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Charge-transfer modified embedded atom method dynamic charge potential for Li–Co–O system
Kong, Fantai,Longo, Roberto C,Liang, Chaoping,Nie, Yifan,Zheng, Yongping,Zhang, Chenxi,Cho, Kyeongjae Institute of Physics 2017 Journal of Physics, Condensed Matter Vol.29 No.47
<P>To overcome the limitation of conventional fixed charge potential methods for the study of Li-ion battery cathode materials, a dynamic charge potential method, charge-transfer modified embedded atom method (CT-MEAM), has been developed and applied to the Li–Co–O ternary system. The accuracy of the potential has been tested and validated by reproducing a variety of structural and electrochemical properties of LiCoO<SUB>2</SUB>. A detailed analysis on the local charge distribution confirmed the capability of this potential for dynamic charge modeling. The transferability of the potential is also demonstrated by its reliability in describing Li-rich Li<SUB>2</SUB>CoO<SUB>2</SUB> and Li-deficient LiCo<SUB>2</SUB>O<SUB>4</SUB> compounds, including their phase stability, equilibrium volume, charge states and cathode voltages. These results demonstrate that the CT-MEAM dynamic charge potential could help to overcome the challenge of modeling complex ternary transition metal oxides. This work can promote molecular dynamics studies of Li ion cathode materials and other important transition metal oxides systems that involve complex electrochemical and catalytic reactions.</P>
Longo, Roberto C.,Liang, Chaoping,Kong, Fantai,Cho, Kyeongjae American Chemical Society 2018 ACS APPLIED MATERIALS & INTERFACES Vol.10 No.22
<P>The structural stability of Li-rich layered oxide cathode materials is the ultimate frontier to allow the full development of these family of electrode materials. Here, first-principles calculations coupled with cluster expansion are presented to investigate the electrochemical activity of phase-separation, core-shell-structured <I>x</I>Li<SUB>2</SUB>MnO<SUB>3</SUB>·(1 - <I>x</I>)LiNiCoMnO<SUB>2</SUB> nanocomposites. The detrimental surface effects of the core region can be countered by the Li<SUB>2</SUB>MnO<SUB>3</SUB> shell, which stabilizes the nanocomposites. The operational voltage windows are accurately determined to avoid the electrochemical activation of the shell and the subsequent structural evolution. In particular, the dependence of the activation voltage with the shell thickness shows that relatively high voltages can still be obtained to meet the energy density needs of Li-ion battery applications. Finally, activation energies of Li migration at the core-shell interface must also be analyzed carefully to avoid the outbreak of a phase transformation, thus making the nanocomposites suitable from a structural viewpoint.</P> [FIG OMISSION]</BR>
Zheng, Yongping,Yang, Dae-Soo,Kweun, Joshua M.,Li, Chenzhe,Tan, Kui,Kong, Fantai,Liang, Chaoping,Chabal, Yves J.,Kim, Yoon Young,Cho, Maenghyo,Yu, Jong-Sung,Cho, Kyeongjae Elsevier 2016 Nano energy Vol.30 No.-
<P><B>Abstract</B></P> <P>Bio-inspired non-precious-metal catalysts based on iron and cobalt porphyrins are promising alternatives to replace costly platinum-based catalysts for oxygen reduction reaction (ORR) in fuel cells. However, the exact nature of the active sites is still not clearly understood, and further optimization design is needed for practical applications. Here, we report a rational catalyst design process by combining density functional theory (DFT) calculations and experimental validations. Two sets of square-planar (MN<SUB>x</SUB>C<SUB>4−x</SUB>) and square-pyramid (MN<SUB>x</SUB>C<SUB>5−x</SUB>) active centers (M=Mn, Fe, Co, Ni) incorporated in graphene were examined using DFT. Fe-N<SUB>5</SUB> and Co-N<SUB>4</SUB> sites were identified theoretically to have the best performance in fuel cells, while Ni-N<SUB>x</SUB>C<SUB>4−x</SUB> sites catalyze the most H<SUB>2</SUB>O<SUB>2</SUB> byproduct. Graphene samples with well-dispersed incorporations of metals were synthesized, and the following electrochemical measurements show an excellent agreement with the theoretical predictions, indicating that a successful design framework and systematic understanding toward the catalytic nature of these materials are established.</P> <P><B>Highlights</B></P> <P> <UL> <LI> Graphene based catalysts design for ORR is demonstrated by combining experiments and modellings. </LI> <LI> Iron porphyrin like active site is unraveled to be five nitrogen coordinated as FeN<SUB>5</SUB>. </LI> <LI> Cobalt porphyrin like active site is shown to be four nitrogen coordinated as CoN<SUB>4</SUB>. </LI> <LI> Nickel porphyrin like catalyst is potentially used for catalytic synthesis of H<SUB>2</SUB>O<SUB>2</SUB>. </LI> </UL> </P> <P><B>Graphical abstract</B></P> <P>[DISPLAY OMISSION]</P>
Zheng, Yongping,Thampy, Sampreetha,Ashburn, Nickolas,Dillon, Sean,Wang, Luhua,Jangjou, Yasser,Tan, Kui,Kong, Fantai,Nie, Yifan,Kim, Moon J.,Epling, William S.,Chabal, Yves J.,Hsu, Julia W. P.,Cho, Kye American Chemical Society 2019 JOURNAL OF THE AMERICAN CHEMICAL SOCIETY - Vol.141 No.27
<P>The correlation between lattice oxygen (O) binding energy and O oxidation activity imposes a fundamental limit in developing oxide catalysts, simultaneously meeting the stringent thermal stability and catalytic activity standards for complete oxidation reactions under harsh conditions. Typically, strong O binding indicates a stable surface structure, but low O oxidation activity, and <I>vice</I><I>versa</I>. Using nitric oxide (NO) catalytic oxidation as a model reaction, we demonstrate that this conflicting correlation can be avoided by cooperative lattice oxygen redox on SmMn<SUB>2</SUB>O<SUB>5</SUB> mullite oxides, leading to stable and active oxide surface structures. The strongly bound neighboring lattice oxygen pair cooperates in NO oxidation to form bridging nitrate (NO<SUB>3</SUB><SUP>-</SUP>) intermediates, which can facilely transform into monodentate NO<SUB>3</SUB><SUP>-</SUP> by a concerted rotation with simultaneous O<SUB>2</SUB> adsorption onto the resulting oxygen vacancy. Subsequently, monodentate NO<SUB>3</SUB><SUP>-</SUP> species decompose to NO<SUB>2</SUB> to restore one of the lattice oxygen atoms that act as a reversible redox center, and the vacancy can easily activate O<SUB>2</SUB> to replenish the consumed one. This discovery not only provides insights into the cooperative reaction mechanism but also aids the design of oxidation catalysts with the strong O binding region, offering strong activation of O<SUB>2</SUB>, high O activity, and high thermal stability in harsh conditions.</P> [FIG OMISSION]</BR>