新型多孔导电陶瓷负载银阴极在锌空气电池中的应用

doi:10.15541/jim20170462

无机材料学报 ›› 2018, Vol. 33 ›› Issue (8): 854-860.DOI: 10.15541/jim20170462 CSTR: 32189.14.10.15541/jim20170462

所属专题：离子电池材料

新型多孔导电陶瓷负载银阴极在锌空气电池中的应用

翁晓琳¹, 刘佩佩¹, 张亚鹏¹, 刘江¹, 刘美林^{1, 2}

1. 华南理工大学环境与能源学院, 新能源研究所, 广州市能源材料表面化学重点实验室, 广州510006;
2. 美国佐治亚理工学院材料科学与工程系, 亚特兰大GA 30332-0245, 美国

收稿日期:2017-09-28 修回日期:2017-11-18 出版日期:2018-08-28 网络出版日期:2018-07-17
作者简介:翁晓琳(1993-), 女, 硕士研究生. E-mail: wxl_rosaline@163.com
基金资助:
国家自然科学基金(21276097);广东省公益研究及能力建设专项基金(2014A010106008);广东省珠江人才计划引进创新创业团队项目(2014ZT05N200);国家自然科学基金委-广东省联合基金(U1601207);Special Funds of Guangdong Province Public Research and Ability Construction (2014A010106008);Guangdong Innovative, Entrepreneurial Research Team Program (2014ZT05N200);Joint Funds of National Science Foundation of China and Guangdong Province (U1601207)

A Novel Porous Electronic Conducting Ceramics Loaded with Silver Nano Particles as Cathode for Zinc-Air Batteries

WENG Xiao-Lin¹, LIU Pei-Pei¹, ZHANG Ya-Peng¹, LIU Jiang¹, LIU Mei-Lin^{1, 2}

1. Guangzhou Key Laboratory for Surface Chemistry of Energy Materials, New Energy Research Institute, School of Environment and Energy, South China University of Technology, Guangzhou 510006, China;
2. School of Materials Science and Engineering, Georgia Institute of Technology, Atlanta GA 30332-0245, USA

Received:2017-09-28 Revised:2017-11-18 Published:2018-08-28 Online:2018-07-17
About author:WENG Xiao-Lin. E-mail: wxl_rosaline@163.com
Supported by:
National Natural Science Foundation of China(21276097)

摘要/Abstract

摘要：

锌空气电池具有能量密度高、成本低及环保等优势, 其空气电极的优劣对电池的输出性能起到决定性的作用。本研究采用一种新型的多孔钙钛矿氧化物La_0.7Sr_0.3CoO_3-_δ(LSC)作为陶瓷基底, 负载银纳米颗粒作为催化剂, 研究其作为锌空电池空气电极的性能。β通过调整制备过程中造孔剂(淀粉)的含量, 优选出性能最佳的Ag-LSC空气电极(阴极), 与锌阳极组装成锌空气电池, 进行电化学性能测试。β结果表明, 当LSC基底的孔隙率为~32%且银含量30 mg/cm²时, 制备的多孔陶瓷负载银阴极组装的锌空气电池功率密度最高(141 mW/cm²)。β在Ag-LSC空气电极表面涂一层聚四氟乙烯(PTFE)疏水材料后, 锌空气电池的使用寿命得到显著延长。

关键词: 锌空气电池, 空气电极, 银纳米颗粒, 多孔钴酸锶镧基底

Abstract:

