Application In Sodium-ion Batteries Research Articles

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.

Controllable hierarchical porous FeSe2 with excellent long cycle lifespan as anode materials for sodium-ion battery

Transition metal selenides are regarded as most promising anode materials for sodium ion battery (SIB) due to their high theoretical specific capacity and environment benignly. Yet the severe volume expansion and sluggish kinetics during cycling leading to capacity fading and material pulverizing restrict its application in SIB. Herein, iron selenides (N–FeSe2) with controlled porous structure is synthesized via facile salt template-assisted method. When N–FeSe2 with hierarchical pore structure serves as anode materials for SIB, a highly reversible capacity of 520.4 mA h g−1 is maintained at 1 A g−1 after 100 cycles. Even at 10 A g−1, the capacity still remains 333 mA h g−1 after 1800 cycles, which shows extraordinary cycle stability. In addition, N–FeSe2 provides excellent diffusion coefficient and high initial Coulomb efficiency (78.9 %), which is attributed to its special hierarchical porous structure and intrinsic pseudocapacitance characteristics. DFT calculations indicate that an increase in vacancy concentration enhances the conductivity of the material, thereby improving its dynamic performance. In this work, a simple and universal synthesis method is developed, and the pore structure and morphology of the final product can be controlled by simple parameter regulation.

The Distance Between Phosphate-Based Polyanionic Compounds and Their Practical Application For Sodium-Ion Batteries.

Sodium-ion batteries (SIBs) are a viable alternative to meet the requirements of future large-scale energy storage systems due to the uniform distribution and abundant sodium resources. Among the various cathode materials for SIBs, phosphate-based polyanionic compounds exhibit excellent sodium-storage properties, such as high operation voltage, remarkable structural stability, and superior safety. However, their undesirable electronic conductivities and specific capacities limit their application in large-scale energy storage systems. Herein, the development history and recent progress of phosphate-based polyanionic cathodes are first overviewed. Subsequently, the effective modification strategies of phosphate-based polyanionic cathodes are summarized toward high-performance SIBs, including surface coating, morphological control, ion doping, and electrolyte optimization. Besides, the electrochemical performance, cost, and industrialization analysis of phosphate-based polyanionic cathodes for SIBs are discussed for accelerating commercialization development. Finally, the future directions of phosphate-based polyanionic cathodes are comprehensively concluded. It is believed that this review can provide instructive insight into developing practical phosphate-based polyanionic cathodes for SIBs.

Understanding the Improved Sodium Ion Storage in Wood-Derived Hard Carbon Anodes by Hydrogen Treatment

Biomass carbon, as a renewable resource, has the ability to be a hard carbon anode material for sodium-ion batteries. Its performance is highly reliant on the surface functional group. Through our work, successfully synthesized the high-performance hard carbon by the treatment of the hydrogen reduction process of rose willow. Moreover, the effects of hydrogen reduction on the evolution of functional groups and the relevant electrochemical performance have been investigated. After undergoing hydrogen reduction treatment, hard carbons’ surface features and layer spacing were greatly enhanced. In addition, the partial surface C=O group was reduced to C-O, which led to the Na+ adsorption active sites and pseudo-capacity increased, thus improving the dynamics of the electrode process. As anticipated, the resulting hard carbon exhibited a capacity of 325 mAh g−1, with an initial coulomb efficiency (ICE) of 80.84%. This study is in an effort to demonstrate the possibility of biomass-based carbon materials in preparation for future commercial applications of sodium-ion batteries.

Covalent Organic Frameworks (COFs): Characteristics and Applications for Lithium-Ion Batteries (LIBs) and Sodium Ion Batteries (SIBs)

Covalent organic frameworks (COFs) belong to a family of porous organic materials that form 2D or 3D tuned structures via a covalent bond formation between organic blocks. COFs exhibit a remarkable array of characteristics that make them highly promising materials for various applications. COFs are characterized by their chemical and physical stability, their highly porous structure, and their easy structural tunability. They emerged as promising candidates for electrode materials in advanced energy storage devices such as sodium-ion batteries (SIBs) and lithium-ion batteries (LIBs). COFs can be precisely customized for each application via pore engineering and framework functionalization as well as the pre- and post-synthesis. Research has been conducted to examine the effect of various functional groups, active redox sites, pore size, and interlayer distances on the performance of COFs as electrode materials. Herein, this review reports the most recent advances in using COFs as electrode materials in both LIBs and SIBs. It also discusses the synthesis of COFs, structural engineering, and pore engineering. The main advantages and challenges that arise with the application of COFs in rechargeable batteries are presented. This review concluded that COFs do have the potential as anode materials in both LIBs and SIBs by virtue of their crystalline structure and high porosity that enable efficient ion diffusion and storage. COFs provided enhanced battery electrochemical performance, improved energy density, and prolonged cycle life.

