Journal of Materials Chemistry A
·
2022
·Vol. 10
·期 21
·11340-11353
·
IF 14.511
Shiqi Sun,Yanjun Chen,Qiang Bai,Que Huang,Changcheng Liu,Shengnan He,Yaxiong Yang,Yanzhong Wang,Li Guo
The emergence of three-dimensional Na3V2(PO4)3 (NVP) has attracted a lot of attention due to its high reversible capacity and long voltage platform. Unfortunately, its popularization and application are limited by its poor intrinsic conductivity. Herein, a convenient sol–gel method is proposed to synthesize potassium/lanthanum/silicon co-substituted NVP. The potassium ions are responsible for extension along the c axis while the other two ions facilitate the expansion of the crystal structure along the other directions. Accordingly, the ternary substitution reduces the resistance existing in the neighboring coordination environment and improves the stability of the crystal framework by enlarging the migration channels for Na+. Significantly, with the simultaneous function of ternary substitution, slight lattice distortions occur in the bulk and more active sites for reversible de-intercalation of Na+ emerge, favorably supplementing the discharge capacity during the period of structural phase transition. Moreover, first-principles calculations demonstrate that the introduction of three heteroatoms could decrease the gap between the conductive and valence bands and reduce the energy barrier for sodium migration. The optimized Na3.03V1.93La0.07(PO4)2.9(SiO4)0.1 possesses a superior sodium storage property in both half- and full-cells. This work reveals the distinctive advantages of ternary substitution on the NVP system through theoretical and experimental methods, contributing to further exploration of other cathode materials.
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JOURNAL OF ALLOYS AND COMPOUNDS
·
2021
·
IF 5.316
Cheng Cheng,Xiaoxian Zang,Wenxiu Hou,Changcong Li,Qing Huang,Xiangang Hu,Chencheng Sun,Yu Zhang,Jun Yang,Fuyuan Ma
The NASICON (Sodium super ion conductor)-type of Na 3 V 2 (PO 4 ) (NVP) has a great potential for energy storage application due to its high voltage plateau, three-dimensional (3D) ionic diffusion channel, perfect thermal stability, and high structural robustness. Here, Na 3 V 2 (PO 4 )-based composites with 3D porous carbon skeleton structure were synthesized via hydrothermal methods . After a series of hydrolysis and polymerization processes, transparent colloid mainly containing (NH 4 ) 4 Na 2 V 10 O 28 phase was formed. The 3D porous hydrogel with the (NH 4 ) 4 Na 2 [V 10 O 28 ]·10H 2 O phase was produced by adjusting the reaction time. The product has a lamellar structure , and its ion is suitable to grow the nanosheets , and the present PO 4 3- groups may be distributed in the (NH 4 ) 4 Na 2 [V 10 O 28 ]·10H 2 O phase of the interlayer structure, leading to the enhanced electronic conductivity . The 3D porous Na 3 V 2 (PO 4 )/C (NVP/C) with the size of 100–200 nm particles can be used as cathode for sodium ion batteries . The NVP/C delivers a specific capacity of 62.1 mAh g −1 at 10 C. The excellent stability of NVP/C can be obtained with 98% capacity retention after 140 cycles at 1 C. After 2000 cycles (5 C), the capacity is still 80.4 mAh g −1 , with the capacity retention of about 86%. Our encouraging results may boost further studies of SIBs device by smart engineering of the electrode materials.
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ACS Applied Materials & Interfaces
·
2017
·
IF 7.504
Lei Chen,Yanming Zhao,Shenghong Liu,Long Zhao
Although the NASICON-type of Na3V2(PO4)3 is regarded as a potential cathode candidate for advanced sodium-ion batteries (SIBs), it has an undesirable rate performance and low cyclability, which are a result of its poor electronic conductivity. Here, we utilized conductive polyaniline (PANI) grown in situ to obtain the hard carbon-coated porous Na3V2(PO4)3@C composite (NVP@C@HC) with a typically simple and effective sol–gel process. Based on the restriction of double carbon layers, the NVP size decreases distinctly, which can curtail the sodium-ion diffusion distance and enhance the electronic conductivity. As expected, the product displays good discharge capacity (111.6 mA h g–1 at 1 C), outstanding rate capacity (60.4 mA h g–1 at 50 C), and remarkable cycling stability (63.3 mA h g–1 with a retention of 83.3% at 40 C over 3000 cycles). Also, it performs a long-term cycling capacity of 58.5 mA h g–1 exceeding 15 000 cycles at 20 C (with a capacity loss of 0.24% per cycle).
