Application In Sodium-ion Batteries Research Articles

Iron‐Based Sulfate for Sodium‐Ion Batteries: Past, Present, and Future

Sodium‐ion batteries (SIBs) are crucial energy equipment that sustain low cost and better environmental benefit. Nevertheless, the practical energy density of SIBs is limited by cathode material. Over last decades, the iron‐based sulfate (IBS) has been extensively studied owing to its numerous advantages, including a large theoretical specific energy (over 100 Wh kg−1), high working potential (above 3.4 V), low cost, good structural stability, and environmental friendliness. Nevertheless, the application of IBS in SIBs is limited by its unsuitable electrolyte and low electronic/ionic conductivity. This review summarizes recently developed results on IBS materials for SIBs, ranging from the phase diagram–composition structure–electrochemical performance to modification research. A generalized summary of the future prospects of IBS‐based materials is also provided, with the hope of inspiring further advances in their application in SIBs.

Enhanced redox kinetics in hierarchical tubular FeSe2 by incorporating Se quantum dots towards high-performance sodium-ion batteries

Metal selenides have emerged as promising Na-storage anode materials owing to their substantial theoretical capacity and high cost-effectiveness. However, the application of metal selenides is hindered by inferior electronic conductivity, huge volume variation, and sluggish kinetics of ionic migration. In response to these challenges, herein, a hierarchical hollow tube consisting of FeSe2 nanosheets and Se quantum dots anchored within a carbon skeleton (HT-FeSe2/Se/C) is strategically engineered and synthesized. The most remarkable feature of HT-FeSe2/Se/C is the introduction of Se quantum dots, which could lead to high electron density near the Fermi level and significantly enhance the overall charge transfer capability of the electrode. Moreover, the distinctive hollow tubular structure enveloped by the carbon skeleton endows the HT-FeSe2/Se/C anode with robust structural stability and fast surface-controlled Na-storage kinetics. Consequently, the as-synthesized HT-FeSe2/Se/C demonstrates a reversible capacity of 253.5 mAh/g at a current density of 5 A/g and a high specific capacity of 343.9 mAh/g at 1 A/g after 100 cycles in sodium-ion batteries (SIBs). Furthermore, a full cell is assembled with HT-FeSe2/Se/C as the anode, and a vanadium-based cathode (Na3V2(PO4)2O2F), showcasing a high specific capacity of 118.1 mAh/g at 2 A/g. The excellent performance of HT-FeSe2/Se/C may hint at future material design strategies and advance the development and application of SIBs

Sb-Doped Biphasic P2/O3-Type Mn-Rich Layered Oxide Cathode Material for High-Performance Sodium-Ion Batteries.

Mn-rich P2-type layered oxide cathode materials suffer from severe capacity loss caused by detrimental phase transition and transition metal dissolution, making their implementation difficult in large-scale sodium-ion battery applications. Herein, we introduced a high-valent Sb5+ substitution, leading to a biphasic P2/O3 cathode that suppresses the P2-O2 phase transformation in the high-voltage condition attributed to the stronger Sb-O covalency that introduces extra electrons to the O atom, reducing oxygen loss from the lattices and improving structural stability, as confirmed by first-principle calculations. Besides, the enhanced Na+ diffusion kinetics and thermodynamics in the modified sample are associated with the enlarged lattice parameters. As a result, the proposed cathode delivers a discharge capacity of 142.6 mAh g-1 at 0.1C between 1.5 and 4.3 V and excellent performance at a high mass loading of 8 mg cm3 with a specific capacity of 131 mAh g-1 at 0.2C. Furthermore, it also possesses remarkable rate capability (90.3 mAh g-1 at 5C), specifying its practicality in high-energy-density sodium-ion batteries. Hence, this work provides insights into incorporating high-valent dopants for high-performance Mn-rich cathodes.

