鎂負(fù)極微觀結(jié)構(gòu)和含氧陰離子緩蝕劑對鎂空氣電池性能的影響
發(fā)布時間：2018-08-04 22:00
【摘要】：能源是保障人類生存和社會發(fā)展的重要物質(zhì)基礎(chǔ),然而在過去的一百多年里,煤、石油以及天然氣等傳統(tǒng)能源被大量消耗,能源危機(jī)已經(jīng)成為世界各國不可回避的問題。同時傳統(tǒng)能源的使用還造成了嚴(yán)重的環(huán)境污染,因此開發(fā)新型綠色能源迫在眉睫。金屬空氣電池具有成本低、無毒、無污染、理論電壓和比能量密度高等優(yōu)點,是傳統(tǒng)能源的理想替代品。鎂是地球上儲量居第八位的元素,具有密度低(1.74 gmL~(-1))、化學(xué)性質(zhì)活潑以及電化學(xué)當(dāng)量高(2.20 Ahg~(-1))等優(yōu)點,是金屬空氣電池的理想負(fù)極材料。但由于其活潑的電化學(xué)性質(zhì),鎂合金在中性鹽電解液中極易被腐蝕,導(dǎo)致鎂空氣電池陽極效率很低。另一方面,鎂空氣電池在放電過程中,鎂負(fù)極表面會產(chǎn)生一層主要成分為氫氧化鎂的放電產(chǎn)物膜,電池在間歇放電時會產(chǎn)生嚴(yán)重的電壓滯后現(xiàn)象。本論文通過極化曲線、阻抗曲線(EIS)以及析氫實驗等測試方法研究了微觀結(jié)構(gòu)和含氧陰離子緩蝕劑對鎂合金電化學(xué)性能的影響,通過連續(xù)放電測試和間歇放電測試等測試方法研究了鎂負(fù)極微觀結(jié)構(gòu)和含氧陰離子緩蝕劑作為電解液添加劑對鎂空氣電池放電性能的影響,通過掃描電子顯微鏡(SEM)、激光共聚焦掃描顯微鏡(LSCM)和能譜儀(EDS)研究了鎂負(fù)極表面放電產(chǎn)物的形貌及成分。主要研究內(nèi)容如下:(1)通過預(yù)壓縮變形及隨后的退火處理制備了不同孿晶含量的AZ31鎂合金,并研究了以這些鎂合金為負(fù)極材料的鎂空氣電池的性能。隨孿晶含量的增加,AZ31鎂合金電化學(xué)活性逐漸增強(qiáng),鎂空氣電池平均放電電壓逐漸變高,電壓滯后時間逐漸變短。(2)研究了織構(gòu)對鎂合金耐腐蝕性能以及鎂空氣電池放電性能的影響。當(dāng)合金表面狀態(tài)為機(jī)械打磨時,AZ31鎂合金TD-ND面比RD-TD面具有更好的耐腐蝕性能,基于TD-ND面鎂負(fù)極的鎂空氣電池具有更高的陽極效率。(3)通過冷軋變形和隨后的退火工藝獲得了不同晶粒尺寸的AZ31鎂合金板材,并研究了以這些合金為負(fù)極材料的鎂空氣電池的性能。隨晶粒尺寸的減小,AZ31鎂合金電化學(xué)活性和耐腐蝕性能逐漸變好,鎂空氣電池陽極效率和放電電壓逐漸增高。(4)Li_2CrO_4可以有效改善AZ31鎂合金在3.5 wt%NaCl溶液中的耐腐蝕性能,AZ31鎂合金在3.5 wt%NaCl+0.1 wt%Li_2CrO_4溶液中的腐蝕電流密度僅為在3.5 wt%NaCl溶液中的1/7。Li_2CrO_4作為電解液添加劑可以有效提高鎂空氣電池間歇放電陽極效率,改善鎂負(fù)極表面放電產(chǎn)物形貌。(5)Na_3PO_4?12H_2O和NaVO_3對AZ31鎂合金在0.6 M NaCl溶液中均有很好的腐蝕抑制效果。在含Na_3PO_4?12H_2O和NaVO_3的兩種溶液中,鎂合金表面分別會產(chǎn)生一層磷酸鹽保護(hù)膜和一層釩酸鹽保護(hù)膜,并減慢合金的自腐蝕速率。磷酸鹽保護(hù)膜比釩酸鹽保護(hù)膜更完整,因此Na_3PO_4?12H_2O對AZ31鎂合金的腐蝕抑制效果更好。Na_3PO_4?12H_2O和NaVO_3作為電解液添加劑均可有效提高電池陽極效率,降低電池間歇放電間歇期的陽極效率損失,改善鎂負(fù)極表面放電產(chǎn)物形貌。相比于NaVO_3而言,Na_3PO_4?12H_2O對電池陽極效率的改善效果更明顯。
[Abstract]:Energy is an important material basis for the protection of human survival and social development. However, in the past more than 100 years, the traditional energy such as coal, oil and natural gas have been greatly consumed. The energy crisis has become an unavoidable problem in the world. At the same time, the use of traditional energy has also made serious environmental pollution, so the new green is developed. Energy is imminent. Metal air battery has the advantages of low cost, non-toxic, no pollution, high theoretical voltage and high specific energy density. It is an ideal substitute for traditional energy. Magnesium is the eighth element in the earth, with low density (1.74 gmL~ (-1)), active chemical properties and high electrochemical equivalent (2.20 Ahg~ (-1)). But because of its active electrochemical properties, magnesium alloys are easily corroded in neutral salt electrolyte, resulting in low anodic efficiency of magnesium air batteries. On the other hand, during the discharge process of magnesium air batteries, a layer of discharge products, mainly composed of magnesium hydroxide, is produced on the surface of magnesium negative electrode, and the battery is intermittent. In this paper, the effect of microstructure and oxygen containing anionic corrosion inhibitor on the electrochemical performance of magnesium alloys was investigated by polarization curve, impedance curve (EIS) and