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1.
Polyanion‐type sodium (Na) vanadium phosphate in the form of Na3V2(PO4)3 has demonstrated reasonably high capacity, good rate capability, and excellent cyclability. Two of three Na ions per formula can be deintercalated at a potential 3.4 V versus Na+/Na with oxidation of V3+/4+. In the reversible process, two Na ions intercalate back resulting in a discharge capacity of 117.6 mAh g?1. Further intercalation is possible but at a low potential of 1.4 V versus Na+/Na accompanied by vanadium reduction V3+/2+, leading to a capacity of 60 mAh g?1. Due to its marvelous electrochemical performance, it has attracted a lot of attention since its discovery in the 1990s. To develop truly useable polyanion‐type vanadium phosphate, better understanding of its crystal configuration, sodium ions' transportation, and electronic structure is essential. Therefore, this review only focuses on the inside of crystal configuration and electronic structure of polyanion‐type vanadium phosphate, Na3V2(PO4)3, since there are a few good reviews on various processing technologies.  相似文献   

2.
Room‐temperature Na‐ion batteries (NIBs) have recently attracted attention as potential alternatives to current Li‐ion batteries (LIBs). The natural abundance of sodium and the similarity between the electrochemical properties of NIBs and LIBs make NIBs well suited for applications requiring low cost and long‐term reliability. Here, the first successful synthesis of a series of Na3(VO1?x PO4)2F1+2x (0 ≤ x ≤ 1) compounds as a new family of high‐performance cathode materials for NIBs is reported. The Na3(VO1?x PO4)2F1+2x series can function as high‐performance cathodes for NIBs with high energy density and good cycle life, although the redox mechanism varies depending on the composition. The combined first‐principles calculations and experimental analysis reveal the detailed structural and electrochemical mechanisms of the various compositions in solid solutions of Na3(VOPO4)2F and Na3V2(PO4)2F3. The comparative data for the Na y (VO1?x PO4)2F1+2x electrodes show a clear relationship among V3+/V4+/V5+ redox reactions, Na+?Na+ interactions, and Na+ intercalation mechanisms in NIBs. The new family of high‐energy cathode materials reported here is expected to spur the development of low‐cost, high‐performance NIBs.  相似文献   

3.
A sodium‐ion battery operating at room temperature is of great interest for large‐scale stationary energy storage because of its intrinsic cost advantage. However, the development of a high capacity cathode with high energy density remains a great challenge. In this work, sodium super ionic conductor‐structured Na3V2?xCrx(PO4)3 is achieved through the sol–gel method; Na3V1.5Cr0.5(PO4)3 is demonstrated to have a capacity of 150 mAh g?1 with reversible three‐electron redox reactions after insertion of a Na+, consistent with the redox couples of V2+/3+, V3+/4+, and V4+/5+. Moreover, a symmetric sodium‐ion full cell utilizing Na3V1.5Cr0.5(PO4)3 as both the cathode and anode exhibits an excellent rate capability and cyclability with a capacity of 70 mAh g?1 at 1 A g?1. Ex situ X‐ray diffraction analysis and in situ impedance measurements are performed to reveal the sodium storage mechanism and the structural evolution during cycling.  相似文献   

4.
Na3V2(PO4)3 is regarded as a promising candidate for sodium ion batteries. Nevertheless, the poor electronic conductivity, low capacities, and unstable structure limit its further investigations. Herein, a new type of Fe/Mn/Co co-substituted Na3V2(PO4)3 with nitrogen-doped carbon coating (NFMC) by a facile sol-gel route is synthesized. The introduced elements feature in both crystal bulk and carbon coating layer. Suitable heteroatom substitution activates more effective Na+ to participate in electrochemical process and reinforce the structure. An extra high voltage platform at 3.8 V resulting from the multi-element synergy (Mn2+/Mn3+/Mn4+; Co2+/Co3+; V4+/V5+) is stably and reversibly existed in NFMC to supply added capacities, which is investigated by quantum physics calculations. The high flux paths for Na+ migration and spin quantum state distribution in NFMC are demonstrated by molar magneton calculation. Significantly, the generated polyatomic coordination environment of M N C (M = Fe/Co/Mn) in carbon layer is first proposed. The most optimized combination structures are obtained from 69 possible structures and demonstrated by X-ray absorption spectroscopy. The superior electrochemical performance is precisely forecasted by innovative deep learning. Predicted values with high precision are obtained based on a small number of operating data, extremely short development period, and provide real-time status references for safer use.  相似文献   

