Na3V2(PO4)3 is considered as one of the most promising cathodes for sodium ion batteries owing to its fast Na+ diffusion, good structural stability and high working potential. However, its practical application is limited by its low intrinsic electronic conductivity. Herein, a carbon coated Cu2+-doped Na3V2(PO4)3 cathode was prepared. The carbon coating not only improve its apparent conductivity, but also inhibit crystal growth and prevent agglomeration of particles. Moreover, Cu2+ doping contributes to an enhanced intrinsic conductivity and decreased Na+ diffusion energy barrier, remarkably boosting its charge transfer kinetics. Based on the structure characterizations, electrochemical performances tests, charge transfer kinetics analyses and theoretical calculations, it\'s proved that such an elaborate design ensures the excellent rate performances (116.9 mA h g-1 at 0.1C; 92.6 mA h g-1 at 10C) and distinguished cycling lifespan (95.8 % retention after 300 cycles at 1C; 84.8 % retention after 3300 cycles at 10C). Besides, a two-phase reaction mechanism is also confirmed via in-situ XRD. This research is expected to promote the development of Na3V2(PO4)3-based sodium ion batteries with high energy/power density and excellent cycling lifespan.

Na3V2(PO4)3 (NVP) encounters significant obstacles, including limited intrinsic electronic and ionic conductivities, which hinder its potential for commercial feasibility. Currently, the substitution of V3+ with Mn2+ is proposed to introduce favorable carriers, enhancing the electronic conductivity of the NVP system while providing structural support and stabilizing the NASICON framework. This substitution also widens the Na+ migration pathways, accelerating ion transport. Furthermore, to bolster stability, Al2O3 coating is applied to suppress the dissolution of transition metal Mn in the electrolyte. Notably, the Al2O3 coating serves a triple role in reducing HClO4 concentration in the electrolyte, inhibiting Mn dissolution, and functioning as the ion-conducting phase. Likewise, carbon nanotubes (CNTs) effectively hinder the agglomeration of active particles during high-temperature sintering, thereby optimizing the conductivity of NVP system. In addition, the excellent structural stability is investigated by in situ XRD measurement, effectively improving the volume collapse during Na+ de-embedding. Moreover, the Na3V5.92/3Mn0.04(PO4)3/C@CNTs@1wt.%Al2O3 (NVMP@CNTs@1wt.%Al2O3) possesses unique porous structure, promoting rapid Na+ transport and increasing the interface area between the electrolyte and the cathode material. Comprehensively, the NVMP@CNTs@1wt.%Al2O3 sample demonstrates a remarkable reversible specific capacity of 122.6 mAh/g at 0.1 C. Moreover, it maintains a capacity of 115.9 mAh/g at 1 C with a capacity retention of 90.2 mAh/g after 1000 cycles. Even at 30 C, it achieves a capacity of 87.9 mAh/g, with a capacity retention rate of 84.87 % after 6000 cycles. Moreover, the NVMP@CNTs@1wt.%Al2O3//CHC full cell can deliver a high reversible capacity of 205.5 mAh/g at 0.1 C, further indicating the superior application potential in commercial utilization.

