Sodium-ion Batteries Research Articles

Internal doping and surface coating: Mn / La-HCF @ Fe-HCF composites as high-performance cathode materials for sodium-ion batteries

Internal doping and surface coating: Mn / La-HCF @ Fe-HCF composites as high-performance cathode materials for sodium-ion batteries

Ball-Milling-Assisted N/O Codoping for Enhanced Sodium Storage Performance of Coconut-Shell-Derived Hard Carbon Anodes in Sodium-Ion Batteries.

Sodium-ion batteries (SIBs) are regarded as cost-effective alternatives or competitors to lithium-ion batteries for large-scale electric energy storage applications. However, their development has been hindered by the high cost of hard carbon (HC) anodes and poor electrochemical performance. To enhance the sodium storage capacity and rate performance of HC, this study accelerated the electrochemical performance of coconut-shell-derived HC anodes for SIBs through N/O codoping using ball milling and pyrolysis. Experimental results demonstrate that the simultaneous introduction of N and O generates a synergistic effect, increasing the surface oxygen-containing functional groups, defects, and interlayer spacing of coconut-shell-derived HC through the codoping of light elements. The excellent strategy has increased the slope capacity and platform capacity of HC, and the synergistic modification of N/O has increased its reversible specific capacity from 272 to 343 mA h g-1 (30 mA g-1), with a retention rate of approximately 92.1% after 100 cycles. In addition, it also exhibits an excellent rate performance, reaching 178 mA h g-1 at 1500 mA g-1. In summary, this study presents an effective strategy for modifying biomass-derived HC.

Innovative Multielement Modification of Pitch-Derived Two-Dimensional Carbon Nanosheets as Anodes for Superior Performance Sodium-Ion Batteries.

The development of advanced anode materials for sodium-ion batteries (SIBs) using pitch-based carbon materials has the advantages of low cost, high electrical conductivity and easy structural modification. In this research, various well-established modification techniques for petroleum pitch are integrated, including the use of recrystallized NaCl as molten salt template, pretreatment and high-temperature carbonization under a pure oxygen atmosphere, and the introduction of heteroatoms (N and S) by hydrothermal methods. The resulting two-dimensional carbon nanosheets with multielement modification exhibit enhanced Na+ storage properties, thereby bringing higher cycling stability and superior rate performance. Due to its specific structure and chemical composition, NS-P-OPDC exhibited a high reversible capacity of 406.77 mAh g-1 at a current density of 100 mA g-1 and a superior rate performance of 193.20 mAh g-1 at a current density of 3 A g-1 after being applied to the anode of SIB half-cell. Especially, a capacity retention of 97.7% was still achieved after 4000 cycles. Meanwhile, the full-cell assembled by Na3V2(PO4)3 (NVP) cathode and NS-P-OPDC anode could provide a reversible capacity of 235.30 mAh g-1 at a current density of 300 mA g-1. This application proves to advance petroleum pitch-based high-performance electrodes toward greater efficiency in electrochemical energy storage.

Zero-Strain Sodium Nickel Ferrocyanide as Cathode Material for Sodium-Ion Batteries with Ultra-Long Lifespan.

Prussian blue analogues are recognized as one of the most promising cathode materials for sodium-ion batteries (SIBs) owing to the open 3D framework structure with large interstitial sites and developed Na-ion diffusion channels. However, high content of anion vacancy and poor structural stability have hampered the prospect of their application. In this work, sodium nickel ferrocyanide (Na1.34Ni[Fe(CN)6]0.92, NNHCF) is proposed as cathode material for SIBs. N-coordinated Ni-ion can boost NNHCF to possess less Fe[(CN)6]4- defect, low Na-ion migration barrier, and more negative formation energy compared with Na0.91Cu[Fe(CN)6]0.77 (NCHCF), thus exhibiting more active sites, fast electrochemical kinetics behavior and great structure stability. It is confirmed that NNHCF undergoes a solid solution mechanism without phase evolution for reversible Na-ion intercalation/deintercalation, employing Fe associated with C atom as redox center for charge compensation. Therefore, NNHCF contributes a high initial energy density of 180.94 Wh·g-1 at 10 mA·g-1, excellent rate capability, superior cycling stability with ultra-long lifespan of 13000 cycles, and low fading rate of 0.0027% per cycle at 500 mA·g-1. This work sheds light on the construction of low-defect PBA cathodes with outstanding dynamics and stability.

