复合电解液中AZ31B镁合金的放电特性及电压滞后
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摘要
通过计时电位法和电化学阻抗谱技术研究Mg(NO_3)_2+Mg(ClO_4)_2复合电解液中AZ31B镁合金电极的放电性能和电压滞后,并初步探讨了镁合金电极表面腐蚀膜的结构变化。结果表明:AZ31B合金在Mg(NO_3)_2:Mg(ClO_4)_2溶液体积比为72∶28和74∶26时恒流放电曲线平稳,在2.5和6 m A·cm~(-2)放电时稳定电位均可达到约-1.24 V,电压滞后时间为5~8 s;放电后表面膜的化学基团与放电前相同,放电破坏了镁合金电极表面腐蚀膜,造成连续串珠状点蚀坑,其膜电阻消失,电荷转移电阻减小至375Ω·cm~2。
In neutral and acidic solution, Mg reacts with water and release hydrogen, which reduces the utilization rate of electrode and brings difficulties to the assembly of the battery. In the alkaline solution, the Mg-surface would form a dense protective film, which make the electrode passivation and prevents discharging. In order to develop proper Mg-alloy suitable for battery electrolytes, the discharge properties and voltage delay of AZ31B Mg-alloy in compound electrolytes with different volume ratio of Mg(NO_3)_2 to Mg(ClO_4)_2 were studied by means of chronopotentiometry and electrochemical impedance spectroscopy and the corrosion products-films formed on the surface of AZ31B Mg-alloy were examined by means of SEM and infra-red spectrometer. Results show that in solutions with volume ratios of Mg(NO_3)_2 to Mg(ClO_4)_2 are 72:28 and 74:26 respectively, the discharge curves of AZ31B Mg-alloy are smooth and steady with stable potentials about-1.24 V(2.5 and 6 m A·cm~(-2)) and the delay time 5~8 s. Chemical groups of the corrosion products-film after discharge is the same as before. However, the surface film of corrosion products has been destroyed by discharge process, resulting in continuous beads-like corrosion pits, therewith the film resistance would disappear and the charge transfer resistance decreases to 375 Ω·cm~2.
In neutral and acidic solution, Mg reacts with water and release hydrogen, which reduces the utilization rate of electrode and brings difficulties to the assembly of the battery. In the alkaline solution, the Mg-surface would form a dense protective film, which make the electrode passivation and prevents discharging. In order to develop proper Mg-alloy suitable for battery electrolytes, the discharge properties and voltage delay of AZ31B Mg-alloy in compound electrolytes with different volume ratio of Mg(NO_3)_2 to Mg(ClO_4)_2 were studied by means of chronopotentiometry and electrochemical impedance spectroscopy and the corrosion products-films formed on the surface of AZ31B Mg-alloy were examined by means of SEM and infra-red spectrometer. Results show that in solutions with volume ratios of Mg(NO_3)_2 to Mg(ClO_4)_2 are 72:28 and 74:26 respectively, the discharge curves of AZ31B Mg-alloy are smooth and steady with stable potentials about-1.24 V(2.5 and 6 m A·cm~(-2)) and the delay time 5~8 s. Chemical groups of the corrosion products-film after discharge is the same as before. However, the surface film of corrosion products has been destroyed by discharge process, resulting in continuous beads-like corrosion pits, therewith the film resistance would disappear and the charge transfer resistance decreases to 375 Ω·cm~2.
