Anode For Sodium-ion Batteries Research Articles

Facile and scalable pulsed electrodeposition of bi-active Bi-Sb alloy for high performance sodium ion batteries

Although sodium ion batteries (SIB) have shown great potential for large-scale energy storage systems, the development of high-performance anode materials for SIB is crucial for their progress. However, the cycling performance of SIB is currently limited by severe volume changes during the sodiation/desodiation process. To overcome this problem, a bi-active metal alloying strategy has been proposed. In this study, we utilized pulsed electrodeposition to prepare bismuth-antimony alloy anode materials. The resulting Bi44.9Sb55.1 alloy anode exhibited exceptional specific capacity, rate performance, and stability. After the second cycle, the discharge/charge capacities were 505.3 mAh·g−1/496.7 mAh·g−1 at 1 A·g−1, with a coulombic efficiency of over 98 %. Even after 50 cycles, the capacities remained at 494.7 mAh·g−1/481.9 mAh·g−1 with a capacity retention rate of 97.9 %. These excellent properties were attributed to the stable structure and suitable voids for electron transport and ion diffusion in the Bi44.9Sb55.1 alloy, which effectively mitigated volume expansion during cycling. The reaction kinetics and mechanism were studied using cyclic voltammetry, in situ X-ray diffraction, and nuclear magnetic resonance techniques. Our work provides valuable insights for the development of bi-active metal alloy anodes for SIB.

In Situ Phase Transformation to form MoO3−MoS2 Heterostructure with Enhanced Printable Sodium Ion Storage

AbstractMolybdenum trioxide (MoO3) possesses high energy density but often suffers from poor electrical conductivity and limited cycling stability when used as a sodium‐ion battery (SIB) anode. To address these issues, the construction of （Molybdenum trioxide‐Molybdenum disulfide）MoO3‐MoS2 heterostructures has proven effective in enhancing electronic conductivity, ion diffusion properties, and structural stability. Guided by the density functional theory (DFT) calculations, which predict favorable Na+ diffusion and adsorption properties, nanorod‐like MoO3‐MoS2 heterostructures are synthesized using a two‐step method. Benefiting from the synergistic effects of the heterostructure and nanosized morphology, the resulting MoO3‐MoS2 electrode exhibits outstanding rate performance (316 mA h g−1 at 10 A g−1) and long‐lasting cycling stability (286 mA h g−1 after 2300 cycles at 5 A g−1) as an SIB anode. In situ XRD measurements reveal that the ultrahigh specific capacity of MoO3‐MoS2 is attributed to the synergistic intercalation‐conversion storage of MoO3 and MoS2. In the pursuit of meeting commercialization requirements, electrodes with adjustable mass loading are also prepared using 3D printing, showcasing the high areal capacity characteristics of the SIBs. This study not only provides theoretical insights into expanding the use of heterojunction materials as SIB anodes but also demonstrates the significant potential for creating high‐energy‐density and cost‐effective SIBs.

Ultralow-Concentration (0.1M) Electrolyte for stable bulk alloy (Sn, Bi) anode in Sodium-ion battery via Regulating Anions Structure

Alloy anodes (e. g. Sn, Bi) applied in sodium-ion batteries (SIBs) have received a lot of interest due to their increased capacity and mild sodiation/desodiation potentials. However, severe capacity fading caused by high volume changes, as well as brittle SEI issues, limit the practical uses. An electrolyte engineering using ultra-low concentration electrolyte strategy containing sodium salt with super bulky BPh4− anions and 1,2-dimethoxyethane (DME) solvent is employed in this work to stabilize micron Sn and Bi anodes, where a cation solvation structure including the type and location of the anions plays a critical role. In this designed 0.1M NaBPh4-DME electrolyte system, Na+ has a faster migration rate due to substantial steric hindrance of BPh4− anions and side reactions on the electrode/electrolyte interface are decreased because it is difficult for BPh4− anions to get close to the alloy anode. This electrolyte design may expose the core cause of alloy anode failure and pave the way for a new approach to stabilizing alloy anodes in SIBs.

