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Electrochemical lithium ion intercalation in Li 0.5Ni 0.25TiOPO 4 examined by in situ X-ray diffraction
Uppsala universitet, Teknisk-naturvetenskapliga vetenskapsområdet, Kemiska sektionen, Institutionen för kemi - Ångström, Strukturkemi.
Uppsala universitet, Teknisk-naturvetenskapliga vetenskapsområdet, Kemiska sektionen, Institutionen för kemi - Ångström, Strukturkemi.
LCME, University Cadi Ayyad, Marrakech, Morocco.ORCID-id: 0000-0003-1322-361X
LCME, University Cadi Ayyad, Marrakech, Morocco.
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2012 (Engelska)Ingår i: Solid State Ionics, ISSN 0167-2738, E-ISSN 1872-7689, Vol. 225, nr SI, s. 547-550Artikel i tidskrift, Meeting abstract (Refereegranskat) Published
Abstract [en]

The complex structural transformations of Li 0.5Ni 0.25TiOPO 4 during electrochemical lithiation have been examined by in situ X-ray diffraction. During the first lithiation two structural changes take place: first a transition to a second monoclinic phase (a = 9.085(4), b = 8.414(5), c = 6.886(5), β = 99.85(4)) and secondly a transition to a third phase with limited long-range order. The third phase is held together by a network of corner sharing Ti-O octahedra and phosphate ions with disordered Ni-Li channels. During delithiation the third phase is partially transformed back to a slightly disordered original phase, Li 0.5Ni 0.25TiOPO 4 without formation of the second intermediate phase. These phase transitions correspond well to the different voltage plateaus that this material shows during electrochemical cycling.

Ort, förlag, år, upplaga, sidor
2012. Vol. 225, nr SI, s. 547-550
Nyckelord [en]
Batteries, In situ X-ray powder diffraction, Lithium intercalation compounds, Corner sharing, De-lithiation, Electrochemical cycling, Electrochemical lithiation, In-situ, Intermediate phase, Lithiation, Lithium Intercalation, Lithium ions, Long range orders, Monoclinic phase, Phosphate ions, Structural change, Structural transformation, Third phase, Solar cells, X ray diffraction, X ray powder diffraction, Lithium
Nationell ämneskategori
Naturvetenskap Oorganisk kemi
Forskningsämne
Kemi med inriktning mot oorganisk kemi
Identifikatorer
URN: urn:nbn:se:uu:diva-186837DOI: 10.1016/j.ssi.2011.11.001ISI: 000311873400113OAI: oai:DiVA.org:uu-186837DiVA, id: diva2:574845
Konferens
18th International Conference on Solid State Ionics, July 3 -8, 2011, Warsaw, Poland
Forskningsfinansiär
StandUpTillgänglig från: 2012-12-06 Skapad: 2012-11-29 Senast uppdaterad: 2017-12-30
Ingår i avhandling
1. Structural Changes in Lithium Battery Materials Induced by Aging or Usage
Öppna denna publikation i ny flik eller fönster >>Structural Changes in Lithium Battery Materials Induced by Aging or Usage
2015 (Engelska)Doktorsavhandling, sammanläggning (Övrigt vetenskapligt)
Abstract [en]

Li-ion batteries have a huge potential for use in electrification of the transportation sector. The major challenge to be met is the limited energy storage capacity of the battery pack: both the amount of energy which can be stored within the space available in the vehicle (defining its range), and the aging of the individual battery cells (determining how long a whole pack can deliver sufficient energy and power to drive the vehicle). This thesis aims to increase our knowledge and understanding of structural changes induced by aging and usage of the Li-ion battery materials involved.

Aging processes have been studied in commercial-size Li-ion cells with two different chemistries. LiFePO4/graphite cells were aged under different conditions, and thereafter examined at different points along the electrodes by post mortem characterisation using SEM, XPS, XRD and electrochemical characterization in half-cells. The results revealed large differences in degradation behaviour under different aging conditions and in different regions of the same cell. The aging of LiMn2O4-LiCoO2/Li4Ti5O12 cells was studied under two different aging conditions. Post mortem analysis revealed a high degree of Mn/Co mixing within individual particles of the LiMn2O4-LiCoO2 composite electrode.

Structural changes induced by lithium insertion were studied in two negative electrode materials: in Li0.5Ni0.25TiOPO4 using in situ XRD, and in Ni0.5TiOPO4 using EXAFS, XANES and HAXPES. It was shown that Li0.5Ni0.25TiOPO4 lost most of its long-range-order during lithiation, and that both Ni and Ti were involved in the charge compensation mechanism during lithiation/delithiation of Ni0.5TiOPO4, with small clusters of metal-like Ni forming during lithiation.

Finally, in situ XRD studies were also made of the reaction pathways to form LiFeSO4F from two sets of reactants: either FeSO4·H2O and LiF, or Li2SO4 and FeF2. During the heat treatment, Li2SO4 and FeF2 react to form FeSO4·H2O and LiF in a first step. In a second step LiFeSO4F is formed. This underlines the importance of the structural similarities between LiFeSO4F and FeSO4·H2O in the formation process of LiFeSO4F.

Ort, förlag, år, upplaga, sidor
Uppsala: Acta Universitatis Upsaliensis, 2015. s. 75
Serie
Digital Comprehensive Summaries of Uppsala Dissertations from the Faculty of Science and Technology, ISSN 1651-6214 ; 1227
Nyckelord
Li-ion batteries, XRD, EXAFS, HAXPES
Nationell ämneskategori
Oorganisk kemi
Forskningsämne
Kemi med inriktning mot oorganisk kemi
Identifikatorer
urn:nbn:se:uu:diva-243328 (URN)978-91-554-9165-9 (ISBN)
Disputation
2015-03-27, Å4001, Ångström laboratory, Uppsala, 09:15 (Engelska)
Opponent
Handledare
Tillgänglig från: 2015-03-04 Skapad: 2015-02-09 Senast uppdaterad: 2015-03-12Bibliografiskt granskad

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Eriksson, RickardGustafsson, TorbjörnEdström, Kristina

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