The lithium intercalation compound Li2CoSiO4 and its behaviour as a positive electrode for lithium batteries

Lyness, Christopher; Delobel, Bruno; Armstrong, A. Robert; Bruce, Peter G.

doi:10.1039/b711552k

Cited by 149 publications

(152 citation statements)

References 29 publications

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“…The reason for observed differences in QS values is not fully understood, however we presume this difference can be ascribed to the different polymorph used in our experiment as it was used by Nyten. It is worth to mention that the existence of different polymorphs in Li 2 FeSiO 4 was not proven yet, however the above opinion is based on the work on Li 2 MnSiO 4 and Li 2 CoSiO 4 [2,3,12,20]. Based on our in-situ Mössbauer experiment we agree with a conclusion given by Nyten [7], that local environment of iron observed with Mössbauer spectroscopy is very similar before and after "phase transition" reflected as a shift of potential from 3.1 to 2.8 V. At the end of Mössbauer part we need to emphasize that Mössbauer parameters of the magnetic phase remain very similar during the oxidation/reduction process in all fitted spectra.…”

Section: Xrd and Mössbauer Analysismentioning

confidence: 99%

“…Some members of the family of Li-orthosilicates Li 2 MSiO 4 (M = Mn, Fe, Co) together with their solid solutions have been recently prepared for structural and electrochemical characterisation for the potential use in Li-ion batteries [1][2][3][4]. This type of cathode material is attractive in view of a possible exploration of both lithium equivalents from the structure which would in practice lead to capacities with theoretical limit at 330 mA h g −1 .…”

Section: Introductionmentioning

confidence: 99%

“…Li 2 MSiO 4 (M = Mn, Fe, Co) materials are iso-structural to lithium phosphate (Li 3 PO 4 ) and can crystallize at least in eight polymorphs [3]. As-prepared samples are usually mixtures of polymorphs due to small difference in formation energy.…”

Section: Introductionmentioning

confidence: 99%

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In-situ XAS study on Li2MnSiO4 and Li2FeSiO4 cathode materials

Dominko

Arčon

Kodre

et al. 2009

Journal of Power Sources

124

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Section: Xrd and Mössbauer Analysismentioning

confidence: 99%

Section: Introductionmentioning

confidence: 99%

See 1 more Smart Citation

In-situ XAS study on Li2MnSiO4 and Li2FeSiO4 cathode materials

Dominko

Arčon

Kodre

et al. 2009

Journal of Power Sources

124

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“…1(d) The third member of the orthosilicate family of cathode materials, Li 2 CoSiO 4 , has received comparatively less attention. [32][33][34] Three polymorphic forms (b II , b I , and g 0 ) have been prepared and investigated with powder diffraction and Li MAS NMR. 32,33 The b II (Pmn2 1 ) polymorph was obtained by hydrothermal synthesis (150 C), and subsequent heat treatments yielded the b I (Pbn2 1 ) form (700 C) and the g 0 (P2/n) form (1100 C then quenching from 850 C).…”

Section: Mnsiomentioning

confidence: 99%

Silicate cathodes for lithium batteries: alternatives to phosphates?

et al. 2011

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Polyoxyanion compounds, particularly the olivine-phosphate LiFePO 4 , are receiving considerable attention as alternative cathodes for rechargeable lithium batteries. More recently, an entirely new class of polyoxyanion cathodes based on the orthosilicates, Li 2 MSiO 4 (where M ¼ Mn, Fe, and Co), has been attracting growing interest. In the case of Li 2 FeSiO 4 , iron and silicon are among the most abundant and lowest cost elements, and hence offer the tantalising prospect of preparing cheap and safe cathodes from rust and sand! This Highlight presents an overview of recent developments and future challenges of silicate cathode materials focusing on their structural polymorphs, electrochemical behaviour and nanomaterials chemistry.

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“…[1][2][3][4] In these silicates, oxide ions form a pseudo-hexagonal closed packed (hcp) structure. The cations occupy a half of its tetrahedral sites and show several kinds of ordered arrangements depending on the transition metals species and the heat treatments during the sample preparation.…”

Section: Introductionmentioning

confidence: 99%

Structural Phase Transition of Li<sub>2</sub>MnSiO<sub>4</sub>

Nakayama

Itoyama

Fujiwara

et al. 2012

Trans. Mat. Res. Soc. Japan

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The orthorhombic Pmnb phase of Li2MnSiO4 has been prepared by solid state reaction of Li2CO3, Mn(CH3COO)2⋅4H2O, and highly dispersed SiO2 at 800 °C and the subsequent slow cooling in Ar gas stream. The crystal structure was refined by the Rietveld method based on the model structure without disorder in the site occupancies, although some anomaly was observed for Mn sites. The DTA curve shows peaks at around 680 and 770 °C on heating and at around 510 °C on cooling indicating a reversible structural phase transition. From the in-situ XRD patterns at high temperature, the first order phase transition from Pmnb to a distorted orthorhombic wurzite-type structure with the random arrangement of Li, Si, and Mn.keywords: order-disorder, wurzite-type structure, DTA, high temperature powder XRD INTRODUCTIONLithium transition metal silicates, Li2MSiO4 (M: Mn, Fe, Co), have been investigated extensively in this decade as a new class of positive electrode materials for lithium ion batteries. 1-4) In these silicates, oxide ions form a pseudo-hexagonal closed packed (hcp) structure. The cations occupy a half of its tetrahedral sites and show several kinds of ordered arrangements depending on the transition metals species and the heat treatments during the sample preparation. 5,6) The homogeneity of the ordered structure may have significant effect on the electrode properties. Several investigations on the details of polymorphism have been reported [7][8][9][10][11][12][13] , mainly for the hydro-thermally prepared and heat-treated samples. However, the phase relations among polymorphs and the microstructures are still unclear. The mutual phase relationships above polymorphs are of interests to obtain the single-phase materials and to clarify the electrochemical properties. In this paper, the structural phase transition of Li2MnSiO4 was investigated using TG-DTA and powder XRD at high temperature.

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The lithium intercalation compound Li2CoSiO4 and its behaviour as a positive electrode for lithium batteries

Abstract: The electrochemical behaviour of 3 polymorphs of the lithium intercalation compound Li2CoSiO4, betaI, betaII and gamma0, as positive electrodes in rechargeable lithium batteries is investigated for the first time.

Cited by 149 publications

References 29 publications

In-situ XAS study on Li2MnSiO4 and Li2FeSiO4 cathode materials

In-situ XAS study on Li2MnSiO4 and Li2FeSiO4 cathode materials

Silicate cathodes for lithium batteries: alternatives to phosphates?

Structural Phase Transition of Li<sub>2</sub>MnSiO<sub>4</sub>

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