Long-life Sodium-ion Batteries Research Articles

Study on the impact of cutoff voltage on structural and electrochemical stability of sodium-ion layered cathodes

NaNi1/3Fe1/3Mn1/3O2 is recognized for its relatively high theoretical specific capacity and operating voltage, rendering it a sodium-ion cathode material with significant commercial potential. A higher cutoff voltage typically enables more sodium ion deintercalation, thereby achieving higher capacity. However, this increased deintercalation can introduce challenges such as structural instability and side reactions with the electrolyte, leading to electrochemical performance degradation. This study focuses on the migration process of transition metal ions under conditions of high charging cutoff voltage and high sodium removal. At a voltage of 4.3 V, the migration of Ni ions facilitates more charge compensation but is accompanied by irreversible Ni migration, inducing an irreversible phase transition to the O’ phase. Conversely, at a cutoff voltage of 4.1 V, the P3 and O3 phases with high sodium removal demonstrate excellent cycling stability. The specific capacities before and after 150 cycles (at 0.5C) are 142.3 and 113.7 mAh/g, respectively, indicating a tolerable internal structural stress within these high sodium removal phases. This contrasts with the differentiated internal structural stresses generated by the P3, O3, and O’ phases during phase transitions at a cutoff voltage of 4.3 V. The research underscores the importance of regulating reversible crystal phases within the tolerance range of internal stress and avoiding irreversible crystal phases to enhance the cycling stability of cathode materials. These findings provide crucial insights for optimizing NNFMO cathode materials and hold significant implications for the design of high-performance, long-life sodium-ion batteries.

N, S, Se-Codoped dual carbon encapsulation and Se substitution in pyrite-type FeS2 for high-rate and long-life sodium-ion batteries

The use of metal sulfides as anodes in sodium-ion batteries (SIBs) faces significant challenges due to slow reaction kinetics and extensive shuttling of sodium polysulfides (NaPSs). In response, a selenium-substituted iron disulfide encapsulated in a nitrogen-sulfur-selenium-codoped dual carbon framework (Se-FeS2@NSSC) has been engineered for high-performance SIBs. Selenium substitution within the FeS2 lattice improves electrical conductivity, facilitates favorable redox kinetics that reducing the possibility of NaPSs generation. Moreover, the dual NSSC encapsulation promotes Na+/electron transport and efficiently manages volume expansion during electrochemical processes. Strong interfacial interaction (Fe-S-C bonding) between Se-FeS2 and NSSC further suppress NaPSs shuttling, significantly alleviating the cell failure and thus prolonging its lifespan. Consequently, Se-FeS2@NSSC demonstrates a top-notch performance, achieving a notable capacity of 725 mAh g-1 at 0.5 A g-1, unparalleled rate capability (355.1 mAh g-1 at 30 A g-1), and sustained cyclic stability (89.6 % capacity is retained after 1250 cycles). Theoretical analyses underscore the critical role of selenium in diminishing bulk stress–strain energies, lowering energy barriers for Na+ diffusion, and decreasing Gibbs free energy for conversion reactions, thereby markedly bolstering electrochemical kinetics and overall performance of Se-FeS2@NSSC. The insights gleaned from this research foster advancements in developing next-generation anodes with high capacity and durability, representing a promising response to the existing hurdles in SIBs technology.

Pitch-based carbon anode for high-energy and long-life sodium-ion battery

Pitch-based carbon generally demonstrate remarkable electrochemical performance for sodium-ion batteries (SIBs). In this paper, the medium temperature pitch is successively subjected to heat treatment under high pressure, extraction of toluene to remove soluble matter, and carbonization of toluene insoluble matter, to prepare the anode material, named pitch toluene insoluble anode (PTIA). The PTIA is characteristic of the coral-like morphology distributed with 100−200 nm pore channels and 2−3 nm mesopores for electrolyte immersion, and the disordered carbon structure is interwoven with graphitic carbon for sodium-ion insertion/desertion and electron transmission. In the PTIA half battery, the reversible specific capacity reaches 276.9 mAh g−1 at 0.1 A g−1 after 300 cycles with a coulombic efficiency of 99.22%. Importantly, the PTIA exhibits good compatibility with vanadium sodium phosphate (NVP) cathode materials, enabling a battery PTIA//NVP to achieve a capacity density of 154 mAh g−1, an energy density of 246.7 Wh kg−1 and a power density of 4800 W kg−1 for 1000 cycles at a current density of 3 A g−1 (16−18 C). The battery has a certain working efficiency at -10−70°C.

