Thermochemical energy storage at high temperature via redox cycles of Mn and Co oxides: Pure oxides versus mixed ones

Abstract Development of thermal energy storage (TES) systems for concentrated solar power (CSP) is essential in order to match a variable electricity demand with an intermittent energy source supply, enhancing energy generation dispatchability. The high energy storage densities and the possibility of working at higher temperature ranges make thermochemical heat storage (TCS) via reduction–oxidation (redox) cycles of metal oxides a promising concept for energy storage. For this purpose, manganese and cobalt oxides have been selected as feasible candidates due to their favourable thermodynamic properties. In order to explore the potential of these materials, the capacity of both pure (Mn 2 O 3 and Co 3 O 4 ) and mixed oxides (Mn 3− x Co x O 4 ) to withstand several charge–discharge cycles was evaluated by thermogravimetrical analysis. Results showed better cyclability for the mixed oxides with low Mn content ( x ≥2.94) and, specially, for the corresponding pure oxides, confirming that these materials may be a viable option for TCS.

[1]  R. D. Shannon Revised effective ionic radii and systematic studies of interatomic distances in halides and chalcogenides , 1976 .

[2]  M. Romero,et al.  Concentrating solar thermal power and thermochemical fuels , 2012 .

[3]  Luisa F. Cabeza,et al.  State of the art on high temperature thermal energy storage for power generation. Part 1—Concepts, materials and modellization , 2010 .

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

[5]  Christian Sattler,et al.  Oxide Based Thermochemical Heat Storage , 2010 .

[6]  J. P. Holgado,et al.  Complete n-hexane oxidation over supported Mn–Co catalysts , 2010 .

[7]  Luisa F. Cabeza,et al.  State of the art on high-temperature thermal energy storage for power generation. Part 2--Case studies , 2010 .

[8]  R. Rojas,et al.  Structural and Thermal Properties of the Tetragonal Cobalt Manganese Spinels MnxCo3-xO4 (1.4 < x < 2.0) , 1996 .

[9]  A. Muan,et al.  Phase Relations in the System Cobalt Oxide–Manganese Oxide in Air , 1963 .

[10]  Keith Lovegrove,et al.  Developing ammonia based thermochemical energy storage for dish power plants , 2003 .

[11]  G. El-Shobaky,et al.  EFFECTS OF BeO-DOPING ON THE THERMAL BEHAVIOUR OF COBALT OXIDES , 1985 .

[12]  H. Müller-Steinhagen,et al.  De- and rehydration of Ca(OH)2 in a reactor with direct heat transfer for thermo-chemical heat storage. Part A: Experimental results , 2013 .

[13]  G. El-Shobaky,et al.  Thermal stability of cobalt oxides doped with V2O5 and MoO3 , 1983 .

[14]  Anders Lyngfelt,et al.  Chemical-looping with oxygen uncoupling for combustion of solid fuels , 2009 .

[15]  Elias K. Stefanakos,et al.  Thermal energy storage technologies and systems for concentrating solar power plants , 2013 .

[16]  Guy Ervin,et al.  Solar heat storage using chemical reactions , 1977 .

[17]  Hans Müller-Steinhagen,et al.  A thermodynamic and kinetic study of the de- and rehydration of Ca(OH)2 at high H2O partial pressures for thermo-chemical heat storage , 2012 .

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

[19]  A. Navrotsky,et al.  Thermodynamic Properties of Manganese Oxides , 1996 .

[20]  J. D. Ford,et al.  Energy storage using the BaO2BaO reaction cycle , 1983 .

[21]  H.William Prengle,et al.  Solar energy with chemical storage for cogeneration of electric power and heat , 1980 .

[22]  D. Ivey,et al.  Investigation of electrochemical behavior of Mn–Co doped oxide electrodes for electrochemical capacitors , 2011 .

[23]  Kevin W Eliceiri,et al.  NIH Image to ImageJ: 25 years of image analysis , 2012, Nature Methods.

[24]  V. Berbenni,et al.  Oxidation behaviour of mechanically activated Mn3O4 by TGA/DSC/XRPD , 2003 .

[25]  Peter G. Bruce,et al.  Synthesis of layered LiMnO2 as an electrode for rechargeable lithium batteries , 1996, Nature.

[26]  Weifeng Wei,et al.  Oxidation resistance and electrical properties of anodically electrodeposited Mn–Co oxide coatings for solid oxide fuel cell interconnect applications , 2009 .

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

[28]  G. El-Shobaky,et al.  Thermal behaviour of cobaltic and cobaltous oxides as influenced by doping with some alkali metal oxides , 1983 .

[29]  Marc A. Rosen,et al.  Assessment of a closed thermochemical energy storage using energy and exergy methods , 2012 .

[30]  Maw-Chwain Lee,et al.  Chemical storage of solar energy kinetics of heterogeneous SO3 and H2O reaction—Reaction analysis and reactor design , 1990 .

[31]  Z. Xu,et al.  Thermal evolution of cobalt hydroxides: a comparative study of their various structural phases , 1998 .

[32]  W. Hou,et al.  CO hydrogenation over nanometer spinel-type Co/Mn complex oxides prepared by sol-gel method , 1998 .

[33]  A. Rousset,et al.  Structure and electrical properties of single-phase cobalt manganese oxide spinels Mn3−xCoxO4 sintered classically and by spark plasma sintering (SPS) , 2009 .