Cathode Material For Sodium-ion Batteries Research Articles

Achieving a Rapid Na+ Migration and Highly Reversible Phase Transition of NASICON for Sodium-Ion Batteries with Suppressed Voltage Hysteresis and Ultralong Lifespan.

Sodium ion batteries have attracted great attention for large scale energy storage devices to replace lithium-ion batteries. As a promising polyanionic cathode material of sodium-ion batteries, Na3V2(PO4)2F3 (NVPF) belonging to NASICON exhibits large gap space and excellent structural stability, leading to a high energy density and ultralong cycle lifespan. To improve its stability and Na ion mobility, K+ cations are introduced into NVPF crystal as in situ partial substitution for Na+. The influence of K+ in situ substitution on crystal structure, electronic properties, kinetic properties, and electrochemical performance of NVPF are investigated. Through ex situ examination, it turns out that K+ occupied Na1 ion, in which the K+ does not participate in the charge-discharge process and plays a pillar role in improving the mobility of Na+. Moreover, the doping of K+ cation can reduce the bandgap energy and improve the electronic conductivity. Besides, the optimal K+ doping concentration in N0.92K0.08VPF/C is found so as to achieve rapid Na+ migration and reversible phase transition. The specific capacity of N0.92K0.08VPF/C is as high as 128.8 mAh g-1 at 0.2 C, and at 10 C its rate performance is excellent, which shows a capacity of 113.3 mAh g-1.

Cation Configuration and Structural Degradation of Layered Transition Metal Oxides in Sodium-Ion Batteries.

Given the pressing depletion of lithium resources, sodium-ion batteries (SIBs) stand out as a cost-effective alternative for energy storage solutions in the near future. Layered transition metal oxides (LTMOs) emerge as the leading cathode materials for SIBs due to their superior specific capacities and abundant raw materials. Nonetheless, achieving long-term stability in LTMOs for SIBs remains a challenge due to the inevitable structural degradation during charge-discharge cycles. The complexity and diversity of cation configurations/superstructures within the transition metal layers (TMO2) further complicate the understanding for newcomers. Therefore, it is critical to summarize and discuss the factors leading to structural degradation and the available strategies for enhancing LTMOs' stability. In this review, the cationic configurations of TMO2 layers are introduced from a crystallographic perspective. It then identifies and examines four key factors responsible for structural decay, alongside the impacts of various modification strategies. Finally, more effective and practical research approaches for investigating LTMOs have been proposed. The work aims to enhance the comprehension of the structural deterioration of LTMOs and facilitate a substantial improvement in their cycle life and energy density.

Anion Substitution to Suppress the Voltage Hysteresis of Na3MnTi(PO4)3 as a Cathode Material for Sodium-Ion Batteries.

The Mn-based polyanion compound Na3MnTi(PO4)3 (NMTP) with a Na superionic conductor (NASICON) structure has attracted incremental attention as a potential cathode material for sodium-ion batteries. However, the occupation of Mn2+ on Na+ vacancies usually leads to severe voltage hysteresis, which in turn results in significant capacity loss, slow Na+ diffusion kinetics, and poor cycling stability. Herein, anion-substituted compounds Na3MnTi(PO4)3-x(SiO4)x (x = 0.1, 0.2, and 0.3) are synthesized. It reveals that the SiO44- substitution could induce partial oxidation of Mn2+ to Mn3+, and the latter has a lower occupancy preference on Na+ vacancies. By the proposed charge compensation strategy, the Mn2+ occupation on Na+ vacancies can be significantly suppressed. As a result, the voltage hysteresis is substantially inhibited, and greatly improved electrochemical performance is achieved. This study offers an alternative strategy to address the voltage hysteresis associated with NMTP and other Mn-based NASICON cathode materials.

First-Principles Study of High-Entropy Sulfides and their Alkali Metal-Doped Modification as Cathode Material for Sodium-Ion Batteries.