引文
[1]Mu W Y,Li Z X,Du J H,et al.Development and application of magnesium batteries[J].Mater.Rev.,2011,25(13):35(慕伟意,李争显,杜继红等.镁电池的发展及应用[J].材料导报,2011,25(13):35)
[2]Yao Y F,Chen C G,Liu Y P,et al.Research progress of magnesium battery[J].Mater.Rev.,2009,23(19):119(尧玉芬,陈昌国,刘渝萍等.镁电池的研究进展[J].材料导报,2009,23(19):119)
[3]Yang Q L,Chen L,Xu J,et al.Study of the corrosion and surface film growth on AZ63 magnesium alloy in Mg SO4solution[J].J.Electrochem.Soc.,2017,164(6):C324
[4]Yang Q L,Xu J,Chen L,et al.The effects of Na HCO3on the voltage delay of Mg cell with AZ31B magnesium alloy in Mg(Cl O4)2electrolytic solution[J].J.Electrochem.Soc.,2017,164(4):A630
[5]Xu J,Yang Q L,Javed M S,et al.The effects of Na F concentration on electrochemical and corrosion behavior of AZ31B magnesium alloy in a composite electrolyte[J].RSC Advances.,2017,7(10):5880
[6]Sivashanmugam A,Kumar T P,Renganathan N G,et al.Performance of a magnesium-lithium alloy as an anode for magnesium batteries[J].J.Appl.Electrochem.,2004,34(11):1135
[7]Gao C Y,Lu Y H,Xu H B.Electrochemical properties of Mg-GaHg alloys applied in dissolved-oxygen seawater battery[J].Period.Ocean Univ.China,2015,45(10):69(高春燕,芦永红,徐海波.海水电池用Mg-Ga-Hg合金的电化学性能[J].中国海洋大学学报,2015,45(10):69)
[8]Si Y J,Xiong Z P,Chen C G,et al.Inhibiting ability of sodium dodecyl benzene sulfonate to AZ31 magnesium alloy[J].Rare Met.Mater.Eng.,2007,36(12):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(12):2244)
[9]Chen C G,Si Y J,Yu D M,et al.Electrochemical behavior of AZ31magnesium alloy in Mg SO4solution[J].Chin.J.Nonferrous Met.,2006,16(5):781(陈昌国,司玉军,余丹梅等.AZ31镁合金在Mg SO4溶液中的电化学行为[J].中国有色金属学报,2006,16(5):781)
[10]Shi Y G,Zhang Y,Hu S F,et al.Electrochemical behavior of AZ31 alloy as anode material for magnesium battery[J].Corros.Prot.,2012,33(12):1051(史永刚,张娅,胡少峰等.AZ31作为镁电池负极材料的电化学性能[J].腐蚀与防护,2012,33(12):1051)
[11]Xiong Y Y,Zhang Y,Hu S F,et al.Effects of additions of La(CH3COO)3and Na F on electrochemical behavior of AZ31 alloys in Mg(Cl O4)2solution[J].J.Chin.Soc.Corros.Prot.,2013,33(3):241(熊媛媛,张娅,胡少峰等.添加剂La(CH3COO)3和Na F对AZ31在Mg(Cl O4)2溶液中电化学性能的影响[J].中国腐蚀与防护学报,2013,33(3):241)
[12]Kumar B V R,Sathyanarayana S.The delayed action of magnesium anodes in primary batteries:Part I.Experimental studies[J].J.Power Sources,1983,10(3):219
[13]Chen L,Chen C G,Wang N N,et al.Electrochemical and structural characterization of AZ63 alloy surface film in Mg SO4solution[J].J.Appl.Electrochem.,2014,44(7):773
[14]Ma Z Q,Pang X,Zuo L,et al.Mechanism of activation of anode of Mg alloy applied in seawater battery[J].Surf.Technol.,2008,37(1):5(马正青,庞旭,左列等.镁海水电池阳极活化机理研究[J].表面技术,2008,37(1):5)
[15]Deng L,Chen L,Yang Q L,et al.The Influence of pulse current on the voltage delay of AZ21 magnesium electrodealloy[J].Chin.J.Eng.,2015,37(10):1358(邓玲,陈琳,杨巧玲等.脉冲电流对AZ21镁电极电压滞后的影响[J].工程科学学报,2015,37(10):1358)
