Construction of simultaneous modified Na3V2(PO4)3/C cathode with K/Zr substitution and carbon nanotubes enwrapping for high performance sodium ion battery

Na₃V₂(PO₄)₃ (NVP) has been deemed to be a prospective cathode material due to the unique NASICON-type framework for sodium ion battery (SIB). Nevertheless, the inferior intrinsic conductive property seriously impedes the development of NVP. Herein, the K/Zr co-substituted and carbon nanotubes (CNTs) enwrapped NVP/C composite is successfully synthesized through a facile sol-gel route. Notably, the introduced K⁺ in Na1 site possesses a pillar effect on the crystal structure to efficiently stabilize the framework. Meanwhile, Zr⁴⁺ with larger ionic radius successfully replaces of V³⁺, which is beneficial to expanding the interplanar spacing to facilitate the migration of Na⁺. Moreover, the enwrapped tubular CNTs can restrict the agglomerations of active grains to diminish the pathways for ionic and electronic transportation. Synthetically, the CNTs and amorphous coated carbon layers jointly construct a cross-linked 3D network to provide accelerated channels for electronic transportation. Consequently, the modified Na_2.96K_0.04V_1.93Zr_0.0525(PO₄)₃/C@CNTs composite exhibits superior electrochemical performance with excellent kinetic properties. Accordingly, it delivers a great capacity value of 110.8 mAh g^?1 at 0.1 C. Besides, it exhibits a reversible capacity of 102 mAh g^?1 at 2 C and maintains 89.7% after 300 cycles. As for a higher rate of 5 C, it releases an initial capacity of 99 mAh g^?1 and a high retention of 90.9% can be obtained after 1300 cycles. Significantly, the optimized sample delivers a high capacity of 91.2 mAh g^?1 at an ultra-high rate of 60 C and sustains 78.3% after 3000 cycles. Furthermore, the symmetric full cell is successfully fabricated and reveals superior high-rate capability with excellent stability. Therefore, this modified Na_2.96K_0.04V_1.93Zr_0.0525(PO₄)₃/C@CNTs composite would be a promising cathode material for practical applications in SIB.     

Encapsulation of N-doped carbon layer via in situ dopamine polymerization endows nanostructured NaTi2(PO4)3 with superior lithium storage performance

NaTi₂(PO₄)₃ (NTP) anode with NASICON structure presents broad prospects for aqueous lithium ion battery. Nevertheless, its intrinsic poor conductivity and structure stability in aqueous solution restrict performance of materials. Herein, we used dopamine hydrochloride to fabricate N-doped carbon encapsulated NaTi₂(PO₄)₃ nanosphere via in situ dopamine polymerization under different solution environments. Composites show obvious improvement on electrochemical performance compared with NTP. Additionally, utilization of Tris-buffer solution endows N-doped carbon encapsulated NaTi₂(PO₄)₃ nanosphere with superior performance to those of composites acquired in other solution environments. Among all samples obtained in Tris-buffer, N-doped carbon encapsulated NaTi₂(PO₄)₃ nanosphere with proper carbon layer shows superb electrochemical performance with discharge capacities of 127.5, 113.8, and 90.9 mA h g⁻¹ at 0.2, 3.0, and 15C, respectively. Superb property may be due to the unique nanosphere structure. Nanospheres with better dispersion can shorten migration path of Li ions. Encapsulation of N-doped carbon layer improves stability in aqueous electrolyte and ameliorates electronic conductivity of materials. N doping enhances hydrophilicity and electronic conductivity, and also forms lots of defects on carbon layer, which contributes to Li ion intercalation/deintercalation. This work reveals that the combination of nanosphere and N-doped carbon layer offers a promising method to raise electrochemical performances of NaTi₂(PO₄)₃.     

