Synthesis and electrochemical properties of pure LiFeSO4F in the triplite structure

Ati, Mohamed; Melot, Brent C.; Chotard, Jean‐Noël; Rousse, Gwenaëlle; Reynaud, Marine; Tarascon, Jean‐Marie

doi:10.1016/j.elecom.2011.08.023

Cited by 89 publications

(131 citation statements)

References 10 publications

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“…19 As a result, the solid-state reaction with FeSO 4 $H 2 O also requires prolonged phase transformation of tavorite to form triplite.…”

Section: 20mentioning

confidence: 99%

“…The particle size of the triplite will have a critical impact on its electrochemical activity because triplite does not have any apparent long-range Li diffusion channels and follows the twophase reaction during charging/discharging. 19 The developed solid-state reaction easily yields nanosized particles. Firstly, the nanosized particles shorten the Li diffusion length and consequently improve the transport of Li and result in good electrochemical activity.…”

mentioning

confidence: 99%

“…Structural changes in triplite LiFeSO 4 F and strong electrostatic repulsion between edge-shared Fe octahedra can be worsened by phase-separating behavior during charging/discharging. 19 In phase-separating compounds, mechanical strain and structural changes induced by insertion/extraction of lithium can be accumulated and can severely degrade the electrochemical properties. 31 Therefore, the minimization of the particle size of triplite LiFeSO 4 F can be a critical step toward improving its electrochemical performance, as is observed with nanosized particles of LiFePO 4 , which is a well-known phase-separating compound; the resulting material can achieve excellent electrochemical performance because nanosized particles themselves induce less mechanical changes than large particles and can facilitate phase transition during charging/discharging.…”

mentioning

confidence: 99%

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High electrochemical performance of 3.9 V LiFeSO₄F directly synthesized by a scalable solid- state reaction within 1 h

2015

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Fe-based polyanion materials such as LiFePO 4 or LiFeBO 3 are safe and can achieve high energy density, so they have been considered as cathode materials for large-scale lithium ion batteries. Among these compounds, LiFeSO 4 F achieves the highest voltage (3.9 V) among Fe 2+ /Fe 3+ redox couples and therefore can have higher energy density than LiFePO 4 . However, full utilization of 3.9 V LiFeSO 4 F is severely limited by its non-scalable synthesis process and poor electrochemical activity. Here, we report a method to synthesize 3.9 V LiFeSO 4 F by a scalable solid-state reaction within 1 h by understanding the thermodynamic stability of 3.9 V LiFeSO 4 F. The resulting material shows the best electrochemical performance reported to date. The process yields nanosized particles that achieve almost full capacity,, which is 93% of the theoretical capacity and that retain excellent capacity, $75 mA h g À1 at 1 C for 150 cycles and high rate capability even at 10 C (6 min). This scalable solid-state reaction for 3.9 V LiFeSO 4 F makes it a plausible replacement for LiFePO 4 in the next generation of lithium ion batteries.

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“…19 As a result, the solid-state reaction with FeSO 4 $H 2 O also requires prolonged phase transformation of tavorite to form triplite.…”

Section: 20mentioning

confidence: 99%

mentioning

confidence: 99%

mentioning

confidence: 99%

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High electrochemical performance of 3.9 V LiFeSO₄F directly synthesized by a scalable solid- state reaction within 1 h

2015

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“…Zinc substitution for iron in LiFe 1−x Zn x SO 4 Fcan also force the tavorite phase to change to the triplite phase and exhibit a working voltage of 3.9 V. When the content of zinc further increases, the structure of LiFe 1−x Zn x SO 4 F changes to the sillimanite phase with a redox voltage of 3.6 V [112,113]. Tarascon et al [112] and Huang et al [112,113] used a traditional ceramic method to synthesize pure triplite LiFeSO 4 F without substitution. The high working voltage of 3.9 V observable for triplite LiFeSO 4 F makes it a competitive cathode material compared to LiFePO 4 , although LiFeSO 4 F has a slightly lower theoretical specific capacity.…”

