On the metastable O2-type LiCoO2
Identifieur interne : 000887 ( Istex/Corpus ); précédent : 000886; suivant : 000888On the metastable O2-type LiCoO2
Auteurs : D. Carlier ; I. Saadoune ; L. Croguennec ; M. Ménétrier ; E. Suard ; C. DelmasSource :
- Solid State Ionics [ 0167-2738 ] ; 2001.
Abstract
The exchange of sodium for lithium in P2-Na0.70CoO2 leads to an unusual O2-LiCoO2 variety. Rietveld refinement of the neutron diffraction pattern of the O2-LiCoO2 phase confirms the stoichiometry and the structural parameters previously reported and shows that the strong Li+–Co3+ electrostatic repulsion occurring through the common face of the CoO6 and LiO6 octahedra leads to small displacements of the lithium and cobalt ions from the center of their octahedra. Magnetic measurements and 7Li MAS NMR confirm a composition very close to the ideal one for the O2 phase. The O2-LiCoO2 phase is metastable and transforms to well-crystallized O3-LiCoO2 upon heating. Even at intermediate temperatures, the formation of LT-LiCoO2 phase is never observed. Various morphologies are obtained for the O3-LiCoO2 phases, depending on the thermal treatment used. A preliminary electrochemical study shows that almost all the lithium ions can be reversibly deintercalated from the O2-LiCoO2 phase.
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DOI: 10.1016/S0167-2738(01)00982-1
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Schweitzer, 33608 Pessac cedex, France</mods:affiliation></affiliation></author><author><name sortKey="Saadoune, I" sort="Saadoune, I" uniqKey="Saadoune I" first="I" last="Saadoune">I. Saadoune</name><affiliation><mods:affiliation>Institut de Chimie de la Matière Condensée de Bordeaux, CNRS and Ecole Nationale Supérieure de Chimie et Physique de Bordeaux, Chateau de Bivazac, 87 av. Dr A. Schweitzer, 33608 Pessac cedex, France</mods:affiliation></affiliation></author><author><name sortKey="Croguennec, L" sort="Croguennec, L" uniqKey="Croguennec L" first="L" last="Croguennec">L. Croguennec</name><affiliation><mods:affiliation>Institut de Chimie de la Matière Condensée de Bordeaux, CNRS and Ecole Nationale Supérieure de Chimie et Physique de Bordeaux, Chateau de Bivazac, 87 av. Dr A. Schweitzer, 33608 Pessac cedex, France</mods:affiliation></affiliation></author><author><name sortKey="Menetrier, M" sort="Menetrier, M" uniqKey="Menetrier M" first="M" last="Ménétrier">M. Ménétrier</name><affiliation><mods:affiliation>Institut de Chimie de la Matière Condensée de Bordeaux, CNRS and Ecole Nationale Supérieure de Chimie et Physique de Bordeaux, Chateau de Bivazac, 87 av. Dr A. Schweitzer, 33608 Pessac cedex, France</mods:affiliation></affiliation></author><author><name sortKey="Suard, E" sort="Suard, E" uniqKey="Suard E" first="E" last="Suard">E. Suard</name><affiliation><mods:affiliation>Institut Laue-Langevin, rue des Martyrs, B.P. 156X, 38042 Grenoble cedex 9, France</mods:affiliation></affiliation></author><author><name sortKey="Delmas, C" sort="Delmas, C" uniqKey="Delmas C" first="C" last="Delmas">C. Delmas</name><affiliation><mods:affiliation>E-mail: delmas@icmcb.u-bordeaux.fr</mods:affiliation></affiliation><affiliation><mods:affiliation>Institut de Chimie de la Matière Condensée de Bordeaux, CNRS and Ecole Nationale Supérieure de Chimie et Physique de Bordeaux, Chateau de Bivazac, 87 av. Dr A. Schweitzer, 33608 Pessac cedex, France</mods:affiliation></affiliation></author></analytic><monogr></monogr><series><title level="j">Solid State Ionics</title><title level="j" type="abbrev">SOSI</title><idno type="ISSN">0167-2738</idno><imprint><publisher>ELSEVIER</publisher><date type="published" when="2001">2001</date><biblScope unit="volume">144</biblScope><biblScope unit="issue">3–4</biblScope><biblScope unit="page" from="263">263</biblScope><biblScope unit="page" to="276">276</biblScope></imprint><idno type="ISSN">0167-2738</idno></series><idno type="istex">309C387EA12B64F1D046DDE4565AFADDD4D5EA98</idno><idno type="DOI">10.1016/S0167-2738(01)00982-1</idno><idno