Materials For Sodium-ion Batteries Research Articles

Revealing the Nature of Binary-Phase on Structural Stability of Sodium Layered Oxide Cathodes.

The emergence of layered sodium transition metal oxides featuring a multiphase structure presents a promising approach for cathode materials in sodium-ion batteries (SIBs), showcasing notably improved energy storage capacity. However, the advancement of cathodes with multiphase structures faces obstacles due to the limited understanding of the integrated structural effects. Herein, we comprehend the integrated structural effects by an in-depth structure-chemistry analysis in the developed layered cathode system NaxCu0.1Co0.1Ni0.25Mn0.4Ti0.15O2 with purposely designed P2/O3 phase integration. Our results affirmed that integrated phase ratio plays a pivotal role in electrochemical/structural stability, particularly at high voltage and with the incorporation of anionic redox. In contrast to previous reports advocating solely for the enhanced electrochemical performance in biphasic structures, we demonstrated an inappropriate composite structure is more destructive than a single-phase design. The in situ X-ray diffraction (XRD) results, coupled with density functional theory (DFT) computations further confirm the biphasic structure with P2:O3 = 4:6 shows suppressed irreversible phase transition at high desodiated states and thus exhibits optimized electrochemical performance. These fundamental discoveries provide clues to the design of high-performance layered oxide cathodes for next-generation SIBs. This article is protected by copyright. All rights reserved.

Regulating Interfacial Compositions to Build a Stable Superlattice Structure of Layered Oxide Cathode Materials for Sodium-Ion Batteries

Regulating Interfacial Compositions to Build a Stable Superlattice Structure of Layered Oxide Cathode Materials for Sodium-Ion Batteries

Exploration of Mixed Polyanionic Compound for Potential High-Voltage Cathode Materials in Sodium-Ion Batteries

Exploration of Mixed Polyanionic Compound for Potential High-Voltage Cathode Materials in Sodium-Ion Batteries

Industrial-scale Hard Carbon Designed to Regulate Electrochemical Polarization for Fast Sodium Storage.

Given the merits of abundant resource, low cost and high electrochemical activity, hard carbons have been regarded as one of the most commercializable anode material for sodium-ion batteries (SIBs). However, poor rate capability is one of the main obstacles that severely hinder its further development. In addition, the relationships between preparation method, material structure and electrochemical performance have not been clearly elaborated. Herein, a simple but effective strategy is proposed to accurately construct the multiple structural features in hard carbon via adjusting the components of precursors. Through detailed physical characterization of the hard carbons derived from different regulation steps, and further combined with in-situ Raman and galvanostatic intermittent titration technique (GITT) analysis, the network of multiple relationships between preparation method, microstructure, sodium storage behavior and electrochemical performance have been successfully established. Simultaneously, exceptional rate capability about 108.8 mAh g-1 at 8 A g-1 have been achieved from RHC sample with high reversible capacity and desirable initial Coulombic efficiency (ICE). Additionally, the practical applications can be extended to cylindrical batterywith excellent cycle behaviors. Such facile approach can provide guidance for large-scale production of high-performance hard carbons and provides the possibility of building practical SIBs with high energy density and durability.

High-Entropy Configuration Strategy to Build High Performance Na-Ion Layered Oxide Cathodes Derived from Simple Techniques.

Layered transition metal oxides are commonly used as the cathode materials in sodium-ion batteries due to their low cost and easy manufacturing. However, the application is hindered by poor rate performance and complex phase transitions. To address these challenges, a new seven-component high-entropy layered oxide cathode material, O3-NaNi0.25Fe0.15Mn0.3Ti0.1Sn0.05Co0.05Li0.1O2 (HEO) has been developed. The entropy stabilization effect plays a crucial role in improving the performance of electrochemical systems and the stability of structures. The HEO exhibits a specific discharge capacity of 154.1 mA h g-1 at 0.1 C and 94.5 mA h g-1 at 7 C. In-situ and ex-situ XRD results demonstrate that the HEO effectively retards complex phase transitions. This work provides a high-entropy design for the storage materials with a high energy density. Meanwhile, it eliminates industry doubts about the performance of sodium ion layered oxide cathode materials.

Manipulating Local Chemistry and Coherent Structures for High-Rate and Long-Life Sodium-Ion Battery Cathodes.