Zinc-air battery has great advantages such as high energy density, low cost and environmentally friendliness. Air electrode plays an important role in electrochemical performance of a zinc-air battery. In this paper, we report our study of a novel air electrode on which a porous perovskite ceramic La_0.7Sr_0.3CoO_3-_δ(LSC) with Ag nanoparticles directly grown. The porous LSC is used as substrate while Ag as catalyst. The porous structure of substrate attributes to the amount and dispersion of Ag nanoparticles which affect the electrochemical performance of air electrode. Therefore, the property of the Ag-LSC electrode is optimized by adjusting the mass content of pore-former (starch). Experimental results show that the Ag-LSC electrode, with a porosity of ~32% and a Ag load of ~30 mg/cm², exhibits the best performance in all tested samples, and a zinc-air battery assembled with such air electrode gives the maximum power density of 141 mW/cm. What’s more, in order to ensure the gas diffusion channels, the hydrophilicity and hydrophobicity of the cathode is modified with PTFE to prevent flooding. After all that, the life-time of the zinc-air battery, with optimization by coating a PTFE layer as hydrophobic agent on the surface of the selected Ag-LSC electrode, prolongs significantly.

Key words: zinc-air battery, air electrode, silver nanoparticle, porous La_0.7Sr_0.3CoO_3-δsubstrate;

中图分类号:

O647

翁晓琳, 刘佩佩, 张亚鹏, 刘江, 刘美林. 新型多孔导电陶瓷负载银阴极在锌空气电池中的应用[J]. 无机材料学报, 2018, 33(8): 854-860.

WENG Xiao-Lin, LIU Pei-Pei, ZHANG Ya-Peng, LIU Jiang, LIU Mei-Lin. A Novel Porous Electronic Conducting Ceramics Loaded with Silver Nano Particles as Cathode for Zinc-Air Batteries[J]. Journal of Inorganic Materials, 2018, 33(8): 854-860.

图/表 11

图1 锌空气电池的工作原理示意图(a)及实物装置图(b)

Fig. 1 Schematic diagram of mechanism (a) and device (b) of the zinc-air battery

图2 不同孔隙率的LSC钙钛矿基底的截面SEM照片

Fig. 2 Cross-sectional SEM images of the LSC substrate with different porosity

图3 LSC负载Ag前(a)后(b)的SEM照片

Fig. 3 SEM images of LSC (a) and Ag-LSC (b) (porosity 32%, loaded Ag 10 mg/cm2)

图4 Ag-LSC阴极的XRD图谱

Fig. 4 XRD patterns of Ag-LSC cathode (porosity 32%, loaded Ag 10 mg/cm2)

图5 不同孔隙率的阴极(银担载量均为10 mg/cm2)组装的锌空气电池输出性能图谱(a)及交流阻抗图(b)

Fig. 5 Output performances (a) and impedance spectra (b) of the zinc-air battery with cathode (loaded Ag 10 mg/cm2) of different porosity

图6 不同含银量的阴极(LSC基底孔隙率为32%)组装的锌空气电池输出性能

Fig. 6 Output performances of the zinc-air batteries with cathodes of different Ag contents (porosity 32%)

图7 不同电流密度下锌空气电池放电性能曲线图

Fig. 7 Discharge curve of the zinc-air battery discharged at different current densities (porosity 32%, loaded Ag 30 mg/cm2)

图8 添加PTFE阴极的SEM照片

Fig. 8 SEM image of the cathode with PTFE

图9 用添加与不添加PTFE的阴极组装的锌空气电池恒流放电曲线图

Fig. 9 Constant current discharge curves of the zinc-air battery composed of cathode with or without PTFE

图10 锌空气电池在电池放电后更换阳极锌粉的恒流放电曲线图

Fig. 10 Constant current discharge curves of the zinc-air battery of changing zinc anode after discharging

图11 锌空气电池阴极放电前后的XPS能谱图

Fig. 11 XPS spectra of the cathode of zinc-air battery before and after discharging(a) Sr3d; (b) La3d; (c) Co2p

