二元钒硼化物的反应合成及其放电性能

doi:10.15541/jim20160389

无机材料学报 ›› 2017, Vol. 32 ›› Issue (4): 407-412.DOI: 10.15541/jim20160389

二元钒硼化物的反应合成及其放电性能

潘宇¹, 路新¹, 魏治国¹, 王国庆², 曲选辉¹

(1. 北京科技大学新材料技术研究院, 北京100083; 2. 新材料与产业技术北京研究院, 北京102200)

收稿日期:2016-06-20 修回日期:2016-09-20 出版日期:2017-04-20 网络出版日期:2017-03-24
作者简介:潘宇(1992–), 男, 硕士研究生. E-mail:1139039719@qq.com
基金资助:
Beijing Natural Science Foundation (2163053);北京市自然科学基金(2163053)

Reaction Synthesis and Discharge Performance of Binary Vanadium Borides

PAN Yu¹, LU Xin¹, WEI Zhi-Guo¹, WANG Guo-Qing², QU Xuan-Hui¹

(1. Institute for Advanced Materials and Technology, University of Science and Technology Beijing, Beijing 100083, China; 2. Material and Industrial Technology Research Institute Beijing, Beijing 102200, China)

Received:2016-06-20 Revised:2016-09-20 Published:2017-04-20 Online:2017-03-24
About author:PAN Yu. E-mail:1139039719@qq.com

摘要/Abstract

摘要：

以单质元素粉末为原料, 采用1500℃高温反应合成不同成分的钒硼化物粉末, 并以制备粉末为活性物质, Ni为导电剂, NH₄HCO₃为造孔剂, 采用粉末冶金工艺制备了多孔V-xB/Ni型(x=2/3~2)负极电极片, 探讨不同物相钒硼化物作为空气电池电极活性物质的高容量输出性能。结果表明, 当原料粉末中V:B原子比为1:1、1:2时, 可分别制得具有单一物相的VB和VB₂化合物粉末, 当V:B=3:2时, 合成产物包含V₃B₂和少量VB相, 当V:B=2:3时, 合成产物为V₂B₃、V₃B₄和少量VB₂三相混合。制备的V-xB/Ni型电极的孔隙率为60.25~61.75%, 放电容量为6129~7901 mAh, 比容量为2724~3511 mAh/g。V-xB/Ni型电极的放电性能随着B含量的增加明显提升, 所制备 V-2B/Ni型电极的放电性能最优, 其比容量为3512 mAh/g, 库伦效率为86.5%, 能量密度达到2504 Wh/kg。

关键词: 反应合成, 钒硼化物, 粉末冶金, 空气电池

Abstract:

Vanadium boride compound powders with different compositions were prepared by reactive synthesis at 1500℃ from elemental powders. Then, with the obtained powders as active materials, Ni powder as conductive agent and NH₄HCO₃ as space-holder, the porous anodes of V-xB/Ni (x=2/3~2) were fabricated by powder metallurgy (PM), respectively. The effects of V-xB compounds with different phases on the discharge performance of the assembled air batteries were studied. The results show that the single-phased VB₂ powder can be obtained from the raw powder with the atomic ratio of V:B=1:2, and so does the VB powder. As for atomic ratio of V:B=3:2, the synthesized powder consists of V₃B₂ and a small amount of VB, while the ratio of V:B=2:3 yields the phase composition of V₂B₃, V₃B₄ and minor VB₂. The prepared V-xB/Ni anodes with porosity of 60.25%-61.75% exhibit good discharge performance, and their capacity can reach the range of 6129-7901 mAh while specific capacity is 2724-3511 mAh/g. With the increase of B content, the discharge performance of V-xB/Ni anodes shows a significant improvement. In comparison, the porous V-2B/Ni anode possesses the superior discharge properties with discharge capacity of 3512 mAh/g, coulombic efficiency of 86.5% and specific energy of 2504 Wh/kg.

Key words: reactive synthesis, V-xB compounds, powder metallurgy, air battery

中图分类号:

TQ174

潘宇, 路新, 魏治国, 王国庆, 曲选辉. 二元钒硼化物的反应合成及其放电性能[J]. 无机材料学报, 2017, 32(4): 407-412.

PAN Yu, LU Xin, WEI Zhi-Guo, WANG Guo-Qing, QU Xuan-Hui. Reaction Synthesis and Discharge Performance of Binary Vanadium Borides[J]. Journal of Inorganic Materials, 2017, 32(4): 407-412.

图/表 8

图1 高温合成V-xB化合物粉末的XRD图谱

Fig. 1 XRD patterns of V-xB compounds powder by high- temperature synthesis

图2 低温烧结制备V-xB/Ni电极片的XRD图谱

Fig. 2 XRD patterns of V-xB/Ni anodes by low-temperature sintering

图3 烧结制备V-xB/Ni型电极片的密度及孔隙度

Fig. 3 Porosity and density of different V-xB/Ni anodes

图4 不同成分多孔V-xB/Ni多孔电极片的断面SEM形貌

Fig. 4 SEM images of porous V-xB/Ni anodes(a) V-(2/3)B/Ni; (b) V-B/Ni; (c) V-(3/2)B/Ni; (d) V-2B/Ni

图5 V-xB/Ni电极片在6 mol/L KOH溶液中的CV曲线

Fig. 5 Cyclic voltammograms of V-xB/Ni anodes in 6 mol/L KOH solution

图6 V-xB/Ni电极在6 mol/L KOH溶液中的100 mA恒流放电曲线

Fig. 6 Discharge curves of V-xB/Ni anodes in 6 mol/L KOH solution at constant current of 100 mA

表1 V-xB/Ni型电极组装成空气电池的放电性能参数

Table 1 Discharge property parameters of air cell assembled by V-xB/Ni anodes

Anodes	Voltage /V	Theoretical capacity/ (mAh·g^-1)	Capacity /mAh	Specific capacity/ (mAh·g^-1)	Percentage of theoretical capacity/%	Specific energy/ (Wh·kg^-1)
V-(2/3)B/Ni	0.67	3410	6129	2724	79.9%	1790
V-B/Ni	0.63	3573	6291	2796	78.3%	1723
V-(3/2)B/Ni	0.69	3735	6776	3012	80.6%	2059
V-2B/Ni	0.72	4060	7901	3512	86.5%	2504

图7 V-xB/Ni电极片放电后的XRD图谱

Fig. 7 XRD patterns of V-xB/Ni anodes after discharge

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二元钒硼化物的反应合成及其放电性能

Reaction Synthesis and Discharge Performance of Binary Vanadium Borides

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