Hierarchical encapsulation engineering boosts tin telluride anode material with fast kinetics and superior structure integrity for sodium-ion batteries

Hierarchical encapsulation engineering boosts tin telluride anode material with fast kinetics and superior structure integrity for sodium-ion batteries

Carbon Dots Enabling High-Performances Sodium-Ion Batteries.

Carbon dots (CDs), known for their quantum size, abundant surface functional groups, excellent biocompatibility, and non-toxicity, have emerged as promising candidates for enhancing various advanced rechargeable batteries. Recent research indicates that electrodes based on or modified with CDs in sodium-ion batteries (SIBs) have shown significant improvements in key performance metrics such as Coulombic efficiency, cycle life, and capacity compared to traditional electrodes. Several key impacts of CDs contribute to these enhancements, including increased conductivity due to their conductive graphitized core, rich absorption sites, and excellent dispersity facilitated by abundant surface functional groups. These features accelerate ion transport through interface edges and ion diffusion paths, inhibit electrode material dissolution, buffer electrode material volume expansion, ensure electrode uniformity and stability, and promote the electrochemical reaction process between the electrode and electrolyte. This review summarizes recent developments, challenges, and opportunities in leveraging CDs as additives in SIBs, focusing on their impact on electrolyte properties, electrode materials, and overall battery performance. It provides a comprehensive understanding of the potential of CDs to significantly advance SIB technology.

Synergistic Bimetallic Effects of BiSb Anodes Enable Long‐Stable Sodium Storage

AbstractAlloy‐type anodes are of interest for their resource‐rich and high theoretical capacity performance in sodium‐ion batteries (SIBs). However, severe volume expansion may lead to rapid capacity decay and electrode pulverization. In this work, metallic Bi with better structure stability is rationally selected as a skeleton to form a 2D BiSb alloy to alleviate the volume expansion. Interestingly, by combining in‐situ XRD and ex‐situ TEM characterizations, a reversible multi‐step alloying sodium storage mechanism of BiSb ↔ Na(Bi, Sb) ↔ Na3(Bi, Sb) in Bi0.4Sb0.6 anode is elucidated, and the partial amorphization and expanded interlayer spacing of BiSb alloy is also revealed, which greatly alleviate volume expansion thereby enhancing electrochemical stability. Furthermore, density functional theory and kinetic calculations demonstrate that Bi0.4Sb0.6 demonstrates lower Na+ adsorption energy and Na+ diffusion energy barriers, ensuring fast electron and ion transportation during sodium storage. Benefiting from the synergistic effects of binary alloy, Bi0.4Sb0.6 exhibits a high reversible capacity and cycling stability of 446 mAh g−1 at 0.1 A g−1, and 70% high capacity after 1100 cycles at 0.5 A g−1. This work provides new insights and opportunities to develop advanced precise alloy‐type anode materials for SIBs.

Optimized architectural engineering and interface modulation in metallic-phase selenide for exceptional sodium-storage performance

Transition metal selenides (TMSs) exhibit promise as anode materials for sodium-ion batteries (SIBs) due to their high specific capacity and diverse electronic properties. However, practical implementation faces challenges such as structural deterioration, solid-electrolyte interphase (SEI) instability, and diminished coulombic efficiency, especially at the nanoscale. Here, we introduce a novel approach that combines surface engineering of Fe3Se4 with an interface engineering strategy (Fe3Se4@NC) to effectively address these issues. By incorporating engineered void spaces and an electrolyte-blocking layer within micrometer-sized secondary clusters, Fe3Se4 nanoparticles gain the ability to expand and contract freely during cycling, thereby preserving interparticle connections and enhancing the structural integrity. The synergy of surface engineering with a nitrogen-doped carbon layer and interface engineering through electrolyte modulation leads to an outstanding 95.1 % initial Coulombic efficiency in the Fe3Se4@NC electrode. Even after 2000 cycles at 5 A g−1, the electrode retains over 89.2 % of its initial capacity with an average specific capacity of 450 mAh g−1. In situ transmission electron microscopy (TEM) and in situ X-ray diffraction (XRD) analysis shed light on the structural evolution and sodiation dynamics during charge/discharge process. Experimental investigations and DFT calculations provide a comprehensive understanding of the SEI composition and the structural stability of the composite.