Nitrogen-Doped Bioderived Mesoporous Hard Carbon as a Promising Anode for Long-Life Sodium-Ion Battery

Nitrogen-Doped Bioderived Mesoporous Hard Carbon as a Promising Anode for Long-Life Sodium-Ion Battery

The C-BixSnSb composite toward fast-charging and long-life sodium-ion batteries

Sodium ion batteries (SIBs) fitted with high-rate and high-capacity anodes are attractive for their higher energy density and faster charging capability. However, it is still a challenge to develop high-energy SIBs with high power and long life, due to the sluggish kinetic and limited Na+ insertion in electrode materials. The inherent crystal structure and constituent element are two important factors to resolve the critical issues faced above. Taking the merits of layer-structure and middle-entropy, herein, we proposed and designed a high ion-conductive composite combing with ternary alloy and layered BixSnSb@C nanofibers, which eliminate ion migration barriers while maintaining the structural framework for superior rate property and cycle stability. Used as anode for SIBs, the multiphase BixSnSb@C with adjustable Bi content exhibits excellent Na storage capability as compared to their single phase counterpart. Specially, up to a rate of 132C (50 A g−1), the capacity is still as high as 400 mAh g−1, meanwhile, after 5000 charge and discharge cycles at a current density of 12C, the capacity still maintains 85 % of its initial capacity, which outperform the individual Bi- or SnSb-based materials. The superior electrochemical performances originate from the middle-entropy nature and layer structure of BiSnSb alloy, which can provide more channels for fast Na+ transport, and accommodate large volume changes. Besides, the activity energy and ions transport resistance of Na+ in different composites were evaluated. Furthermore, the full-cell coupled with NaNi1/3Fe1/3Mn1/3O2 as cathode was formed and a capacity retention of ∼80 % is realized in 100 cycles. The results show that the BixSnSb@C is a potential anode for fast-charging Na-ion batteries and could be used to guide the design of multi-component alloy-base anodes.

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.

Sustainable layered cathode with suppressed phase transition for long-life sodium-ion batteries

Sustainable layered cathode with suppressed phase transition for long-life sodium-ion batteries

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.

Bamboo-derived hard carbon/carbon nanotube composites as anode material for long-life sodium-ion batteries with high charge/discharge capacities

Bamboo-derived hard carbon/carbon nanotube composites as anode material for long-life sodium-ion batteries with high charge/discharge capacities

Synthesis and design of NaNi1/3Fe1/3Mn1/3O2 cathode materials for long-life sodium-ion batteries

To enable the widespread adoption of residential energy storage, sustainable, low-cost, long-life, and energy-dense battery technologies are required. Sodium-ion offers many of these characteristics, however often the system is tailored for energy rather than cycle life. In this work, the effect of synthesis conditions upon the primary and agglomerated secondary particle size and shape of the sodium-ion cathode material NaNi1/3Fe1/3Mn1/3O2 was investigated for optimization of energy and cycle life. A two-level full factorial experimental design was utilized to examine how the synthesis parameters (pH, molar ratio of ammonia/metal precursor salt, and stirring speed) affect the physical and electrochemical properties. This approach enabled a comprehensive investigation of the main effects and interactions of these parameters. The data from multiple synthesis runs were analyzed using statistical methods and regression analysis. This experimental design provided valuable insights into the relationship between synthesis parameters and material properties. Statistical analysis indicates that both physical and electrochemical properties are mainly controlled through pH and NH4OH, while the effects of stirring speed are less pronounced. The optimal synthetic conditions producing the highest cycling performance were extrapolated from the statistical analysis. A validation experiment showed that particles synthesized with optimum parameters displayed a threefold increase in cycling performance together with uniformly distributed particle size and a high tap density.