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CARBON
·
2025
·
IF 11.6
Jin Chen,Pei Liu,Kai Xu,Zhilei Hao,Guohui Tang,Changtian Zhu,Zixuan Ding,Shuai Yin,Zhiqiang Li,Zhen Ding,Yi Wang,Zhanpeng Liu,Siwen Yu,Xing Xin,Fenghua Liu
Na 3 V 2 (PO 4 ) 3 (NVP) material has evolved as a significant candidate for electrode materials in the development of sodium-ion batteries. However, the low conductivity of NVP material leads to low cycling performance, limiting their application in high-efficiency battery materials. To address this issue, this work proposes a novel strategy for materials design through constructing 3D network carbon-coatings on the surface of NVP materials. The carbon-coatings are achieved via a combination of sol-gel technique and heat treatment using pyrolytic carbon (C), carbon nanotubes (CNTs) and graphene (GN). In comparison to NVP@C, the electrochemical properties of NVP@C/GN, NVP@C/CNTs, and NVP@C/GN/CNTs have shown improvements. Among these, NVP@C/GN/CNTs exhibit the most outstanding electrochemical performance in the half-cell test. Specifically, this material demonstrates exceptional cycling stability, with a capacity of 92 mAh g −1 that can be maintained even after 800 cycles at a high-rate performance of 10C, with an attenuation of 10.6 %. The enhanced electrochemical performance is attributed to the specific ternary carbon-coating conductive structure, which significantly shortens the diffusion paths of Na + ions and electrons within NVP, resulting in improved Na + ion and electron transport kinetics. This study provides a new design paradigm for improving the conductivity of cathode material for sodium-ion batteries.
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International Journal of Electrochemical Science
·
2023
·Vol. 14
·期 3
·2815-2821
·
IF 1.5
Xiang Ding,Xiaobing Huang,Shibiao Zhou,Anguo Xiao,Yuandao Chen,Chenggang Zuo,Junling Jin
Na 3 V 2 (PO 4 ) 3 (NVP) is a potential cathode material for sodium ion batteries (SIBs) due to its stable three-dimensional NASICON structure and high theoretical energy density. In this paper, the carbon-coated Na 3 V 2 (PO 4 ) 3 (NVP/C) cathode materials using pitch as carbon source were synthesized by a simple solid-state reaction method combined with microwave calcinations. The electrode performance of as-prepared NVP/C materials were investigated and the results demonstrated that the NVP/C composite with 13.1 wt.% carbon shows the best electrochemical properties. It possesses a high initial discharge capacity of 108.2 mAh g -1 , 90.5 mAh g -1 at 0.2 C and 10 C. After 1000 cycles at the rate of 10 C, the discharge capacity remained almost unchanged, with no capacity fading.
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JOURNAL OF ALLOYS AND COMPOUNDS
·
2024
·
IF 5.8
Rui Du,Chenghao Qian,Changcheng Liu,Que Huang,Yanjun Chen
Currently, the low ionic and electronic conductivities of Na 3 V 2 (PO 4 ) 3 (NVP) have been hindered its further application. In this paper, a simultaneous optimized method of Er 3+ substitution and carbon nanotubes (CNTs) enwrapping is proposed for the first time. Due to the large ionic radius of Er 3+ (89 pm vs 64 pm of V 3+ ), Er 3+ occupying the position of V 3+ makes the crystal structure more stable and alleviates the deformation of the crystal cell. Meanwhile, the interplanar spacing of NVP is broadened after introducing Er 3+ , so the de-intercalation rate of Na + can be accelerated and the kinetic properties are improved. In addition, the enwrapped CNTs connecting with amorphous carbon layers construct a conductive substrate for the fast electronic transportation, which significantly modifies the electronic conductivity. Moreover, the CNTs benefits to inhibit the agglomeration of NVP active materials and make the distribution more uniform and grain size more smaller. The decreasing size indicates a shorter pathway for Na + migration, which improves its apparent ionic diffusivity . Through the above analysis, the dual modification strategy can efficiently improve the kinetic properties of NVP system. Notably, Na 3 V 1.93 Er 0.07 (PO 4 ) 3 / C@CNTs (NVEP-0.07) submits a high capacity of 84.2 mAh g −1 at 50 C and maintains 70.6 mAh g −1 after 8000 cycles, corresponding to a high retention ratio of 83.9 %. The assembled NVEP-0.07 // CHC full cell reveals 146.2 mAh g −1 at 0.1 C, which successfully lightens the LED bulbs, indicating the excellent application potential of NVEP-0.07. Impressively, the recycled XRD/SEM/XPS results demonstrate the significantly improved crystal stability and chemical state of NVEP-0.07.