High-entropy materials (HEMs) have been explored as high-capacity cathode materials for sodium-ion batteries (SIBs) due to their excellent structural stability and abundant metal redox sites. Among them, high-entropy sulfides (HESs) have greater potential and more extensive research than high-entropy oxides, as they exhibit higher charging voltage and theoretical capacity as cathodes. Furthermore, alkali metal doping of HESs can further enhance their performance and broaden their application fields. Inspired by the cocktail effect of HEMs, we performed the first theoretical calculation of the properties of Na(MnFeCoNi)1/2S and its Li-doped derivative, Na7/8Li1/8(MnFeCoNi)1/2S, to understand their potential as SIB cathode materials. Using density functional theory based on first principles, we investigated the structure and electronic characteristics of Na(MnFeCoNi)1/2S and Na7/8Li1/8(MnFeCoNi)1/2S, and calculated their theoretical voltage and capacity, respectively. Compared with Na(MnFeCoNi)1/2S, Na7/8Li1/8(MnFeCoNi)1/2S showed better electronic performance in reducing the band gap and increasing the density of states, ultimately providing a specific capacity of 160.3 mAh ⋅ g-1 and a charging voltage of 4.85 V in sodium-ion storage. Moreover, Na7/8Li1/8(MnFeCoNi)1/2S exhibited remarkable structural stability throughout the sodium-ion deintercalation process, thus it can be reasonably concluded that Na7/8Li1/8(MnFeCoNi)1/2S can serve as an excellent cathode material for future SIB applications.

An Active Strategy to Reduce Residual Alkali for High-Performance Layered Oxide Cathode Materials of Sodium-Ion Batteries.

Residual alkali is one of the biggest challenges for the commercialization of sodium-based layered transition metal oxide cathode materials since it can even inevitably appear during the production process. Herein, taking O3-type Na0.9Ni0.25Mn0.4Fe0.2Mg0.1Ti0.05O2 as an example, an active strategy is proposed to reduce residual alkali by slowing the cooling rate, which can be achieved in one-step preparation method. It is suggested that slow cooling can significantly enhance the internal uniformity of the material, facilitating the reintegration of Na+ into the bulk material during the calcination cooling phase, therefore substantially reducing residual alkali. The strategy can remarkably suppress the slurry gelation and gas evolution and enhance the structural stability. Compared to naturally cooled cathode materials, the capacity retention of the slowly cooled electrode material increases from 76.2% to 85.7% after 300 cycles at 1C. This work offers a versatile approach to the development of advanced cathode materials toward practical applications.

Highly Crystalline Multivariate Prussian Blue Analogs via Equilibrium Chelation Strategy for Stable and Fast Charging Sodium-Ion Batteries.

Prussian blue analogs (PBAs) have been widely recognized as superior cathode materials for sodium-ion batteries (SIBs) owing to numerous merits. However, originating from the rapid crystal growth, PBAs still suffer from considerable vacancy defects and interstitial water, making the preparation of long-cycle-life PBAs the greatest challenge for its practical application. Herein, a novel equilibrium chelation strategy is first proposed to synthesize a high crystallinity (94.7%) PBAs, which is realized by modulating the chelating potency of strong chelating agents via "acid effect" to achieve a moderate chelating effect, forcefully breaking through the bottleneck of poor cyclic stability for PBAs cathodes. Impressively, the as-prepared highly crystalline PBAs represent an unprecedented level of electrochemical performance including ultra-long lifespan (10000 cycles with 86.32% capacity maintenance at 6Ag-1), excellent rate capability (82.0mAhg-1 at 6Ag-1). Meanwhile, by pairing with commercial hard carbon, the as-prepared PBAs-based SIBs exhibit high energy density (350Whkg-1) and excellent capacity retention (82.4% after 1500 cycles), highlighting its promising potential for large-scale energy storage applications.

Off-Stoichiometry of Sodium Iron Pyrophosphate as Cathode Materials for Sodium-Ion Batteries with Superior Cycling Stability.

As one of the important devices for large-scale electrochemical energy storage, sodium-ion batteries have received much attention due to the abundant resources of raw materials. However, whether it is a base station power source, an energy storage power station, or a start-stop power supply, long energy cycle life (more than 5000 cycles), high stability, and safety performance are application prerequisites. Regrettably, currently, few sodium-ion batteries can meet this requirement, mainly due to shortcomings in positive electrode performance. We report a sufficiently stable sodium-ion battery cathode material, Na2Fe0.95P2O7, that retains 97.5% capacity after 5000 charge/discharge cycles. The use of nonstoichiometry in the lattice enables simultaneous modification of the crystal and electronic structure, promoting Na2Fe0.95P2O7 to be extremely stable while still being able to achieve a capacity of 92 mAh g-1 and stable cycling at high temperatures up to 60 °C. Our results confirm the positive effect of nonstoichiometric ratios on the performance of Na2Fe0.95P2O7 and provide a reliable idea to promote the practical application of sodium-ion batteries.