Layered sodium transition-metal (TM) oxides generally suffer from severe capacity decay and poor rate performance during cycling, especially at a high state of charge (SoC). Herein, an insight into failure mechanisms within high-voltage layered cathodes is unveiled, while a two-in-one tactic of charge localization and coherent structures is devised to improve structural integrity and Na+ transport kinetics, elucidated by density functional theory calculations. Elevated Jahn-Teller [Mn3+O6] concentration on the particle surface during sodiation, coupled with intense interlayer repulsion and adverse oxygen instability, leads to irreversible damage to the near-surface structure, as demonstrated by X-ray absorption spectroscopy and in situ characterization techniques. It is further validated that the structural skeleton is substantially strengthened through the electronic structure modulation surrounding oxygen. Furthermore, optimized Na+ diffusion is effectively attainable via regulating intergrown structures, successfully achieved by the Zn2+ inducer. Greatly, good redox reversibility with an initial Coulombic efficiency of 92.6%, impressive rate capability (86.5 mAh g-1 with 70.4% retention at 10C), and enhanced cycling stability (71.6% retention after 300 cycles at 5C) are exhibited in the P2/O3 biphasic cathode. It is believed that a profound comprehension of layered oxides will herald fresh perspectives to develop high-voltage cathode materials for sodium-ion batteries.

Constructing a Size-Controllable Spherical P2-Type Layered Oxides Cathode That Achieves Practicable Sodium-Ion Batteries.

P2-type layered metal oxides are regarded as promising cathode materials for sodium-ion batteries due to their high voltage platform and rapid Na+ diffusion kinetics. However, limited capacity and unfavorable cycling stability resulting from inevitable phase transformation and detrimental structure collapse hinder their future application. Herein, based on P2-type Na0.67Ni0.18Mn0.67Cu0.1Zn0.05O2, we synthesized a series of secondary spherical morphology cathodes with different radii derived from controlling precursors prepared by a coprecipitation method, which can be promoted to large-scale production. Consequently, the synthesized materials possessed a high tap density of 1.52 g cm-3 and a compacted density of 3.2 g cm-3. The half cells exhibited a specific capacity of 111.8 mAh g-1 at a current density of 0.1 C as well as an 82.64% capacity retention with a high initial capacity of 85.80 mAh g-1 after 1000 cycles under a rate of 5 C. Notably, in situ X-ray diffraction revealed a reversible P2-OP4 phase transition and displayed a tiny volume change of 6.96% during the charge/discharge process, indicating an outstanding cycling stability of the modified cathode. Commendably, the cylindrical cell achieved a capacity of 4.7 Ah with almost no change during 1000 cycles at 2 C, suggesting excellent potential for future applications.

Controllable Preparation and Sodium Storage Properties of Sb2Te3–Te Heterojunction

Antimony-based materials possess high theoretical capacities and suitable potential, which could be promising anode materials for sodium-ion batteries (SIB). However, poor stabilities and sluggish kinetics are drawbacks. Building heterojunction is an ideal method to solve these issues. Its unique structure develops internal electric fields spontaneously to boost the charge transport and relieve stress. Nevertheless, the controllable preparation of face-to-face (2D) heterojunctions is still hard-pressed. Herein, Sb2Te3–Te nanoheterojunctions, which consist of two-dimensional Sb2Te3 nanoblades attached to a one-dimensional Te nanorod, are fabricated through a two-step solvothermal method. Among that, the density of nanoblades is adjustable through the engineering feed ratio. When employed as anodes for SIBs, Sb2Te3–Te nanoheterojunctions display a reversible capacity of 463.2[Formula: see text]mAh[Formula: see text]g[Formula: see text] at 100[Formula: see text]mA[Formula: see text]g[Formula: see text]. Even a capacity of 305.5[Formula: see text]mAh[Formula: see text]g[Formula: see text] remains after 1000 cycles under a high current of 1.5[Formula: see text]A[Formula: see text]g[Formula: see text]. Moreover, the density functional theory (DFT) calculations also identify the high conductivity of heterojunction. This work offers an effective way to design the structures and properties of heterojunctions, further expanding their application range.

Air Corrosion of Layered Cathode Materials for Sodium-Ion Batteries: Cation Mixing and a Practical Suppression Strategy.

