碱性铝-空电池AA5052阳极缓蚀剂的作用性能研究

发布时间：2018-02-27 10:21

本文关键词： 铝空电池铝阳极析氢碱性溶液缓蚀剂　出处：《上海电力学院》2017年硕士论文　论文类型：学位论文

【摘要】：铝-空电池是一种新型绿色能源,具有无污染、比容量大、放电稳定等优点。其主要是由铝或铝合金为阳极,空气中的氧为阴极以及中性或碱性电解液三部分组成。在中性电解液中,铝的表面会形成致密的氧化膜,阻碍了铝阳极的活性溶解,使得电流密度变小;在最常用的Na OH溶液中,空气阴极和铝阳极的极化都很小,电池的能量密度高且放电稳定,但铝阳极会发生严重的析氢自腐蚀,导致铝阳极利用率和库伦效率降低,这也是将铝-空电池应用在商业上的主要障碍。目前主要有两种方法可以抑制铝在碱性溶液中的腐蚀:第一,在纯铝中添加一些析氢过电位较高的合金元素;第二,在电解液中添加缓蚀剂。本文通过析氢法、电化学测试、量子化学计算、表面形貌分析等方法研究了山梨酸和氧化锌复配、顺丁烯二酸和反丁烯二酸以及L-天冬氨酸和L-苹果酸对碱性溶液中AA5052铝合金的缓蚀性能。主要得到以下结论:(1)考察了碱性溶液中山梨酸和氧化锌复配增效对AA5052铝合金的缓蚀作用。山梨酸和氧化锌的复配有效的抑制了AA5052铝合金在4 mol/L Na OH溶液中的腐蚀。当添加复配比为30.0 m M山梨酸+2.0 m M氧化锌时,缓蚀效率达到80.4%。由扫描电镜和红外可知,Zn O反应生成Zn单质,在铝表面沉积形成Zn膜,山梨酸在Zn膜及其缺陷处吸附,形成复合膜保护铝合金,既抑制了阴极析氢反应,又抑制了阳极铝溶解反应,降低了铝的自腐蚀速率。恒电流实验表明,AA5052铝合金电极在含有30.0 m M山梨酸+2.0 m M氧化锌复配缓蚀剂的4 mol/L Na OH溶液中放电性能良好且稳定。(2)考察了顺反丁烯二酸对碱性乙二醇溶液中AA5052铝合金的缓蚀作用。在4mol/L氢氧化钠-乙二醇水溶液中添加不饱和丁烯二羧酸(顺丁烯二酸和反丁烯二酸)对AA5052铝合金有明显的缓蚀效果。缓蚀效率的大小为:顺丁烯二酸反丁烯二酸。顺丁烯二酸的能更好的抑制AA5052铝合金的自腐蚀,其最大的缓蚀效率为84.3%。电化学实验表明,AA5052铝合金在加有顺丁烯二酸的4 mol/L氢氧化钠-乙二醇水溶液中具有稳定的放电性能。顺丁烯二酸中的两个相同方向的羧基基团(-COOH)与铝离子之间相互作用形成配位键,成七元环状。量化计算结果表明,七元环状环合物相比链状化合物具有更低的能量,更稳定。(3)考察了L-苹果酸和L-天冬氨酸对碱性乙二醇溶液中AA5052铝合金的缓蚀作用。在4 mol/L氢氧化钠-乙二醇水溶液中添加L-苹果酸和L-天冬氨酸缓蚀剂对AA5052铝合金有明显的缓蚀效果。相比L-苹果酸,L-天冬氨酸能更好的抑制AA5052合金的析氢腐蚀,具有更好的缓蚀效果,最大的缓蚀效率为82.1%。量化计算表明,L-天冬氨酸上氨基的N原子较L-苹果酸上羟基的O原子的Mulliken电荷更低,前者的总Mulliken电荷更小,且具有较高的EHOMO和较低能量间隙的ΔN,说明L-天冬氨酸与铝离子更容易形成配位键。
[Abstract]:Aluminum - air battery is a new type of green energy, has no pollution, high capacity, stable discharge. Its main advantage is made of aluminum or Aluminum Alloy as anode and oxygen in the air as the cathode and neutral or alkaline electrolyte is composed of three parts. In the neutral electrolyte, the surface of the aluminum will form a dense oxide film, hinder the active dissolution of aluminum anode, the current density becomes smaller; the most commonly used in Na OH solution, air cathode and anode polarization of aluminum is very small, the energy density of the battery discharge and high stability, but will occur anodic aluminum hydrogen serious corrosion, caused by aluminum anode utilization and efficiency in Kulun this is also reduced, the aluminum - air battery used in business on the main obstacles. There are mainly two methods of corrosion can inhibit aluminum in alkaline solution: first, adding some alloy elements hydrogen overpotential in high pure aluminum; second, in the electrolyte The addition of inhibitors. The hydrogen evolution method, electrochemical test, quantum chemistry calculation, surface morphology analysis method of sorbic acid and Zinc Oxide compound, maleic acid and fumaric acid and L- aspartic acid and L- malic acid corrosion of AA5052 in alkaline solution Aluminum Alloy. The main conclusions are as follows: (1) investigated the inhibition effect of sorbic acid and alkaline solution