NaPO_3与SDBS缓蚀剂对AZ31镁合金空气电池在NaCl电解液中放电性能的影响
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摘要
研究了以铸态AZ31镁合金为阳极材料的镁空气电池在加入了0.5 g/L NaPO_3、0.5 g/L十二烷基苯磺酸钠(SDBS)、0.5 g/L NaPO_3+0.5 g/L SDBS作为缓蚀剂的3.5%(质量分数) NaCl电解液中的放电性能,测试了AZ31镁合金在不同缓蚀剂溶液中的自腐蚀速率、动电位极化曲线、EIS谱,并使用SEM观察了阳极材料在不同缓蚀剂溶液中的放电形貌。结果表明,加入缓蚀剂可以较好地抑制析氢腐蚀,提高阳极利用率,弱化阳极极化,提高放电电压。其中在NaPO_3+SDBS缓蚀剂溶液中,镁空气电池阳极腐蚀最弱,缓蚀效率可以达到85%,阳极利用率达到43.2%。
Magnesium is a promising anode material for air batteries because of its outstanding characteristics, such as abundance, light mass, and low cost. However, the corrosion susceptibility of Mg-alloy in aqueous solution limits the performance of air battery. In this work, the discharge behavior of air batteries consisted of as-cast AZ31 Mg-alloy as the anode material and 3.5%(mass fraction) NaCl aqueous solution as electrolyte was examined while adding different corrosion inhibitors such as 0.5 g/L sodium phosphate(NaPO3), 0.5 g/L sodium dodecylbenzenesulfonate(SDBS) and 0.5 g/L NaPO3+0.5 g/L SDBS respectively. In the meanwhile the free corrosion rate, potentiodynamic polarization curves and electrochemical impedance spectroscopy(EIS) of AZ31 Mg-alloy were measured and the surface morphology of the tested AZ31 Mg-alloy was characterized by means of scanning electron microscope(SEM). The results show that the addition of corrosion inhibitors is effective for inhibiting hydrogen evolution and the corrosion of anode material. Which can also weaken the anodic polarization and enhance the discharge voltage of the battery. Among others, in the air battery with the corrosion inhibitors of 0.5 g/L NaPO3+0.5 g/L SDBS, the AZ31 Mg-alloy has the minimum corrosion rate of which the inhibition efficiency and anode utilization rate can reach up to 85% and 43.2% respectively.
Magnesium is a promising anode material for air batteries because of its outstanding characteristics, such as abundance, light mass, and low cost. However, the corrosion susceptibility of Mg-alloy in aqueous solution limits the performance of air battery. In this work, the discharge behavior of air batteries consisted of as-cast AZ31 Mg-alloy as the anode material and 3.5%(mass fraction) NaCl aqueous solution as electrolyte was examined while adding different corrosion inhibitors such as 0.5 g/L sodium phosphate(NaPO3), 0.5 g/L sodium dodecylbenzenesulfonate(SDBS) and 0.5 g/L NaPO3+0.5 g/L SDBS respectively. In the meanwhile the free corrosion rate, potentiodynamic polarization curves and electrochemical impedance spectroscopy(EIS) of AZ31 Mg-alloy were measured and the surface morphology of the tested AZ31 Mg-alloy was characterized by means of scanning electron microscope(SEM). The results show that the addition of corrosion inhibitors is effective for inhibiting hydrogen evolution and the corrosion of anode material. Which can also weaken the anodic polarization and enhance the discharge voltage of the battery. Among others, in the air battery with the corrosion inhibitors of 0.5 g/L NaPO3+0.5 g/L SDBS, the AZ31 Mg-alloy has the minimum corrosion rate of which the inhibition efficiency and anode utilization rate can reach up to 85% and 43.2% respectively.
