Ascorbic Acid‐Assisted Synthesis of Mesoporous Sodium Vanadium Phosphate Nanoparticles with Highly sp2‐Coordinated Carbon Coatings as Efficient Cathode Materials for Rechargeable Sodium‐Ion Batteries

Herein, mesoporous sodium vanadium phosphate nanoparticles with highly sp²‐coordinated carbon coatings (meso‐Na₃V₂(PO₄)₃/C) were successfully synthesized as efficient cathode material for rechargeable sodium‐ion batteries by using ascorbic acid as both the reductant and carbon source, followed by calcination at 750 °C in an argon atmosphere. Their crystalline structure, morphology, surface area, chemical composition, carbon nature and amount were systematically explored. Following electrochemical measurements, the resultant meso‐Na₃V₂(PO₄)₃/C not only delivered good reversible capacity (98 mAh g^?1 at 0.1 A g^?1) and superior rate capability (63 mAh g^?1 at 1 A g^?1) but also exhibited comparable cycling performance (capacity retention: ≈74 % at 450 cycles at 0.4 A g^?1). Moreover, the symmetrical sodium‐ion full cell with excellent reversibility and cycling stability was also achieved (capacity retention: 92.2 % at 0.1 A g^?1 with 99.5 % coulombic efficiency after 100 cycles). These attributes are ascribed to the distinctive mesostructure for facile sodium‐ion insertion/extraction and their continuous sp²‐coordinated carbon coatings, which facilitate electronic conduction.     

Ruthenium‐Oxide‐Coated Sodium Vanadium Fluorophosphate Nanowires as High‐Power Cathode Materials for Sodium‐Ion Batteries

Sodium‐ion batteries are a very promising alternative to lithium‐ion batteries because of their reliance on an abundant supply of sodium salts, environmental benignity, and low cost. However, the low rate capability and poor long‐term stability still hinder their practical application. A cathode material, formed of RuO₂‐coated Na₃V₂O₂(PO₄)₂F nanowires, has a 50 nm diameter with the space group of I4/mmm. When used as a cathode material for Na‐ion batteries, a reversible capacity of 120 mAh g^?1 at 1 C and 95 mAh g^?1 at 20 C can be achieved after 1000 charge–discharge cycles. The ultrahigh rate capability and enhanced cycling stability are comparable with high performance lithium cathodes. Combining first principles computational investigation with experimental observations, the excellent performance can be attributed to the uniform and highly conductive RuO₂ coating and the preferred growth of the (002) plane in the Na₃V₂O₂(PO₄)₂F nanowires.     

A Superior Na3V2(PO4)3‐Based Nanocomposite Enhanced by Both N‐Doped Coating Carbon and Graphene as the Cathode for Sodium‐Ion Batteries

A superior Na₃V₂(PO₄)₃‐based nanocomposite (NVP/C/rGO) has been successfully developed by a facile carbothermal reduction method using one most‐common chelator, disodium ethylenediamintetraacetate [Na₂(C₁₀H₁₆N₂O₈)], as both sodium and nitrogen‐doped carbon sources for the first time. 2D‐reduced graphene oxide (rGO) nanosheets are also employed as highly conductive additives to facilitate the electrical conductivity and limit the growth of NVP nanoparticles. When used as the cathode material for sodium‐ion batteries, the NVP/C/rGO nanocomposite exhibits the highest discharge capacity, the best high‐rate capabilities and prolonged cycling life compared to the pristine NVP and single‐carbon‐modified NVP/C. Specifically, the 0.1 C discharge capacity delivered by the NVP/C/rGO is 116.8 mAh g^?1, which is obviously higher than 106 and 112.3 mAh g^?1 for the NVP/C and pristine NVP respectively; it can still deliver a specific capacity of about 80 mAh g^?1 even at a high rate up to 30 C; and its capacity decay is as low as 0.0355 % per cycle when cycled at 0.2 C. Furthermore, the electrochemical impedance spectroscopy was also implemented to compare the electrode kinetics of all three NVP‐based cathodes including the apparent Na diffusion coefficients and charge‐transfer resistances.     

