Detailed Studies of a High-Capacity Electrode Material for Rechargeable Batteries, Li<sub>2</sub>MnO<sub>3</sub>−LiCo<sub>1/3</sub>Ni<sub>1/3</sub>Mn<sub>1/3</sub>O<sub>2</sub>
Naoaki Yabuuchi
Kazuhiro Yoshii
Seung-Taek Myung
Izumi Nakai
Shinichi Komaba
10.1021/ja108588y.s001
https://acs.figshare.com/articles/journal_contribution/Detailed_Studies_of_a_High_Capacity_Electrode_Material_for_Rechargeable_Batteries_Li_sub_2_sub_MnO_sub_3_sub_LiCo_sub_1_3_sub_Ni_sub_1_3_sub_Mn_sub_1_3_sub_O_sub_2_sub_/2675290
Lithium-excess manganese layered oxides, which are commonly described by the chemical formula <i>z</i>Li<sub>2</sub>MnO<sub>3</sub>−(1 − <i>z</i>)LiMeO<sub>2</sub> (Me = Co, Ni, Mn, etc.), are of great importance as positive electrode materials for rechargeable lithium batteries. In this Article, Li<sub><i>x</i></sub>Co<sub>0.13</sub>Ni<sub>0.13</sub>Mn<sub>0.54</sub>O<sub>2−δ</sub> samples are prepared from Li<sub>1.2</sub>Ni<sub>0.13</sub>Co<sub>0.13</sub>Mn<sub>0.54</sub>O<sub>2</sub> (or 0.5Li<sub>2</sub>MnO<sub>3</sub>−0.5LiCo<sub>1/3</sub>Ni<sub>1/3</sub>Mn<sub>1/3</sub>O<sub>2</sub>) by an electrochemical oxidation/reduction process in an electrochemical cell to study a reaction mechanism in detail before and after charging across a voltage plateau at 4.5 V vs Li/Li<sup>+</sup>. Changes of the bulk and surface structures are examined by synchrotron X-ray diffraction (SXRD), X-ray absorption spectroscopy (XAS), X-ray photoelectron spectroscopy (XPS), and time-of-flight secondary ion mass spectroscopy (SIMS). SXRD data show that simultaneous oxygen and lithium removal at the voltage plateau upon initial charge causes the structural rearrangement, including a cation migration process from metal to lithium layers, which is also supported by XAS. This is consistent with the mechanism proposed in the literature related to the Li-excess manganese layered oxides. Oxygen removal associated with the initial charge on the high voltage plateau causes oxygen molecule generation in the electrochemical cells. The oxygen molecules in the cell are electrochemically reduced in the subsequent discharge below 3.0 V, leading to the extra capacity. Surface analysis confirms the formation of the oxygen containing species, such as lithium carbonate, which accumulates on the electrode surface. The oxygen containing species are electrochemically decomposed upon second charge above 4.0 V. The results suggest that, in addition to the conventional transition metal redox reactions, at least some of the reversible capacity for the Li-excess manganese layered oxides originates from the electrochemical redox reaction of the oxygen molecules at the electrode surface.
2011-03-30 00:00:00
ion mass spectroscopy
LixCo 0.13Ni samples
charge
XAS
0.5 Li 2MnO
voltage plateau causes oxygen molecule generation
XPS
electrochemical redox reaction
electrode surface
transition metal redox reactions
Li 2MnO manganese
voltage plateau
oxide
oxygen molecules
lithium
SIMS
cation migration process
SXRD data show