大容量VB2-空气电池负极材料的制备与性能

doi:10.15541/jim20160344

摘要/Abstract

摘要：

VB₂因具有超高理论比容量(4060 mAh/g)而成为具有发展潜力的空气电池负极材料。实验以VB₂为负极活性物质, Ni为导电剂, NH₄HCO₃为造孔剂, 采用粉末冶金方法制备了大容量VB₂-空气电池用多孔负极片, 并探讨了负极片孔隙度对负极所组装空气电池放电性能的影响规律。结果表明, 所制备的多孔VB₂负极片放电性能优异, 放电比容量可以达到3216~3463 mAh/g范围内; 多孔VB₂负极片放电容量、比容量、库伦效率和比能量均与孔隙度密切相关。当添加15wt%NH₄HCO₃造孔剂时, 烧结制备的多孔VB₂负极片的孔隙度为60.91%, 此时VB₂-空气电池放电性能最优: 放电容量为7792 mAh, 放电比容量为3463 mAh/g, 库伦效率为85.30%, 放电比能量为2370 mWh/g。

关键词: VB2-空气电池, 负极, 比容量, 粉末冶金

Abstract:

VB₂ has great potential as an anode material of air batteries due to its high theoretical specific capacity (4060 mAh/g). In present work, the porous anodes for high capacity VB₂-air battery were prepared by using powder metallurgy technology, with VB₂ as the active materials of anodes, Ni as the conductive agents, and NH₄HCO₃ as the space-holder. The effect of porosity on the discharge performances of porous anodes was investigated. The results show that the porous anodes exhibit a good discharge performance with specific capacity up to 3216-3463 mAh/g. The discharge capacity, specific capacity, coulombic efficiency, and specific energy all significantly depend on the porosity of the porous anodes. When the addition of space-holder NH₄HCO₃ is 15wt%, the porous anodes have the porosity of 60.91%, and possess the superior discharge properties with discharge capacity of 7792 mAh, specific capacity of 3463 mAh/g, coulombic efficiency of 85.30%, and specific energy of 2370 mWh/g.

Key words: VB2-air battery, anodes, specific capacity, powder metallurgy

中图分类号:

TQ174

魏治国, 路新, 佟健博, 潘宇, 王国庆, 曲选辉. 大容量VB₂-空气电池负极材料的制备与性能[J]. 无机材料学报, 2017, 32(2): 122-126.

WEI Zhi-Guo, LU Xin, TONG Jian-Bo, PAN Yu, WANG Guo-Qing, QU Xuan-Hui. Preparation and Discharge Performance of Porous VB₂ Anodes for High Capacity VB₂-air Battery[J]. Journal of Inorganic Materials, 2017, 32(2): 122-126.

图/表 6

图1 不同造孔剂添加量制备的多孔VB2负极片的孔隙度

Fig. 1 Porosities of porous VB2 anodes with different contents of space-holder

图2 原始镍粉(a)、VB2粉末(b)和烧结后多孔VB2负极片(c)的 XRD图谱

Fig. 2 XRD patterns of Ni powders (a), VB2 powders (b) and as-sintered porous VB2 anodes (c)

图3 不同造孔剂添加量制备的多孔VB2负极片的断面SEM形貌

Fig. 3 SEM images of porous VB2 anodes added with different contents of space-holder(a) 0; (b) 5wt%; (c) 10wt%; (d) 15wt%; (e) 20wt%; (f) 25wt%

表1 不同多孔VB2负极片的VB2-空气电池放电性能参数

Table 1 Discharge property parameters of VB2-air batteries with different porous anodes

NH₄HCO₃in anodes/ wt%	Porosity/ %	Theoretical capacity/ mAh	Voltage/ V	Capacity/ mAh	Specific capacity/(mAh·g^-1)	Ratio of theoretical capacity	Specific energy/(mWh·g^-1)
0	50.16	9135	0.68	7274	3233	79.63%	2210
5	53.28	9135	0.71	7525	3345	82.38%	2370
10	56.11	9135	0.69	7666	3407	83.92%	2360
15	60.91	9135	0.69	7792	3463	85.30%	2370
20	64.41	9135	0.66	7362	3272	80.59%	2170
25	67.46	9135	0.71	7235	3216	79.20%	2290