type="PII">S0167-2738(01)00982-1</idno></biblStruct></sourceDesc><seriesStmt><idno type="ISSN">0167-2738</idno></seriesStmt></fileDesc><profileDesc><textClass></textClass><langUsage><language ident="en">en</language></langUsage></profileDesc></teiHeader><front><div type="abstract" xml:lang="en">The exchange of sodium for lithium in P2-Na0.70CoO2 leads to an unusual O2-LiCoO2 variety. Rietveld refinement of the neutron diffraction pattern of the O2-LiCoO2 phase confirms the stoichiometry and the structural parameters previously reported and shows that the strong Li+–Co3+ electrostatic repulsion occurring through the common face of the CoO6 and LiO6 octahedra leads to small displacements of the lithium and cobalt ions from the center of their octahedra. Magnetic measurements and 7Li MAS NMR confirm a composition very close to the ideal one for the O2 phase. The O2-LiCoO2 phase is metastable and transforms to well-crystallized O3-LiCoO2 upon heating. Even at intermediate temperatures, the formation of LT-LiCoO2 phase is never observed. Various morphologies are obtained for the O3-LiCoO2 phases, depending on the thermal treatment used. A preliminary electrochemical study shows that almost all the lithium ions can be reversibly deintercalated from the O2-LiCoO2 phase.</div></front></TEI><istex><corpusName>elsevier</corpusName><author><json:item><name>D Carlier</name><affiliations><json:string>Institut de Chimie de la Matière Condensée de Bordeaux, CNRS and Ecole Nationale Supérieure de Chimie et Physique de Bordeaux, Chateau de Bivazac, 87 av. Dr A. Schweitzer, 33608 Pessac cedex, France</json:string></affiliations></json:item><json:item><name>I Saadoune</name><affiliations><json:string>Institut de Chimie de la Matière Condensée de Bordeaux, CNRS and Ecole Nationale Supérieure de Chimie et Physique de Bordeaux, Chateau de Bivazac, 87 av. Dr A. Schweitzer, 33608 Pessac cedex, France</json:string></affiliations></json:item><json:item><name>L Croguennec</name><affiliations><json:string>Institut de Chimie de la Matière Condensée de Bordeaux, CNRS and Ecole Nationale Supérieure de Chimie et Physique de Bordeaux, Chateau de Bivazac, 87 av. Dr A. Schweitzer, 33608 Pessac cedex, France</json:string></affiliations></json:item><json:item><name>M Ménétrier</name><affiliations><json:string>Institut de Chimie de la Matière Condensée de Bordeaux, CNRS and Ecole Nationale Supérieure de Chimie et Physique de Bordeaux, Chateau de Bivazac, 87 av. Dr A. Schweitzer, 33608 Pessac cedex, France</json:string></affiliations></json:item><json:item><name>E Suard</name><affiliations><json:string>Institut Laue-Langevin, rue des Martyrs, B.P. 156X, 38042 Grenoble cedex 9, France</json:string></affiliations></json:item><json:item><name>C Delmas</name><affiliations><json:string>E-mail: delmas@icmcb.u-bordeaux.fr</json:string><json:string>Institut de Chimie de la Matière Condensée de Bordeaux, CNRS and Ecole Nationale Supérieure de Chimie et Physique de Bordeaux, Chateau de Bivazac, 87 av. Dr A. Schweitzer, 33608 Pessac cedex, France</json:string></affiliations></json:item></author><subject><json:item><lang><json:string>eng</json:string></lang><value>Layered oxides</value></json:item><json:item><lang><json:string>eng</json:string></lang><value>LiCoO2</value></json:item><json:item><lang><json:string>eng</json:string></lang><value>Ion-exchange reaction</value></json:item><json:item><lang><json:string>eng</json:string></lang><value>Neutron diffraction</value></json:item><json:item><lang><json:string>eng</json:string></lang><value>Magnetic measurements</value></json:item><json:item><lang><json:string>eng</json:string></lang><value>Electrochemical deintercalation</value></json:item><json:item><lang><json:string>eng</json:string></lang><value>Lithium battery</value></json:item></subject><language><json:string>eng</json:string></language><originalGenre><json:string>Full-length article</json:string></originalGenre><abstract>The exchange of sodium for lithium in P2-Na0.70CoO2 