Hollow spheres constructed by ZnS-CoS2 @N-doped carbon@N-doped carbon as anodes for high-performance sodium-ion batteries

Hollow spheres constructed by ZnS-CoS2 @N-doped Carbon@N-doped carbon (ZnS-CoS2 @NC@NC) are successfully synthesized using template method combined with NC coating procedure. For SIBs anode, ZnS-CoS2 @NC@NC electrode exhibits excellent rate property and sustainable capacity of 164 mAh g−1 at 5 A g−1 after 1000 cycles. The superior sodium storage performance for ZnS-CoS2 @NC@NC composites is benefited from its distinctive structure, in which the hollow architecture for ZnS/CoS2 @NC@NC composites can buffer the volume change of ZnS/CoS2 and enhance electronic/ionic conductivity within charge/discharge processes. Furthermore, the NC shell layer can further alleviate structural degradation of ZnS/CoS2 @NC@NC hollow spheres, and supply more effective active sites.

Molecular Engineering Enabling High Initial Coulombic Efficiency and Rubost Solid Electrolyte Interphase for Hard Carbon in Sodium-Ion Batteries.

Hard carbon (HC) as a potential candidate anode for sodium-ion batteries (SIBs) suffers from unstable solid electrolyte interphase (SEI) and low initial Coulombic efficiency (ICE), which limits its commercial applications and urgently requires the emergence of a new strategy. Herein, an organic molecule with two sodium ions, disodium phthalate (DP), was successfully engineered on the HC surface (DP-HC) to replenish the sodium loss from solid electrolyte interphase (SEI) formation. A stabilized and ultrathin (≈7.4 nm) SEI was constructed on the DP-HC surface, which proved to be simultaneously suitable in both ester and ether electrolytes. Compared to pure HC (60.8 %), the as-designed DP-HC exhibited a high ICE of >96.3 % in NaPF6 in diglyme (G2) electrolyte, and is capable of servicing consistently for >1600 cycles at 0.5 A g-1 . The Na3 V2 (PO4 )3 (NVP)|DP-HC full-cell with a 98.3 % exceptional ICE can be cycled stably for 450 cycles, demonstrating the tremendous practical application potential of DP-HC. This work provides a molecular design strategy to improve the ICE of HC, which will inspire more researchers to concentrate on the commercialization progress of HC.

CoS2/V2O3 heterostructure with coffee ground-derived carbon as superior composite anodes of sodium-ion batteries

CoS2/V2O3 heterostructure with coffee ground-derived carbon as superior composite anodes of sodium-ion batteries

Highly Stable ZnS Anodes for Sodium-Ion Batteries Enabled by Structure and Electrolyte Engineering.

Zinc sulfide is a promising high-capacity anode for practical sodium-ion batteries, considering its high capacity and the low cost of zinc and sulfur sources. However, the pulverization of particulate zinc sulfide causes active mass collapse and penetration-induced short circuits of batteries. Herein, a zinc sulfide encapsulated in a nitrogen-doped carbon shell (ZnS@NC) was developed for high-performance anodes. The confinement effect of nitrogen-doped carbon stabilizes the active mass structure during cycling thanks to the robust chemically and electronically bonded connections between nitrogen-doped carbon and zinc sulfide nanoparticles. Furthermore, the cycling stability of the ZnS@NC anode is boosted by the robust inorganic-rich solid electrolyte interphase (SEI) formed in cyclic and linear ether-based electrolytes. The ZnS@NC anode displayed a reversible specific capacity of 584 mAh g-1, an excellent rate capability of 327 mAh g-1 at 70 A g-1, and a highly stable cycling performance over 10000 cycles. This work provides a practical and promising approach to designing stable conversion anodes for high-performance sodium-ion batteries.

Boosting Manganese Selenide Anode for Superior Sodium-Ion Storage via Triggering α → β Phase Transition.