Superior lithium storage performance of hierarchical N-doped carbon encapsulated NaTi2(PO4)3 microflower

Na-superionic conductor (NASICON) structured NaTi₂(PO₄)₃ (NTP) as anode shows broad prospect in aqueous lithium ion battery. However, inherent low electrical conductivity of NaTi₂(PO₄)₃ remains a pivotal issue to be resolved. Herein, we report N-doped carbon encapsulated NaTi₂(PO₄)₃ microflower (NTP-CN) as anode for aqueous lithium ion battery, which is prepared via solvothermal way. NTP-CN with unique structural feature displays superb electrochemical performances. It delivers the discharge capacities of 131.2, 110.1, and 84.3 mAh g⁻¹ at 0.2, 3.0, and 15 C, respectively, 38.8, 33.8, and 51.1 mAh g⁻¹ higher than these of pristine NTP. NTP-CN also shows remarkable cycling stability at 6 C after 1000 cycles (capacity retention: 88.8%), superior to NTP (70.7%). The outstanding properties of NTP-CN may be due to that microflower structure can increase touching area between electrolyte and electrode, and carbon coating for electrode improves stability in aqueous electrolyte and ameliorates electrical conductivity. Moreover, nitrogen doping can further enhance hydrophilicity and conductivity of the sample, and also form lots of defects on electrode surface, which is beneficial for the intercalation/deintercalation of Li ions. This work reveals that the combination of microflower structure and N-doped carbon layer offers a promising method to improve electrochemical performances of NaTi₂(PO₄)₃.     

High-rate capability of three-dimensional CNTs-decorated NaTi2(PO4)3@C microspheres for sodium energy storage

One of the newest materials for sodium energy storage is NaTi₂(PO₄)₃, which is widely researched due to its considerable Na⁺ conductivity and excellent safety characteristics. However, NaTi₂(PO₄)₃ exhibits unfavorable electronic conductivity, restricting its application in sodium-ion batteries. Herein, three-dimensional CNTs-modified NaTi₂(PO₄)₃@C microspheres were synthesized by spray-drying method and solid-state high-temperature annealing. Within the designed composite, the NaTi₂(PO₄)₃@C nanoparticles were uniformly fixed on the CNTs surfaces, forming a three-dimensional CNTs-NaTi₂(PO₄)₃@C architecture. As an anode in a sodium-ion battery, the resulting CNTs-NaTi₂(PO₄)₃@C exhibited exceptional sodium storage potential, with a high reversible capacity, stable cycling properties, and a good rate capability. An excellent discharge capacity of about 128.5 mAh g^-1 was achieved with a low rate of 0.1C, and the anode displayed a reversible capability of 75.8 mAh g^-1 at 20C over 1000 cycles, with a low capacity fading rate of about 0.011% per cycle. Therefore, this novel strategy is highly effective and can be adopted to enhance the battery properties of other electrode materials.     

Synthesis of nanosheet-structured Na3V2(PO4)3/C as high-performance cathode material for sodium ion batteries using anthracite as carbon source

Recently, Na₃V₂(PO₄)₃ has shown great promise as cathode material for sodium-ion batteries. In this study, a series of carbon-modified Na₃V₂(PO₄)₃ (NVP/C) composites have been synthesized using anthracite as the carbon source. The NVP/C composite shows a nanosheet shape with a 3D continuously conductive network composed of carbon layer and carbon bump. The effect of anthracite dosage on the electrochemical performance of NVP/C has also been investigated. The results show that the NVP/C composite prepared with 10 wt% anthracite (NVP/C-10) exhibits the highest rate capability and a great cycle stability. Especially the NVP/C-10 electrode behaves an average capacity as high as 97 mAh g⁻¹ at a high current rate of 10 C. Moreover, NVP/C-10 still delivers a high specific capacity of 97.5 mAh g⁻¹ even after 800 cycles at 5 C, showing a very low capacity fading ratio of 0.012% per cycle. The excellent rate capability and cycle stability of NVP/C-10 can be ascribed to the synergistic effects of the nanosheet structure and the 3D continuously conductive network. Our results demonstrate that anthracite can be a promising carbon source for the preparation of NVP/C and other polyanion cathode materials as well.     

