Inorganic Chemistry Frontiers
·
2020
·Vol. 7
·期 5
·1289-1297
·
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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DOI
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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DOI
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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DOI
高影响因子
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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高影响因子
CHEMICAL ENGINEERING JOURNAL
·
2019
·
IF 8.355
Jing Zeng,Dongzheng Wu,Xin Wang,Junnan Wu,Jiyang Li,Jing Wang,Jinbao Zhao
The high-voltage cathode material based on the sodium super ionic conductor (NASICON) structured Na 3 V 2 (PO 4 ) 3 (NVP) has been found to be a potential candidate for Mg storage. In this work, to improve its electrochemical performance, we construct honeycomb-like structured NVP/C/G with faster electronic and ionic transport by a convenient and universal spray-drying method for the first time. After electrochemically desodiating two Na from the NVP/C/G (ED-NVP/C/G), the ED-NVP/C/G is tested in highly anhydrous Mg electrolyte, and the insights into its Mg storage property and mechanism are carefully studied. An initial capacity of 87 mAh g −1 with a relatively high average discharge voltage of 2.47 V vs. Mg 2+ /Mg is obtained at 0.1 C. The X-ray diffraction (XRD) results show that the inserted Mg 2+ ions tend to occupy the Na2 (at 18e sites) vacant sites. The investigation of kinetic process by galvanostatic intermittent titration technique (GITT) reveals that the Mg diffusion kinetics is faster during the demagnesiation process. The electrochemical reaction bases on two-phase transition mechanism, and the R ct value shows a positive relationship to the formation of NaV 2 (PO 4 ) 3 phase. Finally, a Mg full cell prototype based on the ED-NVP/C/G cathode with Mg metal anode is built. The rational structure design of NVP/C/G improves the electrochemical performance for Mg storage, and our work also gives new understanding into the Mg storage mechanism in the ED-NVP/C/G structure.
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DOI
高影响因子
Energy Storage Materials
·
2019
·
IF 0
Junfeng Yang,Dongdong Li,Xusheng Wang,Xinxiang Zhang,Jian Xu,Jitao Chen
NASICON-structure Na 3 V 2 (PO 4 ) 3 (NVP) is a potential cathode for sodium ion battery , which however needs nano-crystallization to improve its rate performance. On the other hand, most practical electrodes are fabricated through slurry printing process, which needs to control the particle size to avoid the falling of the composite. Herein, for practical high-loading electrode fabrication, the micro-nano architecture, i.e. the micro particle plus nano channels inside, is suggested in this paper. The micro-nano information about NVP is obtained through Ga + focused ion beam-scanning electron microscopy to reconstruct the 3D model of a single NVP particle, fully exhibiting the continuous nano channels inside the micro sphere . The as-obtained NVP/C sample in the micro size exhibits remarkable enhanced rate performance of 106, 104, 101, 96, 89, 70 and 44 mAh g −1 at rates of 2, 5, 10, 20, 50, 100 and 200 C respectively, compared to the control sample in the nano size with the capacity of 106, 103, 85, 77 and 60 mAh g −1 at 2, 5, 10, 20 and 50 C respectively, meanwhile maintaining good adhesion towards Al foil and electrochemical performance at the areal loading of 10 mg cm −2 .
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DOI
SOLID STATE IONICS
·
2017
·
IF 2.354
Wei Zheng,Xiaobing Huang,Yurong Ren,Haiyan Wang,Shibiao Zhou,Yuandao Chen,Xiang Ding,Tao Zhou
Porous spherical Na 3 V 2 (PO 4 ) 3 /C composites were synthesized by a spray drying-assisted approach combined with microwave calcinations , and then characterized as cathode materials for sodium-ion batteries. The effect of carbon content on Na 3 V 2 (PO 4 ) 3 /C were investigated by X-ray diffraction, scanning electron microscopy, Brunauer–Emmet–Teller method, charge-discharge test, cyclic voltammetry and electrochemical impedance spectra measurements. The results demonstrate that the Na 3 V 2 (PO 4 ) 3 /C composite with 5wt.% carbon exhibits the best electrochemical performance among the as-prepared three Na 3 V 2 (PO 4 ) 3 /C samples. It delivers the discharge capacity of 97.9 mAh g − 1 , 93.5 mAh g − 1 at 0.2 C and 5 C, respectively. Furthermore, 97.9% of its initial capacity is remained after 500 cycles at a high rate of 5 C. The superior electrochemical performance can be ascribed to the improvement of electronic and ionic conductivity by carbon coating and porous spherical structure.
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高影响因子
危险品化学品经营许可证（带存储）