鎂負(fù)極微觀結(jié)構(gòu)和含氧陰離子緩蝕劑對(duì)鎂空氣電池性能的影響
發(fā)布時(shí)間：2018-08-04 22:00
【摘要】：能源是保障人類生存和社會(huì)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(guó)不可回避的問題。同時(shí)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(diǎn),是傳統(tǒng)能源的理想替代品。鎂是地球上儲(chǔ)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(diǎn),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(yáng)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(huì)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(shí)會(huì)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(shí)驗(yàn)等測(cè)試方法研究了微觀結(jié)構(gòu)和含氧陰離子緩蝕劑對(duì)鎂合金電化學(xué)性能的影響,通過連續(xù)放電測(cè)試和間歇放電測(cè)試等測(cè)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(duì)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?jī)?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(shí)間逐漸變短。(2)研究了織構(gòu)對(duì)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(shí),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(yáng)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(yáng)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(yáng)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(duì)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(huì)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(duì)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(yáng)極效率,降低電池間歇放電間歇期的陽(yáng)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(duì)電池陽(yáng)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(jí)別】：博士
【學(xué)位授予年份】：2016
【分類號(hào)】：TG174.42;TM911.41
本文編號(hào)：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(jí)別】：博士
【學(xué)位授予年份】：2016
【分類號(hào)】：TG174.42;TM911.41
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