5.
Urchin‐like CoSe2 assembled by nanorods has been synthesized via simple solvothermal route and has been first applied as an anode material for sodium‐ion batteries (SIBs) with ether‐based electrolytes. The CoSe2 delivers excellent sodiation and desodiation properties when using 1 m NaCF3SO3 in diethyleneglycol dimethylether as an electrolyte and cycling between 0.5 and 3.0 V. A high discharge capacity of 0.410 Ah g?1 is obtained at 1 A g?1 after 1800 cycles, corresponding to a capacity retention of 98.6% calculated from the 30th cycle. Even at an ultrahigh rate of 50 A g?1, the capacity still maintains 0.097 Ah g?1. The reaction mechanism of the as‐prepared CoSe2 is also investigated. The results demonstrate that at discharged 1.56 V, insertion reaction occurs, while two conversion reactions take place at the second and third plateaus around 0.98 and 0.65 V. During the charge process, Co first reacts with Na2Se to form NaxCoSe2 and then turns back to CoSe2. In addition to Na/CoSe2 half cells, Na3V2(PO4)3/CoSe2 full cell with excessive amount of Na3V2(PO4)3 has been studied. The full cell exhibits a reversible capacity of 0.380 Ah g?1. This work definitely enriches the possibilities for anode materials for SIBs with high performance.  相似文献   

6.
Na superionic conductor of Na3MnTi(PO4)3 only containing high earth-abundance elements is regarded as one of the most promising cathodes for the applicable Na-ion batteries due to its desirable cycling stability and high safety. However, the voltage hysteresis caused by Mn2+ ions resided in Na+ vacancies has led to significant capacity loss associated with Mn reaction centers between 2.5–4.2 V. Herein, the sodium excess strategy based on charge compensation is applied to suppress the undesirable voltage hysteresis, thereby achieving sufficient utilization of the Mn2+/Mn3+ and Mn3+/Mn4+ redox couples. These findings indicate that the sodium excess Na3.5MnTi0.5Ti0.5(PO4)3 cathode with Ti4+ reduction has a lowest Mn2+ occupation on the Na+ vacancies in its initial composition, which can improve the kinetics properties, finally contributing to a suppressed voltage hysteresis. Based on these findings, it is further applied the sodium excess route on a Mn-richer phosphate cathode, which enables the suppressed voltage hysteresis and more reversible capacity. Consequently, this developed Na3.6Mn1.15Ti0.85(PO4)3 cathode achieved a high energy density over 380 Wh kg−1 (based on active substance mass of cathode) in full-cell configurations, which is not only superior to most of the phosphate cathodes, but also delivers more application potential than the typical oxides cathodes for Na-ion batteries.  相似文献   

