成果報告書詳細
管理番号20140000000168
タイトル*平成25年度中間年報 固体高分子形燃料電池実用化推進技術開発 基盤技術開発 酸化物系非貴金属触媒
公開日2016/1/26
報告書年度2013 - 2013
委託先名国立大学法人横浜国立大学 住友化学株式会社 凸版印刷株式会社 旭硝子株式会社 太陽化学株式会社 国立大学法人北海道大学 日産アーク株式会社
プロジェクト番号P10001
部署名新エネルギー部
和文要約
英文要約Title:Strategic Development of PEFC Technologies for Practical Application / Non-precious metal oxide based cathode for PEFC (FY2010-FY2014) FY2012 Annual Report

Group 4 and 5 oxide-based catalysts have been investigated as non-precious metal oxide based cathode for polymer electrolyte fuel cells. It was promoted by the following two groups; Group 1: Fundamental research of oxygen reduction activity and durability, Group 2: Manufacturing of catalysts, and design and evaluation of catalyst layer. The results obtained in Group 1 are as follows; We proposed principles of development of oxide-based cathodes as follows; 1. Increase of density of oxygen vacancies, 2. Preparation of highly dispersed fine particles, 3. Optimization of electron conduction path. According to the principles, we proposed new preparation method of group 4 and 5 metal nano-sized oxide-based cathodes to increase oxygen reduction current density. Oxy-metal phthalocyanines were used as precursors and dispersed on carbon nanotube support. The oxide-based catalysts made from oxy-zirconium phthalocyanines had ca. 10 nm diameters. In addition, an oxidation under low oxygen pressure was found to be effective to enhance the oxygen reduction activity. The current density of titanium and zirconium oxide-based catalysts reached 196 and 111 mA/g at 0.85 V, respectively. We have calculated atomic structure and electronic structure of the defective ZrO2 to investigate how the oxygen reduction reaction proceeded on defective ZrO2. The rate determining step was estimated to be first reduction process of oxygen molecules. We found that heat treatment under ammonium gas was effective to increase oxygen reduction activity. A temperature programmed desorption of oxygen was used to reveal the adsorption behavior of oxygen molecules on oxide-based catalysts. We analyzed structures of oxygen reduction reaction sites and electron conduction paths, and their changes in durability tests for Zr-oxide catalyst with ammonium annealing, by using XPS and TEM observations. The results indicate that density of Zr3+ that is formed by oxygen-vacancy increases is a key to increase ORR activity, and degradation of deposited carbon near the catalysts surface is one of the main cause of catalyst degradation. The results obtained in Group 2 are as follows; A hydrothermal decomposition method in supercritical water was optimized to enhance the ORR activity of the ZrO2/C catalysts. Mass production using hydrothermal decomposition method was examined and we got the prospect of the target, 30g/batch. We demonstrated that solution plasma method was useful to produce the nano-carbon ball as electroconductive additive. It was found that the dispersion of catalysts affected the performance of the single cell and the optimization increased the performance of single cell. Current density of 1.2 A/cm2 (IR free) were obtained at 0.6 V in a single cell using zirconium oxide-based cathode. We performed degradation test of single cell and found that single cell was operated over 1200 hours using zirconium oxide-based cathode.
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