Understanding the cation ordering transition in high-voltage spinel LiNi0.5Mn1.5O4 by doping Li instead of Ni
Identifieur interne : 000110 ( Main/Exploration ); précédent : 000109; suivant : 000111Understanding the cation ordering transition in high-voltage spinel LiNi0.5Mn1.5O4 by doping Li instead of Ni
Auteurs : Junghwa Lee ; Nicolas Dupre [France] ; Maxim Avdeev ; Byoungwoo KangSource :
- Scientific Reports [ 2045-2322 ] ; 2017.
Abstract
We determined how Li doping affects the Ni/Mn ordering in high-voltage spinel LiNi0.5Mn1.5O4(LNMO) by using neutron diffraction, TEM image, electrochemical measurements, and NMR data. The doped Li occupies empty octahedral interstitials (16c site) before the ordering transition, and can move to normal octahedral sites (16d (4b) site) after the transition. This movement strongly affects the Ni/Mn ordering transition because Li at 16c sites blocks the ordering transition pathway and Li at 16d (4b) sites affects electrostatic interactions with transition metals. As a result, Li doping increases in the Ni/Mn disordering without the effect of Mn3+ ions even though the Li-doped LNMO undergoes order-disorder transition at 700 °C. Li doping can control the amount of Ni/Mn disordering in the spinel without the negative effect of Mn3+ ions on the electrochemical property.
Url:
DOI: 10.1038/s41598-017-07139-2
PubMed: 28751751
PubMed Central: 5532243
Affiliations:
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Nam-Gu., Pohang, 790-784 Gyeongsangbuk-do South Korea</nlm:aff><wicri:noCountry code="subfield">790-784 Gyeongsangbuk-do South Korea</wicri:noCountry></affiliation></author><author><name sortKey="Dupre, Nicolas" sort="Dupre, Nicolas" uniqKey="Dupre N" first="Nicolas" last="Dupre">Nicolas Dupre</name><affiliation wicri:level="4"><nlm:aff id="Aff2">Institut des Materiaux Jean Rouxel (IMN), Universite de Nantes, CNRS, 2 rue de la Houssiniere, BP 32229, 44322 Nantes Cedex 3, France</nlm:aff><country xml:lang="fr">France</country><wicri:regionArea>Institut des Materiaux Jean Rouxel (IMN), Universite de Nantes, CNRS, 2 rue de la Houssiniere, BP 32229, 44322 Nantes Cedex 3</wicri:regionArea><wicri:noRegion>44322 Nantes Cedex 3</wicri:noRegion><orgName type="university">Université de Nantes</orgName><placeName><settlement type="city">Nantes</settlement><region type="region" nuts="2">Pays de la Loire</region></placeName></affiliation></author><author><name sortKey="Avdeev, Maxim" sort="Avdeev, Maxim" uniqKey="Avdeev M" first="Maxim" last="Avdeev">Maxim Avdeev</name><affiliation><nlm:aff id="Aff3"><institution-wrap><institution-id institution-id-type="ISNI">0000 0004 0432 8812</institution-id><institution-id institution-id-type="GRID">grid.1089.0</institution-id><institution>Australian Nuclear Science and Technology Organisation,</institution></institution-wrap>Locked Bag 2001, Kirrawee, DC NSW 2232 Australia</nlm:aff><wicri:noCountry code="subfield">DC NSW 2232 Australia</wicri:noCountry></affiliation><affiliation><nlm:aff id="Aff4"><institution-wrap><institution-id institution-id-type="ISNI">0000 0004 1936 834X</institution-id><institution-id institution-id-type="GRID">grid.1013.3</institution-id><institution>School of Chemistry,</institution><institution>The University of Sydney,</institution></institution-wrap>Sydney, NSW 2006 Australia</nlm:aff><wicri:noCountry code="subfield">NSW 2006 Australia</wicri:noCountry></affiliation></author><author><name