Coal tar pitch-based carbon composited Sb2Se3 microrod anode toward superior sodium storage performance

Antimony selenide (Sb₂Se₃) with low cost and high theoretical capacity has been explored as a potential alternative anode for sodium ion batteries. However, the large volumetric variation and sluggish dynamics of Sb₂Se₃ lead to unsatisfactory long-term cycling life and inferior rate performance. In order to resolve these issues, we proposed a fabrication of Sb₂Se₃ coated by N-doped carbon derived from coal tar pitch (CTP) by a facile solvothermal method followed by annealing process. The reasonable content of CTP can accommodate the volume expansion, hinder the pulverization and accelerate the charge transfer of Sb₂Se₃ upon the cycling process. As a result, the Sb₂Se₃/CTP6 electrode exhibits superior long cycling property with desodiation/sodiation of 129.2(130.6) mAh g^?1 after 400 cycles at high current density of 5 A g^?1 and outstanding rate performance. The XPS spectrum tests verify the decomposition of Sb₂Se₃ during the cycling in the first time and demonstrate the CTP can effectively enhance the structural stability of Sb₂Se₃. The ex-situ XRD is also utilized to reveal the Na⁺ storage mechanism and phase transition. This work offers a new modification for enhancing the structural stability of alloy-type anode materials.     

Effect of Sn doping on the electrochemical performance of NaTi2(PO4)3/C composite

In this paper, NaTi_2-xSn_x(PO₄)₃/C (x?=?0.0, 0.2, 0.3, and 0.4) composites were fabricated via facile sol-gel method, and employed as anodes for aqueous lithium ion batteries. Effect of Sn doping with various content on electrochemical properties of NaTi₂(PO₄)₃/C was investigated systematically. Sn doping on Ti site has no obvious effect on the lattice structure and morphology of NaTi₂(PO₄)₃/C. Among all samples, NaTi_1.7Sn_0.3(PO₄)₃/C (NC-Sn-3) demonstrates the best electrochemical properties. NC-Sn-3 exhibits the outstanding rate performance, delivering a discharge capacity of 103.3, 95.2, and 87.4?mAh?g^?1 at 0.5, 7, and 20?°C, respectively, 1.7, 30.5, and 56.2?mAh?g^?1 larger than those of pristine NaTi₂(PO₄)₃/C. In addition, NC-Sn-3 shows excellent cycling performance with the capacity retention of 80.6% after 1000 cycles at 5?°C. This work reveals that Sn doped NaTi₂(PO₄)₃/C with outstanding electrochemical properties are potential anode for aqueous lithium ion batteries.     

Improved structural stability and ionic conductivity of Na3Zr2Si2PO12 solid electrolyte by rare earth metal substitutions

Sodium zirconium silicon phosphorus with the composition of Na₃Zr₂Si₂PO₁₂ (NZSP) was prepared by a facile solid state reaction method. The effects of the calcination temperature and rare earth element substitution on the structure and ionic conductivity of the NZSP material were characterized by X-ray diffraction (XRD), scanning electron microscopy (SEM) and AC impedance measurement. The results show that the microstructure and ionic inductivity of the NZSP was strongly affected by the aliovalent substitution of Zr⁴⁺ ions in NZSP with rare earth metal of La³⁺, Nd³⁺ and Y³⁺. At room temperature, the optimum bulk and total ionic conductivity of the pure NZSP solid electrolyte sintered under different conditions were 6.77×10⁻⁴ and 4.56×10⁻⁴ S cm⁻¹, respectively. Substitution of La³⁺, Nd³⁺ and Y³⁺ in place of Zr⁴⁺ exhibited higher bulk conductivity compared with that of pure NZSP. Maximum bulk and ionic conductivity value of 1.43×10⁻³ and 1.10×10⁻³ S cm⁻¹ at room temperature were obtained by Na_3+xZr_1.9La_0.1Si₂PO₁₂ sample. The charge imbalance created by aliovalent substitution improves the mobility of Na⁺ ions in the lattice, which leads to increase in the conductivity. AC impedance results indicated that the total ionic conductivity strongly depends on the substitution element and the feature of the grain boundary.     