leads to an unusual O2-LiCoO2 variety. Rietveld refinement of the neutron diffraction pattern of the O2-LiCoO2 phase confirms the stoichiometry and the structural parameters previously reported and shows that the strong Li+–Co3+ electrostatic repulsion occurring through the common face of the CoO6 and LiO6 octahedra leads to small displacements of the lithium and cobalt ions from the center of their octahedra. Magnetic measurements and 7Li MAS NMR confirm a composition very close to the ideal one for the O2 phase. The O2-LiCoO2 phase is metastable and transforms to well-crystallized O3-LiCoO2 upon heating. Even at intermediate temperatures, the formation of LT-LiCoO2 phase is never observed. Various morphologies are obtained for the O3-LiCoO2 phases, depending on the thermal treatment used. A preliminary electrochemical study shows that almost all the lithium ions can be reversibly deintercalated from the O2-LiCoO2 phase.</abstract><qualityIndicators><score>6.74</score><pdfVersion>1.2</pdfVersion><pdfPageSize>540 x 712 pts</pdfPageSize><refBibsNative>true</refBibsNative><keywordCount>7</keywordCount><abstractCharCount>987</abstractCharCount><pdfWordCount>5693</pdfWordCount><pdfCharCount>31822</pdfCharCount><pdfPageCount>14</pdfPageCount><abstractWordCount>145</abstractWordCount></qualityIndicators><title>On the metastable O2-type LiCoO2</title><pii><json:string>S0167-2738(01)00982-1</json:string></pii><genre><json:string>research-article</json:string></genre><host><volume>144</volume><pii><json:string>S0167-2738(00)X0101-4</json:string></pii><pages><last>276</last><first>263</first></pages><issn><json:string>0167-2738</json:string></issn><issue>3–4</issue><genre><json:string>journal</json:string></genre><language><json:string>unknown</json:string></language><title>Solid State Ionics</title><publicationDate>2001</publicationDate></host><categories><wos><json:string>PHYSICS, CONDENSED MATTER</json:string><json:string>CHEMISTRY, PHYSICAL</json:string></wos></categories><publicationDate>2001</publicationDate><copyrightDate>2001</copyrightDate><doi><json:string>10.1016/S0167-2738(01)00982-1</json:string></doi><id>309C387EA12B64F1D046DDE4565AFADDD4D5EA98</id><score>0.08120052</score><fulltext><json:item><original>true</original><mimetype>application/pdf</mimetype><extension>pdf</extension><uri>https://api.istex.fr/document/309C387EA12B64F1D046DDE4565AFADDD4D5EA98/fulltext/pdf</uri></json:item><json:item><original>false</original><mimetype>application/zip</mimetype><extension>zip</extension><uri>https://api.istex.fr/document/309C387EA12B64F1D046DDE4565AFADDD4D5EA98/fulltext/zip</uri></json:item><istex:fulltextTEI uri="https://api.istex.fr/document/309C387EA12B64F1D046DDE4565AFADDD4D5EA98/fulltext/tei"><teiHeader><fileDesc><titleStmt><title level="a">On the metastable O2-type LiCoO2</title></titleStmt><publicationStmt><authority>ISTEX</authority><publisher>ELSEVIER</publisher><availability><p>ELSEVIER</p></availability><date>2001</date></publicationStmt><notesStmt><note type="content">Fig. 1: The two different oxygen packings of LiCoO2.</note><note type="content">Fig. 2: Sheet gliding involved in the P2→O2 transformation occurring during the ion-exchange process as seen from the (110) section. The black circles are the oxygen ions.</note><note type="content">Fig. 3: X-ray diffraction patterns of the O2-LiCoO2 phase obtained with the various exchange reactions (∗ indicates the position of the (002) peak due to P2-Na0.70CoO2 present as impurity).</note><note type="content">Fig. 4: SEM micrographs of the P2-Na0.70CoO2 precursor (a) and of the O2-LiCoO2 phase obtained after ion-exchange in water (b).</note><note type="content">Fig. 5: Observed and calculated neutron diffraction profiles for the O2-LiCoO2 phase obtained after exchange in water: (•) observed; (—) calculated; lower trace: difference plot; bars: reflections. ∗ indicates the (103) diffraction peak of the P2-Na0.70CoO2 phase.