Na3V2(PO4)2F3@V2O5-x复合材料的制备及储钠性能研究

doi:10.15541/jim20190058

无机材料学报 ›› 2019, Vol. 34 ›› Issue (10): 1097-1102.DOI: 10.15541/jim20190058 CSTR: 32189.14.10.15541/jim20190058

所属专题：离子电池材料

Na₃V₂(PO₄)₂F₃@V₂O_5-_x复合材料的制备及储钠性能研究

王家虎¹,王文馨¹,杜鹏¹,胡芳东¹,姜晓蕾¹(),杨剑²()

^1. 临沂大学化学化工学院, 临沂 276005
^2. 山东大学化学与化工学院, 济南 250000

收稿日期:2019-01-28 修回日期:2019-03-26 出版日期:2019-09-23 网络出版日期:2019-05-29
作者简介:王家虎(1998-), 男, 本科生. E-mail: 2909099985@qq.com
基金资助:
国家自然科学基金(21701079);山东省自然科学基金(ZR2017BB016);地方高校国家级大学生创新创业训练计划项目(201710452017);山东省本科教改项目(Z2018S006)

Synthesis of Na₃V₂(PO₄)₂F₃@V₂O_5-_x as Cathode Material for Sodium-ion Battery

WANG Jia-Hu¹,WANG Wen-Xin¹,DU Peng¹,HU Fang-Dong¹,JIANG Xiao-Lei¹(),YANG Jian²()

^1. School of Chemistry and Chemical Engineering, Linyi University, Linyi 276005, China
^2. School of Chemistry and Chemical Engineering, Shandong University, Jinan 250000, China

Received:2019-01-28 Revised:2019-03-26 Published:2019-09-23 Online:2019-05-29
Supported by:
National Natural Science Foundation of China(21701079);Shandong Provincial Natural Science Foundation(ZR2017BB016);Undergraduate Innovation and Entrepreneurship Training Program(201710452017);Undergraduate Education Reform Project of Shandong Province(Z2018S006)

摘要/Abstract

摘要：

当前制约钠离子电池发展的主要因素包括较低的能量/功率密度和较差的循环性能, 而在正极材料表面包覆含氧缺陷金属氧化物层, 可以有效提高材料的电子导电率, 保证高振实密度、能量密度和功率密度。本文通过温和的溶剂热反应制备Na₃V₂(PO₄)₂F₃纳米片前驱体并结合高温煅烧合成Na₃V₂(PO₄)₂F₃@V₂O_5-_x复合材料。其结构通过XRD、TEM、SEM、XPS和TGA测试进行表征。作为钠离子电池的正极材料, 展现了优异的循环性能和倍率性能。在0.2C倍率下, 首圈放电比容量为123 mAh?g ^-1, 循环140圈后容量保持在109 mAh?g ^-1。当电流密度提高至1C, 首圈放电比容量达到72 mAh?g ^-1, 充放电循环500圈后, 容量保持率高达84%。优异的电化学性能归因于材料表面包覆的具有丰富结构缺陷的无定型层, 有效提高了离子的扩散和电子导电率。此方法将有助于钠离子电池的实际应用。

关键词: 正极材料, 氧缺陷, 电化学性能, 钠离子电池

Abstract:

Low energy/power density and inferior cycling stability are bottlenecks to restrict the applications of sodium-ion batteries. Recently, coating the surface of cathode material by metal oxides containing oxygen vacancies, was regarded as an effective strategy to improve electrical conductivity and power/energy density. In this study, Na₃V₂(PO₄)₂F₃@V₂O_5-_x nanosheets were synthesized via hydrothermal strategy followed by heat treatment. X-ray diffraction, transmission electron microscopy, scanning electron microscopy, X-ray photoelectron spectroscopy, and thermogravimetric analysis were applied to investigate the structure of Na₃V₂(PO₄)₂F₃@V₂O_5-_x. As a cathode of sodium- ion batteries, Na₃V₂(PO₄)₂F₃@V₂O_5-_x delivers excellent cycling stability and rate capability. It exhibits an initial discharge capacity of 123 mAh?g ^-1 at 0.2C, and a discharge capacity of 109 mAh?g ^-1 after 140 cycles. At 1C, its initial reversible capacity is 72 mAh?g ^-1, which remains 84% after 500 cycles. The outstanding electrochemical property could be ascribed to its enhanced sodium-diffusion and improved electronic conductivity induced by disordered surface coating. Furthermore, it encourages more investigations into practical sodium-ion battery applications.

Key words: cathode material, oxygen deficient, electrochemical performance, sodium-ion battery

中图分类号:

O646

王家虎, 王文馨, 杜鹏, 胡芳东, 姜晓蕾, 杨剑. Na₃V₂(PO₄)₂F₃@V₂O_5-_x复合材料的制备及储钠性能研究[J]. 无机材料学报, 2019, 34(10): 1097-1102.

WANG Jia-Hu, WANG Wen-Xin, DU Peng, HU Fang-Dong, JIANG Xiao-Lei, YANG Jian. Synthesis of Na₃V₂(PO₄)₂F₃@V₂O_5-_x as Cathode Material for Sodium-ion Battery[J]. Journal of Inorganic Materials, 2019, 34(10): 1097-1102.

图/表 5

图1 NVPF与NVPF@VO样品的XRD图谱

Fig. 1 XRD patterns of NVPF and NVPF@VO samples

图2 NVPF@VO样品的(a)TEM, (b)SEM, (c)HRTEM照片以及(d)NVPF与NVPF@VO的红外谱图

Fig. 2 (a) TEM, (b) SEM, (c) HRTEM images of NVPF@VO, and (d) FT-IR spectra of NVPF and NVPF@VO

图3 (a) NVPF@VO的V元素XPS精细图谱, (b) NVPF@VO在不同溅射时间下的V元素XPS精细图谱, (c)不同溅射时间下V5+/V4+的摩尔比, 以及(d) NVPF@VO在空气中的热重曲线, 升温速率为2 ℃?min-1

Fig. 3 (a) XPS spectrum of V2p of NVPF@VO, (b) XPS spectra of V2p of NVPF@VO sputtered by Ar+ plasmon for different time, (c) mole ratio of V5+/V4+ varied with the sputtering time, and (d) TG curve of NVPF@VO measured at a heating rate of 2 ℃?min-1 in air

图4 作为钠离子电池正极材料: (a)在0.2C下NVPF的充放电曲线; (b)在0.2C 下NVPF@VO的充放电曲线; (c)NVPF与NVPF@VO在0.2C下的循环性能图; (d)NVPF与NVPF@VO的倍率性能图; (e)NVPF@VO和NVPF在1C下的循环性能图

Fig. 4 NVPF@VO and NVPF as a cathode material for sodium-ion batteries: charge/discharge profiles of (a) NVPF and (b) NVPF@VO at 0.2C, (c) cycling performance and (d) rate capacity of NVPF and NVPF@VO, and (e) long cycling performances of NVPF@VO and NVPF at 1C

图5 (a)NVPF与NVPF@VO的交流阻抗谱图及对应的等效电路图, (b)低频区Zre与ω-1/2之间的关系曲线

Fig. 5 (a) EIS spectra and (b) relationship between the Zre and ω-1/2 in the low frequency region of NVPF and NVPF@VO

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Na₃V₂(PO₄)₂F₃@V₂O_5-_x复合材料的制备及储钠性能研究

Synthesis of Na₃V₂(PO₄)₂F₃@V₂O_5-_x as Cathode Material for Sodium-ion Battery

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