7.
All‐solid‐state rechargeable sodium (Na)‐ion batteries are promising for inexpensive and high‐energy‐density large‐scale energy storage. In this contribution, new Na solid electrolytes, Na3?yPS4?xClx, are synthesized with a strategic approach, which allows maximum substitution of Cl for S (x = 0.2) without significant compromise of structural integrity or Na deficiency. A maximum conductivity of 1.96 mS cm?1 at 25 °C is achieved for Na3.0PS3.8Cl0.2, which is two orders of magnitude higher compared with that of tetragonal Na3PS4 (t‐Na3PS4). The activation energy (Ea) is determined to be 0.19 eV. Ab initio molecular dynamics simulations shed light on the merit of maximizing Cl‐doping while maintaining low Na deficiency in enhanced Na‐ion conduction. Solid‐state nuclear magnetic resonance (NMR) characterizations confirm the successful substitution of Cl for S and the resulting change of P oxidation state from 5+ to 4+, which is also verified by spin moment analysis. Ion transport pathways are determined with a tracer‐exchange NMR method. The functional detects that promote Na ‐ion transport are maximized for further improvement in ionic conductivity. Full‐cell performance is demonstrated using Na/Na3.0PS3.8Cl0.2/Na3V2(PO4)3 with a reversible capacity of ≈100 mAh g‐1 at room temperature.  相似文献   

8.
Batteries and supercapacitors are critical devices for electrical energy storage with wide applications from portable electronics to transportation and grid. However, rechargeable batteries are typically limited in power density, while supercapacitors suffer low energy density. Here, a novel symmetric Na‐ion pseudocapacitor with a power density exceeding 5.4 kW kg?1 at 11.7 A g?1, a cycling life retention of 64.5% after 10 000 cycles at 1.17 A g?1, and an energy density of 26 Wh kg?1 at 0.585 A g?1 is reported. Such a device operates on redox reactions occurring on both electrodes with an identical active material, viz., Na3V2(PO4)3 encapsulated inside nanoporous carbon. This device, in a full‐cell scale utilizing highly reversible and high‐rate Na‐ion intercalational pseudocapacitance, can bridge the performance gap between batteries and supercapacitors. The characteristics of the device and the potentially low‐cost production make it attractive for hybrid electric vehicles and low‐maintenance energy storage systems.  相似文献   

9.
In this work, a full‐cell sodium‐ion battery (SIB) with a high specific energy approaching 300 Wh kg?1 is realized using a sodium vanadium fluorophosphate (Na3V2(PO4)2F3, NVPF) cathode and a tin phosphide (SnPx) anode, despite both electrode materials having greatly unbalanced specific capacities. The use of a cathode employing an areal loading more than eight times larger than that of the anode can be achieved by designing a nanostructured nanosized NVPF (n‐NVPF) cathode with well‐defined particle size, porosity, and conductivity. Furthermore, the high rate capability and high potential window of the full‐cell can be obtained by tuning the Sn/P ratio (4/3, 1/1, and 1/2) and the nanostructure of an SnPx/carbon composite anode. As a result, the full‐cell SIBs employing the nanostructured n‐NVPF cathode and the SnPx/carbon composite anode (Sn/P = 1/1) exhibit outstanding specific energy (≈280 Wh kg?1(cathode+anode)) and energy efficiency (≈78%); furthermore, the results are comparable to those of state‐of‐the‐art lithium‐ion batteries.  相似文献   

10.
Vanadium multiredox-based NASICON-NazV2−yMy(PO4)3 (3 ≤ z ≤ 4; M = Al3+, Cr3+, and Mn2+) cathodes are particularly attractive for Na-ion battery applications due to their high Na insertion voltage (>3.5 V vs Na+/Na0), reversible storage capacity (≈150 mA h g−1), and rate performance. However, their practical application is hindered by rapid capacity fade due to bulk structural rearrangements at high potentials involving complex redox and local structural changes. To decouple these factors, a series of Mg2+-substituted Na3+yV2−yMgy(PO4)3 (0 ≤ y ≤ 1) cathodes is studied for which the only redox-active species is vanadium. While X-ray diffraction (XRD) confirms the formation of solid solutions between the y = 0 and 1 end members, X-ray absorption spectroscopy and solid-state nuclear magnetic resonance reveal a complex evolution of the local structure upon progressive Mg2+ substitution for V3+. Concurrently, the intercalation voltage rises from 3.35 to 3.45 V, due to increasingly more ionic V O bonds, and the sodium (de)intercalation mechanism transitions from a two-phase for y ≤ 0.5 to a solid solution process for y ≥ 0.5, as confirmed by in operando XRD, while Na-ion diffusion kinetics follow a nonlinear trend across the compositional series.  相似文献   