High entropy induced lattice expansion in layered oxide cathode towards fast sodium storage

Although O3-type layered oxides have become viable cathode materials for sodium-ion batteries (SIBs) due to their high energy densities, they still suffer from narrow ion channels and serious structure degradation, severely jeopardizing their electrochemical properties. Here, a stable O3-type layered oxide NaNi0.4Mn0.4M0.2O2 (M= Fe, Cu, Mg, Ti, Sn) (HE-NaNM) was synthesized by a high-entropy doping strategy. Owing to the introduction of the metal cations with ionic radiuses in a range of 0.61-0.73 Å into the layered structure, the lattice is expanded from 15.94 to 16.03 Å in c-axis, associated with a high distortion of TMO6 octahedrons, offering broad channels for sodium-ion transport in the lattices. Moreover, such expanded lattices and highly distorted TMO6 octahedrons enable to efficiently restrain the migration of TM ions and the severe sliding of TMO2 slabs, affording one-step reversible structure evolution between O3 and P3 phase during sodium extraction/insertion without formation of harmful interphases. As a result, a good rate capability of 77.9 mAh g-1 at 10 C and a long-term cycling stability up to 400 cycles at 5 C are achieved for sodium storage.

Inhibiting the Jahn-Teller Effect of Manganese Hexacyanoferrate via Ni and Cu Codoping for Advanced Sodium-Ion Batteries.

Manganese (Mn)-based Prussian blue analogs (PBAs) are of great interest as a prospective cathode material for sodium-ion batteries (SIBs) due to their high redox potential, easy synthesis, and low cost. However, the Jahn-Teller effect and low electrical conductivity of Mn-based PBA cause poor structure stability and unsatisfactory performance during the cycling. Herein, a novel nickel- and copper-codoped K2Mn[Fe(CN)6] cathode is developed via a simple coprecipitation strategy. The doping elements improve the electrical conductivity of Mn-based PBA by reducing the bandgap, as well as suppress the Jahn-Teller effect by stabilizing the framework, as verified by the density functional theory calculations. Simultaneously, the substitution of sodium with potassium in the lattice is beneficial for filling vacancies in the PBA framework, leading to higher average operating voltages and superior structural stability. As a result, the as-prepared Mn-based cathode exhibits excellent reversible capacity (116.0 mAh g-1 at 0.01 A g-1) and superior cycling stability (81.8% capacity retention over 500 cycles at 0.1 A g-1). This work provides a profitable doping strategy to inhibit the Jahn-Teller structural deformation for designing stable cathode material of SIBs.

Exploring the Effect of TiO2 Coating on Na0.85Li0.12Ni0.22Mn0.66O2 Cathode Materials for Na-Ion Batteries

Layered transition metal oxides have great potential as cathode materials for sodium ion batteries, but some limitations like structural instability and poor rate performance restricts its further application. To overcome the above issues, a simultaneously modified P2-type cathode of Na0.85Li0.12Ni0.22Mn0.66O2 with 1% weight TiO2 coating (NLNMO-1%wt TiO2) based on doping and coating approaches was prepared by high-temperature solid-state reaction and liquid phase coating. This new strategy reduces the relative content of Mn3+, which suppresses the Jahn-Teller effect and enhanes the structural stability. The as-prepared cathode shows improved rate capability, with a high reversible capacity of 111.4 mAh g−1 at 1 C and a capacity retention of 94.5% after 100 cycles. At 5 C, it maintains a capacity of 87.1 mAh g−1 at 5 C with capacity retention of 81.8% after 400 cycles. Additionally, it provides a stable CEI film, reducing side reactions and electrode pulverization. which could be confirmed by scanning electron microscopy and high-resolution transmission electron microscopy. Overall, this synergistic modification strategy provides a pathway for improving the electrochemical performance of layered oxide cathode materials for sodium-ion batteries.

Mo-Doped Na4Fe3(PO4)2P2O7/C Composites for High-Rate and Long-Life Sodium-Ion Batteries.