Layered oxide cathodes of sodium-ion batteries (SIBs) are considered promising candidates due to their fascinating high capacity, good cyclability, and environmental friendliness. However, the air sensitivity of layered SIB cathodes causes high electrode manufacturing costs and performance deterioration, hampering their practical application. Herein, a commercial O3-type layered Na(Ni1/3Fe1/3Mn1/3)O2 (NNFM) material is adopted to investigate the air corrosive problem and the suppression strategy. We reveal that once the layered material comes in contact with ambient air, cations migrate from transition metal (TM) layers to sodium layers at the near surface, although Na+ and TM ions show quite different ion radii. Experimental results and theoretical calculations show that more Ni/Na disorder occurs in the air-exposed O3-NNFM materials, owing to a lower Ni migration energy barrier. The cation mixing results in detrimental structural distortion, along with the formation of residual alkali species on the surface, leading to high impedance for Na+ diffusion during charge/discharge. To tackle this problem, an ultrathin and uniform hydrophobic molecular layer of perfluorodecyl trimethoxysilane is assembled on the O3-NNFM surface, which significantly suppresses unfavorable chemistry and structure degradation during air storage. The in-depth understanding of the structural degradation mechanism and suppression strategy presented in this work can facilitate high-energy cathode manufacturing from the perspective of future practical implementation and commercialization.

High stability of Cu-doped O3-type NaNi1/3Fe1/3Mn1/3O2 cathode material for sodium-ion battery

High stability of Cu-doped O3-type NaNi1/3Fe1/3Mn1/3O2 cathode material for sodium-ion battery

Performance of CuP2 Negative Electrode for Na‐Ion Batteries with CNTs As Stabilizer

AbstractTransition metal phosphides (TMPs) are promising anode materials for sodium ion battery, thanks to their high theoretical specific capacities. Nevertheless, they suffer from large volume change and from poor conductivity during prolonged cycling. Here we systematically investigate the role of different kinds of single/multi‐wall carbon nanotubes (SWCNTs/MWCNTs) as additives in order to stabilize copper phosphide particles (CuP2) as anode materials in sodium ion batteries (SIBs). All composites show enhancement in the overall capacity and cycling stability compared to the pristine CuP2 due to the well‐connected CNTs on and between the CuP2 particles. At a high currency density of 1 A g−1, CuP2@SWCNTs composite with 13 wt.% SWCNTs can deliver a specific capacity over 400 mAh g−1 for more than 60 cycles, much better than conventional hard carbon materials. The CNTs enhance the conductivity and reduce capacity loss caused by the volume variation of CuP2 based electrode materials. Post‐mortem analysis by scanning electron microscopy depicts a possible battery failure mechanism, whereby the solid electrolyte interface exists in the form of nanospheres distributing at the surface of the electrode. During the repeated cycling (volume change), more fractures and cracks occur resulting in continuous interfacial reactions and consumption of sodium and electrolyte.

Interfacial Spinel Local Interlocking Strategy Toward Structural Integrity in P3 Oxide Cathodes.

P3-layered transition oxide cathodes have garnered considerable attention owing to their high initial capacity, rapid Na+ kinetics, and less energy consumption during the synthesis process. Despite these merits, their practical application is hindered by the substantial capacity degradation resulting from unfavorable structural transformations, Mn dissolution and migration. In this study, we systematically investigated the failure mechanisms of P3 cathodes, encompassing Mn dissolution, migration, and the irreversible P3-O3' phase transition, culminating in severe structural collapse. To address these challenges, we proposed an interfacial spinel local interlocking strategy utilizing P3/spinel intergrowth oxide as a proof-of-concept material. As a result, P3/spinel intergrowth oxide cathodes demonstrated enhanced cycling performance. The effectiveness of suppressing Mn migration and maintaining local structure of interfacial spinel local interlocking strategy was validated through depth-etching X-ray photoelectron spectroscopy, X-ray absorption spectroscopy, and in situ synchrotron-based X-ray diffraction. This interfacial spinel local interlocking engineering strategy presents a promising avenue for the development of advanced cathode materials for sodium-ion batteries.

Achieving a Deeply Desodiated Stabilized Cathode Material by the High Entropy Strategy for Sodium-ion Batteries.

Manganese-based layered oxides are currently of significant interest as cathode materials for sodium-ion batteries due to their low toxicity and high specific capacity. However, the practical applications are impeded by sluggish intrinsic Na+ migration and poor structure stability as a result of Jahn-Teller distortion and complicated phase transition. In this study, a high-entropy strategy is proposed to enhance the high-voltage capacity and cycling stability. The designed P2-Na0.67Mn0.6Cu0.08Ni0.09Fe0.18Ti0.05O2 achieves a deeply desodiation and delivers charging capacity of 158.1 mA h g-1 corresponding to 0.61 Na with a high initial Coulombic efficiency of 98.2%. The charge compensation is attributed to the cationic and anionic redox reactions conjunctively. Moreover, the crystal structure is effectively stabilized, leading to a slight variation of lattice parameters. This research carries implications for the expedited development of low-cost, high-energy-density cathode materials for sodium-ion batteries.