Enhanced Structural VS4 Grown onto Hollow Carbon Mesoporous Spheres via Surficial Bonding for High Cycling Stability in Sodium-Ion Batteries.

Transition metal sulfides are recognized as an excellent alternative to sodium ion anodes ascribed to the outstanding theoretical capacity. The unique crystal arrangement of VS4 gives it exceptional theoretical capacity, despite challenges like insufficient electrical conductivity and undesirable volume expansion. Herein, a novel stabilized anode featuring a distinctive 3D hollow spherical structure is proposed, providing a simple strategy to synthesize such anodes for VS4-HCMSs bonded via C-O-S and V-O-C interfaces. The kinetic investigations and density functional theory reveal that the unique structure connected by interfacial bonds enhances Na+ transport rate and charge transfer efficiency, while carbon greatly mitigates the volume expansion. Unsurprisingly, the VS4-HCMSs exhibit an impressive first-cycle Coulombic efficiency of 91.31% and an ultrahigh reversible capacity of 612 mAh g-1 after 300 cycles at 0.5 A g-1, even exhibit the reversible capacity of 498.8 mAh g-1 after 1000 cycles at 5 A g-1. Additionally, the NaFePO4//VS4-HCMSs full cell is cycled for 200 cycles at 0.2 C and powered the light-emitting diodes for up to 30 minutes afterward. Overall, this work enhances the conductivity and stability of the material by combining VS4 with hollow carbon mesoporous spheres through interfacial bonding, offering an efficient strategy to anode materials in sodium-ion batteries.

Screening Na-Excess Cation-Disordered Rocksalt Cathodes with High Performance.

The practical application of Na-ion cathode materials is currently restricted by their low energy density and sluggish dynamics, while the cation-disordered rocksalt (DRX) structures offer a possible solution to the challenge. In this study, among the 24 candidates containing d0 elements, we use mixing temperature as a descriptor to screen the synthesizable Na-excess DRX, and we have identified Na1.2Mn0.4Mo0.4O2 as the most promising candidate that exhibits a Na percolating fraction of 53%, which is higher than that of Li1.2Mn0.4Ti0.4O2 (35%) proposed in the previous study due to the larger lattice constant in Na-excess DRX cathodes. More importantly, Na1.2Mn0.4Mo0.4O2 is predicted to have a capacity of 228 mAh/g with an energy density of 552 Wh/kg derived from percolation theory and cluster-expansion Monte Carlo simulations, which is higher than that of Na1.3Nb0.3Mn0.4O2 and Na1.14Mn0.57Ti0.29O2 synthesized recently. For a better understanding, the redox mechanism is explored, which involves Mo4+/Mo6+, Mn3+/Mn4+, and O2-/On- (0 < n < 2), indicating the participation of anionic redox. Meanwhile, the Na+ diffusion prefers a divacancy mechanism via an o-t-o diffusion channel with a low diffusion barrier of 0.29 eV. This study expands the family of DRX for the cathode of Na-ion batteries with enhanced performance.

The Development and Prospect of Stable Polyanion Compound Cathodes in LIBs and Promising Complementers.

Cathode materials are usually the key to determining battery capacity, suitable cathode materials are an important prerequisite to meet the needs of large-scale energy storage systems in the future. Polyanionic compounds have significant advantages in metal ion storage, such as high operating voltage, excellent structural stability, safety, low cost, and environmental friendliness, and can be excellent cathode options for rechargeable metal-ion batteries. Although some polyanionic compounds have been commercialized, there are still some shortcomings in electronic conductivity, reversible specific capacity, and rate performance, which obviously limits the development of polyanionic compound cathodes in large-scale energy storage systems. Up to now, many strategies including structural design, ion doping, surface coating, and electrolyte optimization have been explored to improve the above defects. Based on the above contents, this paper briefly reviews the research progress and optimization strategies of typical polyanionic compound cathodes in the fields of lithium-ion batteries (LIBs) and other promising metal ion batteries (sodium ion batteries (SIBs), potassium ion batteries (PIBs), magnesium ion batteries (MIBs), calcium ion batteries (CIBs), zinc ion batteries (ZIBs), aluminum ion batteries (AIBs), etc.), aiming to provide a valuable reference for accelerating the commercial application of polyanionic compound cathodes in rechargeable battery systems.