Na4Fe3(PO4)2P2O7/C (NFPP) is a promising cathode material for sodium-ion batteries, but its electrochemical performance is heavily impeded by its low electronic conductivity. To address this, pure-phase Mo6+-doped Na4Fe3-xMox(PO4)2P2O7/C (Mox-NFPP, x = 0, 0.05, 0.10, 0.15) with the Pn21a space group is successfully synthesized through spray drying and annealing methods. Density functional theory (DFT) calculations reveal that Mo6+ doping facilitates the transition of electrons from the valence to the conduction band, thus enhancing the intrinsic electron conductivity of Mox-NFPP. With an optimal Mo6+ doping level of x = 0.10, Mo0.10-NFPP exhibits lower charge transfer resistance, higher sodium-ion diffusion coefficients, and superior rate performance. As a result, the Mo0.10-NFPP cathode offers an initial discharge capacity of up to 123.9 mAh g-1 at 0.1 C, nearly reaching its theoretical capacity. Even at a high rate of 10 C, it delivers a high discharge capacity of 86.09 mAh g-1, maintaining 96.18% of its capacity after 500 cycles. This research presents a new and straightforward strategy to enhance the electrochemical performance of NFPP cathode materials for sodium-ion batteries.

Cu doping in TM ordered and disordered layered oxides for Sodium-Ion Batteries: Electrochemical Properties, structure evolution and Cu-Ion migration

The ordered/disordered distribution of transition metal (TM) plays a significant role in determining electrochemical properties including lattice oxygen redox, ion kinetics and structure evolution. From a novel perspective, this work demonstrates how the TM distributions influence the doping effect by means of introducing Cu element into ordered/disordered O3-Nax(NiySb1-y)O2. What’s more, the irreversible Cu migration from TM sites to Na layers upon electrochemical process is found. This migration which would deteriorate electrochemical stability only occurs in honeycomb-ordered compounds, instead of in disordered one. Theoretical calculations reveal that the TM disordered distribution promotes the formation of antibonding orbitals between Cu 3d and O 2p, thereby increasing the barrier of Cu migration to maintain well Na diffusion kinetics. Our discovery rolls out a new guidance for designing advanced cathode materials for sodium-ion batteries and speeds up the research on transition metal migration.

Cycling performance of layered oxide cathode materials for sodium-ion batteries

Cycling performance of layered oxide cathode materials for sodium-ion batteries

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, 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, 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, are comprehended. The results affirm 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, it is demonstrated that an inappropriate composite structure is more destructive than a single-phase design. The in situ X-ray diffraction results, coupled with density functional theory computations further confirm that 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.

Suppressing the Jahn–Teller effect in Mn-based Prussian blue analogues by linear (N[dbnd]O) anions

Manganese-based Prussian blue analogues (PBAs) have been touted as a promising cathode material for sodium-ion batteries (SIBs) due to their low cost, long cycle life and high energy density. However, manganese-based PBAs perform poorly during cycling due to the Jahn-Teller effect. In this study, highly stable manganese nitrosylpentacyanoferrate (Mn[Fe(CN)5NO]) particles were synthesized using a simple hydrothermal method. The presence of nitroso group breaks the symmetry of the crystals to some extent, which is favorable to reduce the Jahn-Teller effect. Through experiments and DFT calculations, we confirm that the presence of linear (NO) anions reduces the lattice volume fluctuations of the samples during charging and discharging, thus contributing to the mitigation of the Jahn-Teller effect. The electrochemical properties of Mn[Fe(CN)5NO] were significantly improved compared to manganese hexacyanoferrate (MnFe[CN]6). Mn[Fe(CN)5NO] exhibited excellent sodium storage performance with an initial discharge capacity as high as 144.5 mAh/g at 20 mA g-1and capacity retention as high as 82.1 % after 400 cycles at 100 mA g−1. This Mn[Fe(CN)5NO] sample provides a promising cathode for sodium-ion batteries in large-scale energy storage systems.

Stabilizing NASICON-type Na4MnCr(PO4)3 by Ti-substitution toward a high-voltage cathode material for sodium ion batteries

