發(fā)布時(shí)間：2018-02-27 10:21

  本文關(guān)鍵詞： 鋁空電池 鋁陽極 析氫 堿性溶液 緩蝕劑　出處：《上海電力學(xué)院》2017年碩士論文　論文類型：學(xué)位論文

【摘要】：鋁-空電池是一種新型綠色能源,具有無污染、比容量大、放電穩(wěn)定等優(yōu)點(diǎn)。其主要是由鋁或鋁合金為陽極,空氣中的氧為陰極以及中性或堿性電解液三部分組成。在中性電解液中,鋁的表面會(huì)形成致密的氧化膜,阻礙了鋁陽極的活性溶解,使得電流密度變小;在最常用的Na OH溶液中,空氣陰極和鋁陽極的極化都很小,電池的能量密度高且放電穩(wěn)定,但鋁陽極會(huì)發(fā)生嚴(yán)重的析氫自腐蝕,導(dǎo)致鋁陽極利用率和庫倫效率降低,這也是將鋁-空電池應(yīng)用在商業(yè)上的主要障礙。目前主要有兩種方法可以抑制鋁在堿性溶液中的腐蝕:第一,在純鋁中添加一些析氫過電位較高的合金元素;第二,在電解液中添加緩蝕劑。本文通過析氫法、電化學(xué)測試、量子化學(xué)計(jì)算、表面形貌分析等方法研究了山梨酸和氧化鋅復(fù)配、順丁烯二酸和反丁烯二酸以及L-天冬氨酸和L-蘋果酸對堿性溶液中AA5052鋁合金的緩蝕性能。主要得到以下結(jié)論:(1)考察了堿性溶液中山梨酸和氧化鋅復(fù)配增效對AA5052鋁合金的緩蝕作用。山梨酸和氧化鋅的復(fù)配有效的抑制了AA5052鋁合金在4 mol/L Na OH溶液中的腐蝕。當(dāng)添加復(fù)配比為30.0 m M山梨酸+2.0 m M氧化鋅時(shí),緩蝕效率達(dá)到80.4%。由掃描電鏡和紅外可知,Zn O反應(yīng)生成Zn單質(zhì),在鋁表面沉積形成Zn膜,山梨酸在Zn膜及其缺陷處吸附,形成復(fù)合膜保護(hù)鋁合金,既抑制了陰極析氫反應(yīng),又抑制了陽極鋁溶解反應(yīng),降低了鋁的自腐蝕速率。恒電流實(shí)驗(yàn)表明,AA5052鋁合金電極在含有30.0 m M山梨酸+2.0 m M氧化鋅復(fù)配緩蝕劑的4 mol/L Na OH溶液中放電性能良好且穩(wěn)定。(2)考察了順反丁烯二酸對堿性乙二醇溶液中AA5052鋁合金的緩蝕作用。在4mol/L氫氧化鈉-乙二醇水溶液中添加不飽和丁烯二羧酸(順丁烯二酸和反丁烯二酸)對AA5052鋁合金有明顯的緩蝕效果。緩蝕效率的大小為:順丁烯二酸反丁烯二酸。順丁烯二酸的能更好的抑制AA5052鋁合金的自腐蝕,其最大的緩蝕效率為84.3%。電化學(xué)實(shí)驗(yàn)表明,AA5052鋁合金在加有順丁烯二酸的4 mol/L氫氧化鈉-乙二醇水溶液中具有穩(wěn)定的放電性能。順丁烯二酸中的兩個(gè)相同方向的羧基基團(tuán)(-COOH)與鋁離子之間相互作用形成配位鍵,成七元環(huán)狀。量化計(jì)算結(jié)果表明,七元環(huán)狀環(huán)合物相比鏈狀化合物具有更低的能量,更穩(wěn)定。(3)考察了L-蘋果酸和L-天冬氨酸對堿性乙二醇溶液中AA5052鋁合金的緩蝕作用。在4 mol/L氫氧化鈉-乙二醇水溶液中添加L-蘋果酸和L-天冬氨酸緩蝕劑對AA5052鋁合金有明顯的緩蝕效果。相比L-蘋果酸,L-天冬氨酸能更好的抑制AA5052合金的析氫腐蝕,具有更好的緩蝕效果,最大的緩蝕效率為82.1%。量化計(jì)算表明,L-天冬氨酸上氨基的N原子較L-蘋果酸上羥基的O原子的Mulliken電荷更低,前者的總Mulliken電荷更小,且具有較高的EHOMO和較低能量間隙的ΔN,說明L-天冬氨酸與鋁離子更容易形成配位鍵。
[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.

【學(xué)位授予單位】：上海電力學(xué)院
【學(xué)位級別】：碩士
【學(xué)位授予年份】：2017
【分類號】：TM911.41

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