Synthesis of Electrochromic Layered Ceramic Materials and their Application to Display Electrodes

1. 目的：< β >-ZrNCL层状结构的颜色在锂嵌入和脱嵌过程中由浅黄绿色可逆地转变为黑色。由于这些颜色变化发生在电化学上，< β >-ZrNCl可以成为电致变色电极材料的有希望的候选材料。本课题以< β >-ZrNCl为电极，研制了一种新型电致变色显示器。(1)以ZrH_2或Zr金属与氯化铵为原料，以高收率制备了< β >-ZrNCl，并对其形成机理进行了初步研究。(2)在ZrCl_4-N_2NH_3体系下，采用射频等离子体VCD法制备了< β >-ZrNCl薄膜。(3)采用（NH_4）_2ZrCl_6蒸气热分解法制备了< β >-ZrNCl CVD膜。根据制备条件的不同，得到了两种取向膜；（001）和（100）取向薄膜，其中晶体基面分别与衬底平行和垂直沉积，薄膜具有良好的透明度，带吸收边缘在3.2 eV。(4)利用< β >ZrNCl的CVD膜在覆有金薄膜的玻璃衬底上构建了电致变色显示器。以1 M LiClo_4/丙酯为电解液。（100）取向薄膜表现出良好的循环性能。(5)为了了解< β >-ZrNCl电极的循环行为，构建了锂电池。当电池深度放电时，< β > -ZrNCl电极变质，电极表面碳酸丙烯分解。

1. ObjectiveThe color of layer structured <beta>-ZrNCL is reversibly changed from pale yellow-green to black on intercalation and deintercalation of lithium. Since these color changes occur electrochemically, <beta>-ZrNCl can be a promising candidate for electrochromic electrode material. In this project, a new electrochromic display has been developed by using <beta>-ZrNCl as the electrode.2. Results and Major Achievements(1) <beta>-ZrNCl was prepared by a novel reaction of ZrH_2 or Zr metal with ammonium chloride in high yields, and the formation mechanism has been elucidated. (2) <beta>-ZrNCl films were prepared by RF plasme VCD the system of ZrCl_4-N_2NH_3.(3) CVD films of <beta>-ZrNCl were prepared by the thermal decomposition of (NH_4)_2ZrCl_6 vapor. Depending on the preparation conditions, two kinds of oriented films were obrtained; (001) and (100) oriented films, where the basal planes of the crystallites were deposited parallel and perpendifuclar to the substrates, respectively, The films had good transparency with the band absorption edge at 3.2 eV.(4) An electrochromic display was constructrd by using the CVD films of <beta>ZrNCl on a Glass substrate covered with gold thin film. 1 M LiClo_4/propyelne carbonate was used as electrolyte. The (100) oriented films showed good cyclic performance.(5) In order to understand the cyclic behavior of the <beta>-ZrNCl electrode, a lithium battery was constructed. When the battery was deeply discharged, the <beta> -ZrNCl electrode deteriorated and the propllene carbonate decomposed on the surface of the electrode.