The sodium superionic conductor Na4MnCr(PO4)3 gains increasing attention owing to its three-dimensional structure and the three-electron reaction. However, rapid structure degradation during cycling is the major challenge for its practical application. Herein, Ti4+ is utilized to replace a portion of Mn2+ in Na4MnCr(PO4)3. The low redox voltage and d0 electronic configuration of the Ti4+ ions are helpful to suppress the structure alteration and improve electronic conduction. Consequently, the as-prepared Na3.4Mn0.7Ti0.3Cr(PO4)3/C cathode exhibits a remarkable good 91.0% capacity retention after 500 cycles at 10C rate, with exceptional rate capacities of 99.5 mAh g−1 and 81.0 mAh g−1 at 5C and 10C rate, respectively. Furthermore, based on ≈2.86-electron reactions involving Mn2+/Mn3+ (3.5 V), Mn3+/Mn4+ (4.1 V), Cr3+/Cr4+ (4.3 V), and Ti3+/Ti4+ (2.1 V), the material can provide an energy density of approximately 541.6 Wh kg−1, slightly surpassing that of Na4MnCr(PO4)3. Ex-situ XRD investigation further elucidates that throughout the entire charge–discharge process, the Ti-substituted material experiences highly reversible solid-solution and two-phase reactions. Additionally, Ti substitution can greatly promote the interfacial charge transfer of the material and suppress the decomposition of the electrolyte during cycling. This work might open a new insight for designing sodium-ion battery cathode materials with good cycling stability and high energy density.

Anchored VN Quantum Dots Boosting High Capacity and Cycle Durability of Na3V2(PO4)3@NC Cathode for Aqueous Zinc-Ion Battery and Organic Sodium-Ion Battery.

Na3V2(PO4)3 is a promising high-voltage cathode for aqueous zinc-ion batteries (ZIBs) and organic sodium-ion batteries (SIBs). However, the poor rate capability, specific capacity, and cycling stability severely hamper it from further development. In this work, Na3V2(PO4)3 (NVP) with vanadium nitride (VN) quantum dots encapsulated by nitrogen-doped carbon (NC) nanoflowers (NVP/VN@NC) are manufactured as cathode using in situ nitridation, carbon coating, and structural adjustment. The outer NC layer increases the higher electronic conductivity of NVP. Furthermore, VN quantum dots with high theoretical capacity not only improve the specific capacity of pristine NVP, but also serve as abundant "pins" between NVP and NC to strengthen the stability of NVP/VN@NC heterostructure. For Zn-ion storage, these essential characteristics allow NVP/VN@NC to attain a high reversible capacity of 135.4mAhg-1 at 0.1Ag-1, and a capacity retention of 91% after 2000 cycles at 5Ag-1. Meanwhile, NVP/VN@NC also demonstrates to be a stable cathode material for SIBs, which can reach a high reversible capacity of 124.5mAhg-1 at 0.1Ag-1, and maintain 92% of initial capacity after 11000 cycles at 5Ag-1. This work presents a feasible path to create innovative high-voltage cathodes with excellent reaction kinetics and structural stability.

A novel bimetallic-polyanion Na4Fe2.82Ni0.18(PO4)2P2O7 cathode with superior rate performance and long cycle-life for sodium-ion batteries

Na4Fe3(PO4)2P2O7, with the advantages of strong structural stability, suitable voltage window, low cost and green pollution-free, is considered as a highly researchable cathode material for sodium-ion batteries. However, the low conductivity of Na4Fe3(PO4)2P2O7 and the inevitable electrochemical inertia from maricite-NaFePO4 impurity during the preparation process lead to the low reversible capacity and poor cycling stability. In this work, a new bimetallic-polyanion cathode material Na4Fe2.82Ni0.18(PO4)2P2O7 capped with an in-situ nitrogen-doped carbon layer is proposed. Ni-substituting inhibits the generation of electrochemical inert maricite-NaFePO4 impurity and enhances the Na+ ion conductivity. Meanwhile, a lower volume-change during the charging/discharging process can be achieved in Na4Fe2.82Ni0.18(PO4)2P2O7 electrode compared with conventional Na4Fe3(PO4)2P2O7 electrode. With the synergistic effect of in-situ N-doping and Ni-substituting, an ultra-high initial discharge capacity (128.4 mAh g−1 at 0.2C), superior rate performance (62.5 mAh g−1 at 50C) and significant long-term cycle life (capacity retention rate of about 83 % after 3000 cycles at 10C) can be achieved in the optimal Na4Fe2.82Ni0.18(PO4)2P2O7@C-N (Ni6-NFPP@C-N) cathode. This study suggests a practical strategy to produce Na4Fe3(PO4)2P2O7-based electrode material with no impurities and superior electrochemical properties for sodium-ion batteries.

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

Four-Electron Redox Reaction in Prussian Blue Analogue Cathode Material for High-Performance Sodium-Ion Batteries

Four-Electron Redox Reaction in Prussian Blue Analogue Cathode Material for High-Performance Sodium-Ion Batteries