参考文献 36

[1]	PEI P, WANG K, MA Z.Technologies for extending zinc-air battery’s cyclelife: a review.Applied Energy, 2014, 128: 315-324.
[2]	SAPKOTA P, KIM H.Zinc-air fuel cell, a potential candidate for alternative energy.Journal of Industrial and Engineering Chemistry, 2009, 15(4): 445-450.
[3]	LI Y, DAI H.Recent advances in zinc-air batteries.Chem. Soc. Rev., 2014, 43(15): 5257-5275.
[4]	FU J, CANO Z P, PARK M G,et al. Electrically rechargeable zinc-air batteries: progress, challenges, and perspectives.Advanced materials, 2017, 29(7): 1-34.
[5]	LEE J-S, TAI KIM S, CAO R,et al.Metal-air batteries with high energy density: Li-air versus Zn-air. Advanced Energy Materials, 2011, 1(1): 34-50.
[6]	RAHMAN M A, WANG X, WEN C.High energy density metal-air batteries: a review .Journal of the Electrochemical Society, 2013, 160(10): A1759-A1771.
[7]	WANG X, SEBASTIAN P J, SMIT M A,et al. Studies on the oxygen reduction catalyst for zinc-air battery electrode.Journal of Power Sources, 2003, 124(1): 278-284.
[8]	YANG C.Preparation and characterization of electrochemical properties of air cathode electrode.International Journal of Hydrogen Energy, 2004, 29(2): 135-143.
[9]	MA Z, PEI P, WANG K,et al. Degradation characteristics of air cathode in zinc air fuel cells.Journal of Power Sources, 2015, 274: 56-64.
[10]	NEBURCHILOV V, WANG H, MARTIN J J,et al. A review on air cathodes for zinc-air fuel cells. Journal of Power Sources, 2010, 195(5): 1271-1291.
[11]	WANG Z L, XU D, XU J J,et al. Oxygen electrocatalysts in metal-air batteries: from aqueous to nonaqueous electrolytes.Chem Soc Rev, 2014, 43(22): 7746-7786.
[12]	LEE D U, XU P, CANO Z P,et al. Recent progress and perspectives on bi-functional oxygen electrocatalysts for advanced rechargeable metal-air batteries.J. Mater. Chem. A, 2016, 4(19): 7107-7134.
[13]	FENG Y Y, ZHANG G R, MA J H,et al. Carbon-supported PtAg nanostructures as cathode catalysts for oxygen reduction reaction.Physical Chemistry Chemical Physics, 2011, 13(9): 3863-3872.
[14]	LOGLIO F, LASTRAIOLI E, BIANCHINI C,et al. Cobalt monolayer islands on Ag(111) for ORR catalysis.ChemSusChem, 2011, 4(8): 1112-1117.
[15]	XIN L, ZHANG Z, WANG Z,et al. Carbon supported Ag nanoparticles as high performance cathode catalyst for H2/O2 anion exchange membrane fuel cell.Frontiers in chemistry, 2013, 1(16): 1-5.
[16]	WANG Z, XIN L, ZHAO X,et al. Carbon supported Ag nanoparticles with different particle size as cathode catalysts for anion exchange membrane direct glycerol fuel cells.Renewable Energy, 2014, 62: 556-562.
[17]	PECH-PECH I E, GERVASIO D F, GOD NEZ-GARCIA A,et al. Nanoparticles of Ag with a Pt and Pd rich surface supported on carbon as a new catalyst for the oxygen electroreduction reaction (ORR) in acid electrolytes: Part 1. Journal of Power Sources, 2015, 276(2015): 365-373.
[18]	ESFANDIARI A, KAZEMEINI M, BASTANI D.Synthesis, characterization and performance determination of an Ag@Pt/C electrocatalyst for the ORR in a PEM fuel cell.International Journal of Hydrogen Energy, 2016, 41(45): 20720-20730.
[19]	WANG T, KAEMPGEN M, NOPPHAWAN P,et al. Silver nanoparticle-decorated carbon nanotubes as bifunctional gas-diffusion electrodes for zinc-air batteries.Journal of Power Sources, 2010, 195(13): 4350-4355.
