Journal of Energy Storage
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2024
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IF 8.9
Mengyue Liu,Kexin Wan,Xinmiao Zhang,Mingkun Wang,Dawei Yang,Jishi Wei,Kun Chang,Hongwei Tang
NASICON-type cathodes as promising candidates have attracted more and more attention, and Na 3 V 2 (PO 4 ) 3 is one of the outstanding representatives. In particular, it can tolerate complex interface reaction processes during the Zn 2+ insertion/desertion in the aqueous environment. However, existing three-dimensional channels in the intrinsic Na 3 V 2 (PO 4 ) 3 always hardly play to their advantages as narrow pathways and some other defects. This work has considered both the conductivity and capacity of this vanadium-based NASICON cathode at the same time, where a sodium-rich cathode material Na 3.2 V 1.8 Mn 0.15 Mg 0.05 (PO 4 ) 3 (NVMMP) with Mn 2+ and Mg 2+ dual-substituents has been designed considering the low cost and environmentally friendly characteristics. The synergistic effects introduced by Mn 2+ and Mg 2+ substitution led to a significant increase in the capacity and cycle life of the optimized NVMMP cathode material (with a capacity retention rate of 90.6 % after 2500 cycles at 2 A g −1 ). Furthermore, the reversible storage mechanism of Zn 2+ in NVMMP cathode materials and the theoretical study of such synergistic substitution on intrinsic electronic conductivity have been revealed by different in/ex-situ characterization techniques and theoretical calculations, where redox processes generated by Mn 3+ /Mn 4+ , enhanced ionic/electron pathway, and the pinning effect caused by injecting inert MgO 6 octahedra into the NASICON framework are key points to high capacity and long-life span.
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高影响因子
Journal of Energy Storage
·
2024
·
IF 8.9
Tao Zhou,Yanjun Chen
The advancement of Na 3 V 2 (PO 4 ) 3 has been impeded by its subpar kinetic characteristics, resulting in suboptimal electrochemical performance . In this case, a dual modification strategy involving Ta and F co-doping is employed, along with the incorporation of carbon nanotubes (CNTs), is introduced. Notably, the substitution of high-valence Ta 5+ for V 3+ ions induces an n-type doping effect, thereby increasing the density of free electrons and enhancing electrochemical performance. Moreover, Ta 5+ possesses a comparatively larger ionic radius than V 3+ , which enhances the ease of Na + transport, leading to an increased rate of ionic diffusion. Furthermore, Ta 5+ ions play a crucial role in reinforcing the crystal structure, thereby strengthening the stability of the NVP system. Importantly, during the high-temperature calcination process, the reduction of carbon results in the conversion of Ta 5+ to Ta 3+ , forming a novel conductive TaN phase through its reaction with N 2 . This TaN phase, known for its high conductivity, intercalates into the NVP bulk as interlayers, forming beneficial grain boundaries. Thanks to this unique TaN//NVP heterojunction , the migration of Na + ions is notably accelerated along the grain boundaries rather than within the NVP bulk. The introduction of F contributes to reducing the grain size of active particles, consequently shortening the pathways for Na + migration and improving kinetic properties. Moreover, the presence of carbon layers and the encapsulation of CNTs collaboratively construct a highly conductive cross-linking network, elevating both electronic conductivity and mitigating NVP particle aggregation during high-temperature sintering. Consequently, the modified NVTPF0.07/@CNTs sample exhibits outstanding performance in both half and full cells, underscoring its substantial potential for application in the field of sodium-ion batteries.