Section: Fluorosulfatesmentioning

confidence: 95%

Polyanion Compounds as Cathode Materials for Li-Ion Batteries

Guo

et al. 2015

Rechargeable Batteries

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The development of high energy density Li-ion batteries depends on finding electrode materials that can meet increasingly stringent demands, in particular cathode materials [1,2]. Cathodes are not only the primary factor producing the working potential of Li-ion batteries, but also determine the number of Li ions (i.e., the practical capacity) which can be utilized. Due to LiFePO 4 having succeeded as a prime example of high powered Li-ion battery material, polyanion-type compounds have attracted wide interests in the field of cathode research for the last two decades. Although polyanion compounds exhibit disadvantages of weight and volume (i.e., they have smaller theoretical gravimetric or volumetric capacities) compared with layered oxide compounds, their inherent advantages are also clear. They have very stable frameworks that provide long-term structural stability, which is essential for extensive cycling and combating safety issues. In addition, the chemical nature of polyanions allows the monitoring of a given M n+ /M (n−1)+ redox couple through the inductive effect introduced by Goodenough [3,4], and gives rise to higher voltage values versus Li + /Li 0 than in oxides. Finally, a large number of atomic arrangements and crystal structures can be adopted by polyanion compounds, which have an extreme versatility with respect to cation and anion substitutions for a given structural type.In the last two decades, compounds with different polyanion groups such as phosphates (PO 4 3− ), pyrophosphates (P 2 O 7 4− ), silicates(SiO 4 4− ), sulfates(SO 4 2− ), borates (BO 3 3− ) as well as their fluorinated compounds have been widely investigated in the literature. In this chapter, some recent studies of polyanion compounds for use in Li-ion batteries are introduced and summarized. Some review papers in this field can also be found in the literature [5,6]. Here, we mainly focus on the different polyanion compounds in use as cathode materials, except for olivine-type LiFePO 4 and its analogues.

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“…LiFeSO 4 F has been prepared through various synthetic processes such as solid-state reaction [140], polymerassisted [228], tradition ceramic preparation [229], electronically conductive coatings, high-energy ball milling [251][252][253][254][255], and solvothermal reaction [224]. The recent synthesizing methods found that tavorite-type LiFeSO 4 F has low thermodynamic stability, unstable at temperatures above 350°C, because of that, producing single-phase of tavorite LiFeSO 4 F It is difficult to occur [103,[256][257][258][259].…”

Section: Lifeso 4 Fmentioning

confidence: 99%

Review on Synthesis, Characterizations, and Electrochemical Properties of Cathode Materials for Lithium Ion Batteries

Bensalah¹,

Dawood²

2016

J Material Sci Eng

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The development of cutting-edge cathode materials is a challenging research topic aiming to improve the energy and power densities of lithium ion batteries (LIB) to cover the increasing demands for energy storage devices. Therefore, highly needed further improvements in the performance characteristics of Li-ion batteries are largely dependent on our ability to develop novel materials with greatly improved Li ion storage capacities. Three different types of cathode materials including intercalation, alloying and conversion materials are reviewed in this paper in order to orientate our researches towards highly performant LIBs batteries. This includes characteristics of different cathode materials and approaches for improving their performances.

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Synthesis and electrochemical properties of pure LiFeSO4F in the triplite structure

Cited by 89 publications

References 10 publications

High electrochemical performance of 3.9 V LiFeSO₄F directly synthesized by a scalable solid- state reaction within 1 h

High electrochemical performance of 3.9 V LiFeSO₄F directly synthesized by a scalable solid- state reaction within 1 h

Polyanion Compounds as Cathode Materials for Li-Ion Batteries

Review on Synthesis, Characterizations, and Electrochemical Properties of Cathode Materials for Lithium Ion Batteries

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Synthesis and electrochemical properties of pure LiFeSO4F in the triplite structure

Cited by 89 publications

References 10 publications

High electrochemical performance of 3.9 V LiFeSO4F directly synthesized by a scalable solid- state reaction within 1 h

High electrochemical performance of 3.9 V LiFeSO4F directly synthesized by a scalable solid- state reaction within 1 h

Polyanion Compounds as Cathode Materials for Li-Ion Batteries

Review on Synthesis, Characterizations, and Electrochemical Properties of Cathode Materials for Lithium Ion Batteries

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High electrochemical performance of 3.9 V LiFeSO₄F directly synthesized by a scalable solid- state reaction within 1 h

High electrochemical performance of 3.9 V LiFeSO₄F directly synthesized by a scalable solid- state reaction within 1 h