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NEW JOURNAL OF CHEMISTRY
·
2020
·Vol. 45
·期 2
·906-914
·
IF 3.288
Hong-bo Huang,Cai-ling Liu,Yue Yang,Shao-hua Luo
A series of lanthanum-doped Na3V2−xLax(PO4)3/C (0 ≤ x ≤ 0.03) composites have been fabricated via a simple sol–gel approach. The influences of La3+ substitution on the structure, morphology and electrochemical properties are systematically studied. Rietveld refinement is applied to explore the actual substitution site of La, which proves that La3+ ions successfully occupy the octahedral V sites. It is suggested that appropriate La doping will reduce the particle size and enhance the reversible capacity and rate capability. Among all the samples, the as-prepared Na3V1.99La0.01(PO4)3/C compound shows the highest electrochemical capability. It delivers a high initial specific capacity of 111.3 mA h g−1 at 0.2C and maintains a capacity of 108.1 mA h g−1 over 100 cycles, exhibiting much better electrochemical performance than the original Na3V2(PO4)3/C. In addition, cyclic voltammetry (CV) and electrochemical impedance spectroscopy (EIS) experiments suggest that low-level La doping can greatly decrease the polarization and increase electrical conductivity with fast reaction kinetics and a higher Na+ diffusion coefficient. The study presented here will provide considerable insights into rare earth element-doping tactics, which will facilitate the commercialization of sodium-ion batteries.
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Sustainable Energy & Fuels
·
2025
·
IF 4.1
Yitao Hui,Xianhe Meng,Aobo Yue,Qi Shen,Bingyu Liu,Nengjun Yu,Qiaoling Kang,Lijing Yan,Chubin Wan,Tingli Ma
Na superionic conductors (NASICONs) have attracted much attention due to their unique framework structure and high capacity. However, the poor intrinsic electron conductivity severely limits further development. This work develops a soft-hard carbon composite modified Na3V2(PO4)3 (NVP) cathode with excellent rate performance and long-term cycling stability. The optimized sample exhibits excellent electrochemical performance and can release a specific discharge capacity of 102.7 mAh g-1 at 1 C rate. At the same time, after 5000 cycles at 20 C rate, the discharge capacity can reach 82.3 mAh g-1, and the capacity retention rate is 100.1 %. The morphological characteristics of the NVP/C samples were investigated, Meanwhile, combined with Raman spectroscopy and electrochemical analysis, these results revealed that the synergistic interaction between soft and hard carbon components significantly enhances electronic conductivity and facilitates rapid ionic transport. This work provides a unique idea for the surface modification and synthesis of NASICON cathode materials for sodium-ion batteries.
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高影响因子
CHEMICAL ENGINEERING JOURNAL
·
2025
·
IF 13.2
Houlin Cheng,Jingxuan Li,Pengcheng Wang,Youzu Xu,Zhiyang Zhang,Qian Feng,Hurong Yao,Zhigao Huang,Jiaxin Li
This work utilized Y 2 O 3 and rGO as additives, and systematically regulated their spatial distribution and composite ratio with Na 3 V 2 (PO 4 ) 3 (NVP) to overcome the bottlenecks faced by NVP, such as intrinsically low electronic conductivity, severe interfacial side reactions, and structural instability during cycling. The modified NVP cathode can significantly enhance its electrochemical performance, and improve its sodium storage and thermal safety performance in the pouch-type full cell. The as-prepared NVP@Y 2 O 3 @rGO material achieves an 84 % capacity retention rate after 1000 cycles at 1C&27 °C, while still delivering a specific capacity of 49.6 mAh g −1 at an ultra-high rate of 30C. Under elevated temperature of 45 °C, it maintains 91.5 % capacity retention after 400 cycles at 1C. In contrast, the pristine NVP retains only 38.2 %. Moreover, it exhibits a reversible capacity of 63.6 mAh g −1 even at an ultra-high rate of 40C. More importantly, pouch-type full cell testing further confirms its superior cycling stability (60.8 % capacity retention after 100 cycles, representing a 30.5 % improvement over the unmodified sample). Mechanistic studies reveal that the combined effects of Y 2 O 3 and rGO effectively facilitate electron/ion transport, suppress electrode-electrolyte interfacial side reactions, mitigate volume change stress, and enhance structural integrity. This work offers new insights for designing high-stability cathode materials for sodium-ion batteries.