</note><note type="content">Fig. 6: Magnetic susceptibility versus temperature for the O2-LiCoO2, O3-LiCoO2, O3-Li0.97CoO2, O3-Li0.60CoO2 and O3-Li1.08CoO2 phases recorded with a 5000 G field.</note><note type="content">Fig. 7: 7Li MAS NMR spectra of the O2 and O3 LiCoO2 phases, recorded with a Hahn echo sequence and a 10-kHz spinning speed. ∗ indicates the spinning sidebands position.</note><note type="content">Fig. 8: First galvanostatic charge–discharge curve of a LiO3-LiCoO2 cell obtained with a C/100 current density rate (a) and of a LiO2-LiCoO2 cell obtained with a C/40 current density rate (b) 100 and 40 h are respectively needed to remove 1 mol of lithium.</note><note type="content">Fig. 9: X-ray diffraction patterns of the materials obtained after different thermal treatments of O2-LiCoO2. Major peaks of the appearing Co3O4 phase are indicated.</note><note type="content">Fig. 10: Expansion of the first Bragg reflection of the XRD patterns observed for the samples obtained after different thermal treatments of O2-LiCoO2.</note><note type="content">Fig. 11: SEM micrographs of the three different O3-LiCoO2 (ex-O2) phases obtained after a thermal treatment at 400 (a), 600 (b) and 800 °C (c) and of the O3-LiCoO2 obtained by solid-state reaction (d).</note><note type="content">Fig. 12: First galvanostatic charge–discharge curve of LiO3-LiCoO2 (ex-O2) cells obtained with a C/100 current density rate (100 h are needed to remove 1 mol of lithium).</note><note type="content">Table 1: Results of the refinement by the Rietveld method of the O2-LiCoO2 neutron diffraction pattern (the O2 phase was obtained by ion-exchange in aqueous medium)</note><note type="content">Table 2: Comparison of the Li–O and Co–O distances in the two types of LiCoO2</note></notesStmt><sourceDesc><biblStruct type="inbook"><analytic><title level="a">On the metastable O2-type LiCoO2</title><author xml:id="author-1"><persName><forename type="first">D</forename><surname>Carlier</surname></persName><affiliation>Institut de Chimie de la Matière Condensée de Bordeaux, CNRS and Ecole Nationale Supérieure de Chimie et Physique de Bordeaux, Chateau de Bivazac, 87 av. Dr A. Schweitzer, 33608 Pessac cedex, France</affiliation></author><author xml:id="author-2"><persName><forename type="first">I</forename><surname>Saadoune</surname></persName><affiliation>Institut de Chimie de la Matière Condensée de Bordeaux, CNRS and Ecole Nationale Supérieure de Chimie et Physique de Bordeaux, Chateau de Bivazac, 87 av. Dr A. Schweitzer, 33608 Pessac cedex, France</affiliation></author><author xml:id="author-3"><persName><forename type="first">L</forename><surname>Croguennec</surname></persName><affiliation>Institut de Chimie de la Matière Condensée de Bordeaux, CNRS and Ecole Nationale Supérieure de Chimie et Physique de Bordeaux, Chateau de Bivazac, 87 av. Dr A. Schweitzer, 33608 Pessac cedex, France</affiliation></author><author xml:id="author-4"><persName><forename type="first">M</forename><surname>Ménétrier</surname></persName><affiliation>Institut de Chimie de la Matière Condensée de Bordeaux, CNRS and Ecole Nationale Supérieure de Chimie et Physique de Bordeaux, Chateau de Bivazac, 87 av. Dr A. Schweitzer, 33608 Pessac cedex, France</affiliation></author><author xml:id="author-5"><persName><forename type="first">E</forename><surname>Suard</surname></persName><affiliation>Institut Laue-Langevin, rue des Martyrs, B.P. 156X, 38042 Grenoble cedex 9, France</affiliation></author><author xml:id="author-6"><persName><forename type="first">C</forename><surname>Delmas</surname></persName><email>delmas@icmcb.u-bordeaux.fr</email><note type="correspondence"><p>Corresponding author. Tel.: +33-5-5684-6296; fax: +33-5-5684-6634</p></note><affiliation>Institut de Chimie de la Matière Condensée de Bordeaux, CNRS and Ecole Nationale Supérieure de Chimie et Physique de Bordeaux, Chateau de Bivazac, 87 av. Dr A. Schweitzer, 33608 Pessac cedex, France</affiliation></author></analytic><monogr><title level="j">Solid State Ionics</title><title level="j" type="abbrev">SOSI</title><idno