铝-空气电池阳极材料及其电解液的研究进展
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摘要
金属-空气电池自进入人们的视野以来,由于其高能量密度和容量、平稳的放电特性、对负载和温度的依赖性低和较低的制造成本等特点,受到越来越多的关注。其中,锂-空气电池因具有极大的应用潜力而引起了学者们极大的研究兴趣;然而,锂-空气电池对周围环境十分敏感,容易造成爆炸,存在安全隐患;此外,锂离子电池的大规模生产和应用造成了原材料锂价格的大幅上涨。为了实现电池的商业化应用,选用来源广泛、经济实惠的电极材料成为必不可少的条件。铝是地壳中含量最多的金属元素,具有矿藏丰富、质量轻、无污染、安全、价格低廉和回收利用率高等优点,是一种潜在的储能材料。铝的理论质量比容量为2 980 mAh·g~(-1),仅次于锂(3 860 mAh·g~(-1)),其体积比容量(8.04 Ah·cm-3)约是锂的四倍(2.05 Ah·cm-3),被认为是金属-空气电池最有吸引力的候选阳极材料,也是化石燃料最有吸引力的替代者之一。然而,铝在空气和水溶液中表面上自发形成的钝化膜会显著降低铝阳极材料的活性;在碱性溶液中,铝-空气电池存在的主要问题是铝阳极材料自腐蚀导致氢析出速率较高,库伦效率降低和含水电解液的流动性可能导致的多孔空气阴极中毛细管的渗透及泄漏。因此,近年来,学者们不断开展深入研究,探索出以下几种改善铝阳极的方法:通过向铝中添加合金元素Ga、In、Sn、Zn、Mg、Bi、Mn等来改变铝阳极材料的活性和减少析氢反应;对电解液添加剂进行研究,发现部分植物提取液作为电解液添加剂可以保持铝阳极活性,降低析氢腐蚀;开发离子液体、固态和凝胶电解液,一方面可以减小铝阳极自腐蚀,提高阳极利用率,另一方面可减小铝-空气电池体积,增加电池的灵活性。目前研究获得性能较好的碱性铝-空气电池的阳极材料有Al-Ga/In-Mg系列、Al-Ga/In-Mg-Sn系列、Al-Ga-In-Bi-Pb系列等合金,其中部分铝阳极合金已经实现了实际应用。近几年研究工作获得了羽扇豆提取物、茄属植物叶的提取物等绿色电解液添加剂,其可以保持铝阳极的电化学活性,降低腐蚀率。此外,研究发现,室温下低聚氟化氢离子液体作为电解液可以活化铝阳极,降低其腐蚀速率,一些便携式铝-空气电池采用固态或凝胶电解液已经在护理医疗设备、商用LED手表方面应用。本文主要从铝阳极材料、电解质和电解质添加剂三方面论述了其对铝-空气电池性能的影响,并简单阐述了铝-空气电池放电的基本原理、面临的挑战和最新研究进展及应用。首先,综述了铝与合金元素的合金化,以此减少铝的自腐蚀,提高电池性能;并介绍了通过一定的加工工艺来改善铝阳极电化学性能的方法。其次,探讨了水溶剂电解质和非水溶剂电解质在铝-空气电池中的应用。同时,也研究了电解质添加剂对铝-空气电池的电化学性能的影响。最后,进一步明确了空气电池未来的研究和发展方向。
Currently,metal-air batteries have attracted increasing attention due to their high energy density and capacity,stable discharge characteristics,low dependence on load and temperature,and low manufacturing costs. Among them,lithium-air batteries have been extensively investigated by virtue of their widespread application potential. However,lithium-air batteries are extremely sensitive to the surrounding environment,and are prone to cause explosion hazards that threaten personal safety. Furthermore,the mass production and application have led to a sharp rise in the price of lithium resources. For the sake of realizing commercial applications of batteries,selecting rich resources and low cost of electrode materials are extremely vital. Aluminum is the most abundant metal element in the earth's crust with a series of superior merits such as wide source,light quality,no pollution,safety,low price and high recovery efficiency,which is considered to be a potential energy storage material. Utilizing the aluminum as electrodes,it shows unique performance,for instance,heoretical mass specific capacity of aluminum is 2 980 mA h·g~(-1),second only to lithium( 3 860 mA h·g~(-1)),its volumetric specific capacity( 8.04 Ah·cm-3) is four times higher than that of lithium( 2.05 Ah·cm-3),making it an ideal candidate anode material for metal-air batteries and one of the most attractive alternatives to fossil fuels.However,the passivation film formed by aluminum on the surface of air and aqueous solution significantly