A Long‐Cycling Aqueous Zinc‐Ion Pouch Cell: NASICON‐Type Material and Surface Modification

Aqueous zinc‐ion batteries (ZIBs) have become the highest potential energy storage system for large‐scale applications owing to the high specific capacity, good safety and low cost. In this work, a NASICON‐type Na₃V₂(PO₄)₃ cathode modified by a uniform carbon layer (NVP/C) has been synthesized via a facile solid‐state method and exhibited significantly improved electrochemical performance when working in an aqueous ZIB. Specifically, the NVP/C cathode shows an excellent rate capacity (e. g., 48 mAh g^?1 at 1.0 A g^?1). Good cycle stability is also achieved (e. g., showing a capacity retention of 88% after 2000 cycles at 1.0 A g^?1). Furthermore, the Zn²⁺ (de)intercalation mechanism in the NVP cathode has been determined by various ex‐situ techniques. In addition, a Zn||NVP/C pouch cell has been assembled, delivering a high capacity of 89 mAhg^?1 at 0.2 A g^?1 and exhibiting a superior long cycling stability.     

A robust carbon coating of Na3V2(PO4)3 cathode material for high performance sodium-ion batteries

Na₃V₂(PO₄)₃ is a very prospective sodium-ion batteries (SIBs) electrode material owing to its NASICON structure and high reversible capacity. Conversely, on account of its intrinsic poor electronic conductivity, Na₃V₂(PO₄)₃ electrode materials confront with some significant limitations like poor cycle and rate performance which inhibit their practical applications in the energy fields. Herein, a simple two-step method has been implemented for the successful preparation of carbon-coated Na₃V₂(PO₄)₃ materials. As synthesized sample shows a remarkable electrochemical performance of 124.1 mAh/g at 0.1 C (1 C = 117.6 mA/g), retaining 78.5 mAh/g under a high rate of 200 C and a long cycle-performance (retaining 80.7 mAh/g even after 10000 cycles at 20 C), outperforming the most advanced cathode materials as reported in literatures.     

Comparative investigations of LiVPO4F/C and Li3V2(PO4)3/C synthesized in similar soft chemical route

Triclinic LiVPO₄F and monoclinic Li₃V₂(PO₄)₃ are synthesized through a soft chemical process with mechanical activation assist, followed by annealing. In this process, ascorbic acid is used as reducing agent as well as carbon source. The as-prepared samples are coated with amorphous carbon. XPS analysis results show the expected valency states of ions in LiVPO₄F and Li₃V₂(PO₄)₃. The electrochemical properties of the prepared LiVPO₄F/C and Li₃V₂(PO₄)₃/C cathodes are evaluated. The as-prepared LiVPO₄F/C cathode shows an initial discharge specific capacity of 140?±?3 mAh?g^?1 at 30 mA?g^?1 in the voltage range of 3.0~4.4 V, compared with that of 138?±?3 mAh?g^?1 possessed by Li₃V₂(PO₄)₃/C. Both samples exhibit good cycle performance at different current densities. The capacity delivered by LiVPO₄F remains 95.5 and 91.7 % of its initial discharge capacity after 50 cycles at 150 and 750 mA?g^?1, respectively, while 97.4 and 90.6 % for Li₃V₂(PO₄)₃/C. But the rate capability of LiVPO₄F/C is not so good compared with as-prepared Li₃V₂(PO₄)₃/C.     

