【摘要】：鋁-空氣電池比能量高,原材料來(lái)源豐富,安全環(huán)保,在車載電源、備用電源等方面具有廣闊的發(fā)展前景。但堿性電解液中鋁陽(yáng)極腐蝕和電池極化現(xiàn)象顯著,阻礙了鋁-空氣電池的商業(yè)化進(jìn)程。對(duì)鋁-空氣電池電解液添加劑進(jìn)行研究以減小腐蝕,改善鋁電極性能具有重要意義。另外通過研究電池放電過程電解液組成變化為降低電池極化提供理論支撐,為放電產(chǎn)物后處理提供方法依據(jù)。對(duì)放電產(chǎn)物進(jìn)行研究,探索產(chǎn)物應(yīng)用價(jià)值,提高電池經(jīng)濟(jì)附加值,有望開辟鋁-空氣電池商業(yè)化應(yīng)用新模式。首先,本文首次提出使用錫酸鈉和干酪素作為復(fù)合緩蝕劑來(lái)抑制堿性電解液中鋁-空氣電池的陽(yáng)極腐蝕。通過集氣實(shí)驗(yàn)、電化學(xué)實(shí)驗(yàn)測(cè)試了該復(fù)合抑制劑對(duì)陽(yáng)極以及電池性能的影響;并對(duì)陽(yáng)極表面形貌進(jìn)行研究,嘗試對(duì)復(fù)合緩蝕劑的緩蝕機(jī)理做了合理的示意解釋。結(jié)果表明,復(fù)合緩蝕劑的最適濃度為0.05 mol·L-1Na2SnO3和0.6 g·L-1干酪素,可使陽(yáng)極析氫腐蝕速率降低接近一個(gè)數(shù)量級(jí)。電化學(xué)性能測(cè)試表明:復(fù)合緩蝕劑主要是通過抑制反應(yīng)的陰極區(qū)速率來(lái)抑制腐蝕的,同時(shí)起到了活化陽(yáng)極的效果。電池放電結(jié)果表明:電池放電性能明顯提高,放電容量增加了將近一倍。晶型和形貌組成分析表明:復(fù)合緩蝕劑是通過在陽(yáng)極表面活性位點(diǎn)上的吸附和沉積而起緩蝕作用的。其次,本文使用紅外(IR)、核磁(NMR)、拉曼、紫外(UV)等光譜學(xué)方法研究了電池放電過程中放電條件的改變對(duì)電解液組成的影響。結(jié)果表明:Al(OH)4-在放電過程中始終處于優(yōu)勢(shì)地位,在其基礎(chǔ)上溶液中會(huì)產(chǎn)生其他低聚態(tài)的含鋁酸根離子,但數(shù)量較少。堿液濃度、溫度和放電電流密度不影響電解液中Al(Ⅲ)的配位數(shù),只對(duì)形成的低聚態(tài)的含鋁酸根的種類和數(shù)量產(chǎn)生影響。同時(shí),電解液中四配位含鋁酸根占據(jù)絕對(duì)主導(dǎo)地位,尤其是Al(OH)4-,是導(dǎo)致電池極化加劇的主要原因。最后,在放電過程中電解液組成研究的基礎(chǔ)上初步探索了通過放電產(chǎn)物制備高端市場(chǎng)氧化鋁的可能性。結(jié)果表明:單純通過改變放電條件可制備出粒度在100nm左右,純度達(dá)到99.99%的高純超細(xì)氧化鋁。添加劑如凝膠、纖維的加入則可使粒度降低到50-100 nm。證實(shí)了通過鋁-空氣電池放電來(lái)制備高純超細(xì)氧化鋁的可能。
[Abstract]:Aluminum-air battery has high specific energy, abundant raw material sources, safe and environmental protection, and has a broad development prospect in vehicle power supply, reserve power supply and so on. However, aluminum anode corrosion and cell polarization in alkaline electrolyte hinders the commercialization of aluminum-air battery. It is of great significance to study the electrolyte additives of Al-air battery in order to reduce corrosion and improve the performance of aluminum electrode. In addition, the study of electrolyte composition during battery discharge provides theoretical support for reducing battery polarization and provides method basis for post-treatment of discharge products. The discharge products are studied to explore the application value of the products and to improve the economic added value of the batteries. It is expected to open up a new commercial application model of the aluminum-air batteries. Firstly, sodium Stannate and casein are used as complex corrosion inhibitors to inhibit the anodic corrosion of Al-air battery in alkaline electrolyte for the first time. The influence of the composite inhibitor on the anode and the performance of the battery was tested by the gas collecting experiment and the electrochemical experiment, and the surface morphology of the anode was studied to explain the corrosion inhibition mechanism of the composite inhibitor. The results showed that the optimum concentration of the complex inhibitor was 0. 05 mol L-1Na2SnO3 and 0. 6 g / L casein, which reduced the corrosion rate of anodic hydrogen evolution by an order of magnitude. The electrochemical performance test showed that the composite inhibitor inhibited the corrosion mainly by inhibiting the cathodic region rate of the reaction and played the role of activating the anode at the same time. The results of battery discharge show that the discharge performance of the battery is obviously improved and the discharge capacity is nearly doubled. The analysis of crystal form and morphology showed that the composite corrosion inhibitor was inhibited by adsorption and deposition on the active site on the anode surface. Secondly, the effects of the discharge conditions on the electrolyte composition were studied by using infrared (IR), NMR (NMR), Raman spectroscopy and UV (UV) spectroscopy. The results show that: Al (OH) _ 4- is always in the dominant position in the discharge process, and on the basis of it, other oligomeric aluminum ions may be produced in the solution, but the quantity is relatively small. The concentration of alkali, temperature and discharge current density have no effect on the coordination number of Al (鈪，

本文編號(hào)：2378881