Reusing the steel slag to design a gradient-doped high-entropy oxide for high-performance sodium ion batteries

Herein, a high-entropy layered oxide (HEO) is proposed as an outstanding cathode material for long-life sodium-ion batteries. Based on the self-segregation of elements from surface to bulk phase, a multi-element gradient doped high-entropy cathode material is prepared by doping steel slag with available elements (Mg, Al, Si, Fe, Ca). The surface high-entropy region vastly improves the air stability of materials and reduces surface impurities and side reactions. The Na-O-Mg configuration of near-surface high-entropy region continuously stimulates the anionic redox activity, and the DEMS shows the high-strength Al-O bonding achieves zero oxygen release. Therefore, the LNSM-0.01 reveals a stable capacity of ∼24 mA h g−1 in the range of 4.0–4.5 V. The Ca2+ in bulk phase high-entropy region disrupts the Na+/vacancy ordering transition and enhances the kinetic performance (90 mA h g−1 at 1000 mA g−1), while Fe2+/3+ provides a large amount number of charge compensation. Further, DFT calculations prove that the entropy stability based on synergistic effect immeasurably reinforce the layered oxide configuration, building a more robust structural framework during cycling. This work deepens the understanding on multi-element gradient doping to prepare HEOs, and provides a novel pathway for resource utilization of solid waste.

Novel NASICON-Type Na-V-Mn-Ni-Containing Cathodes for High-Rate and Long-Life SIBs.

Partial substitution of V by other transition metals in Na3 V2 (PO4 )3 (NVP) can improve the electrochemical performance of NVP as a cathode for sodium-ion batteries (SIBs). Herein, phosphate Na-V-Mn-Ni-containing composites based on NASICON (Natrium Super Ionic Conductor)-type structure have been fabricated by sol-gel method. The synchrotron-based X-ray study, X-ray diffraction (XRD), and X-ray photoelectron spectroscopy (XPS) studies show that manganese/nickel combinations successfully substitute the vanadium in its site within certain limits. Among the received samples, composite based on Na3.83 V1.17 Mn0.58 Ni0.25 (PO4 )3 (VMN-0.5, 108.1 mAh g-1 at 0.2 C) shows the highest electrochemical ability. The cyclic voltammetry, galvanostatic intermittent titration technique, in situ XRD, ex situ XPS, and bond valence site energy calculations exhibit the kinetic properties and the sodium storage mechanism of VMN-0.5. Moreover, VMN-0.5 electrode also exhibits excellent electrochemical performance in quasi-solid-state sodium metal batteries with PVDF-HFP quasi-solid electrolyte membranes. The presented work analyzes the advantages of VMN-0.5 and the nature of the substituted metal in relation to the electrochemical properties of the NASICON-type structure, which will facilitate further commercialization of SIBs.

Zinc doped P2-type layered cathode for high-voltage and long-life sodium ion batteries: impacts of calcination temperature and cooling methods

Zinc doped P2-type layered cathode for high-voltage and long-life sodium ion batteries: impacts of calcination temperature and cooling methods

Synergisticγ-In2 Se3 @rGO Nanocomposites with Beneficial Crystal Transformation Behavior for High-Performance Sodium-Ion Batteries.