研究领域:
材料科学
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电化学
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能源存储
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无机固体化学
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纳米复合材料
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高影响因子
ELECTROCHIMICA ACTA
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2026
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IF 5.8
Zilong Fang,Qi Fan,Anyang Yu,Wei Zhou,Junwei Luo,Changhao Zhu,Xinguantong Zhou,Xiao Yu,Qingyu Xu
Achieving uniform ion flux both at the interface and in the matrix simultaneously remains a challenge with current liquid/solid electrolytes. Herein, we demonstrate a novel strategy to address the issue by designing and synthesizing a polyvinylidene fluoride hexafluoropropylene (PVDF-HFP) based ternary hybrid electrolyte (PTHE). In this unique material architecture, each component synergistically serves a specific purpose: The PVDF-HFP-Zn(OTF) 2 serves as the stable electrolyte skeleton, providing the ion transport network. The Cu-MOF regulates the Zn 2+ solvation structure and anion distribution, achieving uniform ion flux in the electrolyte matrix. Moreover, the thin liquid electrolyte film at the interface promotes ion transport and stabilizes the electrode-electrolyte interface. The PTHE exhibits balanced high performance with respect to cycling stability (3200 h at 0.2 mA cm −2 ) and excellent capacity retention when paired with the Na 3 V 2 (PO 4 ) 3 (NVP) cathode (0.0029 % capacity decay per cycle after 2000 cycles at 0.5 A g −1 ), alongside uniform Zn metal deposition and effective dendrite suppression. Furthermore, the PTHE based NVP-Zn metal quasi-solid battery demonstrates outstanding flexibility (enduring 1000 bending cycles with less than 10% decrease in capacity retention), owing to the existence of the thin liquid electrolyte film. This work provides a novel strategy for developing highly stable flexible NVP-Zn metal quasi-solid batteries by synergistically optimizing ion flux both at the interface and in the matrix.
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高影响因子
APPLIED SURFACE SCIENCE
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2026
·
IF 6.6
Xianyue Zhang,Yongguang Zhang,Nianxue Dong,Jiawei Fan,Haipeng Li,Baoe Li
The slow Na + diffusion and low intrinsic electrical conductivity of Na 3 V 2 (PO 4 ) 3 (NVP) limit its practical application in sodium-ion batteries (SIBs). A synergistic enhancement approach of Si 4+ substitution and N-doped carbon coating has been introduced in this paper to produce a porous coral-like Na 3.1 V 2 (PO 4 ) 2.9 (SiO 4 ) 0.1 @NC-2 (NVPS@NC-2) composite. Si 4+ incorporation into the NVP lattice expands the Na + migration channels and decreases the bandgap so that intrinsic electronic conductivity of NVP was enhanced as confirmed by density functional theory calculations. Additionally, the N-doped carbon coating forms numerous extrinsic defects and creates a novel porous coral-like morphology that boosts the specific surface area. The initial specific capacity of NVPS@NC-2 cathode achieves 115.7 mAh g −1 at a current density of 0.1C. And even at 60/120C, NVPS@NC-2 cathode still exhibits 98.9/66.2 mAh g −1 , maintaining 92.9% and 90.6% capacities after 5000/10000 cycles, respectively, showing its viability for advanced SIBs applications.
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Batteries & Supercaps
·
2021
·Vol. 5
·期 4
·e202100367
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IF 7.093
Yuyao Zhang,Xiaoying Zhu,Dan Kai,Baoliang Chen
Graphical Towards high energy density SIB : Biomass hyaluronic acid (HA) is developed as a novel binder for high-loading Na 3 V 2 (PO 4 ) 3 cathodes in sodium-ion batteries, which delivers a high reversible capacity, a superior rate capability, and a targeted energy density. Fast ion transport, network volume buffer and stable solid permeable interface are demonstrated along with structure-performance mechanisms. Sodium-ion batteries (SIBs) are considered a promising candidate in green energy storage due to their considerable abundance. The low mass loading (less than 2.0 mg cm −2 ) of SIBs-based cathodes cannot meet the energy density on the practical device level, which is mainly restricted by sluggish Na + transport. To the end, a facile and compatible strategy was demonstrated by utilizing hyaluronic acid (HA) binder to achieve fast ion transport and targeted energy density for Na 3 V 2 (PO 4 ) 3 (NVP) cathodes. As a novel functional aqueous binder, HA allowed cathodic materials to organize the unique conductive network. The network-like electrode structure could buffer volume changes during sodiation/desodiation process and provide bi-continuous charge transport channels for both Na + and electrons at the interface. HA promoted the formation of the stable solid permeable interface films, protecting the electrochemical stability of the cathode and ensuring its good cycle performance. These functions of HA binder enabled that NVP delivered a reversible discharge capacity of 107.3 mAh g −1 at 0.5 C (1 C=117 mA g −1 ), which showed no sacrifice of electrochemical performances with mass loading increasing from 1.1 to 4.4 mg cm −2 . Even at a high rate of 20 C, NVP-HA (loading 4.0 mg cm −2 ) could reserve a good capacity of 76.8 mAh g −1 with the retention of 99.3 % after 2000 cycles. This study provides a novel strategy to achieve high energy density for SIBs in large-scale energy storage.