11.
Solid-state sodium batteries have garnered considerable interest. However, their electrochemical performance is hampered by severe interfacial resistance between sodium metal and inorganic solid electrolytes, as well as Na dendrite growth within the electrolytes. To address these issues, a uniform and compact SnF2 film is first introduced onto the surface of the inorganic solid electrolyte Na3.2Zr1.9Ca0.1Si2PO12 (NCZSP) to improve contact through an effective and straightforward process. Through experiments and computations, the in situ conversion reaction between SnF2 and molten Na is adequately confirmed, resulting in a composite conductive layer containing NaxSn alloys and NaF at the interface. As a result, the interfacial resistance of Na/NCZSP is significantly decreased from 813 to 5 Ω cm2, and the critical current density is dramatically increased to 1.8 mA cm−2, as opposed to 0.2 mA cm−2 with bare NCZSP. The symmetric cell is able to cycle stably at 0.2 mA cm−2 for 1300 h at 30 °C and exhibits excellent current tolerance of 0.3 and 0.5 mA cm−2. Moreover, the Na3V2(PO4)3/SnF2-NCZSP/Na full cell displays excellent rate performance and cycling stability. The SnF2-induced interlayer proves significant in improving interfacial contact and restraining sodium dendrite propagation, thus promoting the development of solid-state sodium batteries.  相似文献   

12.
Taken the unlimited Na reservoir worldwide, battery technology based on Na-ion chemistry poses as an ideal candidate for large-scale energy storage systems. Especially, with metallic Na replacing traditional carbon anodes, it's able to maximize the energy density inexpensively. Nevertheless, sodium metal batteries (SMBs) face intrinsically poor stability due to their highly-reactive nature, where low Coulombic efficiency and short lifetime are often witnessed. The situation can be further aggravated at low temperatures due to insurmountable kinetic barriers. Herein, a 1,3-dioxolane-based quasi-solid-state electrolyte (PDGE) is proposed with a high ionic conductivity of 3.68 mS cm−1 even at −20 C for SMBs. Moreover, a weak solvation environment is tailored by PDGE, which possesses a high Na+ transference number of 0.7. Concurrently, the solid electrolyte interphase induced from PDGE presents inorganic Na2O, NaF as the major components, which offers accelerated Na+ diffusion and superior stability upon long-term cycling. With such a quasi-solid-state electrolyte, the Na/Na3V2(PO4)3 full cell exhibits great stability over 1000 cycles at −20 C. This study has significant implications to the development for SMBs under low-temperature conditions.  相似文献   

13.
Surface stabilization of cathode materials is urgent for guaranteeing long‐term cyclability, and is important in Na cells where a corrosive Na‐based electrolyte is used. The surface of P2‐type layered Na2/3[Ni1/3Mn2/3]O2 is modified with ionic, conducting sodium phosphate (NaPO3) nanolayers, ≈10 nm in thickness, via melt‐impregnation at 300 °C; the nanolayers are autogenously formed from the reaction of NH4H2PO4 with surface sodium residues. Although the material suffers from a large anisotropic change in the c‐axis due to transformation from the P2 to O2 phase above 4 V versus Na+/Na, the NaPO3‐coated Na2/3[Ni1/3Mn2/3]O2/hard carbon full cell exhibits excellent capacity retention for 300 cycles, with 73% retention. The surface NaPO3 nanolayers positively impact the cell performance by scavenging HF and H2O in the electrolyte, leading to less formation of byproducts on the surface of the cathodes, which lowers the cell resistance, as evidenced by X‐ray photoelectron spectroscopy and time‐of‐flight secondary‐ion mass spectroscopy. Time‐resolved in situ high‐temperature X‐ray diffraction study reveals that the NaPO3 coating layer is delayed for decomposition to Mn3O4, thereby suppressing oxygen release in the highly desodiated state, enabling delay of exothermic decomposition. The findings presented herein are applicable to the development of high‐voltage cathode materials for sodium batteries.  相似文献   