type="pISSN">0167-2738</idno><idno type="PII">S0167-2738(00)X0101-4</idno><imprint><publisher>ELSEVIER</publisher><date type="published" when="2001"></date><biblScope unit="volume">144</biblScope><biblScope unit="issue">3–4</biblScope><biblScope unit="page" from="263">263</biblScope><biblScope unit="page" to="276">276</biblScope></imprint></monogr><idno type="istex">309C387EA12B64F1D046DDE4565AFADDD4D5EA98</idno><idno type="DOI">10.1016/S0167-2738(01)00982-1</idno><idno type="PII">S0167-2738(01)00982-1</idno></biblStruct></sourceDesc></fileDesc><profileDesc><creation><date>2001</date></creation><langUsage><language ident="en">en</language></langUsage><abstract xml:lang="en"><p>The exchange of sodium for lithium in P2-Na0.70CoO2 leads to an unusual O2-LiCoO2 variety. Rietveld refinement of the neutron diffraction pattern of the O2-LiCoO2 phase confirms the stoichiometry and the structural parameters previously reported and shows that the strong Li+–Co3+ electrostatic repulsion occurring through the common face of the CoO6 and LiO6 octahedra leads to small displacements of the lithium and cobalt ions from the center of their octahedra. Magnetic measurements and 7Li MAS NMR confirm a composition very close to the ideal one for the O2 phase. The O2-LiCoO2 phase is metastable and transforms to well-crystallized O3-LiCoO2 upon heating. Even at intermediate temperatures, the formation of LT-LiCoO2 phase is never observed. Various morphologies are obtained for the O3-LiCoO2 phases, depending on the thermal treatment used. A preliminary electrochemical study shows that almost all the lithium ions can be reversibly deintercalated from the O2-LiCoO2 phase.</p></abstract><textClass><keywords scheme="keyword"><list><head>Keywords</head><item><term>Layered oxides</term></item><item><term>LiCoO2</term></item><item><term>Ion-exchange reaction</term></item><item><term>Neutron diffraction</term></item><item><term>Magnetic measurements</term></item><item><term>Electrochemical deintercalation</term></item><item><term>Lithium battery</term></item></list></keywords></textClass></profileDesc><revisionDesc><change when="2001">Published</change></revisionDesc></teiHeader></istex:fulltextTEI><json:item><original>false</original><mimetype>text/plain</mimetype><extension>txt</extension><uri>https://api.istex.fr/document/309C387EA12B64F1D046DDE4565AFADDD4D5EA98/fulltext/txt</uri></json:item></fulltext><metadata><istex:metadataXml wicri:clean="Elsevier, elements deleted: ce:floats; body; tail"><istex:xmlDeclaration>version="1.0" encoding="utf-8"</istex:xmlDeclaration><istex:docType PUBLIC="-//ES//DTD journal article DTD version 4.5.2//EN//XML" URI="art452.dtd" name="istex:docType"><istex:entity SYSTEM="gr1" NDATA="IMAGE" name="gr1"></istex:entity><istex:entity SYSTEM="gr2" NDATA="IMAGE" name="gr2"></istex:entity><istex:entity SYSTEM="gr3" NDATA="IMAGE" name="gr3"></istex:entity><istex:entity SYSTEM="gr4" NDATA="IMAGE" name="gr4"></istex:entity><istex:entity SYSTEM="gr5" NDATA="IMAGE" name="gr5"></istex:entity><istex:entity SYSTEM="gr6" NDATA="IMAGE" name="gr6"></istex:entity><istex:entity SYSTEM="gr7" NDATA="IMAGE" name="gr7"></istex:entity><istex:entity SYSTEM="gr8" NDATA="IMAGE" name="gr8"></istex:entity><istex:entity SYSTEM="gr9" NDATA="IMAGE" name="gr9"></istex:entity><istex:entity SYSTEM="gr10" NDATA="IMAGE" name="gr10"></istex:entity><istex:entity SYSTEM="gr11" NDATA="IMAGE" name="gr11"></istex:entity><istex:entity SYSTEM="gr12" NDATA="IMAGE" name="gr12"></istex:entity></istex:docType><istex:document><converted-article version="4.5.2" docsubtype="fla"><item-info><jid>SOSI</jid><aid>8157</aid><ce:pii>S0167-2738(01)00982-1</ce:pii><ce:doi>10.1016/S0167-2738(01)00982-1</ce:doi><ce:copyright type="unknown" year="2001"></ce:copyright></item-info><head><ce:title>On the metastable O2-type LiCoO<ce:inf>2</ce:inf></ce:title><ce:author-group><ce:author><ce:given-name>D</ce:given-name><ce:surname>Carlier</ce:surname><ce:cross-ref