Coordination Regulation Strategy in Fabricating Bi2S3@CNFs Composites with Uniform Dispersion for Robust Sodium Storage.

To solve large volume change and low conductivity of Bi2S3-based anodes, a coordination regulation strategy is proposed to prepare Bi2S3 nanoparticles dispersed in carbon fiber (Bi2S3@CNF) composites. It has been discovered that introducing trimesic acid as a ligand can significantly improve the loading and dispersion of Bi3+ in polyacrylonitrile fibers. The results exhibit that Bi2S3 nanoparticles of 200-300 nm are uniformly anchored on the superficial surface layer of CNFs, and Bi2S3 nanoparticles of about 20 nm are evenly dispersed in the interior of CNFs. Assessed as sodium-ion batteries' anode material, the discharge capacity of the Bi2S3@CNF anode in the second cycle is 669.3 mAh g-1 at 0.1 A g-1 and still retains 620.2 mAh g-1 after 100 cycles, with the capacity retention rate of 92.7%. Even at 0.5 A g-1, the specific capacity of the second cycle is 432.99 mAh g-1, which still keeps 400.9 mAh g-1 after 800 cycles, with a retention rate of 92.5%. The excellent cycle stability is mainly attributed to the uniform distribution of small Bi2S3 nanoparticles in CNFs providing abundant active sites, preventing side reactions, relieving volume expansion, improving the electrical conductivity, and accelerating the electrochemical reaction kinetics.

Sputtered Zero‐Excess Electrodes with Metallic Seed Layers for Solid‐State Sodium Batteries

Zero‐excess sodium metal solid‐state batteries offer improved safety, lower cost, higher energy density, and reduced resource dependency compared to today’s lithium‐ion technology. This study demonstrates the fabrication of zero‐excess electrodes with unprecedented stability during plating/stripping cycles. The fabrication process involves the sputter deposition of 20 nm metallic seed layers – zinc, silver, indium, or tin – onto NASICON (Na3.4Zr2Si2.4P0.6O12) ceramic separators, followed by the sputter deposition of a 30 µm copper current collector. The favorable influence of these seed layers on the in‐situ formation of the sodium|NASICON interface is examined through nucleation and cycling experiments, with a sodium metal reservoir serving as the non‐limiting counter electrode. Due to alloy formation the seed layers – particularly tin – stabilize sodium nucleation and cycling substantially and reduce dendrite formation compared to reference cells with bare copper current collectors. Sodium loss during cycling is primarily attributed to local cracking of the current collector and its partial delamination from the NASICON. Compared to polished NASICON, a roughened surface reduces the resistance e.g. of the counter electrode 200‐fold to approx. 1 Ωcm² at 3 MPa and suppresses delamination further.

A small amount of sodium difluoro(oxalate)borate additive induces anion-derived interphases for sodium-ion batteries

In sodium-ion batteries, the properties of the electrode-electrolyte interphases (EEIs) layer formed on the electrode surface, dominate the Na+ de-solvation process and Na+ (de)intercalation behavior, thereby influencing the battery performance. Currently, both high-concentration electrolytes and localized high-concentration electrolytes facilitate the formation of anion-derived and inorganic-rich interfacial chemistry, leading to excellent electrochemical performance. However, the expensive lithium salt and/or fluorinated diluent imposes a major concern. Herein, a small amount additive of 0.5 wt% sodium difluoro(oxalate)borate (NaDFOB) with the electron-rich property is introduced into 1 mol L–1 NaClO4/propylene carbonate electrolyte to construct a robust inorganic-rich EEIs via an anion preferential adsorption-decomposition mechanism. Theoretical calculations and experimental results reveal that the DFOB– anion has a lower adsorption energy than the other components, which will be preferentially adsorbed in the inner Helmholtz plane (IHP) with the closer proximity to two electrode surfaces and thus being firstly decomposed to form inorganic-rich interphases, thereby effectively suppressing side reactions. Consequently, both Na-ion half-cells and full-cells using this electrolyte deliver excellent cycling performance. This strategy that regulates the interphase chemistry on the electrode surface through an anion preferential adsorption-decomposition strategy, provides a promising avenue for developing long-term cycling sodium-ion batteries.

