A novel cationic-ordering fluoro-polyanionic cathode LiV0.5Fe0.5PO4F and its single phase Li+ insertion/extraction behaviour

Huang, Zhen-Dong; Orikasa, Yuki; Masese, Titus; Yamamoto, Kentaro; Mori, Toshiyuki; Minato, Taketoshi; Uchimoto, Yoshiharu

doi:10.1039/c3ra44094j

Cited by 6 publications

(13 citation statements)

References 27 publications

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“…Considering the crystal structures are triclinic, the continuous substitutions lead to a versatile change of interplanar crystal spacing. Refinements reveal that solid-solution domains exist without phase separation [25,32]. Lattice parameters ( a , b , c , α, β, γ) and unit cell volumes ( V ) of end-members ( x = 0 and 1) agree well with our previous results [4,26,33].…”

Section: Resultssupporting

confidence: 80%

“…Solid-solution Li-ion cathode materials transform through a single-phase reaction, leading to a long-term structural stability and improved cyclability, while their end-members transform through a two-phase reaction [24,25,26]. LiFePO 4 F, LiVPO 4 F and LiVPO 4 O have homotypic structures.…”

Section: Introductionmentioning

confidence: 99%

“…We have reported recently the LiFePO 4 F–LiVPO 4 O solid solutions (i.e., LiFe 1− x V x PO 4 F 1− δ O δ (0 ≤ x ≤ 1; 0 ≤ δ ≤ 0.36)) [26]. Otherwise, there are some publications related to LiVPO 4 F–LiVPO 4 O [27,28,29,30,31] and a few to LiFePO 4 F–LiVPO 4 F [25,32] solid solutions. Not much information can be collected from the meeting abstract [32].…”

Section: Introductionmentioning

confidence: 99%

“…Not much information can be collected from the meeting abstract [32]. Huang et al [25] synthesized LiFe 0.5 V 0.5 PO 4 F solid-solution which showed a single-phase behavior over the lithium composition range of Li 1− y Fe 0.5 V 0.5 PO 4 F (0 < y < 0.5) with two alternating electrochemical active regions centered at ~2.76 and ~4.3 V.…”

Section: Introductionmentioning

confidence: 99%

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Structure, Shift in Redox Potential and Li-Ion Diffusion Behavior in Tavorite LiFe1−xVxPO4F Solid-Solution Cathodes

et al. 2019

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Solid-solution Li-ion cathode materials transform through a single-phase reaction thus leading to a long-term structural stability and improved cyclability. In this work, a two- to single-phase Li+-extraction/insertion mechanism is studied through tuning the stoichiometry of transition-metal Fe/V cations to trigger a transition in the chemical reactivity path. Tavorite triclinic-structured LiFe1−xVxPO4F (x = 0, 0.1, 0.3, 0.5, 0.7, 0.9, 1) solid-solution powders were prepared by a facile one-step solid-state method from hydrothermal-synthesized and commercial raw materials. The broad shape of cyclic voltammetry (CV) peaks, sloping charge/discharge profiles and sloping open-circuit voltage (OCV) profiles were observed in LiFe1−xVxPO4F solid-solution cathodes while 0 < x < 1. These confirm strongly a single-phase behavior which is different from the two-phase behavior in the end-members (x = 0 or 1). The electronegativity of M (M = Fe1−xVx) for the redox potential of Fe2+/3+ couple or the M–O4F2 bond length for the V3+/4+ couple plays respectively a dominant role in LiFe1−xVxPO4F solid-solution cathodes.