On the structural evolution of pristine P2-type Na0.67Ni0.33Mn0.67O2 for symmetric full cell application

P2 type Na0.67Ni0.33Mn0.67O2 (NNMO) is a widely studied layered oxide cathode material for sodium-ion batteries (SIBs) because of its high capacity (160 mAhg-1 practically achieved) and broad voltage window (2–4.5 V). The redox activity in NNMO is shown by both Ni2+ and Mn4+ ions, making it a prospective symmetric SIB electrode material. The average working potential of the symmetric full cell is less due to the limited average working voltages of both the redoxes in a half cell between 2 V and 4.5 V, resulting in poor energy density. Herein, we report the feasibility of the NNMO symmetric full cell by widening the operational voltage window of NNMO. The electrochemical performance of NNMO half cells between 0.01 V and 4 V and the structural evolution during cycling are mapped by ex-situ XRD. Na0.44MnO2-like tunnel-type structure (Pbam) with high Na+ content (>0.90) exists at potentials close to the Mn3+/4+ redox reaction during cycling. The phase change was relatively reversible, implying that the NNMO anode works at such low voltages without the hazard of severe capacity losses. The symmetric full cell made using NNMO cycled between 0.01 V and 3 V and, at C/10 rate, delivered a capacity of ∼68 mAhg−1.

Synthesis and Characterization of Na2/3[Fe1/2Mn1/2]O2 Cathode Material for Sodium Ion Batteries

<p><strong>Abstract. </strong>Recently,<strong> </strong>Na<sub>2/3</sub>[Fe<sub>1/2</sub>Mn<sub>1/2</sub>]O<sub>2</sub> has received attention as a potential candidate material for cathode sodium-ion batteries. However, this material was synthesized by a solid-state process, resulting in larger particle size and nonuniform morphology. The larger particle size will sluggish the Na ion diffusion. Here we report the synthesis of Na<sub>2/3</sub>[Fe<sub>1/2</sub>Mn<sub>1/2</sub>]O<sub>2</sub> using a simple sol-gel process. The X-ray diffraction revealed that the sample was identified as Na<sub>2/3</sub>[Fe<sub>1/2</sub>Mn<sub>1/2</sub>]O<sub>2</sub> with a hexagonal crystal structure. However, the impurities are formed at diffraction angles of 36.28°, 45.03°, and 51.23°. Calcination temperature affects the formation of the crystal phase, grain growth, morphology, and particle size. Our findings provide valuable insight into the development of Na<sub>2/3</sub>[Fe<sub>1/2</sub>Mn<sub>1/2</sub>]O<sub>2</sub> material with desirable properties.</p><p> </p><p><strong>Keywords:</strong></p><p>Sol-Gel, Solid State, Grain Growth, Calcination, Na<sub>2/3</sub>[Fe<sub>1/2</sub>Mn<sub>1/2</sub>]O<sub>2</sub></p><p> </p>

Mechanism and enhanced performance of low-dose low-valence molybdenum-doped Na3V2(PO4)2F2O cathodes for sodium batteries

Sodium vanadium oxyfluorophosphate Na3V2(PO4)2F2O is an attractive cathode material for sodium ion batteries due to its high crystalline stability, high specific capacity and high discharge potential. Currently, the poor electronic conductivity and low diffusion rate of Na+ severely impede its development and application. In this work, low-dose Mo2+ doping is proposed through first-principle computation to enhance the structure and performance of Na3V2(PO4)2F2O. It is found that low-dose of Mo2+ doping can reduce the band gap and energy barrier for Na + diffusion in Na3V2(PO4)2F2O. However, heavy doping leads to serious Jahn-Teller distortion of the crystal structure. Therefore, low-dose Mo2+ doping, ranging from x = 0 to x = 0.06 in Na3V2-xMox(PO4)2F2O, is designed and experimentally carried out. The best performance with 118.5 mA h g−1 at 0.1C and 60.6 mA h g−1 at 20C is obtained in Na3V1.96Mo0.04(PO4)2F2O when x = 0.04 in comparison with other doping amounts. The specific discharge capacity at 0.5C decreases gradually from 105.4 to 77.9 mA h g−1 after 400 cycles, indicating a capacity retention of 73.9 %. These results demonstrate that low-dose Mo2+ doping is an effective strategy to enhance the electrochemical performance of Na3V2(PO4)2F2O, making it a promising cathode material for sodium batteries.