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Inorganic Chemistry Frontiers
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2020
·Vol. 7
·期 5
·1289-1297
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IF 5.958
Zhaoyang Wang,Jinmei Liu,Zijuan Du,Haizheng Tao,Yuanzheng Yue
Na3V2(PO4)3 (NVP) features a three-dimensional open structure, which allows fast migration of Na+ ions, and thus, NVP is a superior cathode material for sodium ion batteries. However, the application of the NVP cathode is limited by its low electronic conductivity. To overcome this limitation, we developed an NVP nanocomposite cathode by doping carbon with bromine (Br) and nitrogen (N) during the sol–gel assisted hydrothermal reaction. The Br- and N-doping leads to the formation of amorphous carbon (a-C) on the surface of NVP particles. The nanocomposite possesses multilevel structures containing both pores with different sizes and aggregated grains (200–300 nm). Since the doped N provides electrons to the carbon matrix, the electronic conductivity of the nanocomposite is enhanced. Br-Doping leads to the drop of activation energy for V4+/V5+ redox reaction. The nanocomposite cathode exhibits a high reversible capacity of 41 mA h g−1 at 10C. Both the superior rate and cycling performances could be attributed to the synergistic effect of the multilevel structure and amorphous carbon.
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高影响因子
JOURNAL OF ALLOYS AND COMPOUNDS
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2017
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IF 3.133
Hui Xiao,Xiaobing Huang,Yurong Ren,Haiyan Wang,Jianning Ding,Shibiao Zhou,Xiang Ding,Yuandao Chen
Na 3 V 2 (PO 4 ) 3 /nitrogen doped carbon (NVP/CN) composites have been fabricated by a simple and low cost solid-state technique using folic acid as the carbon-nitrogen source. The structure, morphology and electrochemical performance of NVP/CN composites coated with various carbon-nitrogen layer contents are well investigated. The results reveal that the NVP/CN composite with 3.3 wt% carbon-nitrogen exhibits the largest specific surface area, with a uniform carbon-nitrogen layer thickness of approximately 2 nm. When tested as cathode material for sodium ion battery , NVP/CN composite with 3.3 wt% carbon-nitrogen displays an outstanding high rate properties with the discharge capacity of 95 and 91 mAh g −1 at 10 and 20 C, respectively, and long cycle life up to 3000 times even at a high rate of 10 C due to the smallest charge-transfer resistance and highest Na + diffusion coefficient . The results suggest that folic acid is a promising carbon-nitrogen source for construction of NVP/CN and other cathode materials.
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高影响因子
JOURNAL OF COLLOID AND INTERFACE SCIENCE
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2026
·
IF 9.6
Que Huang,Rui Du,Xu Yang,Yanwu Yu,Zirui Guo,Guohui Li,Qinpei Chen,Jianghui Xie,Hongyuan Ding,Junchao Zhao,Changcheng Liu
With the increasing depletion of traditional energy resources and the continuous rise in usage costs, the development of new energy storage technologies has become a global focus. Although lithium-ion batteries possess excellent electrochemical performance and a well-established industrial infrastructure, they are prone to thermal runaway and pose significant safety risks. As a potential alternative to lithium, sodium-ion batteries demonstrate promising commercial prospects due to their low cost, similar electrochemical properties, and the fact that they are more resistant to thermal runaway and exhibit less violent reactions. Among the numerous cathode materials for sodium-ion batteries, Na 3 V 2 (PO 4 ) 3 (NVP) has attracted significant attention due to its high energy density, structural stability and excellent thermal safety; however, its inherently low electronic and ionic conductivity limits its practical application. To address this, this study modifies NVP by introducing different transition metal elements to regulate the unit cell volume, broaden the ionic migration pathways, and further enhance its electrochemical performance and thermal safety. Electrochemical test results indicate