Carbon coated Na3V2(PO4)3 as novel electrode material for sodium ion batteries

A Na₃V₂(PO₄)₃ sample coated uniformly with a layer of 6 nm carbon has been successfully synthesized by a one-step solid state reaction. This material shows two flat voltage plateaus at 3.4 V vs. Na⁺/Na and 1.63 V vs. Na⁺/Na in a nonaqueous sodium cell. When the Na₃V₂(PO₄)₃/C sample is tested as a cathode in a voltage range of 2.7-3.8 V vs. Na⁺/Na, its initial charge and discharge capacities are 98.6 and 93 mAh/g. The capacity retention of 99% can be achieved after 10 cycles. The electrode shows good cycle performance and moderate rate performance. When it is tested as an anode in a voltage range of 1.0-3.0 V vs. Na⁺/Na, the initial reversible capacity is 66.3 mAh/g and the capacity of 59 mAh/g can be maintained after 50 cycles. These preliminary results indicate that Na₃V₂(PO₄)₃/C is a new promising material for sodium ion batteries.     

Natural graphite enhanced the electrochemical performance of Li<Subscript>3</Subscript>V<Subscript>2</Subscript>(PO<Subscript>4</Subscript>)<Subscript>3</Subscript> cathode material for lithium ion batteries

Natural graphite treated by mechanical activation can be directly applied to the preparation of Li₃V₂(PO₄)₃. The carbon-coated Li₃V₂(PO₄)₃ with monoclinic structure was successfully synthesized by using natural graphite as carbon source and reducing agent. The amount of activated graphite is optimized by X-ray diffraction, scanning electron microscope, transmission electron microscope, Raman spectrum, galvanostatic charge/discharge measurements, cyclic voltammetry, and electrochemical impedance spectroscopy tests. Our results show that Li₃V₂(PO₄)₃ (LVP)-10G exhibits the highest initial discharge capacity of 189 mAh g^?1 at 0.1 C and 162.9 mAh g^?1 at 1 C in the voltage range of 3.0–4.8 V. Therefore, natural graphite is a promising carbon source for LVP cathode material in lithium ion batteries.     

Effect of Al2O3 -coating on the electrochemical performances of Li3V2(PO4)3/C cathode material

The effect of Al₂O₃ -coating on Li₃V₂(PO₄)₃/C cathode material for lithium-ion batteries has been investigated. The crystalline structure and morphology of the synthesized powders have been characterized by XRD, SEM, and HRTEM, and their electrochemical performances are evaluated by CV, EIS, and galvanostatic charge/discharge tests. It is found that Al₂O₃ -coating modification stabilizes the structure of the cathode material, decreases the polarization of electrode and suppresses the rise of the surface film resistance. Electrochemical tests indicate that cycling performance and rate capability of Al₂O₃-coated Li₃V₂(PO₄)₃/C are enhanced, especially at high rates. The Al₂O₃-coated material delivers discharge capacity of 123.03 mAh g^?1 at 4 C rate, and the capacity retention of 94.15 % is obtained after 5 cycles. The results indicate that Al₂O₃ -coating should be an effective way to improve the comprehensive properties of the cathode materials for lithium-ion batteries.     

Realizing Complete Solid‐Solution Reaction in High Sodium Content P2‐Type Cathode for High‐Performance Sodium‐Ion Batteries

P2‐type layered oxides suffer from an ordered Na⁺/vacancy arrangement and P2→O2/OP4 phase transitions, leading them to exhibit multiple voltage plateaus upon Na⁺ extraction/insertion. The deficient sodium in the P2‐type cathode easily induces the bad structural stability at deep desodiation states and limited reversible capacity during Na⁺ de/insertion. These drawbacks cause poor rate capability and fast capacity decay in most P2‐type layered oxides. To address these challenges, a novel high sodium content (0.85) and plateau‐free P2‐type cathode‐Na_0.85Li_0.12Ni_0.22Mn_0.66O₂ (P2‐NLNMO) was developed. The complete solid‐solution reaction over a wide voltage range ensures both fast Na⁺ mobility (10^?11 to 10^?10 cm² s^?1) and small volume variation (1.7 %). The high sodium content P2‐NLNMO exhibits a higher reversible capacity of 123.4 mA h g^?1, superior rate capability of 79.3 mA h g^?1 at 20 C, and 85.4 % capacity retention after 500 cycles at 5 C. The sufficient Na and complete solid‐solution reaction are critical to realizing high‐performance P2‐type cathodes for sodium‐ion batteries.     

