Cathode Material For Sodium-ion Batteries Research Articles

A Review of Degradation Mechanisms and Recent Achievements for Na‐Ion Layered Transition Metal Oxides

AbstractDue to the low price and high specific capacity, sodium ion batteries (SIBs) have become a crucial candidate for the future large‐scale energy storage power station, providing strong support for energy transition. Layered transition metal oxides (LTMOs), as one of the most promising cathode materials for SIBs, are usually accompanied by the sodiation/de‐sodiation during charging/discharging, which leads to the slippage and deformation of the layered structure, and consequently causes to the degradation of electrochemical performance. The degradation mechanisms of LTMOs attributed to the structural change are important references for improving the electrochemical performance of cathode materials. Here, this paper presents the main degradation mechanisms such as irreversible anion redox reaction, Na+/vacancy ordering transition and poor air stability as well as the corresponding modification means. It also summarizes the challenges faced by sodium‐ion LTMOs cathode materials, and gives an outlook on the key issues that need to be solved for future development.

Insights into the Phase Purity and Storage Mechanism of Nonstoichiometric Na3.4 Fe2.4 (PO4 )1.4 P2 O7 Cathode for High-Mass-Loading and High-Power-Density Sodium-Ion Batteries.

Mixed-anion-group Fe-based phosphate materials, such as Na4 Fe3 (PO4 )2 P2 O7 , have emerged as promising cathode materials for sodium-ion batteries (SIBs). However, the synthesis of pure-phase material has remained a challenge, and the phase evolution during sodium (de)intercalation is debating as well. Herein, a solid-solution strategy is proposed to partition Na4 Fe3 (PO4 )2 P2 O7 into 2NaFePO4 ⋅ Na2 FeP2 O7 from the angle of molecular composition. Via regulating the starting ratio of NaFePO4 and Na2 FeP2 O7 during the synthesis process, the nonstoichiometric pure-phase material could be successfully synthesized within a narrow NaFePO4 content between 1.6 and 1.2. Furthermore, the proposed synthesis strategy demonstrates strong applicability that helps to address the impurity issue of Na4 Co3 (PO4 )2 P2 O7 and nonstoichiometric Na3.4 Co2.4 (PO4 )1.4 P2 O7 are evidenced to be the pure phase. The model Na3.4 Fe2.4 (PO4 )1.4 P2 O7 cathode (the content of NaFePO4 equals 1.4) demonstrates exceptional sodium storage performances, including ultrahigh rate capability under 100 C and ultralong cycle life over 14000 cycles. Furthermore, combined measurements of ex situ nuclear magnetic resonance, in situ synchrotron radiation diffraction and X-ray absorption spectroscopy clearly reveal a two-phase transition during Na+ extraction/insertion, which provides a new insight into the ionic storage process for such kind of mixed-anion-group Fe-based phosphate materials and pave the way for the development of high-power sodium-ion batteries.

Optimizing O3-type cathode materials for sodium-ion batteries: Insights from precursor-based structural control and particle sizing strategies

Utilization of secondary spherical structures derived from metal hydroxides as precursor materials is one of the most promising approaches in terms of energy density and industrial viability for sodium-ion batteries. However, the understanding of how the particle size and arrangement of these secondary spherical structures influence electrochemical performance remains limited. Herein, a series of O3-type layered oxide cathode materials with various sizes (6, 8, 10, and 12 μm) and internal structures (hollow and radial arrangements) were tailored based on precursor-based structural control and particle sizing strategies. The relation in precursor size/structure, cathode characteristics, crystal microstress, structural stability, and electrochemical performance was established through a combination of structure, morphology, and electrochemical characterization. Notably, the size of secondary spherical particles exerted influence on microstress, leading to consequential changes in the c-axis. Elevated microstress levels induced compression of the unit cell along the c-axis, hampering sodium ion migration and undermining the stability of secondary spherical particles during cyclic charge-discharge processes. The optimized NaNi1/3Fe1/3Mn1/3O2-10 material exhibits the least micro stress and significant layer distance, delivers a capacity of 110 mAh g−1, and maintains an impressive capacity retention rate of 91.8% after 100 cycles at 10 C. This work offers valuable insights in energy-density cathode materials in sodium ion batteries.