that the optimal doped sample achieves a half-cell/full-cell capacity of up to 122.3 mAh g −1 ; infrared spectroscopy reveals minimal temperature variation during charge-discharge cycles. Accelerated Calorimetry (ARC), Thermogravimetric Analysis (TG) and Differential Scanning Calorimetry (DSC) tests further confirmed that element doping significantly improves the thermal stability of NVP, increases heat absorption and reduces the risk of thermal runaway. Building on this, a Random Forest (RF) machine learning model was developed to systematically analyze thermal runaway data and predict safety performance under different doping conditions. Model evaluation results indicate that the RF model possesses high predictive accuracy and good generalisation ability, enabling it to effectively identify key features influencing safety. Integrating experimental and modelling results, the combination of transition metal element doping modification and machine learning prediction methods provides a new technical pathway and theoretical basis for the design and feasibility assessment of high-safety sodium-ion batteries. Download: Download high-res image (156KB) Download: Download full-size image
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JOURNAL OF COLLOID AND INTERFACE SCIENCE
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2025
·
IF 9.7
Min Xie,Xiaoying Li,Yufan Chen,Xiangyue Liao,Qiaoji Zheng,Heng Zhang,Kwok-Ho Lam,Dunmin Lin
Sodium superionic conductor (NASICON)-type phosphates cathodes have attracted considerable attention due to their high operational voltage and robust three-dimensional (3D) framework; however, the poor intrinsic electronic conductivity and low energy density hinder their broader application. Herein, a novel NASICON-type Na 3 V 1.44 Fe 0.5 Mo 0.06 (PO 4 ) 3 cathode was designed through Fe/Mo dual-doping at the V sites of Na 3 V 2 (PO 4 ) 3 and synthesized via a conventional high-temperature solid-state method. The introduction of Fe 3+ activates the V 4+ /V 5+ redox couple at a high voltage plateau (∼ 4.0 V), while also generates additional Fe 2+ /Fe 3+ and V 4+ /V 5+ redox pairs. Meanwhile, the doing of Mo 6+ creates cation vacancies, effectively modulating the electronic structure of vanadium and promoting ionic transport kinetics. Benefiting from this dual-doping strategy, the Na 3 V 1.44 Fe 0.5 Mo 0.06 (PO 4 ) 3 cathode delivers a high capacity of 123.4 mAh g −1 at 0.2C and an impressive energy density of 406 Wh kg −1 within 2.2–4.2 V. Moreover, it exhibits outstanding cycling stability, presenting a capacity retention of 92 % after 2500 cycles at 30C. This work highlights a viable strategy for advancing high-performance NASICON-type cathodes through complex metal ion doping.
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PubMed
高影响因子
JOURNAL OF COLLOID AND INTERFACE SCIENCE
·
2025
·
IF 9.7
Beibei Ma,Yawen Liang,Xiaokai Ma,Wenjie Wang,Chengcheng Miao,Guanqi Yu,Qizhao Wang,Chunyang Xu,Xinwei Cui
The rising demand for cost-effective and safe energy storage systems has ignited strong global interest in advanced cathodes that surpass lithium-ion batteries in practical applications. Herein, we propose a composite material in which five ions, Ti 4+ , Mn 2+ , Fe 2+ , Zr 4+ , and Mo 6+ , are doped into the lattice of Na 3 V 2 (PO 4 ) 3 and a uniform carbon-coating layer is applied to its surface, resulting in the formation of high-entropy doped Na 3 V 2 (PO 4 ) 3 @C materials (HENVP@C). When employed as the cathode material for Sodium-ion batteries (SIBs) and hybrid lithium/sodium-ion batteries (HLSIBs), HENVP@C shows remarkable Li + /Na + storage capabilities. The results of electrochemical performance tests on half-cells reveal that HENVP@C exhibits a high capacity, along with excellent cycle life and stability. High-entropy doping effectively stabilizes the NASICON structure of HENVP@C, enhances ionic conductivity, and optimizes ion diffusion kinetics, particularly improving its dual-ion pseudocapacitive storage capability. In addition, the surface carbon coating improves the electronic conductivity of the material. The insights presented in this work provide new ideas for designing cathode materials for SIBs and HLSIBs.