reduced the activity of aluminum anode material. In alkaline solution,the primal problem of aluminum-air battery is the high hydrogen precipitation rate,low Coulomb efficiency caused by the self-corrosion of the aluminum anode material,and capillary permeation and leakage in porous air cathode on account of the fluidity of the aqueous electrolyte. Hence,researchers have devoted great effort to ameliorate the activity of aluminum anode materials from the following aspects. Alloying elements like Ga,In,Sn,Zn,Mg,Bi and Mn have been introduced to change the activity of aluminium anode material and reduce hydrogen evolution reaction. Research on electrolyte additives have been carried out,and it is found that some plant extracts served as electrolyte additives are able to maintain the aluminum anode activity and reduce hydrogen evolution corrosion. Ionic liquid electrolytes,solid and gel electrolytes have been developed,which can reduce the aluminum anode corrosion and the volume of aluminum-air batteries,and increase the flexibility of battery.Currently,the anode materials for alkaline aluminum-air batteries exhibiting superior properties are Al-Ga/In-Mg series,Al-Ga/In-Mg-Sn series,and Al-Ga-In-Bi-Pb series alloys. Some of the aluminum anode alloys have already been adopted to daily life. In addition,green electrolyte additives such as extracts of lupin and extracts of nightshade leaves that can maintain the electrochemical activity of aluminum anodes and reduce the corrosion rate have been obtained in recent years. Moreover,the investigators indicated that oligo-hydrogen fluoride ionic liquids at room temperature are capable of activating aluminum anodes and reducing theirs corrosion rate,certain portable aluminum-air batteries with solid or gel electrolytes have been already utilized in care medical equipment and commercial LED watch.This paper chiefly discussed the effects of aluminum anode materials,electrolytes and electrolyte additives on the performance of aluminum-airbatteries,and briefly expounded the basic principles,current challenges and recent developments and applications of aluminum-air batteries.Firstly,summarized the alloying of aluminum and alloying elements which can reduce the self-corrosion of aluminum and ameliorate the battery performance. Then,recommended several methods for enhancing the electrochemical performance of aluminum anodes by certain processing techniques. Besides,the writer probed the circumstances on applying water-solvent electrolytes and non-aqueous solvent electrolytes in aluminum-air batteries,and the effect of electrolyte additives on electrochemical performance of aluminum-air batteries. Finally,the future research and deve-lopment direction of air batteries was further clarified.