Designing hollow Ti3C2@TiSe2 composites for long cycle life of sodium-ion storage

The construction of an anode material with high electrical conductivity and long cycle stability was essential for the practical application of Sodium-ion batteries (SIBs). Hollow Ti3C2@TiSe2 composites were successfully synthesized using in situ selenization methods from MXene-derived materials. The composites obtained in this study exhibited an impressive reversible capacity, attaining a specific capacity of 561 mAh g−1 when tested at a current density of 0.1 A g−1.The specific capacity remained stable at 201 mAh g−1 through 12,000 cycles at a high current density of 10 A g−1. When utilizing Na3V2(PO4)3@C (NVP@C) as the cathode in a full cell, it demonstrated a sustained specific capacity of 138 mAh g−1 over 50 cycles at a current density of 100 mA g−1. Additionally, a capacity of 98 mAh g−1 was maintained over 500 charge-discharge cycles at a higher current density of 1000 mA g−1. The reaction mechanism of Na+ was confirmed through reaction kinetics and ex-situ XRD test. This study demonstrated that the special hollow structure comprised of Ti3C2 and TiSe2 enhanced the material's structural stability as well as the surface activity.

3D flower-like hollow MXene@MoS2 heterostructure for fast sodium storage

Constructing an anode with fast electron transport and high cycling stability is important but challenging for large-scale applications of sodium-ion batteries (SIB). In this study, hierarchical flower-like MXene structures were synthesized using poly (methyl methacrylate) (PMMA) microsphere as templates. Subsequently, a straightforward hydrothermal reaction was utilized to anchor small-sized MoS2 nanosheets. The resulting MXene@MoS2 heterostructure exhibits a distinctive three-dimensional (3D) porous hollow architecture. This structure effectively addresses challenges related to self-aggregation of MoS2 nanosheets and volume expansion of the electrode material during Na+ insertion/extraction processes. Furthermore, the robust hetero-interface supports fast and stable electron transfer, thereby enhancing electrochemical reaction kinetics. The prepared MXene@MoS2 electrode demonstrates the specific capacity of 682.1 mA h g−1 at 0.2 A/g and the reversible capacity of 494.4 mA h g−1 after 1000 cycles at 5 A/g. It is noteworthy that the full battery assembled with the composite material as the anode can still maintain the capacity of 456.2 mA h g−1 after 80 cycles at 0.5 A/g. This outstanding reversible capacity and sustained stability over numerous cycles highlights its potential for a wide range of applications.

Structural regulation enabled stable hollow molybdenum diselenide nanosheet anode for ultrahigh energy density sodium ion pouch cell

For the continued use of sodium-ion batteries (SIBs), which require matching anode materials, it is crucial to create high energy density energy storage devices. Here, hollow nanoboxes shaped carbon supported sulfur-doped MoSe2 nanosheets (S-MoSe2@NC) are fabricated by in situ growth and heterodoping strategy. This ensures that the MoSe2 nanosheets are tightly anchored to the nanoboxes carbon, and the structure can effectively buffer the volume stress caused by sodium ion (de)intercalation, as well as providing abundant ion/electron migration transportations. As anode for SIBs, the S-MoSe2@NC shows a higher rate capability and excellent cycling stability (431.1 mAh/g after 1100 cycles at 10 A/g). This excellent cycle life and high rate ability are due to the structural stability and outstanding electronic conductance with reduced band gap of the S-MoSe2@NC, as evidenced by the diffusion analysis and theoretical calculation. In order to promote the application of SIBs, the S-MoSe2@NC and NaNi1/3Fe1/3Mn1/3O2 were assembled into a pouch cell, and the test found that besides the excellent cycle rate performance, the ultrahigh energy density of 256 Wh kg−1 and flexible characteristics can be achieved. This study has proven that building a structure with a rock-steady foundation and quick ion migration may efficiently control sodium storage and pave the way for novel applications of high-performance transition metal dichalcogenides in sodium storage.

Two-dimensional layered In2P3S9: A novel superior anode material for sodium-ion batteries

Developing reliable and efficient anode materials is essential for the successfully practical application of sodium-ion batteries. Herein, employing a straightforward and rapid chemical vapor deposition technique, two-dimensional layered ternary indium phosphorus sulfide (In2P3S9) nanosheets are prepared. The layered structure and ternary composition of the In2P3S9 electrode result in impressive electrochemical performance, including a high reversible capacity of 704 mA h g−1 at 0.1 A g−1, an outstanding rate capability with 425 mA h g−1 at 5 A g−1, and an exceptional cycling stability with a capacity retention of 88% after 350 cycles at 1 A g−1. Furthermore, sodium-ion full cell also affords a high capacity of 308 and 114 mA h g−1 at 0.1 and 5 A g−1. Ex-situ X-ray diffraction and ex-situ high-resolution transmission electron microscopy tests are conducted to investigate the underlying Na-storage mechanism of In2P3S9. The results reveal that during the first cycle, the P–S bond is broken to form the elemental P and In2S3, collectively contributing to a remarkably high reversible specific capacity. The excellent electrochemical energy storage results corroborate the practical application potential of In2P3S9 for sodium-ion batteries.