sortKey="Kang, Byoungwoo" sort="Kang, Byoungwoo" uniqKey="Kang B" first="Byoungwoo" last="Kang">Byoungwoo Kang</name><affiliation><nlm:aff id="Aff1"><institution-wrap><institution-id institution-id-type="ISNI">0000 0001 0742 4007</institution-id><institution-id institution-id-type="GRID">grid.49100.3c</institution-id><institution>Department of Materials Science and Engineering,</institution><institution>Pohang University of Science and Technology (POSTECH),</institution></institution-wrap>77 Cheongam-Ro. 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Nam-Gu., Pohang, 790-784 Gyeongsangbuk-do South Korea</nlm:aff><wicri:noCountry code="subfield">790-784 Gyeongsangbuk-do South Korea</wicri:noCountry></affiliation></author><author><name sortKey="Dupre, Nicolas" sort="Dupre, Nicolas" uniqKey="Dupre N" first="Nicolas" last="Dupre">Nicolas Dupre</name><affiliation wicri:level="4"><nlm:aff id="Aff2">Institut des Materiaux Jean Rouxel (IMN), Universite de Nantes, CNRS, 2 rue de la Houssiniere, BP 32229, 44322 Nantes Cedex 3, France</nlm:aff><country xml:lang="fr">France</country><wicri:regionArea>Institut des Materiaux Jean Rouxel (IMN), Universite de Nantes, CNRS, 2 rue de la Houssiniere, BP 32229, 44322 Nantes Cedex 3</wicri:regionArea><placeName><region type="region" nuts="2">Pays de la Loire</region><settlement type="city">Nantes</settlement><settlement type="city">Nantes</settlement></placeName><orgName type="university">Université de Nantes</orgName></affiliation></author><author><name sortKey="Avdeev, Maxim" sort="Avdeev, Maxim" uniqKey="Avdeev M" first="Maxim" last="Avdeev">Maxim Avdeev</name><affiliation><nlm:aff id="Aff3"><institution-wrap><institution-id institution-id-type="ISNI">0000 0004 0432 8812</institution-id><institution-id institution-id-type="GRID">grid.1089.0</institution-id><institution>Australian Nuclear Science and Technology Organisation,</institution></institution-wrap>Locked Bag 2001, Kirrawee, DC NSW 2232 Australia</nlm:aff><wicri:noCountry code="subfield">DC NSW 2232 Australia</wicri:noCountry></affiliation><affiliation><nlm:aff id="Aff4"><institution-wrap><institution-id institution-id-type="ISNI">0000 0004 1936 834X</institution-id><institution-id institution-id-type="GRID">grid.1013.3</institution-id><institution>School of Chemistry,</institution><institution>The University of Sydney,</institution></institution-wrap>Sydney, NSW 2006 Australia</nlm:aff><wicri:noCountry code="subfield">NSW 2006 Australia</wicri:noCountry></affiliation></author><author><name sortKey="Kang, Byoungwoo" sort="Kang, Byoungwoo" uniqKey="Kang B" first="Byoungwoo" last="Kang">Byoungwoo Kang</name><affiliation><nlm:aff id="Aff1"><institution-wrap><institution-id institution-id-type="ISNI">0000 0001 0742 4007</institution-id><institution-id institution-id-type="GRID">grid.49100.3c</institution-id><institution>Department of Materials Science and Engineering,</institution><institution>Pohang University of Science and Technology (POSTECH),</institution></institution-wrap>77 Cheongam-Ro. Nam-Gu., Pohang, 790-784 Gyeongsangbuk-do South Korea</nlm:aff><wicri:noCountry code="subfield">790-784 Gyeongsangbuk-do South Korea</wicri:noCountry></affiliation></author></analytic><series><title level="j">Scientific Reports</title><idno type="eISSN">2045-2322</idno><imprint><date