refid="AFF1"><ce:sup>a</ce:sup></ce:cross-ref></ce:author><ce:author><ce:given-name>I</ce:given-name><ce:surname>Saadoune</ce:surname><ce:cross-ref refid="AFF1"><ce:sup>a</ce:sup></ce:cross-ref><ce:cross-ref refid="AFF2"><ce:sup>b</ce:sup></ce:cross-ref></ce:author><ce:author><ce:given-name>L</ce:given-name><ce:surname>Croguennec</ce:surname><ce:cross-ref refid="AFF1"><ce:sup>a</ce:sup></ce:cross-ref></ce:author><ce:author><ce:indexed-name>Menetrier</ce:indexed-name><ce:given-name>M</ce:given-name><ce:surname>Ménétrier</ce:surname><ce:cross-ref refid="AFF1"><ce:sup>a</ce:sup></ce:cross-ref></ce:author><ce:author><ce:given-name>E</ce:given-name><ce:surname>Suard</ce:surname><ce:cross-ref refid="AFF3"><ce:sup>c</ce:sup></ce:cross-ref></ce:author><ce:author><ce:given-name>C</ce:given-name><ce:surname>Delmas</ce:surname><ce:cross-ref refid="COR1">*</ce:cross-ref><ce:cross-ref refid="AFF1"><ce:sup>a</ce:sup></ce:cross-ref><ce:e-address>delmas@icmcb.u-bordeaux.fr</ce:e-address></ce:author><ce:affiliation id="AFF1"><ce:label>a</ce:label><ce:textfn>Institut de Chimie de la Matière Condensée de Bordeaux, CNRS and Ecole Nationale Supérieure de Chimie et Physique de Bordeaux, Chateau de Bivazac, 87 av. Dr A. Schweitzer, 33608 Pessac cedex, France</ce:textfn></ce:affiliation><ce:affiliation id="AFF2"><ce:label>b</ce:label><ce:textfn>Département de Chimie, Faculté des Sciences et Techniques, Av. Abdelkrim El Khattabi, B.P. 618, 40 000 Marrakech, Morocco</ce:textfn></ce:affiliation><ce:affiliation id="AFF3"><ce:label>c</ce:label><ce:textfn>Institut Laue-Langevin, rue des Martyrs, B.P. 156X, 38042 Grenoble cedex 9, France</ce:textfn></ce:affiliation><ce:correspondence id="COR1"><ce:label>*</ce:label><ce:text>Corresponding author. Tel.: +33-5-5684-6296; fax: +33-5-5684-6634</ce:text></ce:correspondence></ce:author-group><ce:date-received day="30" month="7" year="2001"></ce:date-received><ce:date-accepted day="22" month="8" year="2001"></ce:date-accepted><ce:abstract><ce:section-title>Abstract</ce:section-title><ce:abstract-sec><ce:simple-para>The exchange of sodium for lithium in P2-Na<ce:inf>0.70</ce:inf>CoO<ce:inf>2</ce:inf> leads to an unusual O2-LiCoO<ce:inf>2</ce:inf> variety. Rietveld refinement of the neutron diffraction pattern of the O2-LiCoO<ce:inf>2</ce:inf> phase confirms the stoichiometry and the structural parameters previously reported and shows that the strong Li<ce:sup>+</ce:sup>–Co<ce:sup>3+</ce:sup> electrostatic repulsion occurring through the common face of the CoO<ce:inf>6</ce:inf> and LiO<ce:inf>6</ce:inf> octahedra leads to small displacements of the lithium and cobalt ions from the center of their octahedra. Magnetic measurements and <ce:sup loc="pre">7</ce:sup>Li MAS NMR confirm a composition very close to the ideal one for the O2 phase. The O2-LiCoO<ce:inf>2</ce:inf> phase is metastable and transforms to well-crystallized O3-LiCoO<ce:inf>2</ce:inf> upon heating. Even at intermediate temperatures, the formation of LT-LiCoO<ce:inf>2</ce:inf> phase is never observed. Various morphologies are obtained for the O3-LiCoO<ce:inf>2</ce:inf> phases, depending on the thermal treatment used. A preliminary electrochemical study shows that almost all the lithium ions can be reversibly deintercalated from the O2-LiCoO<ce:inf>2</ce:inf> phase.</ce:simple-para></ce:abstract-sec></ce:abstract><ce:keywords class="keyword"><ce:section-title>Keywords</ce:section-title><ce:keyword><ce:text>Layered oxides</ce:text></ce:keyword><ce:keyword><ce:text>LiCoO<ce:inf>2</ce:inf></ce:text></ce:keyword><ce:keyword><ce:text>Ion-exchange reaction</ce:text></ce:keyword><ce:keyword><ce:text>Neutron diffraction</ce:text></ce:keyword><ce:keyword><ce:text>Magnetic measurements</ce:text></ce:keyword><ce:keyword><ce:text>Electrochemical deintercalation</ce:text></ce:keyword><ce:keyword><ce:text>Lithium battery</ce:text></ce:keyword></ce:keywords></head></converted-article></istex:document></istex:metadataXml><mods version="3.6"><titleInfo><title>On the metastable O2-type LiCoO2</title></titleInfo><titleInfo