不同碳导电剂对铁-空气电池性能的影响

doi:10.11949/0438-1157.20231212

摘要/Abstract

摘要：

金属-空气电池（MABs）具有成本低、环境友好、比功率和比能量高等优点，而其中的铁-空气电池（IAB）更具有资源丰富以及高比能量等特点，但IAB在充放电过程中存在的铁电极钝化、腐蚀、自放电、析氢反应以及体积变化等问题制约着其发展。考虑到在铁负极制备过程中通常使用乙炔黑作为导电与支撑活性物质的作用，为了考察其他碳材料对铁电极电化学性能的影响，分别利用乙炔黑、石墨粉和碳纳米管制备了不同的铁电极，并与Pt/C空气电极组装成相应的铁-空气电池，对这些电池进行了不同电流密度下的充放电研究并测试了放电极化曲线。结果表明，碳纳米管修饰铁负极的电池整体性能优异，表现出较高的循环稳定性、较高的充放电电压效率以及功率密度。

关键词: 电化学, 纳米材料, 再生能源, 铁-空气电池

Abstract:

Metal-air batteries (MABs) have the advantages of low cost, environmental friendliness, high specific power and specific energy, among which iron-air batteries (IAB) are more resource-rich and have high specific energy. Problems in IAB such as passivation, corrosion, self-discharge, hydrogen evolution reaction and volume change of iron electrodes restrict its development. Considering that acetylene black is commonly used as a conductive and supportive active material in the preparation of iron negative electrodes, to further investigate the impact of other carbon materials on the electrochemical performance of iron electrodes, we prepared different iron electrodes using acetylene black, graphite powder, and carbon nanotube. Corresponding iron-air batteries were assembled with the prepared iron electrodes and Pt/C air electrode. Charge/discharge curves at different current densities and discharge polarization curves were obtained on these batteries. The results indicate that the overall performance of the carbon nanotube modified iron negative electrode battery is excellent, exhibiting high cycle stability, high charge discharge voltage efficiency, and power density. This work provides reference value for the in-depth study of IAB by preparing stable and reliable iron electrodes.

Key words: electrochemistry, nanomaterials, renewable energy, iron-air batteries

中图分类号:

O 646.51

尹玉华, 方灿, 易清风, 李广. 不同碳导电剂对铁-空气电池性能的影响[J]. 化工学报, 2024, 75(2): 685-694.

Yuhua YIN, Can FANG, Qingfeng YI, Guang LI. Impact of different carbon conductive agents on performance of iron-air battery[J]. CIESC Journal, 2024, 75(2): 685-694.

图/表 11

图1 IE-ab、IE-gr和IE-cn电池在4 mol·L-1 NH4Cl+1 mol·L-1 KCl溶液和不同电流密度下的恒流循环充放电曲线

Fig.1 Cycling discharge/charge performance of IE-ab, IE-gr and IE-cn battery in 4 mol·L-1 NH4Cl+1 mol·L-1 KCl electrolyte at 0.2, 0.6 and 1.0 mA·cm-2

表1 IE-ab、IE-gr和IE-cn电池在0.2 mA·cm-2恒流下的循环充放电测试结果

Table 1 Cycling discharge/charge results of IE-ab， IE-gr and IE-cn battery at 0.2 mA·cm-2

Battery	Cycling number	Voltage gap of charge/ discharge at initial cycle/V	Voltage efficiency at initial cycle/%	Voltage gap of charge /discharge at last cycle/V	Voltage efficiency at last cycle/%
IE-ab	180	0.40	40.5	0.65	16.1
IE-gr	180	0.57	44.9	0.83	20.9
IE-cn	180	0.50	49.3	0.76	31.7

表2 IE-ab、IE-gr和IE-cn电池在1.0 mA·cm-2恒流下的循环充放电测试结果

Table 2 Cycling discharge/charge results of IE-ab， IE-gr and IE-cn battery at 1.0 mA·cm-2

Battery	Cycling number	Voltage gap of charge/ discharge at initial cycle/V	Voltage efficiency at initial cycle/%	Voltage gap of charge /discharge at last cycle/V	Voltage efficiency at last cycle/%
IE-ab	67	0.85	34.7	1.13	10.4
IE-gr	107	0.81	37.2	1.11	15.0
IE-cn	119	0.82	45.6	1.09	17.4

图2 4 mol·L-1 NH4Cl+1 mol·L-1 KCl溶液中，不同扫描速率下不同电极的循环伏安图以及在0.10 V (vs Ag/AgCl)下的阳极和阴极电流对扫速的影响

Fig.2 Cyclic voltammograms at different scan rates in 4 mol·L-1 NH4Cl+1 mol·L-1 KCl electrolyte, and the effect of the scan rate on the anodic and cathodic charging current taken from center of each CV at 0.10 V(vs Ag/AgCl)

图3 IE-ab、IE-gr和IE-cn电池在0.5 mol·L-1 K2SO4溶液中，不同电流密度下的恒流循环充放电曲线

Fig.3 Cycling discharge/charge performance of IE-ab, IE-gr and IE-cn battery in 0.5 mol·L-1 K2SO4 electrolyte at 0.2, 0.6 and 1.0 mA·cm-2

表3 IE-ab、IE-gr和IE-cn电池在0.6 mA·cm-2恒流下的循环充放电测试结果

Table 3 Cycling discharge/charge results of IE-ab， IE-gr and IE-cn battery at 0.6 mA·cm-2

Battery	Cycling number	Voltage gap of charge/ discharge at initial cycle/V	Voltage efficiency at initial cycle/%	Voltage gap of charge /discharge at last cycle/V	Voltage efficiency at last cycle/%
IE-ab	51	1.31	14.5	1.47	1.4
IE-gr	180	1.06	22.3	1.26	18.6
IE-cn	180	0.94	29.7	1.27	33.8

图4 在0.5 mol·L-1 K2SO4溶液和扫描速率10 mV·s-1时，IE-ab、IE-gr和IE-cn的循环伏安曲线

Fig.4 Cyclic voltammograms of IE-ab, IE-gr and IE-cn electrodes in 0.5 mol·L-1 K2SO4 at10 mV·s-1

图5 在不同电解质溶液中，以不同碳材料为导电剂制备的铁-空气电池的极化曲线和功率密度曲线

Fig.5 Polarization and power density curves of iron-air batteries with different iron electrodes in 4 mol·L-1 NH4Cl+1 mol·L-1 KCl and 0.5 mol·L-1 K2SO4 electrolyte

图6 在不同电解质溶液中，IE-cn电极在循环充放电10 h前后的交流阻抗谱

Fig.6 Electrochemical impedance spectra of IE-cn electrode before and after 10 h cycling charge/discharge in 4 mol·L-1 NH4Cl+1 mol·L-1 KCl and 0.5 mol·L-1 K2SO4 electrolyte

图7 IE-cn电极在不同电解质溶液中充电电流12 mA·cm-2、放电电流2 mA·cm-2时的充放电容量-电压曲线

Fig.7 Dependence of charge capacity at 12 mA·cm-2/discharge capacity at 2 mA·cm-2 upon voltage for IE-cn electrode in different electrolytes

图8 在4 mol·L-1 NH4Cl+1 mol·L-1 KCl溶液中，IE-cn电极在循环充放电10 h前后的 XRD谱图(a)以及SEM图[(b), (c)]

Fig.8 X- ray diffraction spectra (a) and SEM images [(b), (c)] of IE-cn electrode before and after 10 h cycling charge/discharge in 4 mol·L-1 NH4Cl+1 mol·L-1 KCl electrolyte

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