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Lithium electrochemical deintercalation from O2-LiCoO2: Structure and physical properties

Identifieur interne : 000248 ( PascalFrancis/Checkpoint ); précédent : 000247; suivant : 000249

Lithium electrochemical deintercalation from O2-LiCoO2: Structure and physical properties

Auteurs : D. Carlier [France] ; I. Saadoune [France, Maroc] ; M. Menetrier [France] ; C. Delmas [France]

Source :

RBID : Pascal:03-0008873

Descripteurs français

English descriptors

Abstract

Electrochemical deintercalation of Li from the metastable O2-LiCoO2 phase has been investigated up to the composition Li0.15CoO2. The single-phase domains that separate the voltage plateaus observed have been characterized by X-ray diffraction. The succession of phases observed upon deintercalation results from reversible sheet gliding or lithium/vacancy ordering, leading to the sequence 02, T#2, T#2', 06, 02, 02. In particular, the T#2 stacking, similar to the T2 phase reported by Dahn and co-workers for the Li2/3Ni1/3Mn2/3O2 phases, corresponds to oxygen ions not sitting on the three positions of a triangular lattice, hence the # character is used. It exhibits very distorted tetrahedral sites for Li. The 06 stacking exhibits two kinds of CoO6 octahedra, which might allow Co3+/Co4+ ordering in alternate sheets. The most deintercalated O2-Li0.15CoO2 phase has never been reported before. Electronic properties and 7Li magic-angle spinning nuclear magnetic resonance show a transition to a metallic state for x< 0.94 (appearance of the T#2 phase with x = 0.72). These stacking changes are proposed to result from the minimization of electrostatic repulsion, except for T#2' (x = 0.50), which is believed to result from a Li/vacancy ordering.