Density functional theory analysis of Na4Mn4Ti5O18 for sodium ion battery electrode

Density functional theory study has been performed on Na4Mn4Ti5O18 to evaluate its application feasibility as an electrode in Na ion battery. Two types of void in the structure of Na4Mn4Ti5O18, viz., Z shaped tunnel and polyhedral pentagonal void, has been observed that act as guest sites for reversible migration of Na+ ions. It is also noted that electrochemically active sites are placed in Z shaped tunnel that act as host for Na+ during anodic response while it acts as the Na+ donor during cathodic response. The Mn atom, located in the Z-shape tunnel, acts as redox active site for both cathodic and anodic response via formation of redox couple Mn+3/Mn+4 and Mn+3/Mn+2 respectively. On the other hand, Mn atom present at square pyramidal site remains inert during charge–discharge process. The redox action in Na4Mn4Ti5O18, occurring due to intercalation and de-intercalation of 2Na+ ions per formula unit, has been noted to exhibit voltage ∼2.63 V and 3.82 V respectively. The theoretical capacity ∼128 mAhg−1 has been estimated corresponding to migration of 2Na+ in Na4Mn4Ti5O18 structure. The present simulation study indicates the possibility of electrode action in Na4Mn4Ti5O18 for sodium ion battery application.

Progress and Prospect of Bimetallic Oxides for Sodium-Ion Batteries: Synthesis, Mechanism, and Optimization Strategy.

Sodium-ion batteries (SIBs) are considered as an alternative to and even replacement of lithium-ion batteries in the near future in order to address the energy crisis and scarcity of lithium resources due to the wide distribution and abundance of sodium resources on the earth. The exploration and development of high-performance anode materials are critical to the practical applications of advanced SIBs. Among various anode materials, bimetallic oxides (BMOs) have attracted special research attention because of their abundance, easy access, rich redox reactions, enhanced capacity and satisfactory cycling stability. Although many BMO anode materials have been reported as anode materials in SIBs, very limited studies summarized the progress and prospect of BMOs in practical applications of SIBs. In this review, recent progress and challenges of BMO anode materials for SIBs have been comprehensively summarized and discussed. First, the preparation methods and sodium storage mechanisms of BMOs are discussed. Then, the challenges, optimization strategies, and sodium storage performance of BMO anode materials have been reviewed and summarized. Finally, the prospects and future research directions of BMOs in SIBs have been proposed. This review aims to provide insight into the efficient design and optimization of BMO anode materials for high-performance SIBs.

Dual Design on Hierarchically Hollow MoTe2/C with Ion/Electron Channel Engineering for High-Performance Sodium Storage.

Transition-metal tellurides have been investigated as novel anode materials for application in sodium-ion batteries (SIBs) due to their rich active sites and unique and controllable layered nanostructures. However, the weak structural strength and inferior intercalation/deintercalation kinetics inhibit the development of transition-metal tellurides. In this work, MoTe2/C composites with two different hollow nanostructures are designed and prepared. By adjustment of the precursor structure, MoTe2/C-2 exhibits superior sodium-storage performance because of its uniquely hollow nanostructure with self-assembled 2D flexible nanosheets grown on the external surface. MoTe2/C-2 delivers a higher specific capacity (276 mAh g-1 at 0.1 A g-1 after 300 cycles), much more than MoTe2/C-1 (201 mAh g-1 at 0.1 A g-1 after 300 cycles), and exhibits a long-time cycling performance (131 mAh g-1 at 1 A g-1 after 2000 cycles). The excellent sodium-storage performance derived from the rational structure design is beneficial for shortening the ion paths, facilitating the sodiation/desodiation process, and reinforcing the intrinsic structural stability, thus boosting the reaction kinetics and prolonging the cycling life. Meanwhile, the assembled full-cell maintains 101 mAh g-1 at 0.1 A g-1 after 50 cycles and lights an electric watch. The findings provide several new views for preparation of more transition-metal tellurides with multi-ion/electron migration channel engineering.