Na3V2(PO4)3(NVP) is an ideal cathode material for sodium ion battery due to its stable three-dimensional frame structure and high operating voltage. However, the low intrinsic conductivity and serious structural collapse limit its further application. In this work, a simultaneous optimized Na3V1.96Ru0.04(PO4)3/C@CNTs cathode material is synthesized by a simple sol-gel method. Specifically, the ionic radius of Ru3+ is slightly larger than that of V3+ (0.68 Å vs 0.64 Å), which not only ensures the feasibility of Ru3+ replacing V3+ site, but also appropriately expands the migration channel of sodium ions in NVP and stabilizes the structure, effectively improving the diffusion efficiency of sodium ions. Moreover, CNTs construct a three-dimensional conductive network between the grains, reducing the impedance at the interface and effectively improving the electronic conductivity. Ex-situ XRD analysis at different SOC were performed to determine the change in the crystal structure of Ru3+doped Na3V2(PO4)3, and the refinement results simultaneously demonstrate the relatively low volume shrinkage value of less than 3 % during the de-intercalation process, further verifying the stabilized crystal construction after Ru3+ substitution. Furthermore, the ex-situ XRD/SEM/CV/EIS after cycling indicate the significantly improved kinetic characteristics and enhanced structural stability. Notably, the modified Na3V1.96Ru0.04(PO4)3/C@CNTs reveals superior rate capability and ultralong cyclic performance. It submits high capacities of 82.3/80.9 mAh g-1 at 80/120C and maintains 71.3/59.6 mAh g-1 after 14800/6250 cycles, indicating excellent retention ratios of 86.6 % and 73.6 %, respectively. This work provides a multi-modification strategy for the realization of high-performance cathode materials, which can be widely applied in the optimization of various materials.

The development of Na3V2(PO4)3 (NVP) has been severely hindered by low conductivity and unstable crystal structure. A simultaneously optimized strategy of Na-rich and Sn substitution is proposed for the first time. SnX-NVP@CNTs with different doping gradients are successfully prepared by the facile sol-gel method. Notably, more hole carriers can be generated by introducing Sn2+, thus improving its electron transport efficiency. In addition, since Sn2+ ions have a larger ion radius; when replacing V3+ ions at pillar positions, the lattice spacing can be enlarged to improve the structural stability of electrode materials. Meanwhile, it is beneficial to the movement of deep-level Na+ ions and improves the utilization rate of electrode materials. Moreover, to achieve charge compensation, it is necessary to introduce excess Na+ to the Sn-doped NVP system, which will increase the number of Na+ involved in the deintercalation process and improve its reversible capacity. Furthermore, the dense coating of CNTs can form an efficient conductive network structure, which improves the electron transport rate and inhibits the accumulation of active grains to accelerate Na+ diffusion. Under the synergistic adjustment of Sn2+ doping and CNTs enwrapping, the prepared Sn0.07-NVP@CNTs exhibit a high reversible capacity of 115.1 mAh/g at 0.1C, and the capacity retention rate reaches 89.35 % after 2000 cycles at 10C. Even after 10,000 cycles at 60C, its reversible capacity dropped from the initial 75.9 to 51.3 mAh/g, with a capacity loss of only 0.003 % per cycle. Besides, the Sn0.07-NVP@CNTs//CHC full battery releases a capacity of 139.9 mAh/g, highlighting its great potential for actual applications.

Na3V2(PO4)3 (NVP), with unique Na super ionic conductivity (NASICON) framework, has become an prospective cathode material. However, the low electronic conductivity and poor structural stability limit its further development. Currently, the optimized carbon nanotubes (CNTs) by selenium doping are utilized to modify NVP system for the first time. Notably, the introduction of selenium in CNTs promotes to generate more defects, resulting in abundant active sites for the de-intercalation of Na+ to achieve more pseudocapacitance. Moreover, the newly formative C-Se bonds possess much stronger bond energy than the original CC (586.6 KJ mol-1 vs 377.4 KJ mol-1) bonds. The structure arrangement of the original CNTs is significantly improved by the doped selenium element, indicating that an enhanced carbon skeleton could be obtained to sustain the structural stability of NVP system. Furthermore, the excess selenium can be doped into the bulk of NVP crystal to replace of partial oxygen. Due to the larger ionic of Se2- (1.98 Å vs 1.4 Å of O2-), the VSe6 group has larger framework, which provides a broadened pathway for Na+ migration to improve the kinetic characteristics. Accordingly, the modified NVP@CNTs:Se = 1:1 sample exhibits superior rate capability and cyclic performance. It reveals high capacities of 78.6 and 76.5 mAh/g at 20 and 60C, maintaining 65.4 and 53.8 mAh/g after 5000 and 7000 cycles with high capacity retention of 84.49 % and 70.32 %, respectively. The assembled NVP@CNTs:Se = 1:1//CHC full cell delivers a high value of 153.6 mAh/g, suggesting the optimized sample also behaves excellent application potentials.