[20]	CHENG F, CHEN J.Metal-air batteries: from oxygen reduction electrochemistry to cathode catalysts.Chem. Soc. Rev., 2012, 41(6): 2172-2192.
[21]	CAO R, LEE J S, LIU M,et al. Recent progress in non-precious catalysts for metal-air batteries.Advanced Energy Materials, 2012, 2(7): 816-829.
[22]	KRAYTSBERG A, EIN-ELI Y.The impact of nano-scaled materials on advanced metal-air battery systems.Nano Energy, 2013, 2(4): 468-480.
[23]	LIU P, LIU J, CHENG S,et al.A high-performance electrode for supercapacitors: silver nanoparticles grown on a porous perovskite-type material La0.7Sr 0.3CoO3-δ substrate Chemical Engineering Journal, 2017, 328: 1-10.
[24]	GWON O, YOO S, SHIN J,et al.Optimization of La1-xSrxCoO3-δ perovskite cathodes for intermediate temperature solid oxide fuel cells through the analysis of crystal structure and electrical properties International Journal of Hydrogen Energy, 2014, 39(35): 20806-20811.
[25]	WANG L, LUO X, BARBIERI D,et al. Controlling surface microstructure of calcium phosphate ceramic from random to custom-design.Ceramics International, 2014, 40(6): 7889-7897.
[26]	DRILLET J F, HOLZER F, KALLIS T,et al. Influence of CO2 on the stability of bifunctional oxygen electrodes for rechargeable zinc/air batteries and study of different CO2 filter materials.Physical Chemistry Chemical Physics, 2001, 3(3): 368-371.
[27]	WANG Q, LUO J, ZHONG Z,et al. CO2 capture by solid adsorbents and their applications: current status and new trends.Energy Environ. Sci., 2011, 4(1): 42-55.
[28]	HAN J J, LI N, ZHANG T Y.Ag/C nanoparticles as an cathode catalyst for a zinc-air battery with a flowing alkaline electrolyte.Journal of Power Sources, 2009, 193(2): 885-889.
[29]	HU J, LIU Q, SHI L,et al. Silver decorated LaMnO3 nanorod/graphene composite electrocatalysts as reversible metal-air battery electrodes.Applied Surface Science, 2017, 402: 61-69.
[30]	HE Q, YANG X, CHEN W,et al. Influence of phosphate anion adsorption on the kinetics of oxygen electroreduction on low index Pt(hkl) single crystals.Physical Chemistry Chemical Physics, 2010, 12(39): 12544-12555.
[31]	INABA M, ANDO M, HATANAKA A,et al. Controlled growth and shape formation of platinum nanoparticles and their electrochemical properties. Electrochimica Acta, 2006, 52(4): 1632-1638.
[32]	LIMA F H B, DE CASTRO J F R, TICIANELLI E A. Silver- cobalt bimetallic particles for oxygen reduction in alkaline media.Journal of Power Sources, 2006, 161(2): 806-812.
[33]	YU A, LEE C, LEE N S,et al. Highly efficient silver-cobalt composite nanotube electrocatalysts for favorable oxygen reduction reaction.ACS applied materials & interfaces, 2016, 8(48): 32833-32841.
[34]	WU X, CHEN F, ZHANG N,et al. Activity trends of binary silver alloy nanocatalysts for oxygen reduction reaction in alkaline media.Small, 2017, 13(15): 1-8.
[35]	CHO YB, MOON S, LEE C,et al. One-pot electrodeposition of cobalt flower-decorated silver nanotrees for oxygen reduction reaction.Applied Surface Science, 2017, 394: 267-274.
[36]	WANG P, YAO L, WANG M,et al. XPS and voltammetric studies on La1.xSrxCoO3-δ perovskite oxide electrodes. Journal of Alloys and Compounds, 2000, 311: 53-56.

新型多孔导电陶瓷负载银阴极在锌空气电池中的应用

A Novel Porous Electronic Conducting Ceramics Loaded with Silver Nano Particles as Cathode for Zinc-Air Batteries

RichHTML

PDF (PC)

可视化

摘要/Abstract

引用本文

使用本文

图/表 11

参考文献 36

相关文章 1

编辑推荐

Metrics

本文评价