Tin-antimony/carbon composite porous fibers: electrospinning synthesis and application in sodium-ion batteries

In this work, tin-antimony/carbon composites porous fibers were successfully synthesized by an electrospinning method combined with two-step heat treatment processes, in which SnCl2 and SbCl3 were used as tin and antimony sources, and polyacrylonitrile (PAN) and polymethyl methacrylate (PMMA) were used as binders and pore-forming agents. The as-synthesized tin-antimony/carbon composites were systematically characterized by x-ray Diffraction (XRD), Transmission Electron Microscope (TEM), Scanning Electron Microscope (SEM), Energy-Dispersive Spectrometer (EDS), x-ray Photoelectron Spectroscopy (XPS), and Thermogravimetric Analysis-Differential Scanning Calorimetry (TG-DSC). The results indicate that the composite material consists of one-dimensional nitrogen-doped carbon porous fibers as the main matrix, with a three-dimensional network structure in which Sn, SnO2, and SnSb particles are encapsulated. Furthermore, the tin-antimony/carbon composites porous fibers were utilized as self-supported negative electrode for sodium-ion batteries. The results showed that the SNbM-2 sample electrode calcined at 800 °C demonstrated the best cycling stability and rate capability among all the sample electrodes, with a discharge capacity of 319.5 mAh·g−1 maintained after 100 cycles at a current density of 0.1 A·g−1. The excellent electrochemical performance of the SNbM-2 sample electrode is benefited from its unique porous structure and the carbon fiber network structure encapsulating Sn, SnO2, and SnSb particles, which could effectively shorten the Na+ ion transport distance and mitigate electrode volume expansion.

Mechanically Robust Self-Organized Crack-Free Nanocellular Graphene with Outstanding Electrochemical Properties in Sodium Ion Battery.

Crack-free nanocellular graphenes are attractive materials with extraordinary mechanical and electrochemical properties, but their homogeneous synthesis on the centimeter scale is challenging. Here, a strong nanocellular graphene film achieved by the self-organization of carbon atoms using liquid metal dealloying and employing a defect-free amorphous precursor is reported. This study demonstrates that a Bi melt strongly catalyzes the self-structuring of graphene layers at low processing temperatures. The robust nanoarchitectured graphene displays a high-genus seamless framework and exhibits remarkable tensile strength (34.8MPa) and high electrical conductivity (1.6 × 104 S m-1 ). This unique material has excellent potential for flexible and high-rate sodium-ion battery applications.

Interface engineering of metal sulfides-based composites enables high-performance anode materials for sodium-ion batteries

Metal sulfides (MSs) have attracted much attention as anode materials for sodium-ion batteries (SIBs) due to their high sodium storage capacity. However, the unsatisfactory electrochemical performance induced by the huge volume change and sluggish kinetics hampered the practical application of SIBs. Herein, guided by the heterostructure interface engineering, novel multicomponent metal sulfide-based anodes, including SnS, FeS, and Fe3N embedded in N-doped carbon nanosheets (SnS/FeS/Fe3N/NC NSs), have been synthesized for high-performance SIBs. The as-prepared SnS/FeS/Fe3N/NC NSs with abundant heterointerfaces and high conductivity of N-doped carbon nanosheet matrix can shorten the Na+ diffusion path and promote reaction kinetics during the sodiation/desodiation process. Moreover, the presence of Fe3N can promote the reversible conversion of SnS and FeS during the cycling process. As a consequence, when evaluated as anode materials for SIBs, the SnS/FeS/Fe3N/NC NSs can maintain a high sodium storage capacity of 473.6 mAh g-1 after 600 cycles at 2.0 A g-1 and can still provide a high reversible capacity of 537.4 mAh g-1 even at 5.0 A g-1 This discovery offers a novel strategy for constructing metal sulfide-based anode materials for high-performance SIBs.

Architectural design of anode materials for superior alkali-ion (Li/Na/K) batteries storage

Developing high-performance anode materials remains a significant challenge for clean energy storage systems. Herein, we investigated the (MXene/MoSe2@C) heterostructure hybrid nanostructure as a superior anode material for application in lithium, sodium, and potassium ion batteries (LIBs, SIBs, and PIBs). Moreover, the anode structure’s stability was examined via the open-source Large-scale atomic/molecular massively Parallel Simulator code. Our results indicated that the migration of SIBs toward the anode material is significantly greater than other ions during charge and discharge cycles. Therefore, SIBs systems can be competitive with PIBs and LIBs systems. In addition, the average values of the potential energies for the anode materials/ions complexes are about ~ − 713.65, ~  − 2030.41, and ~ − 912.36 kcal mol−1 in systems LIBs, SIBs, and PIBs, respectively. This study provides a rational design strategy to develop high-performance anode materials in SIBs/PIBs/LIBs systems, which can be developed for other transition metal chalcogenide-based composites as a superior anode of alkali metal ion battery storage systems.

