水解制氢用高活性微纳米Al-Ga-In-Bi2O3-SnCl2材料的制备及产氢机理研究

Aluminum is one of the important raw materials for hydrogen generation by hydrolysis in the future, However how to remove the oxide film on the surface of aluminum, and improve hydrolysis activity of aluminum is to solve the technical problems of aluminum become hydrogen energy materials. This project aims to study the preparation and hydrogen generation mechanisms of micro-nano Al-Ga-In-Bi2O3-SnCl2 materials with high activity for hydrolysis hydrogen, the hydrolysis properties of the materials and the microstructure of the materials before and after hydrolysis will systematically studied by means of FESEM, EDS, XRD and other analytical methods, the effects of composition and mechanical alloying technology on the activity of hydrolysis hydrogen and hydrolysis hydrogen performance of aluminum alloy will studied; the dynamic variation of reaction products in the reaction interface of hydrolysis hydrogen of the materials will be studied; the possibility of application of Al-Ga-In-Bi2O3-SnCl2 material on hydrogen fuel cells will be discussed. The hydrogen generation mechanisms of the material are revealed through the above researches, and a new aluminum alloy system for hydrolysis hydrogen with low cost, high hydrogen yield and hydrogen generation rate and can be used as a portable or vehicle mounted hydrogen source is obtained. These studies not only enrich the alloy system of aluminum alloy for hydrolysis hydrogen, but also it can realize the integrated hydrogen technology of hydrogen generation, hydrogen storage and hydrogen transportation, those studies for the fossil resource saving, to promote hydrogen widely use and protection of the environment have also great theoretical and practical significance.

铝是未来很有前景的水解制氢用重要原材料之一，但如何消除铝表面的氧化膜，提高其与水反应的活性是解决铝成为氢能源材料的技术难题。本项目针对这一问题拟开展高活性水解制氢用微纳米Al-Ga-In-Bi2O3-SnCl2材料的制备和产氢机理的研究，利用FESEM、EDS、XRD等技术对该材料的水解性能及该材料在水解前后的微观结构进行系统分析，重点研究体系的成分、机械合金化工艺对铝合金的水解制氢活性和产氢性能的影响规律；研究该材料水解制氢时反应产物在反应界面附近的动态变化规律；并探讨该材料在氢燃料电池上应用的可能性。通过上述研究揭示该材料的产氢机理，并得到一种低成本、高产氢率和产氢速度且能作为便携式或车载用氢源的水解制氢用新的铝合金体系。这些研究不仅丰富了水解制氢用铝合金的合金体系，而且能实现集制氢、储氢和运氢于一体的技术，这对节约资源、推动氢能的广泛使用和保护环境具有重大的理论和实际意义

铝基复合材料水解制氢技术是在储氢和运氢系统不完善的情况下实现氢能广泛应用的有效途径。但该技术的高成本限制了其应用。对材料成分和制备工艺参数进行优化，对水解制氢副产物进行回收再利用是降低铝基复合材料水解制氢技术成本的有效方法。本项目以金属铝粉为研究对象，采用“少量多元”的方案，在铝粉中添加低熔点金属Ga和In、无机盐SnCl2和氧化物Bi2O3，利用机械合金化工艺制备具有高水解产氢性能的铝基复合材料。利用均匀实验设计和正交实验设计分别优化材料成分和球磨工艺参数。采用球磨工艺参数（转速为480 r/min、时间为120 min、球料比为15:1、大小球质量比为1:1）制备的Al-1.0 wt.% Ga-1.5 wt.% In-1.0 wt.% Bi2O3-3.0 wt.% SnCl2材料在常压25 °C水温，60 min内的产氢量为1172.3 mL·g-1，最大产氢速率为1030.5 mL·g-1·min-1。研究了复合材料的物相组成、微观形貌、材料表面元素价态、电化学性能等，在此基础上揭示了铝基复合材料材料的产氢机理。水解制氢反应的吉布斯自由能变ΔrGmΘ小于0，该反应不需要外界做功一经引发就能自发进行。球磨过程中，材料塑性变形及Al-Ga固溶体的形成破坏氧化膜，原位生成的AlCl3水解生成HCl，Al与InSn4的共晶反应，Bi2O3在球磨过程中发生的铝热反应，原位生成的Sn、Bi和添加剂Ga、In使材料腐蚀电位负移。在上述因素共同作用下，Al-Ga-In-Bi2O3-SnCl2材料具有良好的水解产氢性能。采用控制变量法研究添加剂含量和球磨工艺参数对材料水解产氢性能的影响。探讨了铝基复合材料水解制氢副产物的理化性质。对水解产物的回收和再利用进行了初步探讨。这对不同产氢性能复合材料的设计和降低铝基复合材料水解制氢技术的成本提供思路与参考。达到了预期目标。