hydrogen evolution test. The microstructure of magnesium anode was studied by continuous discharge test and intermittent discharge test. The effect of the oxygen anion inhibitor as an electrolyte additive on the discharge performance of the magnesium air battery was studied by scanning electron microscope (SEM), laser confocal scanning microscope (LSCM) and energy spectrometer (EDS). The main contents of the study are as follows: (1) pre compression deformation and subsequent annealing are carried out. The AZ31 magnesium alloys with different twin content were prepared and the performance of magnesium air batteries with these magnesium alloys as negative materials was studied. With the increase of the twin content, the electrochemical activity of AZ31 magnesium alloy gradually increased, the average discharge voltage of magnesium air battery became higher and the voltage lag time became shorter. (2) the resistance of texture to magnesium alloy was studied. The effect of corrosion properties and the discharge performance of magnesium air battery. When the surface state of the alloy is mechanical grinding, the TD-ND surface of AZ31 magnesium alloy has better corrosion resistance than that of the RD-TD mask. The magnesium air battery based on the TD-ND surface magnesium anode has higher anode efficiency. (3) different grain sizes are obtained by cold rolling and subsequent annealing. The performance of magnesium air battery with these alloys as negative electrode was studied. With the decrease of grain size, the electrochemical activity and corrosion resistance of AZ31 magnesium alloy gradually became better, and the anode efficiency and discharge voltage of magnesium air battery increased gradually. (4) Li_2CrO_4 can effectively improve the AZ31 magnesium alloy in 3.5 wt%NaCl solution. The corrosion resistance of AZ31 magnesium alloy in 3.5 wt%NaCl+0.1 wt%Li_2CrO_4 solution is only the 1/7.Li_2CrO_4 in 3.5 wt%NaCl solution as an electrolyte additive, which can effectively improve the anodic efficiency of the intermittent discharge of magnesium air batteries and improve the surface discharge morphology of the magnesium negative electrode. (5) Na_3PO_4? 12H_2O and NaVO_3 to AZ31 magnesium The alloy has a good corrosion inhibition effect in 0.6 M NaCl solution. In the two solutions containing Na_3PO_4? 12H_2O and NaVO_3, the surface of magnesium alloy produces a layer of phosphate protection film and a layer of vanadate protective film respectively, and slows the self corrosion rate of the alloy. The phosphate protection film is more complete than the vanadate protective film, so Na_3PO_4? 12H_2O The corrosion inhibition effect on AZ31 magnesium alloy better.Na_3PO_4? 12H_2O and NaVO_3 as the electrolyte additives can effectively improve the anode efficiency of the battery, reduce the anode efficiency loss of the intermittent discharge period of the battery and improve the surface discharge product morphology of the magnesium negative electrode. Compared to NaVO_3, the improvement effect of Na_3PO_4? 12H_2O on the anode efficiency of the battery is improved. It's more obvious.