Reversible Na+-extraction/insertion in nitrogen-doped graphene-encapsulated Na3V2(PO4)2F3@C electrode for advanced Na-ion battery

NASICON-structured sodium vanadium fluorophosphate has caused widespread concern for sodium energy conversion and storage because of its high voltage platform and high theoretical energy density. However, the inferior electrical conductivity is still a big problem, which greatly prevent the applications of Na₃V₂(PO₄)₂F₃ material. Herein, the nitrogen-doped graphene-encapsulated Na₃V₂(PO₄)₂F₃@C (NG-NVPF@C) has been prepared using the sol-gel approach. The physical and electrochemical performances for the resulted NG-NVPF@C composite have been systematically characterized and compared with that of Na₃V₂(PO₄)₂F₃@C (NVPF@C) in this study. The electrochemical tests demonstrate that the as-fabricated NG-NVPF@C displays higher capacity, superior rate property and better cyclic life than NVPF@C. It displays the discharge capacity of 108.6 mAh g⁻¹ at 5C. Moreover, it also possesses the high capacity of 101.6 mAh g⁻¹ at 10C over 300 cycles with the capacity retention of about 96.5%. The improved properties of NG-NVPF@C electrode are assigned to the constructed conductive network by nitrogen-doped graphene, which can modify the conductivity of Na₃V₂(PO₄)₂F₃.     

Reducing atmosphere improves the conductivity of NaTi2(PO4)3/C material for hybrid aqueous rechargeable lithium-ion battery anode

Hybrid aqueous rechargeable lithium-ion batteries (HARLIBs) have lower cost and better safety performance than conventional lithium-ion batteries (organic electrolytes). The challenge faced by HARLIBs are the narrow selection of anode and cathode materials, and overcoming the problems of capacity decay of anode and cathode materials in aqueous electrolytes. NaTi₂(PO₄)₃, which has a stable three-dimensional open framework structure, shows certain applicability in HARLIBs, but its inherent low electronic conductivity leads to poor utilization of active materials and inferior rate performance. In this article, we propose an experimental method that can improve the conductivity of NaTi₂(PO₄)₃/C, and study the electrochemical performance of NaTi₂(PO₄)₃/C aqueous half-cell and NaTi₂(PO₄)₃/C||LiMn₂O₄ hybrid aqueous full cell. The results show that Ti³⁺/oxygen vacancies can endow NaTi₂(PO₄)₃/C with higher conductivity and improve the specific capacity and rate capability (69 mAh·g^?1, 7C). At 1C, the second discharge specific capacity is 98.46 mAh·g^?1. After 100 cycles, the Rct was 2.92 × 10^?2 Ω. The NaTi₂(PO₄)₃/C//LiMn₂O₄ full cell can provide a discharge specific capacity of up to 101.07 mAh·g^?1. The synthesized NaTi₂(PO₄)₃/C material can be applied to the anode electrode of hybrid aqueous lithium-ion full cell.     

Promoting the Li storage performances of Li2ZnTi3O8@Na2WO4 composite anode for Li-ion battery