type="alternative" contentType="CDATA"><title>On the metastable O2-type LiCoO</title></titleInfo><name type="personal"><namePart type="given">D</namePart><namePart type="family">Carlier</namePart><affiliation>Institut de Chimie de la Matière Condensée de Bordeaux, CNRS and Ecole Nationale Supérieure de Chimie et Physique de Bordeaux, Chateau de Bivazac, 87 av. Dr A. Schweitzer, 33608 Pessac cedex, France</affiliation><role><roleTerm type="text">author</roleTerm></role></name><name type="personal"><namePart type="given">I</namePart><namePart type="family">Saadoune</namePart><affiliation>Institut de Chimie de la Matière Condensée de Bordeaux, CNRS and Ecole Nationale Supérieure de Chimie et Physique de Bordeaux, Chateau de Bivazac, 87 av. Dr A. Schweitzer, 33608 Pessac cedex, France</affiliation><role><roleTerm type="text">author</roleTerm></role></name><name type="personal"><namePart type="given">L</namePart><namePart type="family">Croguennec</namePart><affiliation>Institut de Chimie de la Matière Condensée de Bordeaux, CNRS and Ecole Nationale Supérieure de Chimie et Physique de Bordeaux, Chateau de Bivazac, 87 av. Dr A. Schweitzer, 33608 Pessac cedex, France</affiliation><role><roleTerm type="text">author</roleTerm></role></name><name type="personal"><namePart type="given">M</namePart><namePart type="family">Ménétrier</namePart><affiliation>Institut de Chimie de la Matière Condensée de Bordeaux, CNRS and Ecole Nationale Supérieure de Chimie et Physique de Bordeaux, Chateau de Bivazac, 87 av. Dr A. Schweitzer, 33608 Pessac cedex, France</affiliation><role><roleTerm type="text">author</roleTerm></role></name><name type="personal"><namePart type="given">E</namePart><namePart type="family">Suard</namePart><affiliation>Institut Laue-Langevin, rue des Martyrs, B.P. 156X, 38042 Grenoble cedex 9, France</affiliation><role><roleTerm type="text">author</roleTerm></role></name><name type="personal"><namePart type="given">C</namePart><namePart type="family">Delmas</namePart><affiliation>E-mail: delmas@icmcb.u-bordeaux.fr</affiliation><affiliation>Institut de Chimie de la Matière Condensée de Bordeaux, CNRS and Ecole Nationale Supérieure de Chimie et Physique de Bordeaux, Chateau de Bivazac, 87 av. Dr A. Schweitzer, 33608 Pessac cedex, France</affiliation><description>Corresponding author. Tel.: +33-5-5684-6296; fax: +33-5-5684-6634</description><role><roleTerm type="text">author</roleTerm></role></name><typeOfResource>text</typeOfResource><genre type="research-article" displayLabel="Full-length article"></genre><originInfo><publisher>ELSEVIER</publisher><dateIssued encoding="w3cdtf">2001</dateIssued><copyrightDate encoding="w3cdtf">2001</copyrightDate></originInfo><language><languageTerm type="code" authority="iso639-2b">eng</languageTerm><languageTerm type="code" authority="rfc3066">en</languageTerm></language><physicalDescription><internetMediaType>text/html</internetMediaType></physicalDescription><abstract lang="en">The exchange of sodium for lithium in P2-Na0.70CoO2 leads to an unusual O2-LiCoO2 variety. Rietveld refinement of the neutron diffraction pattern of the O2-LiCoO2 phase confirms the stoichiometry and the structural parameters previously reported and shows that the strong Li+–Co3+ electrostatic repulsion occurring through the common face of the CoO6 and LiO6 octahedra leads to small displacements of the lithium and cobalt ions from the center of their octahedra. Magnetic measurements and 7Li MAS NMR confirm a composition very close to the ideal one for the O2 phase. The O2-LiCoO2 phase is metastable and transforms to well-crystallized O3-LiCoO2 upon heating. Even at intermediate temperatures, the formation of LT-LiCoO2 phase is never observed. Various morphologies are obtained for the O3-LiCoO2 phases, depending on the thermal treatment used. A preliminary electrochemical study shows that almost all the lithium ions can be reversibly deintercalated from the O2-LiCoO2 phase.</abstract><note type="content">Fig. 1: The two different oxygen packings of LiCoO2.