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PubMed
高影响因子
RARE METALS
·
2025
·
IF 11
Xiaolei Wu,Ren Huang,Yibing Zhang,Peng Lv,Suhua Chen,Ying Bai
en The polyanionic compound Na 3 V 2 (PO 4 ) 3 (NVP) has emerged as a competitive cathode material for sodium-ion batteries (SIBs), owing to its high-voltage redox activity (3.4 V vs. the Na + /Na reference couple) and NASICON-type framework that enables superior ionic conductivity. However, the electrochemical performance of NVP is hampered by low intrinsic electronic conductivity, particularly under ultra-fast charging and long-term cycling conditions. Herein, a hierarchical micro-nano flower-like Na 3 V 2 (PO 4 ) 3 with a carbon-coating layer (HF-NVP@C) is synthesized by a facile n-propanol-assisted precipitation method. Theoretical analysis and experimental tests reveal that the polar-driven hydrogen bond engineering, manifested in the distinct molecular interaction between n-propanol and ultrapure water (characterized by a shorter O-H bond length of 1.859 Å and higher binding energy of −0.312 eV compared to methanol and ethanol counterparts), underpins the formation of the unique hierarchical micro-nano flower-like architecture. This hierarchical architecture creates an expanded interfacial area, enhances ionic transport pathways, and increases electrochemically active sites. Furthermore, a glucose-derived carbon coating (∼2 nm in thickness) uniformly adheres to the NVP surface, effectively enhancing its electronic conductivity. Thus, the constructed HF-NVP@C exhibits superior rate capability (68.1 mAh g −1 at 150C) and long-term cycling stability (58.7% capacity retention after 5000 cycles at 1C). This work proposes a viable strategy for designing high-performance polyanionic cathodes using hydrogen bond engineering. 摘要 zh 聚阴离子化合物Na 3 V 2 (PO 4 ) 3 @C(NVP)因其具有高电压氧化还原活性(相对于Na + /Na参比电对为3.4 V)以及能实现优异离子电导率的NASICON型骨架结构,已成为一种具有竞争力的钠离子电池(SIBs)正极材料。然而,由于NVP的本征电子电导率较低,导致其在超快充电和长期循环条件下的电化学性能较差。在本文中,通过一种简便的正丙醇辅助沉淀法合成了具有碳包覆层的分级微-纳花状Na 3 V 2 (PO 4 ) 3 @C(HF-NVP@C)。理论分析和实验测试表明,极性驱动的氢键工程体现在正丙醇与超纯水之间独特的分子相互作用上(其O-H键长为1.859 Å,比甲醇和乙醇对应的键长更短,结合能更高-0.312 eV),是形成这种独特分级微-纳花状结构的基础。这种分级结构扩大了活性材料的面积,增强其离子传输通道,并增加电化学活性位点。此外,葡萄糖衍生的碳涂层(约2 nm厚)均匀地附着在NVP表面,有效提高其电子电导率。因此,构建的HF-NVP@C展现出优异的倍率性能(150C下为68.1 mAh g -1 )和长期循环稳定性(1C下循环5000次后容量保持率为58.7%)。这项工作证明氢键工程设计高性能聚阴离子正极材料策略的可行,同时也为开发高性能钠离子电池正极材料提供了研究基础。
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Journal of Energy Storage
·
2023
·
IF 9.4
Jun Cong,Shao-hua Luo,Peng-yu Li,Kun Li,Peng-wei Li,Sheng-xue Yan
Na 3 V 2 (PO 4 ) 3 is particularly suitable as cathode materials for sodium ion batteries (SIBs). Its NASICON structure is not only conducive to the rapid migration of Na + , but also has less volume deformation during Na + deintercalation, and the main frame mechanism remains unchanged. However, owing to its own structure, the electronic conductivity is limited, which limits its practical application. Here, on the basis of carbon coating to enhance the electronic conductivity, the effect of sodium site doping of K + on the structure and properties of Na 3 V 2 (PO 4 ) 3 /C is deeply explored by comparing series Na 3-x K x V 2 (PO 4 ) 3 /C (x = 0, 0.05, 0.1, 0.15, 0.2). The initial discharge capacity of Na 2.9 K 0.1 V 2 (PO 4 ) 3 /C is 107.7 mAh·g −1 in the potential range of 2.5–3.8 V at 0.2C, and the capacity remains 95 % after 300 cycles. The excellent performance of Na 2.9 K 0.1 V 2 (PO 4 ) 3 /C benefits from the large radius of K + as functional support ions, which lightly relieves the deformation pressure of Na + during the deintercalation process, thereby stabilizing the crystal structure. Moreover, the doping of K + plays a critical role in improving the diffusion coefficient of Na + . Density functional theory (DFT) calculations demonstrate that the Na-site doping of K + can enhance the electronic conductivity of the material, which in turn brings excellent electrochemical performance. Prime novelty statement • On the basis of carbon coating, Na 2.9 K 0.1 V 2 (PO 4 ) 3 /C cathode materials with excellent electrochemical performance are obtained by doping K at theNa-site. • The effect of Na-site doping of K + on the structure and properties of Na 3 V 2 (PO 4 ) 3 /C is deeply explored by comparing series Na 3-x K x V 2 (PO 4 ) 3 /C (x = 0, 0.05, 0.1, 0.15, 0.2). • The mechanism of excellent electrochemical performance and structural stability caused by Na-site doping of K + is revealed theoretically by DFT calculation.
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