[2]Yao Y F,Chen C G,Liu Y P,et al.Research progress of magnesium battery[J].Mater.Rev.,2009,23(19):119(尧玉芬,陈昌国,刘渝萍等.镁电池的研究进展[J].材料导报,2009,23(19):119)
[3]Yang Q L,Chen L,Xu J,et al.Study of the corrosion and surface film growth on AZ63 magnesium alloy in Mg SO4solution[J].J.Electrochem.Soc.,2017,164(6):C324
[4]Yang Q L,Xu J,Chen L,et al.The effects of Na HCO3on the voltage delay of Mg cell with AZ31B magnesium alloy in Mg(Cl O4)2electrolytic solution[J].J.Electrochem.Soc.,2017,164(4):A630
[5]Xu J,Yang Q L,Javed M S,et al.The effects of Na F concentration on electrochemical and corrosion behavior of AZ31B magnesium alloy in a composite electrolyte[J].RSC Advances.,2017,7(10):5880
[6]Sivashanmugam A,Kumar T P,Renganathan N G,et al.Performance of a magnesium-lithium alloy as an anode for magnesium batteries[J].J.Appl.Electrochem.,2004,34(11):1135
[7]Gao C Y,Lu Y H,Xu H B.Electrochemical properties of Mg-GaHg alloys applied in dissolved-oxygen seawater battery[J].Period.Ocean Univ.China,2015,45(10):69(高春燕,芦永红,徐海波.海水电池用Mg-Ga-Hg合金的电化学性能[J].中国海洋大学学报,2015,45(10):69)
[8]Si Y J,Xiong Z P,Chen C G,et al.Inhibiting ability of sodium dodecyl benzene sulfonate to AZ31 magnesium alloy[J].Rare Met.Mater.Eng.,2007,36(12):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(12):2244)
[9]Chen C G,Si Y J,Yu D M,et al.Electrochemical behavior of AZ31magnesium alloy in Mg SO4solution[J].Chin.J.Nonferrous Met.,2006,16(5):781(陈昌国,司玉军,余丹梅等.AZ31镁合金在Mg SO4溶液中的电化学行为[J].中国有色金属学报,2006,16(5):781)
[10]Shi Y G,Zhang Y,Hu S F,et al.Electrochemical behavior of AZ31 alloy as anode material for magnesium battery[J].Corros.Prot.,2012,33(12):1051(史永刚,张娅,胡少峰等.AZ31作为镁电池负极材料的电化学性能[J].腐蚀与防护,2012,33(12):1051)
[11]Xiong Y Y,Zhang Y,Hu S F,et al.Effects of additions of La(CH3COO)3and Na F on electrochemical behavior of AZ31 alloys in Mg(Cl O4)2solution[J].J.Chin.Soc.Corros.Prot.,2013,33(3):241(熊媛媛,张娅,胡少峰等.添加剂La(CH3COO)3和Na F对AZ31在Mg(Cl O4)2溶液中电化学性能的影响[J].中国腐蚀与防护学报,2013,33(3):241)
[12]Kumar B V R,Sathyanarayana S.The delayed action of magnesium anodes in primary batteries:Part I.Experimental studies[J].J.Power Sources,1983,10(3):219
[13]Chen L,Chen C G,Wang N N,et al.Electrochemical and structural characterization of AZ63 alloy surface film in Mg SO4solution[J].J.Appl.Electrochem.,2014,44(7):773
[14]Ma Z Q,Pang X,Zuo L,et al.Mechanism of activation of anode of Mg alloy applied in seawater battery[J].Surf.Technol.,2008,37(1):5(马正青,庞旭,左列等.镁海水电池阳极活化机理研究[J].表面技术,2008,37(1):5)
[15]Deng L,Chen L,Yang Q L,et al.The Influence of pulse current on the voltage delay of AZ21 magnesium electrodealloy[J].Chin.J.Eng.,2015,37(10):1358(邓玲,陈琳,杨巧玲等.脉冲电流对AZ21镁电极电压滞后的影响[J].工程科学学报,2015,37(10):1358)