Sodium-ion batteries (SIBs) have been extensively studied owing to the abundance and low-price of Na resources. However, the infeasibility of graphite and silicon electrodes in sodium-ion storage makes it urgent to develop high-performance anode materials. Herein, α-MnSe nanorods derived from δ-MnO2 (δ-α-MnSe) are constructed as anodes for SIBs. It is verified that α-MnSe will be transferred into β-MnSe after the initial Na-ion insertion/extraction, and δ-α-MnSe undergoes typical conversion mechanism using a Mn-ion for charge compensation in the subsequent charge-discharge process. First-principles calculations support that Na-ion migration in defect-free α-MnSe can drive the lattice distortion to phase transition (alpha → beta) in thermodynamics and dynamics. The formed β-MnSe with robust lattice structure and small Na-ion diffusion barrier boosts great structure stability and electrochemical kinetics. Hence, the δ-α-MnSe electrode contributes excellent rate capability and superior cyclic stability with long lifespan over 1000 cycles and low decay rate of 0.0267% per cycle. Na-ion full batteries with a high energy density of 281.2 Wh·kg-1 and outstanding cyclability demonstrate the applicability of δ-α-MnSe anode.

Metal Phosphide Anodes in Sodium-Ion Batteries: Latest Applications and Progress.

Sodium-ion batteries (SIBs), as the next-generation high-performance electrochemical energy storage devices, have attracted widespread attention due to their cost-effectiveness and wide geographical distribution of sodium. As a crucial component of the structure of SIBs, the anode material plays a crucial role in determining its electrochemical performance. Significantly, metal phosphide exhibits remarkable application prospects as an anode material for SIBs because of its low redox potential and high theoretical capacity. However, due to volume expansion limitations and other factors, the rate and cycling performance of metal phosphides have gradually declined. To address these challenges, various viable solutions have been explored. In this paper, the recent research progress of metal phosphide materials for SIBs is systematically reviewed, including the synthesis strategy of metal phosphide, the storage mechanism of sodium ions, and the application of metal phosphide in electrochemical aspects. In addition, future challenges and opportunities based on current developments are presented.

Highly Crystalline Poly(heptazine imide)-Based Carbonaceous Anodes for Ultralong Lifespan and Low-Temperature Sodium-Ion Batteries.

Carbon nitrides with layered structures and scalable syntheses have emerged as potential anode choices for the commercialization of sodium-ion batteries. However, the low crystallinity of materials synthesized through traditional thermal condensation leads to insufficient conductivity and poor cycling stability, which significantly hamper their practical applications. Herein, a facile salt-covering method was proposed for the synthesis of highly ordered crystalline C3N4-based all-carbon nanocomposites. The sealing environment created by this strategy leads to the formation of poly(heptazine imide) (PHI), the crystalline phase of C3N4, with extended π-conjugation and a fully condensed nanosheet structure. Meanwhile, theoretical calculations reveal the high crystallinity of C3N4 significantly reduces the energy barrier for electron transition and enables the generation of efficient charge transfer channels at the heterogeneous interface between carbon and C3N4. Accordingly, such nanocomposites present ultrastable cycling performances over 5000 cycles, with a high reversible capacity of 245.1 mAh g-1 at 2 A g-1 delivered. More importantly, they also exhibit an outstanding low-temperature capacity of 196.6 mAh g-1 at -20 °C. This work offers opportunities for the energy storage use of C3N4 and provides some clues for developing long-life and high-capacity anodes operated under extreme conditions.

Fe3Se4 decorating carbon nanotubes with superior sodium storage performance for sodium-ion batteries

Due to the ideal theoretical capacity, high initial coulombic efficiency, satisfactory electronic conductivity, and environmental friendliness, iron-based selenides have been intensively explored and developed as anodes for sodium-ion batteries (SIBs). However, they still face numerous obstacles in the commercialization process, such as large volume changes. In this work, a nanocomposite of Fe3Se4 decorated carbon nanotubes (Fe3Se4/CNTs) was designed and prepared through a simple solvothermal method and subsequent selenization process. SEM and TEM images manifest that the Fe3Se4 nanoparticles are well anchored to the two-dimensional CNTs. In the composite, Fe3Se4 can provide high sodium storage capacity, meanwhile, CNTs acts as a self-supporting framework, which effectively enhances the electronic conductivity and mitigates the drastic volume expansion of Fe3Se4/CNTs electrode during electrochemical process. Thus, the Fe3Se4/CNTs electrode presents satisfactory sodium storage capacity and cycling stability. At 1 A g−1, it delivers a high capacity of 424 mA h g−1 after 500 cycles, with a superior capacity retention of ~100 %. In addition, cyclic voltammetry (CV), galvanostatic intermittent titration (GITT), and ex-situ X-ray diffraction (XRD) were employed to analyze the sodium storage mechanism and sodium ion diffusion ability in the Fe3Se4/CNTs electrode. This work provides an effective method for developing high-performance anodes for SIBs.