Structurally Stable, Low H2O Prussian Blue Analogs toward High Performance Sodium Storage

AbstractPrussian blue analogues (PBAs) are recognized as promising cathode materials for sodium‐ion batteries (SIBs) due to their facile synthesis, low‐cost, high capacity, and environmental friendliness. However, high water content (>10 wt%) in the framework and unsatisfactory structural stability of PBAs are still the bottlenecks for industrial applications. Herein, interstitial K‐doping is employed to minimize the interstitial water and enhance the structural stability of Na2‐xFeMn[Fe(CN)6] (FeMnPBA), thereby boosting the sodium storage performance. The 3% K‐doping (K‐FeMnPBA3) demonstrates a much‐reduced water content of 6.9%, accompanied by a notably enhanced capacity of 139.1 mAh g−1 at 100 mA g−1 and a remarkable capacity retention of 77.1% after 700 cycles. Furthermore, the K‐FeMnPBA3/hard carbon (HC) pouch cell achieves a stable cyclability with 82.6% capacity retention after 600 cycles. This research offers valuable insights into low‐water PBAs for practical applications in SIBs.

Enhancing Sodium-Ion Transport by Hollow Nanotube Structure Design of a V5S8@C Anode for Sodium-Ion Batteries.

V5S8 has received extensive attention in the field of sodium-ion batteries (SIBs) due to its two-dimensional (2D) layered structure, and weak van der Waals forces between V-S accelerate the transport of sodium ions. However, the long-term cycling of V5S8 still suffers from volume expansion and low conductivity. Herein, a hollow nanotube V5S8@C (H-V5S8@C) with improved conductivity was synthesized by a solvothermal method to alleviate cracking caused by volume expansion. Benefiting from the large specific surface area of the hollow nanotube structure and uniform carbon coating, H-V5S8@C exhibits a more active site and enhanced conductivity. Meanwhile, the heterojunction formed by a few residual MoS2 and the outer layer of V5S8 stabilizes the structure and reduces the ion migration barrier with fast Na+ transport. Specifically, the H-V5S8@C anode provides an enhanced rate performance of 270.1 mAh g-1 at 15 A g-1 and high cycling stability of 291.7 mAh g-1 with a retention rate of 90.98% after 300 cycles at 5 A g-1. This work provides a feasible approach for the structural design of 2D layered materials, which can promote the practical application of fast-charging sodium-ion batteries.

Entropy Tuning Stabilizing P2‐Type Layered Cathodes for Sodium‐Ion Batteries

AbstractThe P2‐type layered transition metal oxide cathodes confront formidable challenges, including irreversible deleterious phase transitions, transition metals migration, and sluggish Na+ diffusion kinetics, which hamper their rapid commercial application in sodium ion batteries (SIB). In this work, an entropy tuning with dual‐site substitution strategy is proposed to address the aforementioned issues. In the tailored [Na0.67Zn0.05]Ni0.22Cu0.06Mn0.66Ti0.01O2 (NZNCMTO) cathodes, the strategic incorporation of Zn ions serves to occupy Na sites, intentionally disrupting the Na/vacancy ordering and establishing a reinforcing “pillar” effect within the layered framework. Furthermore, the substitution of Cu and Ti for Ni and Mn bolsters covalent bonding with the lattice oxygen, thereby impeding the migration of the transition metal ions and leading to a near‐zero strain structural evolution during charge and discharge process. Density functional theory calculations confirmed that entropy‐tuned NZNCMTO substantially lowered the migration energy barrier for Na+ ions diffusion and improved electronic conductivity. Consequently, the NZNCMTO cathode exhibits an impressive high practical capacity of 91.54 mAh g−1 at a high discharge rate of 10 C, along with outstanding cycling stability, maintaining near 100% capacity retention over 500 cycles at a current density of 10 C. This work presents an innovative blueprint for designing high‐performance sodium‐ion battery cathode materials.