14.
An evolutionary modification approach, boron doped carbon coating, is initially used to improve the electrochemical properties of electrode materials of lithium‐ion batteries, such as Li3V2(PO4)3, and demonstrates apparent and significant modification effects. Based on the precise analysis of X‐ray photoemission spectroscopy results, Raman spectra, and electrochemical impedance spectroscopy results for various B‐doped carbon coated Li3V2(PO4)3 samples, it is found that, among various B‐doping types (B4C, BC3, BC2O and BCO2), the graphite‐like BC3 dopant species plays a huge role on improving the electronic conductivity and electrochemical activity of the carbon coated layer on Li3V2(PO4)3 surface. As a result, when compared with the bare carbon coated Li3V2(PO4)3, the electrochemical performances of the B‐doped carbon coated Li3V2(PO4)3 electrode with a moderate doping amount are greatly improved. For example, when cycled under 1 C and 20 C in the potential range of 3.0–4.3 V, this sample shows an initial capacity of 122.5 and 118.4 mAh g?1, respectively; after 200 cycles, nearly 100% of the initial capacity is retained. Moreover, the modification effects of B‐doped carbon coating approach are further validated on Li4Ti5O12 anode material.  相似文献   

15.
Aqueous zinc‐ion batteries are receiving increasing attention; however, the development of high‐voltage cathodes is limited by the narrow voltage window of conventional aqueous electrolytes. Herein, it is reported that Na3V2(PO4)2O1.6F1.4 exhibits the excellent performance, optimal to date, among polyanion cathode materials in a novel neutral water‐in‐bisalts electrolyte of 25 m ZnCl2 + 5 m NH4Cl. It delivers a reversible capacity of 155 mAh g?1 at 50 mA g?1, a high average operating potential of ≈1.46 V, and stable cyclability of 7000 cycles at 2 A g?1.  相似文献   

16.
Substitution of liquid electrolyte with solid-state electrolytes (SSEs) has emerged as a very urgent and challenging research area of rechargeable batteries. NASICON (Na3Zr2Si2PO12) is one of the most potential SSEs for Na-ion batteries due to its high ionic conductivity and low thermal expansion. It is proven that the ionic conductivity of NASICON can be improved to 10−3 S cm−1 by Sc-doping, of which the mechanism, however, has not been fully understood. Herein, a series of Na3+xScxZr2−xSi2PO12 (0 ≤ x  ≤  0.5) SSEs are prepared. To gain a deep insight into the ion transportation mechanism, synchrotron-based X-ray absorption spectroscopy (XAS) is employed to characterize the electronic structure, and solid-state nuclear magnetic resonance (SS-NMR) is used to analyze the dynamics. In this study, Sc is successfully doped into Na3Zr2Si2PO12 to substitute Zr atoms. The redistribution of sodium ions at certain specific sites is proven to be critical for sodium ion movement. For x ≤ 0.3, the promotion of sodium ion movement is attributed to sodium ion concentration increase at the Na2 sites and decrease at the Na1 and Na3 sites. For x > 0.3, the inhibition of sodium ion movement is due to the phase change from monoclinic to rhombohedral and an increasing impurity content.  相似文献   