P-doped hard carbon material for anode of sodium ion battery was prepared by using polyphosphoric acid modified petroleum asphalt as precursor

The practical value of hard carbon anode in sodium ion batteries has garnered significant attention. Asphalt-derived hard carbon offers lower cost and scale advantages compared to expensive resin and bio-based hard carbon materials. However, the synthesis of asphalt-derived hard carbon with significantly enhanced reversible capacity remains challenging. This study focuses on synthesizing P-doped hard carbon material using polyphosphoric acid-modified petroleum asphalt as a precursor and the pre-oxidation method. Doping P elements in hard carbon induces deformation of the molecular layer structure within the pseudo-graphite domains, expanding graphite layer spacing and increasing the number of internal closed micropores, thereby enhancing the sodium storage capacity of the matrix. The reversible capacity of P-doped hard carbon (PHC-1300) increased from 240.3 mA h g−1 to 359.9 mA h g−1 during the initial charge-discharge cycle at a rate of 0.05 C compared to undoped hard carbon (HC-1300). Moreover, phosphate exhibits higher reduction ability than adjacent carbon atoms, generating electron holes that partially compensate for limited electron conduction capability in hard carbon material. The electronic conductivity of the material increases from 26.1114 S cm−1 to 36.6418 S cm−1, demonstrating a significant enhancement compared to high graphitized soft carbon (SC-1300).Therefore, the practical significance of employing this straightforward precursor modification method to prepare P-doped hard carbon warrants attention.

Bimetallic selenide heterostructure with directional built-in electric-field confined in N-doped carbon nanofibers for superior sodium storage with ultralong lifespan

Constructing heterostructure is considered as an effective strategy to address the sluggish electronic and ionic kinetics of anode materials for sodium ion batteries (SIBs). However, realizing the orientated growth and uniform distribution of the heterostructure is still a great challenge. Herein, the regulated novel CoSe2/NiSe2 heterostructure confined in N-doped carbon nanofibers (CoSe2/NiSe2@N-C) are prepared by using Co/Ni-ZIF template, in which, the CoSe2/NiSe2 heterostructures realize uniform distribution on a micro level. Benefiting from the unique heterostructure and N-doped carbon nanofibers, the CoSe2/NiSe2@N-C deliveries superior rate capability and durable cycle lifespan with a reversible capacity of 400.5 mA h g−1 after 5000 cycles at 2 A g−1. The Na-ion full battery with CoSe2/NiSe2@N-C anode and layered oxide cathode displays a remarkable energy density of 563 W h kg−1 with 241.1 W kg−1 at 0.1 A g−1. The theoretical calculations disclose that the periodic and directional built-in electric-field along with the heterointerfaces of CoSe2/NiSe2@N-C can accelerate electrochemical reaction kinetics. The in (ex) situ experimental measurements reveal the reversible conversion reaction and stable structure of CoSe2/NiSe2@N-C during Na+ insertion/extraction. The study highlights the potential ability of precisely controlled heterostructure to stimulate the electrochemical performances of advanced anode for SIBs.

3D connected porous structure hard carbon derived from paulownia xylem for high rate performance sodium ion battery anode

Biomass-derived hard carbon has garnered significant attention due to its high capacity, low cost and abundant resources. However, the application of biomass hard carbon is limited by the low initial coulombic efficiency and rate capability. Based on these issues, natural fortune paulownia wood with numerous pores has been used as the precursor to investigate the effects on initial coulombic efficiency and rate capability at different heating temperatures. As the heating temperature increased from 1000 °C to 1400 °C, the graphitization degree of the prepared hard carbon gradually increased, and the defect concentration gradually decreased, resulting in an increase in ICE from 76.8 % to 85.9 %, and a significant increase in the proportion of platform capacity from 49 % to 69 %. The prepared HC-1400 exhibits a reversible capacity of 313 mAh g−1 at 0.1 C, and can still achieve a capacity retention rate of 92 % after 500 cycles at 1 C (charge) and 5 C (discharge). Meanwhile, due to the excellent inheritance of the 3D connected porous structure of paulownia xylem, the prepared hard carbon even exhibits an excellent capacity of 209 mAh g−1 at 10 C. In addition, the assembled HC-1400||Na3V2(PO4)3 full battery also demonstrated a high energy density of 204.4 Wh kg−1 at 0.5 C, and still exhibited 116.6 Wh kg−1 even at a high rate of 10 C. This study will provide strong guidance for designing and preparing hard carbon with both high capacity and high rate performance for sodium-ion batteries anode.