Vanadium substituted Fe, Cr co-doped high performance C/Na3V2(PO4)2F3 cathode for sodium-ion batteries

In recent years, Na3V2(PO4)2F3 (NVPF) has been considered as one of the most promising candidates for cathodes in sodium ion batteries (SIBs). However, presence of vanadium makes the material costly. Besides, its electrochemical properties are hampered due to its low electronic conductivity. Herein, carbon coated Fe, Cr co-doped Na3V2(PO4)2F3 has been synthesized using rota-tumbler assisted sol–gel method. The effects of co-doping on structure, morphology and electrochemical performances are systematically studied. It is confirmed that co-doping of Fe and Cr can enhance the electrochemical performances of NVPF. Among all, Na3V1.9Fe0.095Cr0.005(PO4)2F3 shows a high initial capacity of 119.85 mAhg−1 at 0.1C and maintains a capacity retention of 88.58 % after 500 cycles at 1C. Increase in the size of the saddle point, planes of monocapped trigonal prisms and the hexagonal cavities help in decreasing the ion diffusion activation energy, thus improving the diffusivity of the doped material. The improved electrochemical performances can be attributed to the increase in the electronic conductivity of the material. Besides, vanadium reduction in the cathode aids in manufacturing cost reduction. Our work demonstrates that carbon coated Na3V1.9Fe0.095Cr0.005(PO4)2F3 can be considered as a potential cathode candidate for practical applications in SIBs.

Constructing three-dimensional architectures to design advanced anodes materials for sodium-ion batteries: from nanoscale to microscale

Sodium-ion batteries (SIBs) are emerging as a possible substitute for lithium-ion batteries (LIBs) in low-cost and large-scale electrochemical energy storage systems owing to the lack of lithium resources. The properties of SIBs are correlated to the electrode materials, while the performance of electrode materials is significantly affected by the morphologies. In recent years, several kinds of anode materials involving carbon-based anodes, titanium-based anodes, conversion anodes, alloy-based anodes, and organic anodes have been systematically researched to develop high-performance SIBs. Nanostructures have huge specific surface areas and short ion diffusion pathways. However, the excessive solid electrolyte interface film and worse thermodynamic stability hinder the application of nanomaterials in SIBs. Thus, the strategies for constructing three-dimensional (3D) architectures have been developed to compensate for the flaws of nanomaterials. This review summarizes recent achievements in 3D architectures, including hollow structures, core-shell structures, yolk-shell structures, porous structures, and self-assembled nano/micro-structures, and discusses the relationship between the 3D architectures and sodium storage properties. Notably, the intention of constructing 3D architectures is to improve materials performance by integrating the benefits of various structures and components. The development of 3D architecture construction strategies will be essential to future SIB applications.

PH-manipulated large-scale synthesis of Na3(VOPO4)2F at low temperature for practical application in sodium ion batteries

Na3(VOPO4)2F (NVOPF) is an ideal cathode for high-energy-density sodium ion batteries (SIBs), due to its impressive output voltage and stable structure.

DFT Study of Borophene/Graphene (B/G) Heterostructure Properties as Sodium-Ion Battery Anode

As an alternative to lithium-ion batteries, sodium-ion batteries are gaining more attention as a solution to issues including the high cost and restricted supply of lithium. Nonetheless, issues including low voltage, limited capacity, and low electrode material capacity need to be fixed for sodium-ion battery applications. The proposed borophene/graphene heterostructure anode material for sodium-ion batteries was studied using density functional theory (DFT) to ascertain its properties. The findings demonstrate that there is sufficient interlayer spacing in the borophene/graphene heterostructure to allow for Na-intercalation. The interspace heterostructure has the highest Na adsorption energy of -2.02 eV. As a result, its maximum energy specific capacity is around 969.65 mAh/g. The borophene/graphene heterostructure anode exhibits strong diffusivity of Na ions, as evidenced by the activation energy of Na ion mobility in the heterostructure being less than 0.2 eV.