Generally, the transport of electrons and Na+ is seriously constrained in Na3V2(PO4)3 (NVP) due to intense interactions of V-O and PO bonds. Besides, polyamide acid (PAA) is hardly used in the sol-gel route due to insolubility. This work develops a facile liquid synthesis strategy based on modified PAA, achieving in-situ construction of a porous N-doped carbon framework with rich defects to improve the kinetics of NVP. The addition of triethylamine (TEA) reacts with carboxyls in PAA to achieve acid-base neutralization, turning PAA into polyamide salts with good solubility. The special morphology construction mechanism of this unique system was observed by ex-situ scanning electron microscopy (SEM) and Transmission electron microscopy (TEM). Specifically, PAA undergoes in-situ conversion into chain-like polyimide (PI) through a thermal polymerization mechanism during the pre-sintering process. Meanwhile, NVP precursors are evenly dispersed in the PI fibers, efficiently reducing the particle size. After the final treatment, the favorable porous carbon skeleton could be generated derived from the partial decomposition of PI, on which small active grains are in situ grown. The resulting N-doped carbon substrate contains rich defects, benefiting from the migration of Na+. Furthermore, the porous construction is conducive to alleviating the stress and strain generated by the high current impact, increasing the contact area between electrodes/electrolytes to improve the utilization efficiency of active substances. Comprehensively, the optimized samples exhibit a capacity of 82.1 mAh g-1 at 15C with a retention rate of 95.45 % after 350 cycles. It submits a capacity of 67.6 mAh g-1 at 90C and remains 52.2 mAh g-1 after 1500 cycles. Even in full cells, it reveals a value of 110.6 mAh g-1. This work guides the application of in-situ multiple modifications of polymers in electrode materials.

Na3V2(PO4)3 (NVP) is highly valued based on the stable construction among the polyanionic compounds. Nevertheless, the drawback of low intrinsic conductivity has been impeded its further application. In this paper, the internal channels of the crystal structure are extended by the introduction of larger radius Ce3+, which increases the transport rate of Na+. The introduction of Mo6+ replacing the V site leads to a beneficial n-type doping effect and facilitates the transportation of electrons. Besides, CeO2 cladding is introduced to further enhance the electronic conductivity of NVP system. Initially, CeO2 serves as an n-type semiconductor and functions as a conductive additive to significantly enhance the electronic conductivity of the electrode, thereby improving the electrochemical characteristics. Moreover, CeO2 functions as an oxygen buffer, aiding in the maintenance of active metal dispersion during operation and enabling efficient electron transfer between CeO2 and [VO6] octahedra in NVP, thus fostering outstanding electrical connectivity between the oxides. CeO2 cladding can be effectively integrated with the carbon layer to stabilize the NVP system. Comprehensively, the modified Na3V1.79Ce0.07Mo0.07(PO4)3/C@8wt.%CeO2 (CeMo0.07@8wt.%CeO2) composite exhibits excellent rate and cycling properties. It delivers a capacity of 113.4 mAh/g at 1C with a capacity retention rate of 80.3 % after 150 cycles. Even at 10C and 40C, it also submits high capacities of 84.7 mAh/g and 76 mAh/g, respectively. Furthermore, the CHC//CeMo0.07@8wt.%CeO2 asymmetric full cell possesses excellent sodium storage property, indicating its prospective application potentials.