Crystal transformation of metal compound cathodes during charge/discharge processes in alkali metal-ion batteries usually generates profound impact on structural stability and electrochemical performance, while the theme in anode materials, which always occurs and completes during the first redox cycle, is rarely explored probably due to the fast transformation dynamics. Herein, for the first time, a unique crystal transformation behavior with slow dynamics in anode of sodium-ion batteries (SIBs) is reported, which further promotes electrochemical performance. Specifically, irreversible γ → β crystal transformation of In2 Se3 is observed, induced by the persistent size degradation of In2 Se3 particles during repeated sodiation/desodiation, supported by a series of ex situ characterizations, such as HRTEM, XRD, and XPS of γ-In2 Se3 /reduced graphene oxide (γ-In2 Se3 @rGO) nanocomposite. The hybrid electrode shows ultrahigh long-term cycling stability (378mA h g-1 at 1.0 A g-1 after 1000 cycles) and excellent rate capability (272mA h g-1 at 20.0 A g-1 ). Full battery with Na3 V2 (PO4 )3 cathode also manifests superior performance, promising β-In2 Se3 dominated electrode materials in high-power and long-life SIBs. The first-principle calculations suggest the crystal transformation enhances electric conductivity of β-In2 Se3 and facilitates its accessibility to sodium. In combination with the synergistic effect between rGO matrix, substantially enhanced electrochemical performance is realized.

NaNbV(PO4)3: Multielectron NASICON-Type Anode Material for Na-Ion Batteries with Excellent Rate Capability.

NASICON-type NaNbV(PO4)3 electrode material synthesized by the Pechini sol-gel technique undergoes a reversible three-electron reaction in a Na-ion cell which corresponds to the Nb5+/Nb4+, Nb4+/Nb3+, and V3+/V2+ redox processes and provides a reversible capacity of 180 mAh·g-1. The sodium insertion/extraction takes place in a narrow potential range at an average potential of 1.55 V versus Na+/Na. Structural characterization by operando and ex situ X-ray diffraction disclosed the reversible evolution of the NaNbV(PO4)3 polyhedron framework during cycling, while XANES measurements in the operando regime confirmed the multielectron transfer upon sodium intercalation/extraction into NaNbV(PO4)3. This electrode material demonstrates extended cycling stability and excellent rate capability maintaining the capacity value of 144 mAh·g-1 at 10 C current rates. It can be regarded as a superior anode material suitable for application in high-power and long-life sodium-ion batteries.

P2-Type Moisture-Stable and High-Voltage-Tolerable Cathodes for High-Energy and Long-Life Sodium-Ion Batteries.

P2-Na0.67Ni0.33Mn0.67O2 represents a promising cathode for Na-ion batteries, but it suffers from severe structural degradation upon storing in a humid atmosphere and cycling at a high cutoff voltage. Here we propose an in situ construction to achieve simultaneous material synthesis and Mg/Sn cosubstitution of Na0.67Ni0.33Mn0.67O2 via one-pot solid-state sintering. The materials exhibit superior structural reversibility and moisture insensitivity. In-operando XRD reveals an essential correlation between cycling stability and phase reversibility, whereas Mg substitution suppressed the P2-O2 phase transition by forming a new Z phase, and Mg/Sn cosubstitution enhanced the P2-Z transition reversibility benefiting from strong Sn-O bonds. DFT calculations disclosed high chemical tolerance to moisture, as the adsorption energy to H2O was lower than that of the pure Na0.67Ni0.33Mn0.67O2. A representative Na0.67Ni0.23Mg0.1Mn0.65Sn0.02O2 cathode exhibits high reversible capacities of 123 mAh g-1 (10 mA g-1), 110 mAh g-1 (200 mA g-1), and 100 mAh g-1 (500 mA g-1) and a high capacity retention of 80% (500 mA g-1, 500 cycles).