An effective strategy to prepare non-graphitic carbon with increased pseudo-graphitic content for sodium-ion battery anode with enhanced plateau capacity

The practical application of sodium-ion batteries is mainly hindered by relatively low energy density, which can be effectively overcome by increasing the pseudo-graphitic content in non-graphitic carbon (NGC) anodes. Herein, a simple and efficient strategy was reported to promote the growth of pseudo-graphitic domains in NGC thanks to the synergistic effect of pre-carbonization and NaOH etching using semi-coke as precursor. Based on pre-carbonization at 800 °C and NaOH etching with NaOH/carbon ratio of 0.5 at 600 °C, the resultant NGC (FC-800–0.5–600) exhibits a 13 % increase in percentage of pseudo-graphitic structure meanwhile 14 % decrease for graphite-like structure, but similar content of highly disordered structure compared with its counterpart. Notably, although similar in sloping capacity, FC-800–0.5–600 possesses much higher plateau capacity (<0.1 V) of 218.6 mAh g−1 than its counterpart (174.9 mAh g−1), which is attributed to the enhanced “interlayer intercalation” effect related with pseudo-graphitic structure. Thus, FC-800–0.5–600 can deliver an impressive reversible capacity of 326.8 mAh g−1 at 20 mA g−1, together with a considerable ICE of 84.7 %. This work proposed an effective strategy to increase pseudo-graphitic structure content in NGC, providing a rational guide for designing high-performance anodes in SIBs for practical use.

High-performance ε-VOPO4 cathode materials for sodium ion battery applications

The nanoscale ε-VOPO4 materials were successfully prepared by hydrothermal synthesis of H2VOPO4 precursors and further calcination. XRD and AFM characterization showed that the prepared nano-ε-VOPO4 belonged to monoclinic crystalline system with high purity of physical phase and an average particle size of 150 nm. FT-IR spectroscopy showed that the characteristic peak of the H2VOPO4 precursor (at 797 cm−1) disappeared after calcination and a characteristic peak representing ε-VOPO4 was captured at 914 cm−1. Furthermore, the XPS results showed that the V in the prepared ε-VOPO4 was mainly +5 valence. In order to further evaluate the potential of ε-VOPO4 as an energy storage material, it was applied as cathode material in sodium ion battery system. Electrochemical tests have demonstrated that ε-VOPO4 has satisfactory electrochemical performance as cathode material for sodium ion batteries. The initial capacities of ε-VOPO4 electrode materials reached 162.3, 135.1, 86.7, 51.4, and 29.7 mAh g−1 at 0.05, 0.2, 1, 2, and 5 C, respectively, and the long-cycle performance results showed that the electrochemical stability was still superior after 200 cycles at a current density of 0.5 C. Meanwhile, the density functional theory calculation shows that the optimized lattice constants (a = 7.279 Å, b = 6.896 Å and c = 7.268 Å) are in good agreement with the experimental data. Notably, the experimental ε-VOPO4 material has a higher voltage plateau than the theoretical calculation, which shows the potential advantage of ε-VOPO4 as a new generation electrode material for high energy storage systems.

A topological nodal surface carbon honeycomb for sodium-ion battery anode

Motivated by the successful synthesis of three-dimensional (3D) graphene monoliths, we propose a 3D carbon honeycomb structure, tC40, composed of graphene-nanoribbons linked with 5-5-8 defects based on first-principles calculations. This structure is not only dynamically, thermally, and mechanically stable, but also possesses interesting electronic properties, including the multiple topological nodal surfaces on the high-symmetry plane k3=0 with double and quadruple degeneracies of bands in the reciprocal space, and the nontrivial surface states connecting different topological nodal surfaces parallel to the z-axis. By using the k·p model, we further show that, unlike previously reported nodal surfaces, the energy dispersion of the quadruply degenerated nodal surface is proportional to the k32, while the Hamiltonian of the doubly degenerated nodal surface is formed by the essential degeneracy of the valence and conduction bands. In addition, we explore the application of this nodal surface carbon as an anode material for sodium-ion batteries (SIBs), and find that tC40 exhibits good performance with a high reversible capacity of 186 mAh·g−1, a low sodium ion migration barrier of 0.1 eV, and a small charging/discharging volume change of 0.79 %. This work expands the family of topological carbon materials and their applications in SIBs.

Binary Metallic CuCo5 S8 Anode for High Volumetric Sodium-Ion Storage.

With the rapid improvement of compact smart devices, fabricating anode materials with high volumetric capacity has gained substantial interest for future sodium-ion batteries (SIBs) applications. Herein, a novel bimetal sulfide CuCo5 S8 material is proposed with enhanced volumetric capacity due to the intrinsic metallic electronic conductivity of the material and multi-electron transfer during electrochemical procedures. Due to the intrinsic metallic behavior, the conducting additive (CA) could be removed from the electrode fabrication without scarifying the high rate capability. The CA-free CuCo5 S8 electrode can achieve a high volumetric capacity of 1436.4 mA h cm-3 at a current density of 0.2 A g-1 and 100 % capacity retention over 2000 cycles in SIBs, outperforming most metal chalcogenides, owing to the enhanced electrode density. Reversible conversion reactions are revealed by combined measurements for sodium systems. The proposed new strategy offers a viable approach for developing innovative anode materials with high-volumetric capacity.