The stable three-dimensional framework and high operating voltage of sodium superionic conductor (NASICON)-type Na3V2(PO4)3 has the potential to work with long cycle life and high-rate performance; however, it suffers from the poor intrinsic electronic conductivity and low energy density. Herein, Ga3+ is introduced into Na3V2(PO4)3 to activate the V4+/V5+ redox couple at a high potential of 4.0 V for enhancing energy density of the materials (Na3V2-xGax(PO4)3). After the partial substitution of Ga3+ for V3+, three redox couples (V2+/V3+, V3+/V4+ and V4+/V5+) of V are reversibly converted in the voltage range of 1.4-4.2 V, suggesting multi-electrons (>2e-) involved in the reversible reaction, and simultaneously the electronic conductivity of the materials is effectively enhanced. As a result, the cathode with x = 0.75 exhibits excellent electrochemical properties: in the voltage range of 2.2-4.2 V, delivering an initial capacity of 105 mAh/g at 1C with a capacity retention rate of 92.3% after 400 cycles, and providing a stable reversible capacity of 88.3 mAh/g at 40C; and in the voltage range of 1.4-4.2 V, presenting the reversible capacity 152.3 mAh/g at 1C (497.6 Wh kg-1), and cycling stably for 1000 cycles at 20C with a capacity decay of 0.02375% per cycle. It is found that the Na3V2-xGax(PO4)3 cathodes possess the sodium storage mechanism of single-phase and bi-phase reactions. This investigation presents a useful strategy to enhance the energy density and cycling life of NASICON-structured polyanionic phosphates by activating high-potential V4+/V5+ redox couple.

Na3V2(PO4)3 (NVP), possessing good ionic conduction properties and high voltage plateau, has been deemed as the most prospective material for sodium ion batteries. However, the weak intrinsic electronic conductivity has hindered its further commercialization. Herein, an ingenious strategy of Bi3+ substitution at V3+ site in NVP system is proposed. The ionic radius of Bi3+ is slightly larger than that of V3+, which can further expand the crystal structure inside the NVP, thus accelerating the migration of Na+. Meanwhile, the appropriate amount of carbon coating and carbon nanotubes (CNTs) enwrapping construct an effective three-dimensional network, which provides a conductive framework for electronic transfer. Furthermore, the introduction of CNTs also inhibit the agglomeration of active grains during the sintering process, reducing the particle size and shortening the diffusion path of Na+. Comprehensively, the conductivity, ionic diffusion ability and structural stability of the modified Na3V2-xBix(PO4)3/C@CNTs (0 ≤ x ≤ 0.05) sample are significantly improved. The Na3V1.97Bi0.03(PO4)3/C@CNTs sample obtains a reversible capacity of 97.8 mAh g-1 at 12C and maintains a value of 80.6 mAh g-1 after 9000 ultra-long cycles. As for the super high rate at 80C, it exhibits a high capacity of 84.34 mAh g-1 and retains a capacity of 73.34 mAh g-1 after 6000 cycles. The superior electrochemical performance is derived from the enhancement of the crystal structure by Bi3+ doping and the highly conductive network consisting of carbon coating layers and enwrapped CNTs.

Low electronic conductivity and poor properties at high rate have hindered the application of Na3V2(PO4)3 (NVP). Herein, a facile synthesis of NVP with porous carbon skeleton is proposed. Specifically, Na2CO3 and glucose, acting as hard templates, are introduced to the precursors after initial firing stage, and Na2CO3 particles are removed by flushing after the final heatment. Due to the thermal conductivity of Na2CO3, the secondary addition of glucose can generate distinctive graphitized porous carbon skeleton, which bonds well with the amorphous carbon coating to construct stable and conductive network. The porous construction can alleviate the stress and strain caused by the current impact through deformation. Furthermore, ex-situ EIS reveals the highly conductive carbon skeleton can significantly reduce the surface resistance and result in an increase of effective voltage to promote the de-intercalation of Na+. Moreover, the ex-situ X-ray photoelectron spectroscopy (XPS) at different potentials confirms the stabilized existence of VOC bonds. Benefiting from the unique carbon skeleton, the PC-NVP releases capacity of 116.9 mAh g-1 at 0.1C. Even at 120C, PC-NVP still exhibits a high capacity of 84.7 mAh g-1, retaining a value of 41.3 mAh g-1 after 16,000 cycles, corresponding to a low decay rate of 0.0032% per cycle.