Structural evolution and redox chemistry of robust ternary layered oxide cathode for sodium-ion batteries

Nickel/manganese-based O3-type layered oxides have been widely deemed to be a family of promising cathode materials for sodium-ion batteries (SIBs) owing to the large theoretical specific capacity and low manufacturing cost, but being usually challenged by unsatisfied electrochemical performance. In this study, a novel ternary layered oxide NaNi1/2Mn1/4Ti1/4O2 is reported as a robust high-capacity cathode for SIBs, and its structural evolution and redox chemistry in the potential range of 1.5–4.2 V (vs Na+/Na) are carefully explored by coupling X-ray diffraction technique, X-ray photoelectron spectroscopy, transmission electron microscope, FTIR spectroscopy, and galvanostatic measurement. Experimental facts reveal that the material undergoes multiple structural phase evolutions involving two solid-solution regions and one two-phase region based on the redox chemistry of Ni2+/Ni3+ and Ni3+/Ni4+ couples. It exhibits excellent electrochemical performance with a high reversible capacity of 145.2 mAh g−1 and an impressive capacity retention of 85.1% after 100 cycles due to the unique structure with robust ternary composition and stable coating interface. The coating interface is mainly related with formation of the amorphous carbonate layer at preparation step and the CEI film containing alkoxy group during the first charge. In addition, initial Na extraction from the material suffers from a “potential jump” phenomenon owing to severe electrochemical polarization caused by large interfacial impedance and charge-transfer impedance. This work provides new insights on interfacial change, structural evolution and redox reaction of high-capacity O3-type layered oxide cathode during Na extraction/insertion.

The N-doped carbon coated Na3V2(PO4)3 with different N sources as cathode material for sodium-ion batteries: Experimental and theoretical study

NASICON (super ion conductor)-type Na3V2(PO4)3 (NVP) is considered to be one of the most promising cathode materials for sodium-ion batteries (SIBs) due to its good structural stability, fast Na+ diffusion coefficient, and excellent electrochemical properties. However, the poor intrinsic conductivity and electronic conductivity and severe volume shrinkage of NVP, resulting in serious limitations in the practical application of NVP materials. Carbon, especially N-doped carbon modification, is the most effective method and strategy to improve the conductivity of NVP. The study of N source and N content in carbon plays a very important role in improving the electronic properties. Herein, N-doped carbon coated NVP composites was synthesized via the classical sol-gel method using common, green and inexpensive urea and polyvinylpyrrolidone (PVP) as N sources, respectively. According to EIS tests and GITT tests, N-doped carbon layers with urea as the N source significantly improved the conductivity of the carbon layers and the Na+ diffusion kinetics. The effects of N-doped carbon layers on the electrode kinetics and electrochemical properties of NVP materials were investigated in detail. The optimized U-NC15@NVP composite exhibited a maximum discharge capacity of 114.2 mAh g−1 at 0.2C and 92.1% capacity retention after 400 cycles at 1C. When the optimal U-NC15@NVP electrode was selected to assemble a symmetric full cell, the reversible discharge capacity was 75.0 mAh g−1 after 100 cycles at 1C. The density functional theory (DFT) calculations establish that N-doped carbon can generate lots of active sites and external defects, which is beneficial to reduce the energy bandwidth of the carbon layer and thus improve the conductivity of the carbon layer. Additionally, it can also reduce the Na+ diffusion barrier and improve the adsorption energy for Na+. Experimental tests and theoretical calculations show that N-doped carbon can significantly increase the conductivity of the carbon layer and improve the electrochemical properties of NVP.

Regulation of Coordination Chemistry for Ultrastable Layered Oxide Cathode Materials of Sodium-Ion Batteries.

Layered transition-metal (TM) oxide cathodes have attracted growing attention in sodium-ion batteries (SIBs). However, their practical implementation is plagued by Jahn-Teller distortion and irreversible cation migration, leading to severe voltage decay and structure instability. Herein, O3-Na0.898K0.058Ni0.396Fe0.098Mn0.396Ti0.092O2 (KT-NFM) is reported as an ultrastable cathode material via multisite substitution with rigid KO6 pillars and flexible TiO6 octahedra. The K pillars induce contracted TMO2 slabs and their strong Coulombic repulsion to inhibit Ni/Fe migration; and Ti incorporation reinforces the hybridization of Ni(3deg*)-O(2p) to mitigate the undesired O3-O'3 phase transition. These enable the reversible redox of Ni2+↔Ni3 . 20+ and Fe3+↔Fe3.69+ for 138.6 mAh g-1 and ultrastable cycles with >90% capacity retention after 2000 cycles in a pouch cell of KT-NFM||hard carbon. This will provide insights into the design of ultrastable layered cathode materials of sodium-ion batteries and beyond.