Ion Dynamics at the Intermediate Charging State of the Sodium Vanadium Fluorophosphate Cathode.

Na super ionic conductor (NASICON)-type polyanionic vanadium fluorophosphate Na3V2O2(PO4)2F (NVOPF) is a promising cathode material for high-energy sodium-ion batteries. The dynamic diffusion and exchange of sodium ions in the lattice of NVOPF are crucial for its electrochemical performance. However, standard characterizations are mostly focused on the as-synthesized material without cycling, which is different from the actual battery operation conditions. In this work, we investigated the hopping processes of sodium in NVOPF at the intermediate charging state with 23Na solid-state nuclear magnetic resonance (ssNMR) and density functional theory (DFT) calculations. Our experimental characterizations revealed six distinct sodium coordination sites in the intermediate structure and determined the exchange rates among these sites at variable temperatures. The theoretical calculations showed that these dynamic processes correspond to different ion transport pathways in the crystalline lattice. Our combined experimental and theoretical study uncovered the underlying mechanisms of the ion transport in cycled NVOPF and these understandings may help the optimization of cathode materials for sodium-ion batteries.

Unveiling the potential of Na2FePO4F@PEG composite as cathode material for sodium-ion batteries

The economic and environmental advantages of Na2FePO4F fluorophosphate have positioned it as a highly promising cathode material for sodium-ion batteries (SIBs). This recognition stems from its demonstrated potential to address key challenges in energy storage systems, making it a subject of extensive research and studies.In this paper, the preparation of Na2FePO4F powder through a simplified, upscaling, and cost-effective approach that involves the direct use of phosphoric acid is described, aiming to evaluate its electrochemical performance. The obtained orthorhombic structure (S.G. Pbcn) is mixed with varying percentages of polyethylene glycol as a carbon source (15% and 20%) to generate large specific surfaces, improve electronic conductivity, and achieve an optimized carbon content for these materials. The 15% and 20% PEG-coated Na2FePO4F are evaluated at a 2 - 4 V voltage range at C/15 in Na-half cells using two electrolyte formulations: 5% FEC 1 M NaClO4:PC and 1 M NaPF6:PC. The NaPF6/FEC electrolyte exhibits better electrochemical characteristics and high cycling stability, especially in the case of the 15% PEG-coated material. These findings are also supported by the data from differential plots and rate capabilities, highlighting the potential of the coated material for applications in high-performance energy storage applications.

Peanut-shell derived hard carbon as potential negative electrode material for sodium-ion battery

Peanut-shell derived hard carbon as potential negative electrode material for sodium-ion battery

Vanadium nitride induced method to construct cobalt sulfides homologous heterojunction toward ultrafast and high-capacity sodium-ion storage

In recent years, heterojunction has attracted widespread attention as an anode for sodium-ion batteries since they can effectively optimize the materials’ rate performance and cycling stability. However, the advantage is choked by multi-element composition and stepwise synthesis process. Herein, cobalt sulfide (Co9S8/CoS) homologous heterojunction deposited at vanadium nitride/carbon nanofibers is synthesized as an excellent anode for high-performance sodium-ion batteries in one step by employing the “3d-orbital electron complementary effect” combined with high-temperature heat-treatment technology. The Co9S8/CoS homologous heterojunction successfully overcomes the inherent drawback of Co9S8 and possesses an ultrafast charging/discharging process, outstanding reversible specific capacity, and remarkable rate capability. A systematic study reveals that vanadium nitride is a key trigger for forming Co9S8/CoS heterojunction. When used as anode materials for sodium-ion batteries, it reaches a high specific capacity of 353.0 mAh/g at a current density of 10 A/g (615.8 mAh/g at a current density of 0.05 A/g) due to the presence of heterointerface. Theoretical calculations show that the construction of the heterostructure enhances the sodium-ion storage capacity and storage kinetics compared with pristine Co9S8. This discovery opens an interesting strategy for constructing homogeneous heterojunctions and broadens the horizons for designing energy storage and conversion materials.