conductivity (∼1.25 × 106 S m−1) and high theoretical capacity (703 mAh g−1), has gained interest as an anode material for sodium-ion batteries (SIBs). Despite its potential, NiCo2S4 (NCS) has extensive volume expansion during cycling. This study introduces the NCS-multi-walled carbon nanotube (MWCNT) onto a carbon fiber (CF) electrode (NCS and NCS-MWCNT@CF), developed through electrodeposition, which addresses these limitations. The unique sheet-like morphology of NCS, featuring abundant pores, ensures good access to the electrolyte. Incorporating a three-dimensional conductive CF framework that acts as a free-standing current collector helps prevent the agglomeration of NCS particles and mitigates volume expansion by providing enough buffer space in the layers of the CF matrix. Our findings reveal that NCS on CF electrodes deliver a second cycle capacity of 620 mA g−1 at 30 mA g−1 and retain 72% capacity after 200 cycles. At 200 mA g−1, the NCS@CF electrodes deliver 378 mAh g−1 in the second cycle with 68% capacity retention in the 200th cycle, whereas NCS-MWCNT@CF delivers 538 mAh g−1 at 200 mA g−1, maintaining 86 % capacity after 100 cycles, making it a potential anode for SIBs.

In situ synthesis of SnPS3/Ti3C2Tx hybrid anode via molten salt etching method for superior sodium-ion batteries

Recently, SnPS3 has gained attention as an impressive sodium-ion battery anode material because of its significant theoretical specific capacity derived from the conversion-alloying reaction mechanism. Nevertheless, its practical applicability is restricted by insufficient rate ability, and severe capacity loss due to inadequate electrical conductivity and dramatic volume expansion. Inspired by the electrochemical enhancement effect of MXene substrates and the innovative Lewis acidic etching for MXene preparation, SnPS3/Ti3C2Tx MXene (T = –Cl and –O) is constructed by synchronously phospho-sulfurizing Sn/Ti3C2Tx precursor. Benefiting from the boosted Na+ diffusion and electron transfer rates, as well as the mitigated stress expansion, the synthesized SnPS3/Ti3C2Tx composite demonstrates enhanced rate capability (647 mA h g−1 at 10 A g−1) alongside satisfactory long-term cycling stability (capacity retention of 94.6% after 2000 cycles at 5 A g−1). Importantly, the assembled sodium-ion full cell delivers an impressive capacity retention of 97.7% after undergoing 1500 cycles at 2 A g−1. Moreover, the sodium storage mechanism of the SnPS3/Ti3C2Tx electrode is elucidated through in-situ and ex-situ characterizations. This work proposes a novel approach to ameliorate the energy storage performance of thiophosphites by facile in-situ construction of composites with MXene.

DFT-D study of carbon-doped β12 borophene as a desirable anode material for sodium-ion batteries

In the quest for the elaboration of advanced energy storage systems (EESs), sodium-ion batteries (SIBs) have emerged as a hopeful alternative to their lithium-ion counterparts, owing to the abundant availability of sodium. This article delves into the utilization of carbon-doped β12 borophene as an anode material for SIBs using density functional theory (DFT) calculations. Based on the band structure calculations, the metallic electronic character of this structure facilitates rapid electron transfer, contributing to its superior performance. Moreover, the remarkably low-energy barrier of 0.066–0.328 eV for migration ensures efficient sodium ion transport, which is critical for new fast-charge technology and better charge/discharge performance. Our investigation reveals that carbon-doped β12 Borophene’s two-dimensional structure, high electrical conductivity, and theoretical capacity of 1972 mAh g−1 make it an ideal candidate for SIB anodes, offering a new avenue for the development of low cost and high-capacity energy storage solutions.

Study on the Performance of Aniline Electrodeposited on MnO2 Nanowire as an Anode for Sodium-Ion Batteries.