of Zhongshan Zinc Oxide synergism of AA5052 Aluminum Alloy. Combination of sorbic acid and Zinc Oxide effectively inhibited the corrosion of AA5052 Aluminum Alloy in 4 mol/L Na OH solution. When adding the complex ratio of 30 m M +2.0 m M Zinc Oxide sorbic acid, corrosion inhibitor efficiency of 80.4%. by scanning electron microscopy and infrared, Zn O reaction Zn elements, forming a Zn film deposited on the aluminum surface, the adsorption of sorbic acid in Zn membrane and its defects, the formation of composite membrane protective Aluminum Alloy, can suppress the cathodic hydrogen evolution reaction and inhibition The anode dissolution reaction, reduce the corrosion rate of aluminum. The galvanostatic experiments showed that AA5052 Aluminum Alloy electrode containing 30 m M +2.0 m M Zinc Oxide sorbic acid inhibitor 4 mol/L Na OH solution discharge performance is good and stable. (2) CIS inhibition effect of fumaric acid on AA5052 base ethylene glycol solution Aluminum Alloy were investigated. In 4mol/L NaOH aqueous solution with glycol unsaturated carboxylic acid (two butene addition of maleic acid and fumaric acid) have obvious corrosion inhibiting effect on AA5052 Aluminum Alloy. The inhibition efficiency of size: maleic acid, fumaric acid corrosion along. Maleic acid can better inhibit AA5052 Aluminum Alloy, the maximum inhibition efficiency of 84.3%. electrochemical experiments showed that AA5052 in Aluminum Alloy with maleic acid with stable discharge of 4 mol/L NaOH in aqueous solutions of ethylene glycol maleic two. Two carboxyl groups in the same direction of acid (-COOH) and the aluminum ion interactions to form coordination bonds, as Qiyuan ring. Quantitative calculation results show that, compared to the seven membered ring ring compounds chain compound has lower energy, more stable. (3) investigated the inhibition effect of L- malic acid and L- days of winter the amino acid of AA5052 alkaline glycol solution Aluminum Alloy. Adding L- L- malic acid and aspartic acid in 4 mol/L NaOH in aqueous solutions of ethylene glycol inhibitor has obvious corrosion inhibiting effect on AA5052 Aluminum Alloy. Compared to L- malic acid, hydrogen corrosion inhibition of AA5052 alloy L- aspartic acid can be better that has better inhibition effect, the maximum inhibition efficiency for 82.1%. quantitative calculation shows that the L- aspartic acid amino N atoms with L- malic acid hydroxyl on the O atom of Mulliken charge is lower, the total charge of Mulliken smaller, and has a high EHOMO and low The delta N of the energy gap indicates that the L- aspartic acid is more likely to form the coordination bond with the aluminum ion.

【学位授予单位】：上海电力学院
【学位级别】：硕士
【学位授予年份】：2017
【分类号】：TM911.41

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