【學(xué)位授予單位】：重慶大學(xué)
【學(xué)位級別】：博士
【學(xué)位授予年份】：2016
【分類號】：TG174.42;TM911.41
本文編號：2165300
[Abstract]:Energy is an important material basis for the protection of human survival and social development. However, in the past more than 100 years, the traditional energy such as coal, oil and natural gas have been greatly consumed. The energy crisis has become an unavoidable problem in the world. At the same time, the use of traditional energy has also made serious environmental pollution, so the new green is developed. Energy is imminent. Metal air battery has the advantages of low cost, non-toxic, no pollution, high theoretical voltage and high specific energy density. It is an ideal substitute for traditional energy. Magnesium is the eighth element in the earth, with low density (1.74 gmL~ (-1)), active chemical properties and high electrochemical equivalent (2.20 Ahg~ (-1)). But because of its active electrochemical properties, magnesium alloys are easily corroded in neutral salt electrolyte, resulting in low anodic efficiency of magnesium air batteries. On the other hand, during the discharge process of magnesium air batteries, a layer of discharge products, mainly composed of magnesium hydroxide, is produced on the surface of magnesium negative electrode, and the battery is intermittent. In this paper, the effect of microstructure and oxygen containing anionic corrosion inhibitor on the electrochemical performance of magnesium alloys was investigated by polarization curve, impedance curve (EIS) and hydrogen evolution test. The microstructure of magnesium anode was studied by continuous discharge test and intermittent discharge test. The effect of the oxygen anion inhibitor as an electrolyte additive on the discharge performance of the magnesium air battery was studied by scanning electron microscope (SEM), laser confocal scanning microscope (LSCM) and energy spectrometer (EDS). The main contents of the study are as follows: (1) pre compression deformation and subsequent annealing are carried out. The AZ31 magnesium alloys with different twin content were prepared and the performance of magnesium air batteries with these magnesium alloys as negative materials was studied. With the increase of the twin content, the electrochemical activity of AZ31 magnesium alloy gradually increased, the average discharge voltage of magnesium air battery became higher and the voltage lag time became shorter. (2) the resistance of texture to magnesium alloy was studied. The effect of corrosion properties and the discharge performance of magnesium air battery. When the surface state of the alloy is mechanical grinding, the TD-ND surface of AZ31 magnesium alloy has better corrosion resistance than that of the RD-TD mask. The magnesium air battery based on the TD-ND surface magnesium anode has higher anode efficiency. (3) different grain sizes are obtained by cold rolling and subsequent annealing. The performance of magnesium air battery with these alloys as negative electrode was studied. With the decrease of grain size, the electrochemical activity and corrosion resistance of AZ31 magnesium alloy gradually became better, and the anode efficiency and discharge voltage of magnesium air battery increased gradually. (4) Li_2CrO_4 can effectively improve the AZ31 magnesium alloy in 3.5 wt%NaCl solution. The corrosion resistance of AZ31 magnesium alloy in 3.5 wt%NaCl+0.1 wt%Li_2CrO_4 solution is only the 1/7.Li_2CrO_4 in 3.5 wt%NaCl solution as an electrolyte additive, which can effectively improve the anodic efficiency of the intermittent discharge of magnesium air batteries and improve the surface discharge morphology of the magnesium negative electrode. (5) Na_3PO_4? 12H_2O and NaVO_3 to AZ31 magnesium The alloy has a good corrosion inhibition effect in 0.6 M NaCl solution. In the two solutions containing Na_3PO_4? 12H_2O and NaVO_3, the surface of magnesium alloy produces a layer of phosphate protection film and a layer of vanadate protective film respectively, and slows the self corrosion rate of the alloy. The phosphate protection film is more complete than the vanadate protective film, so Na_3PO_4? 12H_2O The corrosion inhibition effect on AZ31 magnesium alloy better.Na_3PO_4? 12H_2O and NaVO_3 as the electrolyte additives can effectively improve the anode efficiency of the battery, reduce the anode efficiency loss of the intermittent discharge period of the battery and improve the surface discharge product morphology of the magnesium negative electrode. Compared to NaVO_3, the improvement effect of Na_3PO_4? 12H_2O on the anode efficiency of the battery is improved. It's more obvious.