图4 不同负极片组装VB2-空气电池的放电曲线

Fig. 4 Discharge curves of the VB2-air batteries with different porous VB2 anodes(a) Discharge capacity; (b) Specific capacity and coulombic efficiency

图5 多孔VB2负极片(孔隙度为60.91%)放电前后的XRD图谱

Fig. 5 XRD patterns of porous VB2 anodes with porosity of 60.91%(a) Before discharge; (b) After discharge

参考文献 17

[1]	FREITAS M B J G, PEGORETTI V C, PIETRE M K. Recycling manganese from spent Zn-MnO2 primary batteries. Journal of power sources, 2007, 164(2): 947-952.
[2]	WANG M, ZHANG C, ZHANG Z,et al. Distribution and integrated assessment of lead in an abandoned lead-acid battery site in Southwest China before redevelopment.Ecotoxicol Environ Saf, 2016, 128: 126-132.
[3]	GARCIA E M, TAROCO H A, MATENCIO T,et al. Electrochemical recycling of cobalt from spent cathodes of lithium-ion batteries: its application as supercapacitor. Journal of Applied Electrochemistry, 2012, 42(6): 361-366.
[4]	GONCALVES S A, GARCIA E M, TAROCO H A,et al. Development of non-enzymatic glucose sensor using recycled cobalt from cell phone Li-ion batteries.Waste Manag., 2015, 46: 497-502.
[5]	WU X H, WU W W, LI Y N,et al. Synthesis and electrochemical performance of rod-like CuFe2O4 as an anode material for Na-ion battery. Materials Letters, 2015, 138: 192-195.
[6]	CHENG F Y, CHEN J.Metal-air batteries: from oxygen reduction electrochemistry to cathode catalysts.Chem. Soc. Rev., 2012, 41(6): 2172-2192.
[7]	LI Z F, YANG J W, XU G F,et al. Non-precious cathode electrocatalyst for magnesium air fuel cells: activity and durability of iron-polyphthalocyanine absorbed on carbon black.Journal of Power Sources, 2013, 242: 157-165.
[8]	XIN G B, WANG X J, WANG C Y,et al. Porous Mg thin films for Mg-air batteries.Dalton Trans, 2013, 42(48): 16693-16696.
[9]	YANG H X, WANG Y D, CHA C S.Metal borides: competitive high capacity anode materials for aqueous primary batteries.Electrochemical and Solid-State Letters, 2004, 7(7): A212-A215.
[10]	WANG Y, GUANG X Y, CAO Y L,et al. Mechanochemical synthesis and electrochemical characterization of VBx as high capacity anode materials for air batteries.Journal of Alloys and Compounds, 2010, 501(1): L12-L14.
[11]	LICHT S, WU H, YU X,et al. Renewable highest capacity VB2/ air energy storage.Chem. Commun.（Camb), 2008, 28(28): 3257-3259.
[12]	MORI R.A new structured aluminium-air secondary battery with a ceramic aluminium ion conductor.RSC Advances, 2013, 3(29): 11547-11551.
[13]	LICHT S, HETTIGE C, LAU J,et al. Nano-VB2 synthesis from elemental vanadium and boron: nano-VB2 Anode/air batteries.Electrochemical and Solid-State Letters, 2012, 15(1): A12-A14.
[14]	LEFLER M, STUART J, LICHT S,et al. Higher capacity, improved conductive matrix VB2/Air batteries.Journal of The Electrochemical Society, 2016, 163(5): A781-A784.
[15]	RHODES C, STUART J, LOPEZ R,et al. Evaluation of properties and performance of nanoscopic materials in vanadium diboride/air batteries.Journal of Power Sources, 2013, 239: 244-252.
[16]	LI P C, HU C C, LEE T C,et al. Synthesis and characterization of carbon black/manganese oxide air cathodes for zinc-air batteries.Journal of Power Sources, 2014, 269: 88-97.
[17]	MAYILVEL DINESH M, SAMINATHAN K, SELVAM M,et al. Water soluble graphene as electrolyte additive in magnesium-air battery system.Journal of Power Sources, 2015, 276: 32-38.