In this work, a reasonable strategy for the construction of Li₂ZnTi₃O₈@Na₂WO₄ composite was employed to promote the Li storage performances of Li₂ZnTi₃O₈. The Li₂ZnTi₃O₈@Na₂WO₄ composites (5, 10, and 15 wt%) were then prepared by a solution dispersion method. The introduction of Na₂WO₄ does not change the structures of the samples and they show similar morphologies with particle sizes from 100 to 200 nm. Suitable amount of Na₂WO₄ modification effectively improves the electrochemical performance of Li₂ZnTi₃O₈. Li₂ZnTi₃O₈@Na₂WO₄ composites (0, 5, 10, and 15 wt%) deliver the discharge/charge capacities of 137.4/136.4, 164.2/162.3, 189.2/188.1, and 154.5/153.3 mAh g^?1 at 0.5 A g^?1 after 100 cycles, respectively. Li₂ZnTi₃O₈@Na₂WO₄ composites (10 wt%) has the highest reversible capacities among all samples. The Na₂WO₄ shell with an excellent electronic conductivity can reduce electrode polarization, decrease the charge transfer resistance, enhance the Li-ion diffusion coefficient of Li₂ZnTi₃O₈, and then improve the electrochemical kinetics of composites. In addition, the formation of Ti–O bonds at the interface can be helpful for the stabilization of the composite, being beneficial for the improvement of their cycling stabilities. These results reveal that Na₂WO₄ coating is a facile and effective strategy to promote the Li storage performance of Li₂ZnTi₃O₈.     

Design of Ti4+-doped Li3V2(PO4)3/C fibers for lithium energy storage

In this work, we propose a facile approach to fabricate Ti⁴⁺-doped Li₃V₂(PO₄)₃/C (abbreviated as C-LVTP) nanofibers using an electrospinning route followed by a high temperature treatment. In this designed nanocomposite, the ultrafine LVTP dots are homogeneously dispersed into one-dimensional carbon nanofibers and the Ti⁴⁺ doping does not destroy the crystal structure of monoclinic Li₃V₂(PO₄)₃. Compared to the undoped Li₃V₂(PO₄)₃/C (abbreviated as C-LVP), the as-fabricated C-LVTP fibers present higher reversible capacity, superior high-rate capability as well as better cyclic property. Especially, the C-LVT_7%P cathode delivers not only high capacities of 187.2 and 160.3 mAh g^?1 at 0.5 and 10 C respectively, but also stable cyclic property with the reversible capacity of 135.8 mAh g^?1 at 20 C following 500-cycle spans. The good battery characteristics of C-LVT_7%P can be mainly ascribed to Ti⁴⁺ doping, which can increase the electrical conductivity and Li⁺ diffusion coefficient.     

Aluminum-doping effects on three-dimensional Li3V2(PO4)3@C/CNTs microspheres for electrochemical energy storage

A series of three-dimensional Al³⁺-doped Li₃V₂(PO₄)₃@C/CNTs microspheres have been fabricated for the first time using a facile spray drying route followed through a solid-state reaction process. The crystalline structure, morphology, microstructure and lithium storage performance for the fabricated composites have been researched using Raman spectrum, XRD, XPS, SEM, TEM, EDS and various electrochemical tests. Benefiting from the Al³⁺ doping and formed three-dimensional networks by the carbon film and CNTs, the Li ⁺ diffusion coefficient and electrical conductivity of Li₃V₂(PO₄)₃ are significantly enhanced. All the Al³⁺-doped composites possess superior lithium storage properties including high capacity and good cyclic-life. Thus, Al³⁺ doping is a prospective strategy to promote the rate properties of Li₃V₂(PO₄)₃ for lithium energy storage.     

Effect of Al doping on electrochemical performance of NaTi2(PO4)3/C anode for aqueous sodium ion battery

The Na_1+xAl_xTi_2?x(PO₄)₃/C (x?=?0, 0.05, 0.10, 0.20) composites serving as anode for aqueous sodium ion battery are successfully synthesized through a facile sol–gel route. The results indicate that introduction of proper amount of aluminum has no obvious effect on the structure and morphology of NaTi₂(PO₄)₃/C. Among the four synthesized samples, Na_1.1Al_0.1Ti_1.9(PO₄)₃/C (NATP-0.10) exhibits the best electrochemical performance. NATP-0.10 delivers a discharge specific capacity of 115.8, 106.9, 98.4, and 89.1 mAh g^?1 at 2, 5, 10, and 20 C rate, respectively, and still retains 114.7 mAh g^?1 when the current density comes back to 2 C. Additionally, NATP-0.10 exhibits an initial discharge capacity of 102.9 mAh g^?1 and still retains a reversible capacity of 90.1 mAh g^?1 at 10 C rate after 200 cycles. Cyclic voltammetry and electrochemical impedance spectroscopy demonstrate the better electrochemical performance of NATP-0.10 is due to the faster sodium migration and enhanced electrochemical kinetics.

