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ACS Appl Mater Interfaces. 2016 Oct 12;8(40):26842-26850. Epub 2016 Sep 29.

About the Compatibility between High Voltage Spinel Cathode Materials and Solid Oxide Electrolytes as a Function of Temperature.

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Samsung Advanced Institute of Technology - USA , 255 Main Street, Suite 702, Cambridge, Massachusetts 02142, United States.
Institute of Energy and Climate Research, Materials Synthesis and Processing (IEK-1), Forschungszentrum Jülich GmbH , 52425 Jülich, Germany.
Jülich Aachen Research Alliance: JARA-Energy, Forschungszentrum Jülich GmbH , 52425 Jülich, Germany.
Department of Materials Science and Engineering, Massachusetts Institute of Technology , 77 Massachusetts Avenue, Cambridge, Massachusetts 02139, United States.
Department of Materials Science and Engineering, UC Berkeley , 210 Hearst Mining Building, Berkeley, California 94720-1760, United States.


The reactivity of mixtures of high voltage spinel cathode materials Li2NiMn3O8, Li2FeMn3O8, and LiCoMnO4 cosintered with Li1.5Al0.5Ti1.5(PO4)3 and Li6.6La3Zr1.6Ta0.4O12 electrolytes is studied by thermal analysis using X-ray-diffraction and differential thermoanalysis and thermogravimetry coupled with mass spectrometry. The results are compared with predicted decomposition reactions from first-principles calculations. Decomposition of the mixtures begins at 600 °C, significantly lower than the decomposition temperature of any component, especially the electrolytes. For the cathode + Li6.6La3Zr1.6Ta0.4O12 mixtures, lithium and oxygen from the electrolyte react with the cathodes to form highly stable Li2MnO3 and then decompose to form stable and often insulating phases such as La2Zr2O7, La2O3, La3TaO7, TiO2, and LaMnO3 which are likely to increase the interfacial impedance of a cathode composite. The decomposition reactions are identified with high fidelity by first-principles calculations. For the cathode + Li1.5Al0.5Ti1.5(PO4)3 mixtures, the Mn tends to oxidize to MnO2 or Mn2O3, supplying lithium to the electrolyte for the formation of Li3PO4 and metal phosphates such as AlPO4 and LiMPO4 (M = Mn, Ni). The results indicate that high temperature cosintering to form dense cathode composites between spinel cathodes and oxide electrolytes will produce high impedance interfacial products, complicating solid state battery manufacturing.


atomistic modeling; garnet; interfacial reactivity; solid electrolyte; solid ion conductor


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