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Section: Resultssupporting

confidence: 80%

Section: Introductionmentioning

confidence: 99%

Section: Introductionmentioning

confidence: 99%

Section: Introductionmentioning

confidence: 99%

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Structure, Shift in Redox Potential and Li-Ion Diffusion Behavior in Tavorite LiFe1−xVxPO4F Solid-Solution Cathodes

et al. 2019

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“…Citric acid and high surface area carbon (Ketjen black) were used as the carbon source for the carbothermal reduction process. 25 The total carbon content obtained from the trace elements analysis was $4.1 wt%. The SEM images shown in Fig.…”

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confidence: 99%

Vanadium phosphate as a promising high-voltage magnesium ion (de)-intercalation cathode host

et al. 2015

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Magnesium batteries (MBs) have been considered as one of the most promising safe and low cost energy storage systems. Herein, vanadium phosphates, prepared by the electrochemical de-lithiation of Li 3 V 2 (PO 4 ) 3 , are investigated as a high-voltage cathode host for Mg 2+ (de)-intercalation. The reversible (de)-intercalation of Mg 2+ into (from) the host structure of V 2 (PO 4 ) 3 are verified by the comprehensive analysis of the results from the electrochemical tests, synchrotron Xray diffraction and absorption, and inductively coupled plasma measurements. Its exceptional high average working voltage ($3.0 V vs. Mg/Mg 2+ ) surpasses other reported values of cathode hosts for MBs.Prime attention has been inclined towards the development of alternative energy storage devices, which have a comparable electrochemical performance, but are safer and of considerably lower cost than lithium ion batteries, in order to meet the escalating new energy demand in the future low carbon society. Mg batteries have gained considerable concerns since the development of a prototype rechargeable Mg battery, where Mg 2+ ions replace Li + as the charge carrier, in 2000. 1 Compared to Li anode, Mg anode is low-cost and shows (3020 $ per ton, vs. $69 000 $ per ton for Li) much higher abundance (13.9%, vs. 7 Â 10 À4 % for Li) and higher theoretical volumetric energy density (3832 mA h cm À3 , vs. 2062 mA h cm À3 for Li). 1,2 Moreover, Mg is stable upon air exposure and is free of dendritic deposition during repeated cycling, and thus, is inherently safer than Li. 1,2 Although Mg batteries are deemed as promising alternatives for a gamut of large-scale storage devices that could couple with renewable energy sources to load the electric grid, and the low working voltage, as well as low capacity of the cathode material limits the attainable energy; thereby, hampering the commercial realization of Mg batteries. 3 One of the most effective and direct solutions is to nd a proper cathode host with high average working voltages, as well as high capacities.To date, as shown in Table S1, † several cathode materials, including Chevrel phases A x Mo 6 T 8 (A ¼ metal, T ¼ S, Se) 4,5 Mg x MSiO 4 (M ¼ Fe, Mn, Co), 6-9 transition metal oxides (V 2 O 5 , 10-14 MnO 2 ) 15-17 and transition metal chalcogenides (MoS 2 , TiS 2 and WSe 2 ), 18-21 have been reported as feasible cathode materials for Mg batteries, which exhibit reasonable reversible capacities. Considerable effort has been devoted to bypassing the intrinsically sluggish solid-state diffusion of Mg 2+ within the host cathodes via morphological design strategies, such as nano-sizing and carbon-coating. 18-21 However, most of the reported cathode materials show relatively low working voltages (see Table S1 †). Therefore, the pursuit for novel high voltage cathode materials that exhibit a high capacity is crucial for the development of high energy density Mg battery systems.Vanadium phosphates (viz., Li 3 V 2 (PO 4 ) 3 (hereaer denoted as LVP)) has proven to be promising high performance cathod...

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First-principles investigation of the structural stability and electronic properties of LiV1–xMxPO4F (M = Mn, Fe, Co, and Ni)

Jiang

Liu

et al. 2020

J Solid State Electrochem

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A novel cationic-ordering fluoro-polyanionic cathode LiV0.5Fe0.5PO4F and its single phase Li+ insertion/extraction behaviour

Cited by 6 publications

References 27 publications

Structure, Shift in Redox Potential and Li-Ion Diffusion Behavior in Tavorite LiFe1−xVxPO4F Solid-Solution Cathodes

Structure, Shift in Redox Potential and Li-Ion Diffusion Behavior in Tavorite LiFe1−xVxPO4F Solid-Solution Cathodes

Vanadium phosphate as a promising high-voltage magnesium ion (de)-intercalation cathode host

First-principles investigation of the structural stability and electronic properties of LiV1–xMxPO4F (M = Mn, Fe, Co, and Ni)

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