17.
Sodium‐ion battery (SIB) is especially attractive in cost‐effective energy storage device as an alternative to lithium‐ion battery. Particularly, metal phosphides as potential anodes for SIBs have recently been demonstrated owing to their higher specific capacities compared with those of carbonaceous materials. Unfortunately, most reported metal phosphides consist of irregular particles ranged from several hundreds nanometers to tens of micrometers, thus delivering limited cyclic stability. This paper reports the sodium storage properties of additive‐free Cu3P nanowire (CPNW) anode directly grown on copper current collector via an in situ growth followed by phosphidation method. Therefore, as a result of its structure features, CPNW anode demonstrates highly stable cycling ability with an ≈70% retention in capacity at the 260th cycle, whereas most reported metal phosphides have limited cycle numbers ranged between 30 and 150. Besides, the reaction mechanism between Cu3P and Na is investigated by examining the intermediate products at different charge/discharge stages using ex situ X‐ray diffraction measurements. Furthermore, to explore the practical application of CPNW anode, a pouch‐type Na+ full cell consisting of CPNW anode and Na3V2(PO4)3 cathode is assembled and characterized. As a demonstration, a 10 cm × 10 cm light‐emmiting diode (LED) screen is successfully powered by the Na+ full cell.  相似文献   

18.
Severe capacity degradation at low temperatures (<−20°С) hampers wide applications of lithium-ion batteries (LIBs) in consumer electronics and electric vehicles. Existing works are dedicated to electrolyte modification because that electrolyte controls both Li+ transportation and interfacial reaction. However, the efforts on electrolytes are always hard to balance rate performance and low-temperature capacity due to their high viscosity. Herein, a binary coating layer for Li3V2(PO4)3 cathode material without changing electrolyte formulation is proposed, which significantly improves the high-rate capability and low-temperature performance of batteries. YPO4 nanoparticles are in situ formed in the amorphous surface carbon layer under the reaction between Li3V2(PO4)3 and Y(NO3)3 during post-thermal treatment. The C+YPO4 binary coating reduces the side reactions of Li3V2(PO4)3 at high voltage. In addition, the binary surface coating also improves the interfacial kinetics of the electrode at low temperatures. Benefiting from these advantages, the Li3V2(PO4)3 cathode material can cycle stably at ultra-high rates up to 50 C. In addition, the capacity retention at −20 and −40 °С are improved to 89.1% and 75.7%, respectively. This binary surface-coated Li3V2(PO4)3 cathode material shows promising application potential in low-temperature LIBs.  相似文献   

19.
Stable and dendrite-free Na metal plating–stripping is achieved on the graphite electrode. The sodium-ether cointercalated graphite exhibits ultrahigh Na deposition efficiency of 99.86% over 900 cycles at a current density of 2 mA cm−2. The discharge process involves the [Na-ether]+ cointercalation and Na deposition. Density functional theory calculations demonstrate that the cointercalated graphite is critical for uniform Na deposition and stable Coulombic efficiency, which is ascribed to both the robust binding sites to Na by the diglyme molecules and a low lattice mismatch for Na growth on the cointercalated graphite. Also, a full cell consisting of Na4Fe3(PO4)2(P2O7) cathode and 0.5 mAh cm−2 Na predeposited graphite anode shows excellent cycling stability. The full cell delivers a capacity of 95 mAh g−1 based on the weight of cathode materials, with a high capacity retention of 91% over 300 cycles.  相似文献   

20.
Sodium metal batteries are promising for cost-effective energy storage, however, the sluggish ion transport in electrolytes and detrimental sodium-dendrite growth stall their practical applications. Herein, a cross-linking quasi-solid electrolyte with a high ionic conductivity of 1.4 mS cm−1 at 25 °C is developed by in-situ polymerizing poly (ethylene glycol) diacrylate-based monomer. Benefiting from the refined solvation structure of Na+ with a much lower desolvation barrier, random Na+ diffusion on the Na surface is restrained, so that the Na dendrite formation is suppressed. Consequently, symmetrical Na||Na cells employing the electrolyte can be cycled >2000 h at 0.1 mA cm−2. Na3V2(PO4)3||Na batteries reveal a high discharge specific capacity of 66.1 mAh g−1 at 15 C and demonstrate stable cycling over 1000 cycles with a capacity retention of 83% at a fast rate of 5 C.  相似文献   

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