引文
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[13] Lv M X. Power Source Technology[M]. Tianjin:Tianjin Universi‐ty Press, 1996(吕鸣详.电源技术[M].天津:天津大学出版社, 1996)
[14] Cao D X, Wu L, Wang G L, et al. Electrochemical oxidation be‐havior of Mg-Li-Al-Ce-Zn and Mg-Li-Al-Ce-Zn-Mn in sodium chloride solution[J]. J. Power Sources, 2008, 183:799
[15] Yuasa M, Huang X S, Suzuki K, et al. Discharge properties of MgAl-Mn-Ca and Mg-Al-Mn alloys as anode materials for primary magnesium-air batteries[J]. J. Power Sources, 2015, 297:449
[16] Xiong H Q, Zhu H L, Luo J, et al. Effects of heat treatment on the discharge behavior of Mg-6wt.%Al-1wt.%Sn alloy as anode for magnesium-air batteries[J]. J. Mater. Eng. Perform., 2017, 26:2901
[2] Cheng F Y, Chen J. Metal-air batteries:From oxygen reduction elec‐trochemistry to cathode catalysts[J]. Chem. Soc. Rev., 2012, 41:2172
[3] Yang W Q, Yang S H, Sun G Q, et al. Development and application of magnesium fuel cell[J]. Chin. J. Power Sources, 2005, 29:182(杨维谦,杨少华,孙公权等.镁燃料电池的发展及应用[J].电源技术, 2005, 29:182)
[4] Ma Y B, Li N, Li D Y, et al. Performance of Mg-14Li-1Al-0.1Ce as anode for Mg-air battery[J]. J. Power Sources, 2011, 196:2346
[5] Dinesh M M, Saminathan K, Selvam M, et al. Water soluble gra‐phene as electrolyte additive in magnesium-air battery system[J]. J.Power Sources, 2015, 276:32
[6] Zhang Y. Optimization for the electrode materials and the electro‐lytes of the magnesium air battery[D]. Shanghai:Shanghai Jiao‐tong University, 2014(张赟.镁空气电池电极材料及电解液的优化[D].上海:上海交通大学, 2014)
[7] Li X H, Deng S D, Mu G N, et al. Inhibition effect of nonionic sur‐factant on the corrosion of cold rolled steel in hydrochloric acid[J].Corros. Sci., 2008, 50:420
[8] Li L J, Yao Z M, Lei J L, et al. Adsorption and corrosion inhibition behavior of sodium dodecylbenzenesulfonate on AZ31 magnesium alloy[J]. Acta Phys.-Chim. Sin., 2009, 25:1332(李凌杰,姚志明,雷惊雷等.十二烷基苯磺酸钠在AZ31镁合金表面的吸附及其缓蚀作用[J].物理化学学报, 2009, 25:1332)
[9] Si Y J, Xiong Z P, Chen C G, et al. Inhibiting ability of sodium do‐decyl benzene sulfonate to AZ31 magnesium alloy[J]. Rare Met.Mater. Eng., 2007, 36:2244(司玉军,熊中平,陈昌国等.十二烷基苯磺酸钠对AZ31镁合金缓蚀作用研究[J].稀有金属材料与工程, 2007, 36:2244)
[10] Deng J F. The Influence of magnesium anodewith different pro‐cessing conditionsand inhibitor on magnesium air battery[D].Chongqing:Chongqing University, 2013(邓金凤.镁负极加工状态与缓蚀剂对镁空气电池的影响[D].重庆:重庆大学, 2013)
[11] Cao C N, Zhang J Q. An Introduction to Electrochemical Imped‐ance Spectroscopy[M]. Beijing:Science Press, 2002(曹楚南,张鉴清.电化学阻抗谱导论[M].北京:科学出版社,2002)
[12] Zhou N, Hou L F, Wei Y H, et al. Inhibition effect of sodium phos‐phate on the corrosion of AZ31 magnesium alloy in 3.5 wt%NaCl solution[J]. Rare Met. Mater. Eng., 2015, 44:2260(周娜,侯利锋,卫英慧等.磷酸钠在NaCl溶液中对AZ31镁合金的缓蚀作用[J].稀有金属材料与工程, 2015, 44:2260)
[13] Lv M X. Power Source Technology[M]. Tianjin:Tianjin Universi‐ty Press, 1996(吕鸣详.电源技术[M].天津:天津大学出版社, 1996)
[14] Cao D X, Wu L, Wang G L, et al. Electrochemical oxidation be‐havior of Mg-Li-Al-Ce-Zn and Mg-Li-Al-Ce-Zn-Mn in sodium chloride solution[J]. J. Power Sources, 2008, 183:799
[15] Yuasa M, Huang X S, Suzuki K, et al. Discharge properties of MgAl-Mn-Ca and Mg-Al-Mn alloys as anode materials for primary magnesium-air batteries[J]. J. Power Sources, 2015, 297:449
[16] Xiong H Q, Zhu H L, Luo J, et al. Effects of heat treatment on the discharge behavior of Mg-6wt.%Al-1wt.%Sn alloy as anode for magnesium-air batteries[J]. J. Mater. Eng. Perform., 2017, 26:2901