Manganese dioxide is an ideal anode for sodium-ion batteries due to its rich crystal shapes. However, its low conductivity, low reversible discharge capacity, slow diffusion kinetics, and poor cyclic stability limit its potential for industrial application. The design of manganese dioxide (MnO2) with various morphologies, such as nanowires, nanorods, and nanoflowers, has proven effective in enhancing its electrochemical performance. Stacking nanowire structures is of interest as they increase the open space by forming an interconnected network, thus facilitating favorable diffusion pathways for sodium ions. Concurrently, the substantial increase in the electrolyte contact area efficiently mitigates the strain induced by the volume expansion associated with the repetitive migration and insertion of sodium ions. Based on previous research, this work presents the structural design of flexible MnO2/polyaniline (MnO2/PANI) nanowires assembled on carbon cloth (CC), an innovation in MnO2 modification. Compared to conventional MnO2 nanowires, the MnO2/PANI nanowires exhibit enhanced structural stability and improved dynamic performance, thereby marking a significant advancement in their material properties. This MnO2/PANI composite exhibits a rate capacity of approximately 200 mA h g-1 after 60 cycles at a current density of 0.1 A g-1, and maintains a rate capacity of 182 mA h g-1 even after 200 cycles under the same current density. This study not only provides new insights into the underlying mechanisms governing energy storage in MnO2/PANI nanowires but also paves the way for their further development and optimization as anodes for sodium-ion batteries, thereby opening up fresh avenues for research and application.

Transition Metal Selenide-Based Anodes for Advanced Sodium-Ion Batteries: Electronic Structure Manipulation and Heterojunction Construction Aspect.

In recent years, sodium-ion batteries (SIBs) have gained a foothold in specific applications related to lithium-ion batteries, thanks to continuous breakthroughs and innovations in materials by researchers. Commercial graphite anodes suffer from small interlayer spacing (0.334 nm), limited specific capacity (200 mAh g-1), and low discharge voltage (<0.1 V), making them inefficient for high-performance operation in SIBs. Hence, the current research focus is on seeking negative electrode materials that are compatible with the operation of SIBs. Many studies have been reported on the modification of transition metal selenides as anodes in SIBs, mainly targeting the issue of poor cycling life attributed to the volume expansion of the material during sodium-ion extraction and insertion processes. However, the intrinsic electronic structure of transition metal selenides also influences electron transport and sodium-ion diffusion. Therefore, modulating their electronic structure can fundamentally improve the electron affinity of transition metal selenides, thereby enhancing their rate performance in SIBs. This work provides a comprehensive review of recent strategies focusing on the modulation of electronic structures and the construction of heterogeneous structures for transition metal selenides. These strategies effectively enhance their performance metrics as electrodes in SIBs, including fast charging, stability, and first-cycle coulombic efficiency, thereby facilitating the development of high-performance SIBs.

Understanding and Mitigating Lattice Collapse Degradation in Layered Oxide Materials for Sodium-Ion Battery Anode.

Na2Ti3O7 has attracted significant attention due to its ecofriendliness and cost-effectiveness for sodium-ion batteries. However, their limited cycling stability hampers their practical applications. Herein, we elucidate a mechanism of structural degradation caused by the heterogeneous phase transition in the Na2Ti3O7 anode using aberration-corrected (scanning) transmission electron microscopy (S)TEM and in situ TEM. It is found that the unevenly distributed phase transition results in the accumulation of strain, which promotes the growth of microcracks and eventually leads to structural decomposition and electrochemical failure. Motivated by this degradation mechanism, nanowires were proposed, and the structural stability is thus improved with the lattice strain effectively released. These findings deepen our understanding of ion transport and degradation mechanisms in intercalated layered electrode materials while emphasizing the significance of the material structure engineered for improving electrode performance.

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.

A soft carbon materials with engineered composition and microstructure for sodium battery anodes

Sodium-ion batteries (SIBs) have advantages in high sodium resources, providing powerful supplement to the current energy storage system. However, the lack of low-cost and high-performance anode materials still limits its practical application. Herein, a soft carbon anode derived from petroleum coke was successfully synthesized by engineering its composition and microstructure through resin and sodium phosphate compositing with optimal heat treatment process, delivering significant merits over existing composite anode in term of price density, initial Coulombic efficiency (ICE) and carbon yield. Resin helps to increase micropores and inhibit graphitization. Na3PO4 contributes to expand layer spacing and increase reversible groups, meanwhile facilitates the cross-linking of graphite microcrystalline and provides additional sodium supplement with improved ICE and conductivity. Through the synergistic effect by the additives, the optimized sample (P-ONH-1200) exhibits a superior reversible charge specific capacity of 311.9 mAh g−1 with high cycling stability, ICE (90.7 %) in SIBs, and high carbon yield (70 %). It also gains rate performance of 209.7 mAh g−1 at 4 C with 98 % retention after 1000 cycles. The full cell with Na3V2(PO4)3 (NVP) cathode at 1.05 N/P ratio exhibits an excellent stability with a capacity retention of 70 % after 500 cycles at 1 C. It provides a model reference for the microstructure regulation of petroleum coke and a revenue for preparation high-performance soft carbon anode for SIBs.

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.