Moderate active Fe3+ doping enables improved cationic and anionic redox reactions for wide-voltage-range sodium storage

Layered metal oxides are promising cathode materials for sodium-ion batteries (SIBs) due to their high theoretical specific capacity and wide Na+ diffusion channels. However, the irreversible phase transitions and cationic/anionic redoxes cause fast capacity decay. Herein, P2-type Na0.67Mg0.1Mn0.8Fe0.1O2 (NMMF-1) cathode material with moderate active Fe3+ doping has been designed for sodium storage. Uneven Mn3+/Mn4+distribution is observed in NMMF-1 and the introduction of Fe3+ is beneficial for reducing the Mn3+ contents both at the surface and in the bulk to alleviate the Jahn–Teller effect. The moderate Fe3+/Fe4+ redox can realize the best tradeoff between capacity and cyclability. Therefore, the NMMF-1 demonstrates a high capacity (174.7 mAh g−1 at 20 mA g−1) and improved cyclability (78.5% over 100 cycles) in a wide-voltage range of 1.5–4.5 V (vs. Na+/Na). In-situ X-ray diffraction reveals a complete solid-solution reaction with a small volume change of 1.7% during charge/discharge processes and the charge compensation is disclosed in detail. This study will provide new insights into designing high-capacity and stable layered oxide cathode materials for SIBs.

In Situ Growth of Sodium Manganese Hexacyanoferrate on Carbon Nanotubes for High-Performance Sodium-Ion Batteries.

Sodium manganese hexacyanoferrate (NaMnHCF) has emerged as a research hotspot among Prussian blue analogs for sodium-ion battery cathode materials due to its advantages of high voltage, high specific capacity, and abundant raw materials. However, its practical application is limited by its poor electronic conductivity. In this study, we aim to solve this problem through the in situ growth of NaMnHCF on carbon nanotubes (CNTs) using a simple coprecipitation method. The results show that the overall electronic conductivity of NaMnHCF is significantly improved after the introduction of CNTs. The NaMnHCF@10%CNT sample presents a specific capacity of 90 mA h g-1, even at a current density of 20 C (2400 mA g-1). The study shows that the optimized composite exhibits a superior electrochemical performance at different mass loadings (from low to high), which is attributed to the enhanced electron transport and shortened electron pathway. Surprisingly, the cycling performance of the composites was also improved, resulting from decreased polarization and the subsequent reduction in the side reactions at the cathode/electrolyte interface. Furthermore, we revealed the evolution of potential plateau roots from the extraction of crystal water during the charge-discharge process of NaMnHCF based on the experimental results. This study is instructive not only for the practical application of NaMnHCF materials but also for advancing our scientific understanding of the behavior of crystal water during the charge-discharge process.

Prolonging the Cycle Stability of Anion Redox P3-Type Na0.6Li0.2Mn0.8O2 through Al2O3 Atomic Layer Deposition Surface Modification.

Sodium-ion batteries (SIBs) are becoming an alternative option for large-scale energy storage systems owing to their low cost and abundance. The lattice oxygen redox (LOR), which has the potential to increase the reversible capacity of materials, has promoted the development of high-energy cathode materials in SIBs. However, the utilization of oxygen anion redox reactions usually results in harmful lattice oxygen release, which hastens structural deformation and declines electrochemical performance, severely hindering their practical application. Herein, a ribbon-ordered superstructured P3-type Na0.6Li0.2Mn0.8O2 (NLMO) cathode with a uniform Al2O3 coating through atomic layer deposition (ALD) was synthesized. The cycling stability and rate capability of the materials were improved by a proper thickness of the Al2O3 layer. Differential electrochemical mass spectrometry (DEMS) results clearly suggest that the Al2O3 coating can inhibit the CO2 release caused by the highly active surface of the NLMO material. Moreover, the results of transmission electron microscopy (TEM) and etching X-ray photoelectron spectroscopy (XPS) show that the Al2O3 coating can effectively prevent electrolyte and electrode side reactions and the dissolution of Mn. This surface engineering strategy sheds light on the way to prolong the cycling stability of anionic redox cathode materials.

Suppressing the P2–O2 phase transition of P2-type Ni/Mn-based layered oxide by synergistic effect of Zn/Ti co-doping for advanced sodium-ion batteries

P2-type Ni/Mn-based layered oxides are regarded to be promising cathode materials for advanced sodium-ion batteries (SIBs) owing to their rapid sodium ion diffusion kinetics, high working voltage, and high theoretical capacity. However, P2-type Ni/Mn-based layered oxides are prone to phase transition during charging and discharging processes, resulting in serious capacity fading. Here, introduction of Zn and Ti into transition-metal layers of P2-type layered Na0.66Ni0.33Mn0.67O2 can effectively inhibit P2–O2 phase transition at high voltage, leading to the improved cycling endurance. When being used as cathode materials for SIBs, Na0.66Ni0.27Zn0.06Mn0.61Ti0.06O2 (NNZMT) can deliver a discharge specific capacity of 106.6 mAh g−1, with 95.17% capacity retention after the 100th cycle at 100 mA g−1 within 2.1–4.3 V, which are much higher than those (58.4 mAh g−1 and 45.2%) of Zn/Ti-undoped Na0.66Ni0.33Mn0.67O2 (NNM). Besides, NNZMT displays a much better rate capability compared to the NNM sample. The full cell, based on P2-type layered NNZMT as cathode material and hard carbon as anode material, can provide an initial discharge specific capacity of 94.1 mAh g–1, with a capacity retention of 75.6% after 100 cycles at 100 mA g–1 within 1.0–4.2 V. This research work confirms that low-lost Zn/Ti co-doping strategy is an effective approach for designing and preparing cathode materials for advanced SIBs.