Double Restriction of Bismuth Nanoparticles by Carbon Matrixes for Ultralong−lifespan Sodium Storage

Alloying-type bismuth (Bi) anodes show a high theoretical capacity for sodium-ion batteries (SIB), yet their huge volume expansion and electrode pulverization resulted in poor electrochemical stability. Herein, we proposed a feasible strategy for the preparation of carbon/Bi composite material in which the Bi nanoparticles are uniformly dispersed in the double-layered carbon matrix. Benefiting from the synergistic confinement of the external coating of graphene and the internal layer of MOF-derived carbon, the volumetric expansion and large chemo-mechanical stress of Bi nanoparticles are effectively buffered. Therefore, the GAB@GO-800 anode exhibits a dramatically reversible capacity of 328 mA h g−1 at 0.1 A g−1, exceptional rate capability (299 mA h g−1 at 5 A g−1), and ultrahigh stability of 255 mA h g−1 at 2 A g−1 over 2000 cycles. Such hybrid carbon confinemental strategy via a combination of graphene coating and MOF-derived carbon is expected to be a promising method for the alloying-type anodes of SIBs.

Trifunctional L-Cysteine Assisted Construction of MoO2 /MoS2 /C Nanoarchitecture Toward High-Rate Sodium Storage.

The volume collapse and slow kinetics reaction of anode materials are two key issues for sodium ion batteries (SIBs). Herein, an "embryo" strategy is proposed for synthesis of nanorod-embedded MoO2 /MoS2 /C network nanoarchitecture as anode for SIBs with high-rate performance. Interestingly, L-cysteine which plays triple roles including sulfur source, reductant, and carbon source can be utilized to produce the sulfur vacancy-enriched heterostructure. Specifically, L-cysteine can combine with metastable monoclinic MoO3 nanorods at room temperature to encapsulate the "nutrient" of MoOx analogues (MoO2.5 (OH)0.5 and MoO3 ·0.5H2 O) and hydrogen-deficient L-cysteine in the "embryo" precursor affording for subsequent in situ multistep heating treatment. The resultant MoO2 /MoS2 /C presents a high-rate capability of 875 and 420mAhg-1 at 0.5 and 10Ag-1 , respectively, which are much better than the MoS2 -based anode materials reported by far. Finite element simulation and analysis results verify that the volume expansion can be reduced to 42.8% from 88.8% when building nanorod-embedded porous network structure. Theoretical calculations reveal that the sulfur vacancies and heterointerface engineering can promote the adsorption and migration of Na+ leading to highly enhanced thermodynamic and kinetic reaction. The work provides an efficient approach to develop advanced electrode materials for energy storage.

Closed pore engineering of activated carbon enabled by waste mask for superior sodium storage

Carbonaceous materials with closed pore structure have emerged as intriguing anode materials for sodium-ion batteries (SIBs). However, it remains a significant challenge to precisely regulate the structure of closed pores to achieve superior electrochemical Na-storage performance. Herein, a simple but practical strategy is proposed to convert the open pores in activated carbon (AC) into closed pores with the assistance of polypropylene (PP) waste masks. This transition occurs via the carbonization of light aromatic compounds from PP, which deposit on the entrance of the AC's open pore and generate PP-based carbon layer thus regulating the pore configuration of AC. When configured as an anode for SIBs, the hard carbon with optimal closed pores (CMAC-2) delivered a high reversible capacity of 335.5 mAh g−1 with satisfactory initial coulombic efficiency of 88.7 % as well as remarkable cycle and rate capability. Additionally, the assembled O3-NaNi1/3Fe1/3Mn1/3O2//CMAC-2 full cell achieves a high energy density of 277.5 Wh kg−1 (based on the total mass of anode and cathode) with an outstanding rate capability. This work not only offers an ingenious method to fabricate closed pore structure with boosted Na+ storage performance, but also provides a sustainable practice by repurposing polyolefin waste into value-added energy storage products.