when="2017">2017</date></imprint></series></biblStruct></sourceDesc></fileDesc><profileDesc><textClass></textClass></profileDesc></teiHeader><front><div type="abstract" xml:lang="en"><p id="Par1">We determined how Li doping affects the Ni/Mn ordering in high-voltage spinel LiNi<sub>0.5</sub>Mn<sub>1.5</sub>O<sub>4</sub>(LNMO) by using neutron diffraction, TEM image, electrochemical measurements, and NMR data. The doped Li occupies empty octahedral interstitials (16c site) before the ordering transition, and can move to normal octahedral sites (16d (4b) site) after the transition. This movement strongly affects the Ni/Mn ordering transition because Li at 16c sites blocks the ordering transition pathway and Li at 16d (4b) sites affects electrostatic interactions with transition metals. As a result, Li doping increases in the Ni/Mn disordering without the effect of Mn<sup>3+</sup> ions even though the Li-doped LNMO undergoes order-disorder transition at 700 °C. Li doping can control the amount of Ni/Mn disordering in the spinel without the negative effect of Mn<sup>3+</sup> ions on the electrochemical property.</p></div></front><back><div1 type="bibliography"><listBibl><biblStruct><analytic><author><name sortKey="Ariyoshi, K" uniqKey="Ariyoshi K">K Ariyoshi</name></author><author><name sortKey="Iwakoshi, Y" uniqKey="Iwakoshi Y">Y Iwakoshi</name></author><author><name sortKey="Nakayama, N" uniqKey="Nakayama N">N Nakayama</name></author><author><name sortKey="Ohzuku, T" uniqKey="Ohzuku T">T Ohzuku</name></author></analytic></biblStruct><biblStruct><analytic><author><name sortKey="Ma, X" uniqKey="Ma X">X Ma</name></author><author><name sortKey="Kang, B" uniqKey="Kang B">B Kang</name></author><author><name sortKey="Ceder, G" uniqKey="Ceder G">G Ceder</name></author></analytic></biblStruct><biblStruct><analytic><author><name sortKey="Chemelewski, Kr" uniqKey="Chemelewski K">KR Chemelewski</name></author><author><name sortKey="Manthiram, A" 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uniqKey="Manthiram A">A Manthiram</name></author></analytic></biblStruct><biblStruct><analytic><author><name sortKey="Liu, J" uniqKey="Liu J">J Liu</name></author><author><name sortKey="Huq, A" uniqKey="Huq A">A Huq</name></author><author><name sortKey="Moorhead Rosenberg, Z" uniqKey="Moorhead Rosenberg Z">Z Moorhead-Rosenberg</name></author><author><name sortKey="Manthiram, A" uniqKey="Manthiram A">A Manthiram</name></author><author><name sortKey="Page, K" uniqKey="Page K">K Page</name></author></analytic></biblStruct></listBibl></div1></back></TEI><affiliations><list><country><li>France</li></country><region><li>Pays de la Loire</li></region><settlement><li>Nantes</li></settlement><orgName><li>Université de Nantes</li></orgName></list><tree><noCountry><name sortKey="Avdeev, Maxim" sort="Avdeev, Maxim" uniqKey="Avdeev M" first="Maxim" last="Avdeev">Maxim Avdeev</name><name sortKey="Kang, Byoungwoo" sort="Kang, Byoungwoo" uniqKey="Kang B" first="Byoungwoo" last="Kang">Byoungwoo Kang</name><name sortKey="Lee, Junghwa" sort="Lee, Junghwa" uniqKey="Lee J" first="Junghwa" last="Lee">Junghwa Lee</name></noCountry><country name="France"><region name="Pays de la Loire"><name sortKey="Dupre, Nicolas" sort="Dupre, Nicolas" uniqKey="Dupre N" first="Nicolas" last="Dupre">Nicolas Dupre</name></region></country></tree></affiliations></record>Pour manipuler ce document sous Unix (Dilib)
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