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<div type="abstract" xml:lang="en">Electrochemical deintercalation of Li from the metastable O2-LiCoO
<sub>2</sub>
phase has been investigated up to the composition Li
<sub>0.15</sub>
CoO
<sub>2</sub>
. The single-phase domains that separate the voltage plateaus observed have been characterized by X-ray diffraction. The succession of phases observed upon deintercalation results from reversible sheet gliding or lithium/vacancy ordering, leading to the sequence 02, T#2, T#2', 06, 02, 02. In particular, the T#2 stacking, similar to the T2 phase reported by Dahn and co-workers for the Li
<sub>2/3</sub>
Ni
<sub>1/3</sub>
Mn
<sub>2/3</sub>
O
<sub>2</sub>
phases, corresponds to oxygen ions not sitting on the three positions of a triangular lattice, hence the # character is used. It exhibits very distorted tetrahedral sites for Li. The 06 stacking exhibits two kinds of CoO
<sub>6</sub>
octahedra, which might allow Co
<sup>3+</sup>
/Co
<sup>4+</sup>
ordering in alternate sheets. The most deintercalated O2-Li
<sub>0.15</sub>
CoO
<sub>2</sub>
phase has never been reported before. Electronic properties and
<sup>7</sup>
Li magic-angle spinning nuclear magnetic resonance show a transition to a metallic state for x< 0.94 (appearance of the T#2 phase with x = 0.72). These stacking changes are proposed to result from the minimization of electrostatic repulsion, except for T#2' (x = 0.50), which is believed to result from a Li/vacancy ordering.</div>
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phase has been investigated up to the composition Li
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<sub>2</sub>
. The single-phase domains that separate the voltage plateaus observed have been characterized by X-ray diffraction. The succession of phases observed upon deintercalation results from reversible sheet gliding or lithium/vacancy ordering, leading to the sequence 02, T#2, T#2', 06, 02, 02. In particular, the T#2 stacking, similar to the T2 phase reported by Dahn and co-workers for the Li
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Mn
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</fC03>
<fC03 i1="12" i2="X" l="FRE">
<s0>Propriété électronique</s0>
<s5>14</s5>
</fC03>
<fC03 i1="12" i2="X" l="ENG">
<s0>Electronic properties</s0>
<s5>14</s5>
</fC03>
<fC03 i1="12" i2="X" l="SPA">
<s0>Propiedad electrónica</s0>
<s5>14</s5>
</fC03>
<fC03 i1="13" i2="X" l="FRE">
<s0>Morphologie cristalline</s0>
<s5>15</s5>
</fC03>
<fC03 i1="13" i2="X" l="ENG">
<s0>Crystal morphology</s0>
<s5>15</s5>
</fC03>
<fC03 i1="13" i2="X" l="SPA">
<s0>Morfología cristalina</s0>
<s5>15</s5>
</fC03>
<fC03 i1="14" i2="X" l="FRE">
<s0>Caractéristique électrique</s0>
<s5>16</s5>
</fC03>
<fC03 i1="14" i2="X" l="ENG">
<s0>Electrical characteristic</s0>
<s5>16</s5>
</fC03>
<fC03 i1="14" i2="X" l="SPA">
<s0>Característica eléctrica</s0>
<s5>16</s5>
</fC03>
<fC03 i1="15" i2="X" l="FRE">
<s0>Cycle charge décharge</s0>
<s5>17</s5>
</fC03>
<fC03 i1="15" i2="X" l="ENG">
<s0>Discharge charge cycle</s0>
<s5>17</s5>
</fC03>
<fC03 i1="15" i2="X" l="SPA">
<s0>Ciclo carga descarga</s0>
<s5>17</s5>
</fC03>
<fC03 i1="16" i2="X" l="FRE">
<s0>Capacité spécifique</s0>
<s5>18</s5>
</fC03>
<fC03 i1="16" i2="X" l="ENG">
<s0>Specific capacity</s0>
<s5>18</s5>
</fC03>
<fC03 i1="16" i2="X" l="SPA">
<s0>Capacidad específica</s0>
<s5>18</s5>
</fC03>
<fC03 i1="17" i2="X" l="FRE">
<s0>Spectrométrie RMN</s0>
<s5>19</s5>
</fC03>
<fC03 i1="17" i2="X" l="ENG">
<s0>NMR spectrometry</s0>
<s5>19</s5>
</fC03>
<fC03 i1="17" i2="X" l="SPA">
<s0>Espectrometría RMN</s0>
<s5>19</s5>
</fC03>
<fC03 i1="18" i2="X" l="FRE">
<s0>Diffraction RX</s0>
<s5>20</s5>
</fC03>
<fC03 i1="18" i2="X" l="ENG">
<s0>X ray diffraction</s0>
<s5>20</s5>
</fC03>
<fC03 i1="18" i2="X" l="SPA">
<s0>Difracción RX</s0>
<s5>20</s5>
</fC03>
<fC03 i1="19" i2="3" l="FRE">
<s0>Lithium 7</s0>
<s5>21</s5>
</fC03>
<fC03 i1="19" i2="3" l="ENG">
<s0>Lithium 7</s0>
<s5>21</s5>
</fC03>
<fC03 i1="20" i2="X" l="FRE">
<s0>LiCoO(2)</s0>
<s4>INC</s4>
<s5>32</s5>
</fC03>
<fC03 i1="21" i2="X" l="FRE">
<s0>Co Li O</s0>
<s4>INC</s4>
<s5>33</s5>
</fC03>
<fC07 i1="01" i2="X" l="FRE">
<s0>Métal alcalin Composé</s0>
<s2>NC</s2>
<s2>NA</s2>
<s5>06</s5>
</fC07>
<fC07 i1="01" i2="X" l="ENG">
<s0>Alkali metal Compounds</s0>
<s2>NC</s2>
<s2>NA</s2>
<s5>06</s5>
</fC07>
<fC07 i1="01" i2="X" l="SPA">
<s0>Metal alcalino Compuesto</s0>
<s2>NC</s2>
<s2>NA</s2>
<s5>06</s5>
</fC07>
<fC07 i1="02" i2="X" l="FRE">
<s0>Métal transition Composé</s0>
<s2>NC</s2>
<s2>NA</s2>
<s5>07</s5>
</fC07>
<fC07 i1="02" i2="X" l="ENG">
<s0>Transition metal Compounds</s0>
<s2>NC</s2>
<s2>NA</s2>
<s5>07</s5>
</fC07>
<fC07 i1="02" i2="X" l="SPA">
<s0>Metal transición Compuesto</s0>
<s2>NC</s2>
<s2>NA</s2>
<s5>07</s5>
</fC07>
<fN21>
<s1>001</s1>
</fN21>
<fN82>
<s1>PSI</s1>
</fN82>
</pA>
</standard>
</inist>
<affiliations>
<list>
<country>
<li>France</li>
<li>Maroc</li>
</country>
<region>
<li>Aquitaine</li>
<li>Nouvelle-Aquitaine</li>
</region>
<settlement>
<li>Pessac</li>
</settlement>
</list>
<tree>
<country name="France">
<region name="Nouvelle-Aquitaine">
<name sortKey="Carlier, D" sort="Carlier, D" uniqKey="Carlier D" first="D." last="Carlier">D. Carlier</name>
</region>
<name sortKey="Delmas, C" sort="Delmas, C" uniqKey="Delmas C" first="C." last="Delmas">C. Delmas</name>
<name sortKey="Menetrier, M" sort="Menetrier, M" uniqKey="Menetrier M" first="M." last="Menetrier">M. Menetrier</name>
<name sortKey="Saadoune, I" sort="Saadoune, I" uniqKey="Saadoune I" first="I." last="Saadoune">I. Saadoune</name>
</country>
<country name="Maroc">
<noRegion>
<name sortKey="Saadoune, I" sort="Saadoune, I" uniqKey="Saadoune I" first="I." last="Saadoune">I. Saadoune</name>
</noRegion>
</country>
</tree>
</affiliations>
</record>

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