Dynamic Lock-And-Release Mechanism Enables Reduced ΔG at Low Temperatures for High-Performance Polyanionic Cathode in Sodium-Ion Batteries.

Low-temperature synthesis of polyanionic cathodes for sodium-ion batteries is highly desirable but often plagued by prolonged reaction times and suboptimal crystallinity. To address these challenges, a novel self-adaptive coordination field regulation (SACFR) strategy based on a dynamic lock-and-release (DLR) mechanism is introduced. Specifically, urea is used as a DLR carrier during synthesis, which dynamically "locks" and "releases" vanadium ions for controlled release, simultaneously "locking" H+ ions to enhance phosphate group release, thereby creating a self-adaptive coordination field that can intelligently respond to real-time demands of the reaction system. This dynamic coordination behavior contributes to both an improvement in reaction kinetics and a significant reduction in Gibbs free energy change (ΔG). As a result, the kinetic efficiency and thermodynamic spontaneity of the reaction are greatly enhanced, enabling the efficient synthesis of high-crystalline Na3V2O2(PO4)2F (NVOPF) at 90 °C within just 3 hours. The as-prepared NVOPF cathode exhibits exceptional rate performance and ultra-stable cycling stability across a broad temperature range. Furthermore, the successful kilogram-scale synthesis underscores the practical potential of the innovative strategy. This work pioneers the regulation of coordination field chemistry for polyanionic cathode synthesis, providing transformative insights into material design.

Dehydration Conditions and Ultrafast Rehydration of Prussian White: Phase Transition Dynamics and Implications for Sodium-Ion Batteries.

Prussian White (PW) is a strategic cathode material for sodium-ion batteries, offering a high theoretical capacity and voltage. However, the crystalline structure and the electrochemical performance of PW strongly depend on the hydration level, which is difficult to control, leading to discrepancies in the results and interpretations presented in the literature. This work aims to provide a deeper insight into the dehydration process of PW materials and a better understanding of the impact of their fast rehydration, upon exposure to moisture, on their characterization. For this purpose, a Na1.87Mn[Fe(CN)6]0.99·1.99H2O sample was synthesized by a coprecipitation method and subsequently dehydrated to remove water. After thorough characterization, our findings show that drying parameters, such as temperature and pressure, strongly influence the post-drying result. Moreover, the dehydrated samples rehydrate within minutes of exposure to air, which may explain some discrepancies observed in the literature and highlights the necessity to work under fully air-tight conditions.

Charge-Compensation-Driven Failure Mechanism of Ni Redox in Fe-Rich Ni/Fe/Mn-Based O3-Type Layered Oxide Sodium-Ion Cathodes.

For cathode materials of sodium-ion batteries, O3-type Ni/Fe/Mn-based (Na-NFM) layered oxides have garnered extensive attention because of high economic viability, environmental friendliness, and the potential for high energy density. Among them, Fe-rich compositions exhibit higher initial charge capacity and lower bill-of-material costs, while they fade rapidly and exhibit low initial coulombic efficiency, hindering their commercialization prospects. In this work, we investigate the failure of Fe-rich Na-NFM materials through X-ray absorption spectroscopy methods. The results reveal a combined failure mechanism that encompasses not only the conventional theory of Fe migration but also an abnormal Ni-redox deterioration, which has not yet been reported. More factors related to the failure of Fe-rich Na-NFM layered oxides are discussed in detail. These findings are expected to inspire targeted research efforts toward Fe-rich Na-NFM materials, thereby accelerating the practical application of sodium-ion batteries.

Effect of glycerin on the physical properties of polyvinyl alcohol/sodium alginate blend