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ChemSusChem
·
2022
·Vol. 15
·期 11
·e202200313
·
IF 9.14
Gaoli Guo,Xiaoping Tan,Kaidi Wang,Huang Zhang
Aqueous zinc batteries have been regarded as a promising energy storage technology due to their high energy, high material abundance, low toxicity, and intrinsic safety. NASICON-type materials have been proposed as efficient cathodes for rechargeable batteries, yet they suffer from fast degradation and low Coulombic efficiency in aqueous batteries. Here we demonstrate that a rationally designed aqueous electrolyte containing a supporting Na salt and polymer additive can efficiently suppress the water activity through hydrogen bonding and facilitate the anion involvement in interfacial reactions, thus enabling the stable operation of sodium superionic conductor (NASICON) cathodes in aqueous zinc batteries. As exemplified by a Na 3 V 2 (PO 4 ) 3 cathode, the cell with zinc metal anode exhibits high cycling Coulombic efficiencies (around 99.9 % in average) with a steady output voltage and capacity retention for 300 cycles. This work addresses the potential issues with NASICON-type cathodes in aqueous zinc batteries and proposes an effective solution via fundamental interphasial chemistry to design efficient and sustainable aqueous electrolytes. Graphical Engineering electrode-electrolyte interphase : A rationally designed aqueous electrolyte with bi-cation and polymer additive is reported for aqueous zinc batteries with NASICON cathodes. As exemplified by a Na 3 V 2 (PO 4 ) 3 cathode, the full cells exhibited remarkable cycling stability and efficiency, benefiting from the well-suppressed material dissolution by electrolyte-induced interfacial engineering.
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ACS Applied Materials & Interfaces
·
2019
·
IF 8.456
Xingwei Liu,Xiaoyu Jiang,Faping Zhong,Xiangming Feng,Weihua Chen,Xinping Ai,Hanxi Yang,Yuliang Cao
Sodium-ion batteries (SIBs) have been viewed as a promising candidate for grid-scale energy storage systems owing to their low cost and abundant Na resources. However, insufficient safety and poor cycling performance of current SIBs are hampering their implementation. Herein, we develop a symmetric SIB by employing Na3V2(PO4)3 as both cathode and anode along with the nonflammable triethyl phosphate dissolving 0.9 M NaClO4 as the electrolyte. The symmetric SIB demonstrates a superior rate capability (35.1 mA h g–1 at 32 C) and excellent cycling performance with a capacity retention of 88.9% after 500 cycles at 2 C. This work demonstrates a new avenue to construct safe and long-cycle-life SIBs with a simple electrode manufacturing process.
研究领域:
储能
·
电化学
·
材料科学
·
电池技术
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高影响因子
DALTON TRANSACTIONS
·
2023
·Vol. 52
·期 15
·4708-4716
·
IF 4
Zhaoyang Wang,Jiaxuan Han,Dong Wang,Lingyang Liu,Wenjing Shi,Fangyu Xiong,Haizheng Tao
Na3V2(PO4)3 (NVP) is regarded as one of the most promising cathode materials for sodium-ion batteries (SIBs). However, it suffers from a dense bulk structure and low intrinsic electronic conductivity, which lead to limited electrochemical performances. Herein, we propose a surfactant-assisted molding strategy to regulate the pore-forming process in NVP/C composite cathode materials. More precisely, the forming process of the pores in NVP could be easily controlled by utilizing the huge difference in critical micelle concentration of a surfactant (cetyltrimethylammonium bromide, CTAB) in water and ethanol. By reasonably modulating the ratio of water and ethanol in the solution, the as-synthesized NVP/C sample exhibited a three-dimensional interconnected structure with hierarchical micro/meso/macro-pores. Benefiting from these hierarchical porous structures in NVP/C, the structural stability, contact surface with the electrolyte, and electronic/ionic conductivity were improved simultaneously; whereby the optimized porous NVP/C sample exhibited an excellent high-rate performance (61.3 mA h g−1 at 10 C) and superior cycling stability (90.2% capacity retention after 500 cycles at 10 C).
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