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A delithiated LiNi0.65Co0.25Mn0.10O2 electrode material: A structural, magnetic and electrochemical study
Uppsala University, Disciplinary Domain of Science and Technology, Technology, Department of Engineering Sciences, Solid State Physics.
Uppsala University, Disciplinary Domain of Science and Technology, Chemistry, Department of Materials Chemistry, Structural Chemistry. (strukturkemi)
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2009 (English)In: Electrochimica Acta, ISSN 0013-4686, E-ISSN 1873-3859, Vol. 54, no 11, 3211-3217 p.Article in journal (Refereed) Published
Abstract [en]

A crystalline LiNi0.65Co0.25Mn0.10O2 electrode material was synthesized by the combustion method at 900 °C for 1 h. Rietveld refinement shows less than 3% of Li/Ni disorder in the structure. Lithium extraction involves only the Ni2+/Ni4+ redox couple while Co3+ and Mn4+ remain electrochemically inactive. No structural transition was detected during cycling in the whole composition range 0 < x < 1.0. Furthermore, the hexagonal cell volume changes by only 3% when all lithium was removed indicating a good mechanical stability of the studied compound. LiNi0.65Co0.25Mn0.10O2 has a discharge capacity of 150 mAh/g in the voltage range 2.5–4.5 V, but the best electrochemical performance was obtained with an upper cut-off potential of 4.3 V. Magnetic measurements reveal competing antiferromagnetic and ferromagnetic interactions – varying in strength as a function of lithium content – yielding a low temperature magnetically frustrated state. The evolution of the magnetic properties with lithium content confirms the preferential oxidation of Ni ions compared to Co3+ and Mn4+ during the delithiation process.

Place, publisher, year, edition, pages
Elsevier Ltd , 2009. Vol. 54, no 11, 3211-3217 p.
National Category
Chemical Sciences Engineering and Technology
Research subject
Inorganic Chemistry
URN: urn:nbn:se:uu:diva-121033DOI: 10.1016/j.electacta.2008.11.057ISI: 000265342100039OAI: oai:DiVA.org:uu-121033DiVA: diva2:304424
Available from: 2010-03-18 Created: 2010-03-18 Last updated: 2016-04-14Bibliographically approved
In thesis
1. Fundamental Properties of Functional Magnetic Materials
Open this publication in new window or tab >>Fundamental Properties of Functional Magnetic Materials
2010 (English)Doctoral thesis, comprehensive summary (Other academic)
Abstract [en]

Magnetic properties of powders, thin films and single crystals have been investigated using magnetometry methods. This thesis provides analysis and conclusions that are supported by the results obtained from spectroscopic and diffraction measurements as well as from theoretical calculations.

First, the magnetic behavior of transition metal (TM) doped ZnO with respect to doping, growth conditions and post annealing has been studied. Our findings indicate that the magnetic behavior stems from small clusters or precipitates of the dopant, with ferromagnetic or antiferromagnetic interactions. At the lowest dopant concentrations, the estimated cluster sizes are too small for high resolution imaging. Still, the clusters may be sufficiently large to generate a finite spontaneous magnetization even at room temperature and could easily be misinterpreted as an intrinsic ferromagnetic state of the TM:ZnO compound.

Second, influence of lattice strain on both magnetic moment and anisotropy has been investigated for epitaxial MnAs thin films grown on GaAs substrates. The obtained magnetic moments and anisotropy values are higher than for bulk MnAs. The enhanced values are caused by highly strained local areas that have a stronger dependence on the in-plane axis strain than out-of plane axis strain.

Finally, spin glass behavior in Li-layered oxides, used for battery applications, and a double perovskite material has been investigated. For both Li(NiCoMn)O2 and (Sr,La)MnWO6, a mixed-valence of one of the transition metal ions creates competing ferromagnetic and antiferromagnetic interactions resulting in a low temperature three-dimensional (3D) spin glass state. Additionally, Li(NiCoMn)O2 with large cationic mixing exhibits a percolating ferrimagnetic spin order in the high temperature region and coexists with a two-dimensional (2D) frustrated spin state in the mid temperature region. This is one of the rare observations where a dimensional crossover from 2D to 3D spin frustration appears in a reentrant material.

Place, publisher, year, edition, pages
Uppsala: acta universitatis upsaliensis, 2010. 74 p.
Digital Comprehensive Summaries of Uppsala Dissertations from the Faculty of Science and Technology, ISSN 1651-6214 ; 790
Magnetic anisotropy, magnetic aging, magnetic semiconductors, exchange interactions, magnetic oxides, spin glasses, lithium-ion batteries, short-range magnetic order
National Category
Physical Sciences
Research subject
Engineering Science with specialization in Solid State Physics
urn:nbn:se:uu:diva-133257 (URN)978-91-554-7953-4 (ISBN)
Public defence
2010-12-17, Polhemsalen, Ångströmlaboratoriet, Lägerhyddsvägen 1, Uppsala, 09:15 (English)
Felaktigt tryckt som Digital Comprehensive Summaries of Uppsala Dissertations from the Faculty of Science and Technology 720Available from: 2010-11-25 Created: 2010-11-04 Last updated: 2011-03-21Bibliographically approved

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