Hybridization of PPy/C toward high capacity and stability for sodium-ion batteries

Hybrid composites are widely regarded as the most promising choice for anode material in sodium-ion batteries. However, integrating high capacity and excellent cyclic stability into composites remains challenging. This work demonstrates a thin-liquid-layer polymerization approach to fabricate an integrated porous polypyrrole/carbon composite (PPy/C) for a high-performance sodium storage anode. By adjusting the monomer concentration reasonably and combining with heterostructure engineering, the optimized PPy/C was used as the anode for sodium-ion batteries, achieving rapid electrochemical kinetics and satisfactory reversible capacity. The reaction mechanism between PPy and Na+ in the Faraday reaction was revealed by ex-situ electrochemical impedance spectroscopy (EIS). DFT calculations illustrate that the synergistic effect between porous carbon and PPy can regulate the electron transfer mode around Na atoms, which contributes to anchoring Na in the PPy/C composite structure. Moreover, the PPy/C offers an ultrahigh capacity of 552 mA h g−1 at 0.1 A g−1 and a capacity retention rate of 86.5 % after 200 cycles. A full cell assembled with PPy/C and Na3V2(PO4)3 demonstrates a high energy density of 243.1 W h kg–1 at 125 W kg−1 power density. This work would offer valuable thought for advancing the practical application of conductive polymer/carbon composites.

Dual-Functionalized Ca Enables High Sodiation Kinetics for Hard Carbon in Sodium-Ion Batteries.

Hard carbons (HCs), while a leading candidate for sodium-ion battery (SIB) anode materials, face challenges in their unfavorable sodiation kinetics since the intricate microstructure of HCs complicates the Na+ diffusion channel. Herein, a Hovenia dulcis-derived HC realizes a markedly enhanced high-rate performance in virtue of dual-functionalized Ca. The interlayer doped Ca2+ effectively enlarges the interlayer spacing, while the in situ-formed CaSe templates induce the formation of hierarchical pore structures and intrinsic defects, significantly providing fast Na+ diffusion channels and abundant active sites and thus enhancing the sodium storage kinetics. Achieved by the synergistic effect of regulation of intrinsic microcrystalline and pore structures, the optimized HC shows remarkable performance enhancements, including a high reversible capacity of 350.3 mA h g-1 after 50 cycles at 50 mA g-1, a high-capacity retention rate of 95.3% after 1000 cycles, and excellent rate performance (108.4 mA h g-1 at 2 A g-1). This work sheds light on valuable insight into the structural adjustment of high-rate HCs, facilitating the widespread utilization of SIBs.

Metal-organic framework derived Co1-xS@C nanoboxes for long-life Na+ storage

Transition metal sulfides appear excellent electrochemical properties in the realm of anode for sodium-ion batteries and hold significant potential for practical application in large-scale devices in the future. However, their development is hindered by inferior inherent conductivity and tremendous volume strain during discharge and charge processes. In this study, Co1-xS@C nanoboxes were synthesized utilizing Co-Co PBA as a precursor. The electrochemical sodium storage performance of Co1-xS@C electrode was characterized, revealing an extremely long-life and stable performance. At 1.0 A g−1 and 2.0 A g−1, the electrode delivered capacities of 255.8 mAh g−1 and 197.6 mAh g−1 after 5000 and 10,000 cycles respectively, with negligible capacity attenuation. The pseudo-capacitance behavior of Co1-xS@C NBs electrode in sodium storage was quantitatively calculated through CV test at varying sweep speeds. The significant contribution of pseudo-capacitance resulted in its exceptional rate capacity and electrochemical stability. Furthermore, kinetic analysis revealed that the existence of a carbon shell enhanced the Na+ diffusion kinetics and charge transfer kinetics of Co1-xS@C NBs. This strategy provides a reference for enhancing the Na+ storage performance of other transition metal sulfides.