Conducting Graphene Decorated Li3V2(PO4)3/C for Lithium‐Ion Battery Cathode with Superior Rate Capability and Cycling Stability

In this study, core‐shell structured Li₃V₂(PO₄)₃/C wrapped in graphene nanosheets has been successfully prepared. The reduction of graphene oxide and the synthesis of Li₃V₂(PO₄)₃/C are carried out simultaneously using a chemical route followed by a solid‐state reaction. The effects of conducting graphene are studied by X‐ray diffraction (XRD), scanning electron microscopy (SEM), transmission electron microscopy (TEM), Raman spectra and electrochemical measurements. The results reveal that the graphene sheets not only form a compact and uniform coating layer throughout the Li₃V₂(PO₄)₃/C, but also stretch out and cross‐link into a conducting network around the Li₃V₂(PO₄)₃/C particles. Thus, the graphene decorated Li₃V₂(PO₄)₃/C electrode exhibits superior high‐rate capability and long‐cycle stability. It delivers a reversible discharge capacity of 178.2 mAh·g^?1 after 60 cycles at a current density of 0.1 C, and the rate performances of 176, 169.3, 156.1 and 135.7 mAh·g^?1 at 1, 2, 5 and 10 C, respectively. The superior electrochemical properties make the graphene decorated Li₃V₂(PO₄)₃/C composite a promising cathode material for high‐performance lithium‐ion battery.     

Designed One-Pot Strategy for Dual-Carbon-Protected Na3V2(PO4)3 Hybrid Structure as High-Rate and Ultrastable Cathode for Sodium-Ion Batteries

Sodium-ion batteries have attracted tremendous attention due to their much lower cost and similar working principle compared with lithium-ion batteries, which have been invited great expectation as energy storage devices in grid-level applications. The sodium superionic conductor Na₃V₂(PO₄)₃ has been considered as a promising cathode candidate; however, its intrinsic low electronic conductivity results in poor rate performance and unsatisfactory cycling performance, which severely impedes its potential for practical applications. Herein, we developed a facile one-pot strategy to construct dual carbon-protected hybrid structure composed of carbon coated Na₃V₂(PO₄)₃ nanoparticles embedded with carbon matrix with excellent rate performance, superior cycling stability and ultralong lifespan. Specifically, it can deliver an outstanding rate performance with a 51.5 % capacity retention from 0.5 to 100 C and extraordinary cycling stability of 80.86 % capacity retention after 6000 cycles at the high rate of 20 C. The possible reasons for the enhanced performance could be understood as the synergistic effects of the strengthened robust structure, facilitated charge transfer kinetics, and the mesoporous nature of the Na₃V₂(PO₄)₃ hybrid structure. This work provides a cost-effective strategy to effectively optimize the electrochemical performance of a Na₃V₂(PO₄)₃ cathode, which could contribute to push forward the advance of its practical applications.     

A High-Energy NASICON-Type Na3.2MnTi0.8V0.2(PO4)3 Cathode Material with Reversible 3.2-Electron Redox Reaction for Sodium-Ion Batteries

Na superionic conductor (NASICON) structured cathode materials with robust structural stability and large Na⁺ diffusion channels have aroused great interest in sodium-ion batteries (SIBs). However, most of NASICON-type cathode materials exhibit redox reaction of no more than three electrons per formula, which strictly limits capacity and energy density. Herein, a series of NASICON-type Na_3+xMnTi_1−xV_x(PO₄)₃ cathode materials are designed, which demonstrate not only a multi-electron reaction but also high voltage platform. With five redox couples from V^5+/4+ (≈4.1 V), Mn^4+/3+ (≈4.0 V), Mn^3+/2+ (≈3.6 V), V^4+/3+ (≈3.4 V), and Ti^4+/3+ (≈2.1 V), the optimized material, Na_3.2MnTi_0.8V_0.2(PO₄)₃, realizes a reversible 3.2-electron redox reaction, enabling a high discharge capacity (172.5 mAh g⁻¹) and an ultrahigh energy density (527.2 Wh kg⁻¹). This work sheds light on the rational construction of NASICON-type cathode materials with multi-electron redox reaction for high-energy SIBs.     

