The cobalt-oxide/iron-oxide binary system for use as high temperature thermochemical energy storage material

Abstract The use of thermochemical reactions is a promising approach for heat storage applications. Redox-reactions involving multivalent cations are recently envisaged for high temperature applications. In temperature range of 900–1000 °C, however, where heat storage required for concentrated solar power (CSP) processes only few metal oxides with sufficient heat storage capabilities do exist. Binary systems, on the other hand, could provide a wider range of suitable materials. In the present experimental study the cobalt-oxide/iron-oxide binary system is investigated. For pure iron-oxide the transformation of Fe 2 O 3 /Fe 3 O 4 occurs at 1392 °C with a reaction enthalpy of 599 J/g. The reaction temperature, however, is far too high for CSP applications. Cobalt-oxide, on the other hand, reacts from Co 3 O 4 /CoO at 915 °C with an enthalpy of 576 J/g. Iron-doped cobalt-oxides transform at similar temperature as pure cobalt-oxide but the reaction enthalpy gradually decreases with increasing iron content. Microstructural stability and related long-term reversibility of the chemical reaction, however, is higher with respect to pure cobalt-oxide. Compositions of around 10% iron-oxide were identified having appropriate enthalpies and being beneficial in terms of microstructural stability.

[1]  I. Barin,et al.  Thermochemical properties of inorganic substances , 1973 .

[2]  K. Jacob,et al.  Thermodynamics of Cobalt (II, III) Oxide (Co3O4): Evidence of Phase Transition , 1988 .

[3]  A. Pelton,et al.  Thermodynamic evaluation and modeling of the Fe–Co–O system , 2004 .

[4]  P. A. Larsen,et al.  Kinetic and thermodynamic considerations for oxygen absorption/desorption using cobalt oxide , 2006 .

[5]  P. Murray Cation distribution in the spinels CoxFe3−xO4 , 1976 .

[6]  G. Balaji,et al.  Synthesis, reactivity, and cations inversion studies of nanocrystalline MnFe2O4 particles , 2002 .

[7]  M. Fine,et al.  Spinodal Decomposition in the System CoFe2O4-Co3O4 , 1971 .

[8]  R. Dieckmann,et al.  Defects and transport in the solid solution (Co,Fe)1−Δ O at 1200°CI. Nonstoichiometry , 1994 .

[9]  L. Diamandescu,et al.  From Magnetite to Cobalt Ferrite , 2001 .

[10]  A. Pelton,et al.  Model calculations of phase stabilities of oxide solid solutions in the CoFeMnO system at 1200°C , 1994 .

[11]  Chen-Bin Wang,et al.  Characterization of cobalt oxides studied by FT-IR, Raman, TPR and TG-MS , 2008 .

[12]  A. Vijayalakshmi,et al.  Synthesis of Ultrafine Cobalt Ferrite by Thermal Decomposition of Citrate Precursor , 1998 .

[13]  A. Pelton,et al.  Thermodynamics of Mn3O4 — Co3O4, Fe3O4 — Mn3O4, and Fe3O4 — Co3O4 Spinels by Phase Diagram Analysis , 1979 .

[14]  R. Tamme,et al.  High Temperature Thermochemical Heat Storage for Concentrated Solar Power Using Gas–Solid Reactions , 2011 .

[15]  M. Fine,et al.  Coercive Force of Spinodally Decomposed Cobalt Ferrite with Excess Cobalt , 1970 .

[16]  Christian Sattler,et al.  Solar-heated rotary kiln for thermochemical energy storage , 2012 .

[17]  D. Mette,et al.  Thermochemische EnergiespeicherThermochemical Energy Storage , 2011 .