Currently,metal-air batteries have attracted increasing attention due to their high energy density and capacity,stable discharge characteristics,low dependence on load and temperature,and low manufacturing costs. Among them,lithium-air batteries have been extensively investigated by virtue of their widespread application potential. However,lithium-air batteries are extremely sensitive to the surrounding environment,and are prone to cause explosion hazards that threaten personal safety. Furthermore,the mass production and application have led to a sharp rise in the price of lithium resources. For the sake of realizing commercial applications of batteries,selecting rich resources and low cost of electrode materials are extremely vital. Aluminum is the most abundant metal element in the earth's crust with a series of superior merits such as wide source,light quality,no pollution,safety,low price and high recovery efficiency,which is considered to be a potential energy storage material. Utilizing the aluminum as electrodes,it shows unique performance,for instance,heoretical mass specific capacity of aluminum is 2 980 mA h·g~(-1),second only to lithium( 3 860 mA h·g~(-1)),its volumetric specific capacity( 8.04 Ah·cm-3) is four times higher than that of lithium( 2.05 Ah·cm-3),making it an ideal candidate anode material for metal-air batteries and one of the most attractive alternatives to fossil fuels.However,the passivation film formed by aluminum on the surface of air and aqueous solution significantly reduced the activity of aluminum anode material. In alkaline solution,the primal problem of aluminum-air battery is the high hydrogen precipitation rate,low Coulomb efficiency caused by the self-corrosion of the aluminum anode material,and capillary permeation and leakage in porous air cathode on account of the fluidity of the aqueous electrolyte. Hence,researchers have devoted great effort to ameliorate the activity of aluminum anode materials from the following aspects. Alloying elements like Ga,In,Sn,Zn,Mg,Bi and Mn have been introduced to change the activity of aluminium anode material and reduce hydrogen evolution reaction. Research on electrolyte additives have been carried out,and it is found that some plant extracts served as electrolyte additives are able to maintain the aluminum anode activity and reduce hydrogen evolution corrosion. Ionic liquid electrolytes,solid and gel electrolytes have been developed,which can reduce the aluminum anode corrosion and the volume of aluminum-air batteries,and increase the flexibility of battery.Currently,the anode materials for alkaline aluminum-air batteries exhibiting superior properties are Al-Ga/In-Mg series,Al-Ga/In-Mg-Sn series,and Al-Ga-In-Bi-Pb series alloys. Some of the aluminum anode alloys have already been adopted to daily life. In addition,green electrolyte additives such as extracts of lupin and extracts of nightshade leaves that can maintain the electrochemical activity of aluminum anodes and reduce the corrosion rate have been obtained in recent years. Moreover,the investigators indicated that oligo-hydrogen fluoride ionic liquids at room temperature are capable of activating aluminum anodes and reducing theirs corrosion rate,certain portable aluminum-air batteries with solid or gel electrolytes have been already utilized in care medical equipment and commercial LED watch.This paper chiefly discussed the effects of aluminum anode materials,electrolytes and electrolyte additives on the performance of aluminum-airbatteries,and briefly expounded the basic principles,current challenges and recent developments and applications of aluminum-air batteries.Firstly,summarized the alloying of aluminum and alloying elements which can reduce the self-corrosion of aluminum and ameliorate the battery performance. Then,recommended several methods for enhancing the electrochemical performance of aluminum anodes by certain processing techniques. Besides,the writer probed the circumstances on applying water-solvent electrolytes and non-aqueous solvent electrolytes in aluminum-air batteries,and the effect of electrolyte additives on electrochemical performance of aluminum-air batteries. Finally,the future research and deve-lopment direction of air batteries was further clarified.
引文
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32 Liang M G,Wen J B,He J G,et al.Transactions of Materials and Heat Treatment,2015,36(6),41(in Chinese).梁明岗,文九巴,贺俊光,等.材料热处理学报,2015,36(6),41.
33 Shilyaeva Y,Gavrilov S,Matyna L.Journal of Thermal Analysis&Calorimetry,2014,118(2),937.
34 Abedin S Z E,Endres F.Journal of Applied Electrochemistry,2004,34(10),1071.
35 Yan X J,Fu Y,Lang X Z.Nonferrous Metals Engineering,2006,58(1),42(in Chinese).翟秀静,符岩,郎晓珍.有色金属工程,2006,58(1),42.
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37 Shang Y J.Hot Working Technology,2017(12),68(in Chinese).尚用甲.热加工工艺,2017(12),68.
38 Li Y J,Zhang W Z,Marthinsen K.Acta Materialia,2012,60(17),5963.
39 Choi S,Lee D,Kim G,et al.Advanced Functional Materials,2017,27(35),1702244.
40 Srinivas M,Adapaka S K,Neelakantan L.Journal of Alloys and Compounds,2016,683,647.
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44 Fan L,Lu H.Journal of Power Sources,2015,284,409.
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