Facile synthesis of β-Li3VF6: A new electrochemically active lithium insertion material

Basa, Anna; Gonzalo, Elena; Kühn, A.; Garcı́a-Alvarado, F.

doi:10.1016/j.jpowsour.2012.01.148

Cited by 21 publications

(30 citation statements)

References 31 publications

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“…(1)) [45]. Electrochemical lithium extraction for monoclinic Li 3 VF 6 was shown by Gocheva et al [46], but could not be confirmed by Basa et al [17] and our group (results not published). However, to verify the theoretical assumption of Li extraction in Li 3 CrF 6 , assuming that Cr IV /Cr III is the electrochemically active redox couple (Eq.…”

Section: Electrochemical Characterizationcontrasting

confidence: 74%

Electrochemical characterization of monoclinic and orthorhombic Li3CrF6 as positive electrodes in lithium-ion batteries synthesized by a sol–gel process with environmentally benign chemicals

Lieser

Winkler

Geßwein

et al. 2015

Journal of Power Sources

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Section: Electrochemical Characterizationcontrasting

confidence: 74%

Electrochemical characterization of monoclinic and orthorhombic Li3CrF6 as positive electrodes in lithium-ion batteries synthesized by a sol–gel process with environmentally benign chemicals

Lieser

Winkler

Geßwein

et al. 2015

Journal of Power Sources

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“…[8][9][10][11] The first lithium transition metal fluoride with an applicable electrochemical performance reported in literature was monoclinic Li 3 FeF 6 . 12 Specific discharge capacities of monoclinic and orthorhombic Li 3 FeF 6 , 13-16 monoclinic Li 3 VF 6 , 17 Li 2 TiF 6 , 18 and LiFeFeF 6 19,20 were reported to be at least 75 mAh/g. Lithium transition metal fluorides were investigated for their Li insertion and extraction potential, Li diffusion properties, and influence of divalent cation doping [21][22][23][24] using several theoretical methods.…”

mentioning

confidence: 99%

Electrochemical Characterization of LiMnFeF₆for Use as Positive Electrode in Lithium-Ion Batteries

Lieser

Biasi

Geßwein

et al. 2014

J. Electrochem. Soc.

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To replace common commercial lithium metal oxides or polyanionic cathode materials, lithium transition metal fluorides are of particular interest, as they potentially provide a high energy density, safety, and cyclability. The quaternary fluoride LiMnFeF 6 that crystallizes in the Na 2 SiF 6 -type structure was synthesized without toxic chemicals by a sol-gel process with trifluoroacetic acid as fluorine source. After structural and morphological characterization, the as-synthesized material was ball-milled with carbon. The novel composite cathode material produced in this way was cycled versus lithium. The electrochemical potential range, cycling ability, and rate performance were investigated and the electrochemically active redox couple Fe 3+ /Fe 2+ was confirmed by Mössbauer spectroscopy. Structural changes of the LiMnFeF 6 host structure after Li insertion were investigated by X-ray powder diffraction.Currently, lithium transition metal oxides and phosphates are the most preferred cathode materials for portable and stationary applications. Compared to LiMn 2 O 4 , LiCoO 2 , or LiNiO 2 , positive electrode materials with at least two different transition metal cations like LiNi 0.5 Mn 1.5 O 4 or LiNi 1-x-y Mn x Co y O 2 possess better electrochemical properties like a higher redox potential, increased specific capacity or enhanced cycling performance. 1-3 In general, substitution of oxygen in the cathode host structure by the more electronegative fluorine results in a higher redox potential, leading to an increased energy density of the positive electrode. 4,5 Since the report of Abraham 6 and Arai et al. 7 on metal fluoride-containing positive electrodes, lithium insertion and conversion during cycling of the host material (e.g. FeF 3 , CuF 2 ) has been investigated in great detail. [8][9][10][11] The first lithium transition metal fluoride with an applicable electrochemical performance reported in literature was monoclinic Li 3 FeF 6 . 12 Specific discharge capacities of monoclinic and orthorhombic Li 3 FeF 6 , 13-16 monoclinic Li 3 VF 6 , 17 Li 2 TiF 6 , 18 and LiFeFeF 6 19,20 were reported to be at least 75 mAh/g. Lithium transition metal fluorides were investigated for their Li insertion and extraction potential, Li diffusion properties, and influence of divalent cation doping 21-24 using several theoretical methods. Several patents cover the use of Li 3 FeF 6 , Li 3 VF 6 , Li 2 TiF 6 , Li 2 NiF 4 , and LiFeFeF 6 as positive electrode materials for Li-ion batteries. [25][26][27][28][29] In the last four years, this class of materials attracted increasing attention. Still, lithium transition metal fluorides are not yet competitive with established electrode materials for use in lithium-ion batteries.However, electrochemical properties of ternary Li y MF x or quaternary LiM (1) M (2) F 6 (with M (1) = M (2) , e.g. M = Cr, Mn, Fe, Co, Ni) 3d lithium transition metal fluorides have not yet been studied due to their challenging synthesis process. It usually requires the usage of hazardous chemicals like hydro...