Graphical abstract

Al doping Na_1+xAl_xTi_2?x(PO₄)₃/C (x?=?0, 0.05, 0.10, 0.20) composites were firstly used as anodes in aqueous SIBs. The electrochemical performance of NaTi₂(PO₄)₃/C has been improved by introducing a proper amount of Al.

     

Modification of the morphology of Na3V2(PO4)2F3 as cathode material for sodium-ion batteries by polyvinylpyrrolidone

NASICON-type Na₃V₂(PO₄)₂F₃ (NVPF) is proposed to be a potential cathode material for sodium-ion battery because of its good structural stability, relatively high capacity and voltage platform. Nonetheless, the poor-rate performance, resulting from its low conductivity, has become a massive obstacle to its practical application. In this work, carbon coating together with morphology controlling were introduced to solve the issue of NVPF. This experiment used a hydrothermal method to prepare Na₃V₂(PO₄)₂F₃@C (NVPF@C) and explored the impact of surfactants (polyvinylpyrrolidone (PVP)) on the positive material performance of sodium-ion battery. Through various characterisation, NVPF@C compared its performance with that of untreated products, and verified that appropriate surfactant modification could enhance the performance of the electron conduction and sodium ion diffusion, thus effectively improved the performance of NVPF. Through comparison, it was found that appropriate surface modification with PVP can achieve the effects of specific crystal surface exposure and clusters of porous micron ball structure, and improve the electrochemical performance of NVPF best. Under the charge and discharge ratio of 0.2C, its initial reversible capacity was 127.8 mA h g^?1. After 100 cycles, its discharge capacity was 106.1 mA h g^?1, and the cycling retention rate reached 82.8%. Compared to the original NVPF, its performance has been dramatically improved.     

Synthesis and electrochemical properties of a composite LiMn0.63Fe0.37PO4 with Li3V2(PO4)3 for lithium-ion battery cathode materials

A composite materials LiMn_0.63Fe_0.37PO₄ with Li₃V₂(PO₄)₃ can be synthesized by a sol-gel method using N,N-dimethylformamide (DMF) as a dispersing agent. The structures, characteristics of the appearance, and electrochemical properties of the composites have been studied by X-ray diffraction (XRD), high-resolution transmission electron microscopy (HRTEM), charge/discharge tests, cyclic voltammetry (CV), and electrochemical impedance spectroscopy (EIS). The composites contained LiMnPO₄/C (LMP/C), LiFePO₄/C (LFP/C), and Li₃V₂(PO₄)₃/C (LVP/C) phases with a nano-sized dispersion. The TEM images showed that the composites are crystalline with a grain size of 10–50 nm. The Mn2p, V2p, and Fe2p valence states were analyzed by X-ray photoelectron spectroscopy (XPS). The incorporation of LVP and LFP with LMP effectively enhanced the electrochemical kinetics of the LMP phase by a structural modification and shortened the lithium diffusion length in LMP. The capacity of the composite 0.79LiMn_0.63Fe_0.37PO₄·0.21Li₃V₂(PO₄)₃/C remained at 152.3 mAh g⁻¹ (94.7%) after 50 cycles at a 0.05 C rate. The composite exhibited excellent reversible capacities 159.4, 150, 140.1, 133.7 and 123.6 mAh g⁻¹ at charge-discharge rates of 0.05, 0.1, 0.2, 0.5 and 1 C, respectively.     