【學(xué)位授予單位】：重慶大學(xué)
【學(xué)位級別】：博士
【學(xué)位授予年份】：2016
【分類號】：TG174.42;TM911.41
【參考文獻(xiàn)】
相關(guān)期刊論文 前10條
1 胡程旺;王日初;彭超群;馮艷;王乃光;;Ce添加對AP65鎂合金顯微組織及電化學(xué)性能的影響[J];中國有色金屬學(xué)報;2015年07期
2 CHENG Gang;XU Qiang;ZHANG Ming;DING Fei;LIU XingJiang;JIAO LiFang;;Electrochemical reversibility of magnesium deposition-dissolution on aluminum substrates in Grignard reagent/THF solutions[J];Chinese Science Bulletin;2013年27期
3 石春梅;曾小勤;常建衛(wèi);努麗燕娜;丁文江;;AZ31合金用于鎂二次電池負(fù)極材料的電化學(xué)性能[J];中國有色金屬學(xué)報;2010年05期
4 沈健;彭博;陶占良;陳軍;;鎂二次電池正極材料和電解液研究[J];化學(xué)進(jìn)展;2010年Z1期
5 陳淵;尹志新;樊新波;;5052鋁合金表面晶粒超細(xì)化后腐蝕性能研究[J];熱加工工藝;2010年02期
6 堯玉芬;陳昌國;劉渝萍;王榮;;鎂電池的研究進(jìn)展[J];材料導(dǎo)報;2009年19期
7 張林森;張愛勤;王力臻;李振亞;;以Mn_3O_4為催化劑的鋅-空氣電池性能[J];電源技術(shù);2009年07期
8 王艷;曹中秋;付雅君;楊在興;;不同晶粒尺寸Cu-50Cr合金在酸性介質(zhì)中的腐蝕電化學(xué)行為研究[J];腐蝕科學(xué)與防護(hù)技術(shù);2009年02期
9 鄧姝皓;易丹青;蘭博;周伶玲;冀成年;趙麗紅;;熱處理對鎂合金負(fù)極材料組織和性能的影響[J];電源技術(shù);2008年08期
10 曹中秋;邊靜;薛榮;劉偉華;;Electrochemical corrosion behavior of Cu-40Ni-20Cr alloys with different grain sizes in solutions containing chloride ions[J];Transactions of Nonferrous Metals Society of China;2007年06期
相關(guān)博士學(xué)位論文 前1條
1 王利飛;孿生對AZ31B鎂合金板材V型彎曲中性層偏移的影響[D];重慶大學(xué);2015年
相關(guān)碩士學(xué)位論文 前6條
1 程毅;鎂干電池負(fù)極材料和緩蝕劑的研究[D];重慶大學(xué);2012年
2 譚欣;海水激活電池用鎂合金陽極材料的研究[D];中南大學(xué);2011年
3 張燈;鋰空氣電池的基礎(chǔ)研究[D];復(fù)旦大學(xué);2010年
4 鄭偉偉;鎂電極在不同電解質(zhì)溶液中電化學(xué)性能初步研究[D];天津大學(xué);2009年
5 堯玉芬;鎂電池電解液的研究[D];重慶大學(xué);2009年
6 鐘麗應(yīng);稀土元素對AZ91鎂合金組織結(jié)構(gòu)和腐蝕行為的影響[D];浙江大學(xué);2008年
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