Y-tube assisted coprecipitation synthesis of iron-based Prussian blue analogues cathode materials for sodium-ion batteries.

Prussian blue analogues possess numerous advantages as cathode materials for sodium-ion batteries, including high energy density, low cost, sustainability, and straightforward synthesis processes, making them highly promising for practical applications. However, during the synthesis, crystal defects such as vacancies and the incorporation of crystal water can lead to issues such as diminished capacity and suboptimal cycling stability. In the current study, a Y-tube assisted coprecipitation method was used to synthesize iron-based Prussian blue analogues, and the optimized feed flow rate during synthesis contributed to the successful preparation of the material with a formula of Na1.56Fe[Fe(CN)6]0.90□0.10·2.42H2O, representing a low-defect cathode material. This approach cleverly utilizes the Y-tube component to enhance the micro-mixing of materials in the co-precipitation reaction, featuring simplicity, low cost, user-friendly, and the ability to be used in continuous production. Electrochemical performance tests show that the sample retains 69.8% of its capacity after 200 cycles at a current density of 0.5C (1C = 140 mA g-1) and delivers a capacity of 71.9 mA h g-1 at a high rate of 10C. The findings of this research provide important insights for the development of high-performance Prussian blue analogues cathode materials for sodium-ion batteries.

Metal-ions-coordinated Cross-linked Quasi-solid-state Polymer Electrolyte towards High Energy-density and Long-life Prussian Blue Analogs Cathode

As one of the most promising cathode materials for sodium-ion batteries, Prussian Blue Analogues (PBAs) cathodes face challenges in terms of poor cycling stability, owing to the poor interfacial stability....

A high-rate and air-stable cathode material for sodium-ion batteries: yttrium-substituted O3-type Ni/Fe/Mn-based layered oxides

The electrochemical properties of O3-NaNi1/3Fe1/3−xMn1/3YxO2 cathode materials for sodium ion batteries are significantly improved by using yttrium substitution strategy to realize the micro-modulation of the crystal structure.

Unraveling and suppressing the voltage decay of high-capacity cathode materials for sodium-ion batteries

The steric heterogeneity of Mn redox derived from the oxygen loss is the trigger of voltage decay in high-capacity oxygen-redox sodium-based layered oxides. Moreover, an electron localization strategy is developed to eliminate the voltage decay.

Insights into dynamic structural evolution and its sodium storage mechanisms of P2/P3 composite cathode materials for sodium-ion batteries.

Cobalt substitution for manganese sites in Na0.44MnO2 initiates a dynamic structural evolution process, yielding a composite cathode material comprising intergrown P2 and P3 phases. The novel P2/P3 composite cathode exhibits a reversible phase transition process during Na+ extraction/insertion, showcasing its attractive battery performance in sodium-ion batteries.

Enhancing the performance of NaVPO4F cathode materials for sodium-ion batteries through graphite incorporation and polyethylene glycol 6000 modification

An NVPF material with good performance was synthesized, showing a stable structure and efficient and fast sodium ion transport.

High-entropy prussian blue analogs with 3D confinement effect for long-life sodium-ion batteries

By combining the benefits of high entropy (HE) and carbon wrapping (CW), HEPBAs@0.1C achieves excellent electrochemical performance and unprecedented stability in the ambient environment.

Insights into the capacity fading and failure mechanism of an O3-NaNi1/3Fe1/3Mn1/3O2 layered oxide cathode material for sodium-ion batteries

Low-cost sodium-ion batteries hold great potential for large-scale energy storage owing to the abundance of sodium reserves.

普鲁士蓝类似物作为钠离子电池正极材料的应用进展

普鲁士蓝类似物作为钠离子电池正极材料的应用进展

An ultra-stable Mn-based Prussian blue compound effectively suppresses Jahn–Teller distortion as a superior cathode material for sodium-ion batteries

By regulating the nucleation rate of the coprecipitation reaction, cubic NaMHCF was successfully prepared, which can effectively inhibit the Jahn–Teller effect and can work normally as the cathode of SIB even in low-temperature environments.