铜（Ⅱ）掺杂Li3V2（PO4）3/C的结构与性能

用一步碳热还原法制备了Li3V2-xCux(PO4)3/C(x=0.00、0.02、0.05、0.08、0.10、0.15)复合正极材料,并研究了掺杂对材料结构、微观形貌、充放电性能的影响。结果表明掺杂少量铜(Ⅱ)不会影响材料Li3V2(PO4)3的基本结构,但会在Li3V2(PO4)3中形成电子缺陷,提高晶体内部原子的无序化程度,降低极化和电荷转移电阻。从而改善材料的电化学性能。Li3V1.98Cu0.02(PO4)3/C的10 C放电容量比Li3V2(PO4)3/C提高了20 mA.h/g,具有较好的倍率性能。     

MOF-derived hollow Co(Ni)Se2/N-doped carbon composite material for preparation of sodium ion battery anode

Hollow and porous three-dimensional Co(Ni)Se₂/N-doped carbon composite particles prepared by a simple process using metal organic framework (MOF) precursors as the template are used as a high-efficiency anode material for sodium ion batteries. The composite material having a regular rhombohedral dodecahedral structure contains the N-doped porous carbon shell and the nano-metal selenide (CoSe₂ and NiSe₂) embedded in the carbon shell. Moreover, the metal selenide has a high capacity density, and the N-doped porous carbon structure can enhance the electrical conductivity and structural stability of the material to suppress volume expansion. Their effective synergistic combination shows excellent electrochemical performance. As the anode of the sodium ion battery, Co(Ni)Se₂@NCC exhibits a very high specific capacity of up to 735.2 mA h g⁻¹ after 100 cycles and superior rate performance. In addition to these, excellent kinetic performance and cycle stability and coulombic efficiency are sufficient to prove that this material has broad prospects in sodium-ion battery anodes.     

Mg2+-doped Na3V2(PO4)3/C decorated with graphene sheets: An ultrafast Na-storage cathode for advanced energy storage

NASICON-type Na₃V₂(PO₄)₃ is one of the most promising cathode materials for sodium-ion batteries, delivering about two Na⁺-ions extraction/insertion from/into the unit structure. However, the low electronic conductivity which leads to bad rate capability and poor cycle performance, limits its practical application for sodium-ion batteries. To overcome the kinetic problem, we attempt to prepare the carbon-coated Na₃V₂(PO₄)₃ nanocrystals further decorated by graphene sheets and doped with Mg²⁺ ion via the two steps of sol-gel process and solid-state treatment for the first time. Such architecture synergistically combines the advantages of two-dimensional graphene sheets and 0-dimensional Mg²⁺-doped Na₃V₂(PO₄)₃/C nanoparticles. It greatly increases the electron/Na⁺-ion transport kinetics and assures the electrode structure integrity, leading to attractive electrochemical performance. When used as sodium-ion batteries cathode, the hybrid composite delivers an initial discharge capacity of 115.2 mAh g⁻¹ at 0.2 C rate, and retains stable discharge capacities of 113.1, 109.0, 102.4, 94.0 and 85.2 mAh g⁻¹ at high current rates of 1, 2, 5, 10 and 20 C rate, respectively. Thus, this nanostructure design provides a promising pathway for developing high-performance Na₃V₂(PO₄)₃ material for sodium-ion batteries.     

Effect of Fe-doping followed by C+SiO2 hybrid layer coating on Li3V2(PO4)3 cathode material for lithium-ion batteries

A novel Li₃V₂(PO₄)₃ composite modified with Fe-doping followed by C+SiO₂ hybrid layer coating (LVFP/C-Si) is successfully synthesized via an ultrasonic-assisted solid-state method, and characterized by XRD, XPS, TEM, galvanostatic charge/discharge measurements, CV and EIS. This LVFP/C-Si electrode shows a significantly improved electrochemical performance. It presents an initial discharge capacity as high as 170.8 mA h g⁻¹ at 1 C, and even delivers an excellent initial capacity of 153.6 mA h g⁻¹ with capacity retention of 82.3% after 100 cycles at 5 C. The results demonstrate that this novel modification with doping followed by hybrid layer coating is an ideal design to obtain both high capacity and long cycle performance for Li₃V₂(PO₄)₃ and other polyanion cathode materials in lithium ion batteries.