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“…A deeper discharge of the material was reported to lead to LiF formation, indicating a conversion reaction at low potentials. Similarly, a nanocomposite of Li 3 VF 6 was reported to reversibly intercalate up to one Li + per fluoride unit [43]. Calculations predict that fluorides such as LiCaCoF 6 could provide very high intercalation voltages [44].…”

Section: Electrode Materialsmentioning

confidence: 98%

“…Using nanocomposites with carbon can not only help with the volume change but also with the inherently low electrical conductivity of fluoride materials. Due to the work on primary batteries pure fluorides are generally considered only as conversion cathodes but some reports on intercalation fluorides have been published [41][42][43]. For example, Li3FeF6 has been reported to show intercalation of 0.7-1 Li + ions per fluoride unit in a carbon nanocomposite form, resulting in a reversible capacity of 100-140 mAh/g [41,42].…”

Section: Electrode Materialsmentioning

confidence: 99%

Metal Fluorides as Lithium-Ion Battery Materials: An Atomic Layer Deposition Perspective

2018

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Lithium-ion batteries are the enabling technology for a variety of modern day devices, including cell phones, laptops and electric vehicles. To answer the energy and voltage demands of future applications, further materials engineering of the battery components is necessary. To that end, metal fluorides could provide interesting new conversion cathode and solid electrolyte materials for future batteries. To be applicable in thin film batteries, metal fluorides should be deposited with a method providing a high level of control over uniformity and conformality on various substrate materials and geometries. Atomic layer deposition (ALD), a method widely used in microelectronics, offers unrivalled film uniformity and conformality, in conjunction with strict control of film composition. In this review, the basics of lithium-ion batteries are shortly introduced, followed by a discussion of metal fluorides as potential lithium-ion battery materials. The basics of ALD are then covered, followed by a review of some conventional lithium-ion battery materials that have been deposited by ALD. Finally, metal fluoride ALD processes reported in the literature are comprehensively reviewed. It is clear that more research on the ALD of fluorides is needed, especially transition metal fluorides, to expand the number of potential battery materials available.

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Facile synthesis of β-Li3VF6: A new electrochemically active lithium insertion material

Cited by 21 publications

References 31 publications

Electrochemical characterization of monoclinic and orthorhombic Li3CrF6 as positive electrodes in lithium-ion batteries synthesized by a sol–gel process with environmentally benign chemicals

Electrochemical characterization of monoclinic and orthorhombic Li3CrF6 as positive electrodes in lithium-ion batteries synthesized by a sol–gel process with environmentally benign chemicals

Electrochemical Characterization of LiMnFeF₆for Use as Positive Electrode in Lithium-Ion Batteries

Metal Fluorides as Lithium-Ion Battery Materials: An Atomic Layer Deposition Perspective

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Facile synthesis of β-Li3VF6: A new electrochemically active lithium insertion material

Cited by 21 publications

References 31 publications

Electrochemical characterization of monoclinic and orthorhombic Li3CrF6 as positive electrodes in lithium-ion batteries synthesized by a sol–gel process with environmentally benign chemicals

Electrochemical characterization of monoclinic and orthorhombic Li3CrF6 as positive electrodes in lithium-ion batteries synthesized by a sol–gel process with environmentally benign chemicals

Electrochemical Characterization of LiMnFeF6for Use as Positive Electrode in Lithium-Ion Batteries

Metal Fluorides as Lithium-Ion Battery Materials: An Atomic Layer Deposition Perspective

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Electrochemical Characterization of LiMnFeF₆for Use as Positive Electrode in Lithium-Ion Batteries