Ti, F Codoped Sodium Manganate of Layered P2-Na 0.7 MnO 2.05 Cathode for High Capacity and Long-Life Sodium-Ion Battery

Open AccessRenewablesRESEARCH ARTICLES14 Jan 2023Ti, F co-doped Sodium Manganate of Layered P2-Na0.7MnO2.05 Cathode for High Capacity and Long-life Sodium Ion Battery Pengchao Wen, Haodong Shi, Dandan Guo, Aimin Wang, Yan Yu and Zhong-Shuai Wu Pengchao Wen Google Scholar More articles by this author , Haodong Shi Google Scholar More articles by this author , Dandan Guo Google Scholar More articles by this author , Aimin Wang Google Scholar More articles by this author , Yan Yu Google Scholar More articles by this author and Zhong-Shuai Wu Google Scholar More articles by this author https://doi.org/10.31635/renewables.022.202200012 SectionsSupplemental MaterialAboutPDF ToolsAdd to favoritesDownload CitationsTrack Citations ShareFacebookTwitterLinked InEmail The development of layered sodium manganese oxides cathode materials with high capacity and structural stability is one of the keys to boost the performance of sodium-ion batteries (SIBs), but remains a great challenge. Herein, a titanium and fluorine co-doped P2 type sodium manganate of Na0.7MnO2.05 cathode material (NMO-0.1TF) is developed as high-capacity and long-durable cathode for high-performance SIBs. The titanium and fluorine co-doping could significantly reduce the structural deformation, synergistically improved structural stabilization, inhibit the formation of irreversible phases and enhance electrochemical kinetics. As a result, the NMO-0.1TF||Na battery working in the voltage ranges of 2.0-4.2 V exhibits a high specific capacity of 227 mAh g-1 at current density of 20 mA g-1, and excellent rate performance (76 mAh g-1 at a high current density of 3 A g-1). Such battery still delivers an outstanding cycle stability, shows a high initial discharge capacity of 133 mAh g-1 at 1 A g-1, and maintains the initial capacity of 96.2% after 200 cycles. More importantly, the assembled full battery of NMO-0.1TF||hard carbon validates high capacity and impressive cyclability. Therefore, this co-doped NMO-0.1TF cathode with high capacity and excellent stability presents brilliantly practical application for developing high energy density SIBs. Download figure Download PowerPoint Previous articleNext article FiguresReferencesRelatedDetails Issue AssignmentNot Yet AssignedSupporting Information Copyright & Permissions© 2023 Chinese Chemical Society Downloaded 7 times PDF downloadLoading ...

Ti, F Codoped Sodium Manganate of Layered P2-Na 0.7 MnO 2.05 Cathode for High Capacity and Long-Life Sodium-Ion Battery

Ti, F Codoped Sodium Manganate of Layered P2-Na _0.7 MnO _2.05 Cathode for High Capacity and Long-Life Sodium-Ion Battery

A low-strain metal organic framework for ultra-stable and long-life sodium-ion batteries

As sodium-ion batteries (SIBs) attract more attention, various host materials allowing Na-ions insertion/extraction are being developed. Among them, Prussian blue analogues (PBAs), as typical metal organic frameworks, are regarded as promising cathodes for SIBs because of their open frame structure and simple synthesis process. However, the presence of [Fe(CN)6] vacancies and crystal water in PBA framework usually induce poor electrochemical performance. Herein, high quality Na-rich monoclinic nickel hexacyanoferrate Na1.95Ni[Fe(CN)6]0.89·2.87H2O with nanocubes morphology (NiHCF–NCs) has been prepared through a simple diethylenetriaminepentaacetic acid disodium (Na2DTPA)-assisted coprecipitation strategy. Benefiting from inhibiting defects and low-strain sodium storage mechanism, as-obtained NiHCF–NCs exhibits superior electrochemical properties in terms of high capacity (81.3 mAh g−1), excellent rate capability (64.5 mAh g−1 at 4000 mA g−1), and outstanding cycle performance (97.1% capacity retention over 2000 cycles). Moreover, full-cell assembled with NiHCF–NCs cathode and NaTi2(PO4)3@C anode presents competitive behaviors of good rate capability and ultra-long cycle lifespan over 5000 cycles, greatly promoting the development of SIBs in practical application.

A fluorinated O3-type layered cathode for long-life sodium-ion batteries

The fluorination of O3-type layered Na[Ni0.5Mn0.5]O2 cathodes effectively mitigates destructive phase transitions and concomitant microcracking and suppresses the parasitic reaction with electrolyte.