Preparation and electrochemical performance of Na-doped Li3V2(PO4)3/C cathode material

Na-doped Li₃V₂(PO₄)₃/C (LVP/C) cathode materials are prepared by a sol–gel method. X-ray diffraction results show that the Na ion has been well doped into the crystal structure of LVP/C and does not disturb the extraction–insertion behavior of lithium ion seriously. The initial discharge capacity of the Na-doped LVP/C is 112.2?mA?h g^?1 at 5?C, and the capacity retention reaches 98.3?% over 80 cycles. Cyclic voltammetry and electrochemical impedance spectra indicate that the reversibility of electrochemical redox reaction and the charge-transfer resistance of LVP/C cathode material have been significantly improved by Na doping. The improved performances can be attributed to the more convenient route for lithium ion diffusion and the lower activation energy of the extraction–insertion of lithium ion due to the weakness of Li-O bond.     

High Crystalline Prussian White Nanocubes as a Promising Cathode for Sodium‐ion Batteries

Prussian blue and its analogues (PBAs) have been recognized as one of the most promising cathode materials for room‐temperature sodium‐ion batteries (SIBs). Herein, we report high crystalline and Na‐rich Prussian white Na₂CoFe(CN)₆ nanocubes synthesized by an optimized and facile co‐precipitation method. The influence of crystallinity and sodium content on the electrochemical properties was systematically investigated. The optimized Na₂CoFe(CN)₆ nanocubes exhibited an initial capacity of 151 mA h g^?1, which is close to its theoretical capacity (170 mA h g^?1). Meanwhile, the Na₂CoFe(CN)₆ cathode demonstrated an outstanding long‐term cycle performance, retaining 78 % of its initial capacity after 500 cycles. Furthermore, the Na₂CoFe(CN)₆ Prussian white nanocubes also achieved a superior rate capability (115 mA h g^?1 at 400 mA g^?1, 92 mA h g^?1 at 800 mA g^?1). The enhanced performances could be attributed to the robust crystal structure and rapid transport of Na ions through large channels in the open‐framework. Most noteworthy, the as‐prepared Na₂CoFe(CN)₆ nanocubes are not only low‐cost in raw materials but also contain a rich sodium content (1.87 Na ions per lattice unit cell), which will be favorable for full cell fabrication and large‐scale electric storage applications.     

Electrochemical and Structural Study of Layered P2‐Type Na2/3Ni1/3Mn2/3O2 as Cathode Material for Sodium‐Ion Battery

P2‐type Na_2/3Ni_1/3Mn_2/3O₂ was synthesized by a controlled co‐precipitation method followed by a high‐temperature solid‐state reaction and was used as a cathode material for a sodium‐ion battery (SIB). The electrochemical behavior of this layered material was studied and an initial discharge capacity of 151.8 mA h g^?1 was achieved in the voltage range of 1.5–3.75 V versus Na⁺/Na. The retained discharge capacity was found to be 123.5 mA h g^?1 after charging/discharging 50 cycles, approximately 81.4 % of the initial discharge capacity. In situ X‐ray diffraction analysis was used to investigate the sodium insertion and extraction mechanism and clearly revealed the reversible structural changes of the P2‐Na_2/3Ni_1/3Mn_2/3O₂ and no emergence of the O2‐Ni_1/3Mn_2/3O₂ phase during the cycling test, which is important for designing stable and high‐performance SIB cathode materials.     