Interlaced Micro-Fibrous Hard Carbon As Superior Anode for Na-Ion Battery: Insights into the Sodium Storage Mechanism and Solid Electrolyte Interface

Hard carbon has been proved to be a promising negative electrode material for sodium-ion battery (SIBs) application. In this study, we have synthesized carbonaceous anode material by pyrolysis of tissue paper waste at different temperatures ranging from 800° to 1400°C. The tissue paper pyrolyzed at 1400°C has shown highest desodiation capacity of 350 mAhg-1 at 20 mAg-1 with stable cyclic performance and 70% capacity retention after 400 cycles at 200 mAg-1. The morphology, structure and surface chemistry of the cycled hard carbon electrodes were examined by ex-situ FE-SEM, XRD, Raman and XPS. The characterization results obtained reveal the detailed insights of the solid electrolyte interface and sodium storage mechanism of the hard carbon. The parameters of diffusion kinetics were evaluated by Electrochemical Impedance Spectroscopy (EIS) and CV analysis at different sweep rates. The results obtained in the study establish tissue paper waste as a promising precursor material to synthesize carbonaceous anode for SIBs by a simple one-step pyrolysis process.

Elevating the Practical Application of Sodium-Ion Batteries through Advanced Characterization Studies on Cathodes

Sodium-ion batteries (SIBs) have emerged as promising alternatives to their lithium-ion counterparts due to the abundance of sodium resources and their potential for cost-effective energy storage solutions. The chemistry for SIBs has been investigated since the 1980s, but it went through a slow research and development process. Recently, there has been an acceleration in technology maturation due to a supply chain crisis originating from unequal resource distribution and sustainability and safety concerns regarding lithium-ion batteries. However, the practical application of SIBs has been hindered primarily by challenges related to cathode materials, specifically, surface and structural stabilities in different conditions. Through the integration of advanced techniques such as in situ spectroscopy, operando diffraction, and high-resolution microscopy, a comprehensive understanding of the cathode’s dynamic behavior and degradation mechanisms can be achieved. The identified structural modifications, phase transitions, and degradation pathways offer critical insights into the design of robust cathode materials with prolonged cycling stability, fast charging capability, high energy density, great low-temperature performance, and safety. This review underscores the pivotal role of cutting-edge characterization techniques in guiding the development of high-performance sodium-ion batteries, thereby fostering the realization of sustainable and efficient energy storage solutions for diverse technological applications.

Sericin-derived carbon wrapped NiS2/V2O3 heterostructure for high-rate capability sodium-ion batteries

Sodium-ion batteries (SIBs) present a prospective solution for energy storage, benefitting from their cost-effectiveness and the abundant availability of sodium reserves on Earth. The effective design of electrode materials with superior cyclability and exceptional rate capability are essential for their widespread application. In this paper, a heterostructure between binary nickel sulfide (NiS2) and vanadium trioxide (V2O3) was initially synthesized by a feasible hydrothermal and subsequent high-temperature calcination technique, which consisted of coin-like V2O3 tiny sheets adhering to the surface of NiS2 microsphere. After coating a layer of sericin-derived carbon (SC) films onto surface of NiS2/V2O3, as-synthesized NiS2/V2O3@SC composite anodes for SIBs exhibited impressive electrochemical Na+ storage performances involving an initial discharge capacity of 671.2 mAh g−1 at 1 A g−1, a capacity decay of only 0.043 and 0.066 % per cycle within 1000 cycles at 1 A g−1 and 8 A g−1, and the rate capability of 32 A g−1 with a capacity output of 406.4 mAh g−1. The NiS2/V2O3 heterostructure with a hierarchical structure will beneficially alleviate agglomeration and volumetric expansion of active materials, improve electrical conductivity, and more importantly, enhance electrochemical kinetic transport of Na+, which makes it a potential anode application for SIBs.