Oxygen storage capacity and thermal stability of brownmillerite-type Ca2(Al1-xGax)MnO5+δ oxides

Understanding the oxygen uptake/release mechanism in oxygen storage materials is of great importance in the design of energy-related materials and their corresponding applications. In this work, the effects of Ga doping amount on the oxygen storage capacity and thermal stability of Ca-2(Al1-xGax)MnO5+delta (0 <= x <= 1) with a brownmillerite-type structure were investigated. Ca2AlMnO5+delta can reversibly store/release a large amount of excess oxygen (similar to 3.0 wt%) at low temperature (between 300 and 600 degrees C) under oxidative atmospheres. With the increasing Ga doping amount in Ca-2(Al1-xGax)MnO5+delta, these materials uptake less oxygen at higher temperature which can be attributed to the difficulty in the oxidation of tetrahedral GaO4 blocks into octahedral GaO6 blocks under 1 atm O-2. However, with the increasing of Ga-substitution amount, these Ca-2(Al1-xGax)MnO5+delta (0 <= x < 1) can start to uptake oxygen at lower temperatures during the cooling process under flowing O-2 due to the distorted structure. The results demonstrated that Ca-2(Al1-xGax)MnO5+delta (0 < x < 1) can reversibly store/release large amounts of oxygen via just controlling the surrounding temperature and/or oxygen partial pressure but without using reductive gases, which would enable them great potentials in many applications. (C) 2019 Elsevier B.V. All rights reserved.