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Publication . Article . 2015

Spinel materials for Li-ion batteries: new insights obtained byoperandoneutron and synchrotron X-ray diffraction

Matteo Bianchini; François Fauth; Emmanuelle Suard; Jean Bernard Leriche; Christian Masquelier; Laurence Croguennec;
Open Access
Published: 07 Nov 2015 Journal: Acta Crystallographica Section B Structural Science, Crystal Engineering and Materials, volume 71, pages 688-701 (issn: 2052-5206, Copyright policy )
Publisher: International Union of Crystallography (IUCr)
Country: France
In the last few decades Li-ion batteries changed the way we store energy, becoming a key element of our everyday life. Their continuous improvement is tightly bound to the understanding of lithium (de)intercalation phenomena in electrode materials. Here we address the use ofoperandodiffraction techniques to understand these mechanisms. We focus on powerful probes such as neutrons and synchrotron X-ray radiation, which have become increasingly familiar to the electrochemical community. After discussing the general benefits (and drawbacks) of these characterization techniques and the work of customization required to adapt standard electrochemical cells to anoperandodiffraction experiment, we highlight several very recent results. We concentrate on important electrode materials such as the spinels Li1 + xMn2 − xO4(0 ≤x≤ 0.10) and LiNi0.4Mn1.6O4. Thorough investigations led byoperandoneutron powder diffraction demonstrated that neutrons are highly sensitive to structural parameters that cannot be captured by other means (for example, atomic Debye–Waller factors and lithium site occupancy). Synchrotron radiation X-ray powder diffraction reveals how LiMn2O4is subject to irreversibility upon the first electrochemical cycle, resulting in severe Bragg peak broadening. Even more interestingly, we show for the first time an ordering scheme of the elusive composition Li0.5Mn2O4, through the coexistence of Mn3+:Mn4+1:3 cation ordering and lithium/vacancy ordering. More accurately written as Li0.5Mn3+0.5Mn4+1.5O4, this intermediate phase loses the Fd\overline 3m symmetry, to be correctly described in theP213 space group.
Subjects by Vocabulary

Microsoft Academic Graph classification: Lithium chemistry.chemical_element chemistry Crystallography Synchrotron law.invention law Bragg peak Electrochemical cell Powder diffraction Chemical physics Diffraction Physics Neutron diffraction Synchrotron radiation


Materials Chemistry, Metals and Alloys, Atomic and Molecular Physics, and Optics, Electronic, Optical and Magnetic Materials, batteries, spinel, synchrotron X-ray diffraction, neutron diffraction, operando, [CHIM.MATE]Chemical Sciences/Material chemistry

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