大容量VB₂-空气电池负极材料的制备与性能

Preparation and Discharge Performance of Porous VB₂ Anodes for High Capacity VB₂-air Battery

RichHTML

PDF (PC)

可视化

摘要/Abstract

引用本文

使用本文

图/表 6

参考文献 17

相关文章 15

编辑推荐

Metrics

本文评价

[1]	宿拿拿, 韩静茹, 郭印毫, 王晨宇, 石文华, 吴亮, 胡执一, 刘婧, 李昱, 苏宝连. 基于ZIF-8的三维网络硅碳复合材料锂离子电池性能研究[J]. 无机材料学报, 2022, 37(9): 1016-1022.
[2]	苏东良, 崔锦, 翟朋博, 郭向欣. 石榴石型Li_6.4La₃Zr_1.4Ta_0.6O₁₂对Si/C负极表面固体电解质中间相的调控机制研究[J]. 无机材料学报, 2022, 37(7): 802-808.
[3]	肖美霞, 李苗苗, 宋二红, 宋海洋, 李钊, 毕佳颖. 表面端基卤化Ti₃C₂ MXene应用于锂离子电池高容量电极材料的研究[J]. 无机材料学报, 2022, 37(6): 660-668.
[4]	王禹桐, 张非凡, 许乃才, 王春霞, 崔立山, 黄国勇. 水系锂离子电池负极材料LiTi₂(PO₄)₃的研究进展[J]. 无机材料学报, 2022, 37(5): 481-492.
[5]	王晶, 徐守冬, 卢中华, 赵壮壮, 陈良, 张鼎, 郭春丽. 钠离子电池中空结构CoSe₂/C负极材料的制备及储钠性能研究[J]. 无机材料学报, 2022, 37(12): 1344-1350.
[6]	李昆儒, 胡省辉, 张正富, 郭玉忠, 黄瑞安. 源于溪木贼的高性能锂离子电池三维多孔生物质硅/碳复合负极材料[J]. 无机材料学报, 2021, 36(9): 929-935.
[7]	郭猛, 张丰年, 苗洋, 刘宇峰, 郁军, 高峰. La(Co_0.2Cr_0.2Fe_0.2Mn_0.2Ni_0.2)O₃钙钛矿高熵陶瓷粉体的制备及其电学性能[J]. 无机材料学报, 2021, 36(4): 431-435.
[8]	李锐,王浩,付强,田子玉,王建旭,马小健,杨剑,钱逸泰. 构建亲锂铜基3D集流体实现金属锂的均匀沉积[J]. 无机材料学报, 2020, 35(8): 882-888.
[9]	湛菁,徐昌藩,龙怡宇,李启厚. 聚丙烯酰胺凝胶法制备Bi₂Mn₄O₁₀及其电化学性能[J]. 无机材料学报, 2020, 35(7): 827-833.
[10]	朱泽阳,魏济时,黄健航,董向阳,张鹏,熊焕明. 晶格空位ZnO纳米棒的制备及其在镍锌电池中的应用[J]. 无机材料学报, 2020, 35(4): 423-430.
[11]	郑时有, 董飞, 庞越鹏, 韩盼, 杨俊和. 纳米金属氧化物基锂离子电池负极材料研究进展[J]. 无机材料学报, 2020, 35(12): 1295-1306.
[12]	郭丝霖, 康帅, 陆文强. 一步法制备锗/MXene复合材料及其作为锂离子电池负极的研究[J]. 无机材料学报, 2020, 35(1): 105-111.
[13]	谭毅, 王凯. 高比能量锂离子电池硅基负极材料研究进展[J]. 无机材料学报, 2019, 34(4): 349-357.
[14]	冯晓晶, 王恭凯, 王晓然, 何珺, 王新, 彭会芬. Cr ³⁺掺杂LiSn₂(PO₄)₃负极材料的电化学性能研究[J]. 无机材料学报, 2019, 34(4): 358-364.
[15]	胡茜,刘洪波,夏笑虹,谷智强. 聚苯胺炭柱撑石墨烯复合材料的制备及其电化学性能的研究[J]. 无机材料学报, 2019, 34(2): 145-151.