Because of the abundance of sodium resources, sodium-ion batteries (NIBs) offer a promising alternative electrochemical energy storage solution. One of the current roadblocks to the development of NIBs technology is a lack of electrode materials capable of reversibly storing/releasing sodium ions for a sufficiently long time. Thus, this work aims to study, theoretically, the effect of glycerin incorporation on polyvinyl alcohol (PVA)/sodium alginate (Na Alg) blend as electrode materials for NIBs. The electronic, thermal, and quantitative structure-activity relationship (QSAR) descriptors of polymer electrolytes based on a blend of PVA and Na Alg and glycerin are the main topics of this work. These properties are examined here using semi-empirical methods and the density functional theory (DFT). Bandgap energy (Eg) is examined because the structural analysis reveals details regarding the interactions between PVA/Na Alg and glycerin. The findings indicate that the addition of glycerin caused the Eg value to drop to 0.2814 eV. The molecular electrostatic potential surface, or MESP, shows the electron-rich and deficit regions throughout the electrolyte system as well as the distribution of molecular charges. Thermal parameters that are studied include enthalpy (H), entropy (ΔS), heat capacity (Cp), Gibbs’ free energy (G), and heat of formation. Additionally, the study examines several QSAR descriptors, such as total dipole moment (TDM), total energy (E), ionization potential (IP), Log P, and Polarizability. The results show that H, ΔS, Cp, G, and TDM increased with increasing temperature and glycerin content. Meanwhile, heat of formation, IP, and E decreased, improving reactivity and polarizability. Additionally, the cell voltage increased to 2.488 V due to glycerin addition. The overall DFT and PM6 calculations of cost-effective PVA/Na Alg based glycerin electrolytes indicate that they can partially replace lithium-ion batteries due to their multifunctionality, but requires further improvement and investigations.

Obtaining V2(PO4)3 by sodium extraction from single-phase NaxV2(PO4)3 (1 < x < 3) positive electrode materials.

We report on single-phase NaxV2(PO4)3 compositions (1.5 ≤ x ≤ 2.5) of the Na super ionic conductor type, obtained from a straightforward synthesis route. Typically, chemically prepared c-Na2V2(PO4)3, obtained by annealing an equimolar mixture of Na3V2(PO4)3 and NaV2(PO4)3, exhibits a specific sodium-ion distribution (occupancy of the Na(1) site of only 0.66(4)), whereas that of the electrochemically obtained e-Na2V2(PO4)3 (from Na3V2(PO4)3) is close to 1. Unlike conventional Na3V2(PO4)3, when used as positive electrode materials in Na-ion batteries, the NaxV2(PO4)3 compositions lead to unusual single-phase Na+ extraction/insertion mechanisms with continuous voltage changes upon Na+ extraction/insertion. We demonstrate that the average equilibrium operating voltage observed upon Na+ deintercalation from single-phase Na2V2(PO4)3 is increased up to an average value of ~3.70 V versus Na+/Na (thanks to the activation of the V4+/V5+ redox couple) compared to 3.37 V versus Na+/Na in conventional Na3V2(PO4)3, thus leading to an increase in the theoretical energy density from 396.3 Wh kg-1 to 458.1 Wh kg-1. Electrochemical and chemical Na+ deintercalation from c-Na2V2(PO4)3 enables complete Na-ion extraction, increasing energy density.

Very High-Capacity Li/Na-Ion battery anodes Enabled by Blue phosphorene and boron phosphide vdW heterostructure

The fascinating features of van der Waals heterostructure (vdWH) based electrodes and their potential to overcome the limiting properties of single-material systems have sparked a great deal of scientific attention. In this study, we investigate the potential of a blue phosphorene/boron phosphide (Blue-P/BP) vdWH as an anode material for both lithium-ion (Li-ion) and sodium-ion (Na-ion) batteries using first-principles calculations. We suggest that this vdWH could act as an effective anode material for metal-ion batteries, due to their high theoretical capacity and strong binding strength. Intriguingly, the theoretical specific capacity exhibits remarkable values, notably reaching 4510 mAhg−1 for Li and 3849 mAhg−1 for Na, which surpasses all capacities reported in the existing literature. Additionally, electronic structure calculations reveal a significant charge transfer that enhances the metallic characteristics, thereby increasing electrical conductivity. As we delve deeper into the electronic structure and calculate diffusion barriers and pathways, we observe that ionic diffusion (∼0.12/0.11 eV) is notably rapid compared to graphitic anodes (∼0.2 eV). We also found that intercalating Li/Na atoms in the Blue-P/BP vdWH results in low operating potentials of 0.38 V for Li and 0.34 V for Na. This research highlights the substantial enhancement of electrochemical performance of Blue-P/BP vdWH and holds great promise as high-power-density anode materials for Li/Na-ion batteries, facilitating rapid charge and discharge rates.