TY - JOUR
T1 - Thermochemistry of cation disordered Li ion battery cathode materials, (M′ = Nb and Ta, M′′ = Mn and Fe)
AU - Subramani, Tamilarasan
AU - Navrotsky, Alexandra
N1 - Funding Information:
This study was supported by the U.S. Department of Energy, grant DE-FG02-03ER46053.
Publisher Copyright:
This journal is © The Royal Society of Chemistry.
PY - 2020
Y1 - 2020
N2 - High temperature oxide melt solution calorimetry studies on (M′ = Nb5+, M′′ = Mn3+ and Fe3+ and x = 0.20, 0.30 and 0.40) oxides and a new family of Ta containing Li excess disordered cathode materials, (M′ = Ta5+, M′′ = Fe3+ and x = 0.20, 0.30 and 0.40), synthesized by a rapid quenching method, are reported in this study. The enthalpies of formation determined from high temperature calorimetry studies reveal that the stability of compounds increases with the increasing Li content per formula unit. The reaction between more basic Li2O and acidic transition metal oxides results in the more negative enthalpies of formation for these compounds. The work reveals that the formation enthalpy term plays a more important role in the stabilization of such disordered Li ion materials at room temperature whereas configurational entropy along with lattice entropy (vibrational and magnetic) contributes to the stabilization at high temperature from which the samples are quenched.
AB - High temperature oxide melt solution calorimetry studies on (M′ = Nb5+, M′′ = Mn3+ and Fe3+ and x = 0.20, 0.30 and 0.40) oxides and a new family of Ta containing Li excess disordered cathode materials, (M′ = Ta5+, M′′ = Fe3+ and x = 0.20, 0.30 and 0.40), synthesized by a rapid quenching method, are reported in this study. The enthalpies of formation determined from high temperature calorimetry studies reveal that the stability of compounds increases with the increasing Li content per formula unit. The reaction between more basic Li2O and acidic transition metal oxides results in the more negative enthalpies of formation for these compounds. The work reveals that the formation enthalpy term plays a more important role in the stabilization of such disordered Li ion materials at room temperature whereas configurational entropy along with lattice entropy (vibrational and magnetic) contributes to the stabilization at high temperature from which the samples are quenched.
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U2 - 10.1039/c9ra09759g
DO - 10.1039/c9ra09759g
M3 - Article
AN - SCOPUS:85079570289
SN - 2046-2069
VL - 10
SP - 6540
EP - 6546
JO - RSC Advances
JF - RSC Advances
IS - 11
ER -