</note><note type="content">Fig. 2: Sheet gliding involved in the P2→O2 transformation occurring during the ion-exchange process as seen from the (110) section. The black circles are the oxygen ions.</note><note type="content">Fig. 3: X-ray diffraction patterns of the O2-LiCoO2 phase obtained with the various exchange reactions (∗ indicates the position of the (002) peak due to P2-Na0.70CoO2 present as impurity).</note><note type="content">Fig. 4: SEM micrographs of the P2-Na0.70CoO2 precursor (a) and of the O2-LiCoO2 phase obtained after ion-exchange in water (b).</note><note type="content">Fig. 5: Observed and calculated neutron diffraction profiles for the O2-LiCoO2 phase obtained after exchange in water: (•) observed; (—) calculated; lower trace: difference plot; bars: reflections. ∗ indicates the (103) diffraction peak of the P2-Na0.70CoO2 phase.</note><note type="content">Fig. 6: Magnetic susceptibility versus temperature for the O2-LiCoO2, O3-LiCoO2, O3-Li0.97CoO2, O3-Li0.60CoO2 and O3-Li1.08CoO2 phases recorded with a 5000 G field.</note><note type="content">Fig. 7: 7Li MAS NMR spectra of the O2 and O3 LiCoO2 phases, recorded with a Hahn echo sequence and a 10-kHz spinning speed. ∗ indicates the spinning sidebands position.</note><note type="content">Fig. 8: First galvanostatic charge–discharge curve of a LiO3-LiCoO2 cell obtained with a C/100 current density rate (a) and of a LiO2-LiCoO2 cell obtained with a C/40 current density rate (b) 100 and 40 h are respectively needed to remove 1 mol of lithium.</note><note type="content">Fig. 9: X-ray diffraction patterns of the materials obtained after different thermal treatments of O2-LiCoO2. Major peaks of the appearing Co3O4 phase are indicated.</note><note type="content">Fig. 10: Expansion of the first Bragg reflection of the XRD patterns observed for the samples obtained after different thermal treatments of O2-LiCoO2.</note><note type="content">Fig. 11: SEM micrographs of the three different O3-LiCoO2 (ex-O2) phases obtained after a thermal treatment at 400 (a), 600 (b) and 800 °C (c) and of the O3-LiCoO2 obtained by solid-state reaction (d).</note><note type="content">Fig. 12: First galvanostatic charge–discharge curve of LiO3-LiCoO2 (ex-O2) cells obtained with a C/100 current density rate (100 h are needed to remove 1 mol of lithium).</note><note type="content">Table 1: Results of the refinement by the Rietveld method of the O2-LiCoO2 neutron diffraction pattern (the O2 phase was obtained by ion-exchange in aqueous medium)</note><note type="content">Table 2: Comparison of the Li–O and Co–O distances in the two types of LiCoO2</note><subject><genre>Keywords</genre><topic>Layered oxides</topic><topic>LiCoO2</topic><topic>Ion-exchange reaction</topic><topic>Neutron diffraction</topic><topic>Magnetic measurements</topic><topic>Electrochemical deintercalation</topic><topic>Lithium battery</topic></subject><relatedItem type="host"><titleInfo><title>Solid State Ionics</title></titleInfo><titleInfo type="abbreviated"><title>SOSI</title></titleInfo><genre type="journal">journal</genre><originInfo><dateIssued encoding="w3cdtf">20011211</dateIssued></originInfo><identifier type="ISSN">0167-2738</identifier><identifier type="PII">S0167-2738(00)X0101-4</identifier><part><date>20011211</date><detail type="volume"><number>144</number><caption>vol.</caption></detail><detail type="issue"><number>3–4</number><caption>no.</caption></detail><extent unit="issue pages"><start>197</start><end>398</end></extent><extent unit="pages"><start>263</start><end>276</end></extent></part></relatedItem><identifier type="istex">309C387EA12B64F1D046DDE4565AFADDD4D5EA98</identifier><identifier type="DOI">10.1016/S0167-2738(01)00982-1</identifier><identifier type="PII">S0167-2738(01)00982-1</identifier><recordInfo><recordContentSource>ELSEVIER</recordContentSource></recordInfo></mods></metadata><serie></serie></istex></record>Pour manipuler ce document sous Unix (Dilib)
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