A Cation and Anion Dual Doping Strategy for the Elevation of Titanium Redox Potential for High‐Power Sodium‐Ion Batteries

Titanium‐based polyanions have been intensively investigated for sodium‐ion batteries owing to their superior structural stability and thermal safety. However, their low working potential hindered further applications. Now, a cation and anion dual doping strategy is used to boost the redox potential of Ti‐based cathodes of Na₃Ti_0.5V_0.5(PO₃)₃N as a new cathode material for sodium ion batteries. Both the Ti³⁺/Ti⁴⁺ and V³⁺/V⁴⁺ redox couples are reversibly accessed, leading to two distinctive voltage platforms at ca. 3.3 V and ca. 3.8 V, respectively. The remarkably improved cycling stability (86.3 %, 3000 cycles) can be ascribed to the near‐zero volume strain in this unusual cubic symmetry, which has been demonstrated by in situ synchrotron‐based X‐ray diffraction. First‐principles calculations reveal its well‐interconnected 3D Na diffusion pathways with low energy barriers, and the two‐sodium‐extracted intermediate NaTi_0.5V_0.5(PO₃)₃N is also a stable phase according to formation energy calculations.     

Single-Ion Conducting Polymer Electrolyte for Superior Sodium-Metal Batteries

Sodium-metal batteries (SMBs) are considered a potential alternative to high-energy lithium-metal batteries (LMBs). However, the high reactivity of metallic sodium towards common liquid organic electrolytes renders such battery technology particularly challenging. Herein, we propose a multi-block single-ion conducting polymer electrolyte (SIPE) doped with ethylene carbonate as suitable electrolyte system for SMBs. This novel SIPE provides a very high ionic conductivity (2.6 mS cm⁻¹) and an electrochemical stability window of about 4.1 V at 40 °C, enabling stable sodium stripping and plating and excellent rate capability of Na||Na₃V₂(PO₄)₃ cells up to 2 C. Remarkably, such cells provide a capacity retention of about 85 % after 1,000 cycles at 0.2 C thanks to the very high Coulombic efficiency (99.9 %), resulting from an excellent interfacial stability towards sodium metal and the Na₃V₂(PO₄)₃ cathode.     

Li3V2(PO4)3/C和Li2.5Na0.5V2(PO4)3/C的结构和电化学性能的比较研究

采用溶胶-凝胶法合成了锂离子正极材料Li3V2(PO4)3/C(LVP/C)及Li2.5Na0.5V2(PO4)3/C,并用XRD、循环伏安及交流阻抗等方法,研究了大量Na+掺杂对材料结构和电化学性能影响。结果表明,大量钠离子的掺杂会使LVP结构由单斜向菱方转变。掺杂化合物Li2.5Na0.5V2(PO4)3/C在0.5 C充电1 C放电时,首次放电容量为118 mAh.g-1,50次循环后容量保持率为92.4%,并发现与单斜LVP存在多个放电平台不同,Li2.5Na0.5V2(PO4)3/C仅在3.7 V处有一个放电平台。     

Effects of phenolic resin on the electrochemical performance of Li3V2(PO4)3/C cathode materials

As a kind of lithium-ion battery cathode material, monoclinic lithium vanadium phosphate/carbon Li₃V₂(PO₄)₃/C was synthesized by adopting phenolic resin as carbon source, both for reducing agent and coating material. The crystal structure and morphology of the samples were characterized through X-ray diffraction (XRD) and scanning electron microscope (SEM). Galvanostatic charge-discharging experiments and electrochemical impedance spectrum (EIS) were utilized to determine the electrochemical insertion properties of the samples. XRD data revealed that phenolic resin does not change the crystal structure of Li₃V₂(PO₄)₃/C. Furthermore, the morphology of grains and the electronic conductivity of Li₃V₂(PO₄)₃/C were improved. Galvanostatic charge-discharging and EIS results showed that the optimal electrochemical properties and the minimum charge-transfer resistance of Li₃V₂(PO₄)₃/C can be reached when added by 5 wt.% of redundant carbon (except the carbon needed to reduce V⁵⁺ to V³⁺). The initial discharge capacity is 128.4 mAh g^?1 at 0.2 C rate and 101.2 mAh g^?1 at 5 C in the voltage range of 3.0～4.3 V.