Synthesis and electrical property of Li2−FeSi1−P O4 as positive electrodes by spark-plasma-sintering process

Arachi, Yoshinori; Higuchi, Yuko; Nakamura, Ryota; Takagi, Yoshihiro; Tabuchi, Mitsuharu

doi:10.1016/j.jpowsour.2012.12.111

Cited by 9 publications

(12 citation statements)

References 18 publications

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“…In the literature, two solid solutions between LFP and structurally related iron silicates have been reported: LiFePO 4 –Fe 2 SiO 4 and LiFePO 4 –Li 2 FeSiO 4 . Considering the first, an “Fe-rich” complete solid solution ( olivine -Li 1– y Fe 1+ y P 1– y Si y O 4 ) between LFP and Fe 2 SiO 4 was described by Recham et al, which can be rationalized by the homeotypic crystal structures of the compounds (Figure ).…”

Section: Introductionmentioning

confidence: 88%

“…Phosphorus-substituted Li 2 FeSiO 4 was synthesized directly in the SPS according to Arachi et al at 900 °C from Li 2 CO 3 , FeC 2 O 4 •2H 2 O, SiO 2 , and NH 4 H 2 PO 4 with a nominal composition of "Li 1.9 FeP 0.1 Si 0.9 O 4 ". 25 2.3. Control Annealing Experiments in Sealed Silica Ampules.…”

Section: Methodsmentioning

confidence: 99%

“…24 For the second proposed solid solution, o-Li 3−z Fe z P 1−z Si z O 4 , between the orthorhombic compounds γ-Li 3 PO 4 and Li 2 FeSiO 4 , no prior NMR experiments have been reported in the literature to the best of our knowledge. Thus, we directly synthesized a member of this solid solution (nominal "Li 1.9 FeP 0.1 Si 0.9 O 4 "; Figure S10) via SPS according to the methods of Arachi et al 25 The associated X-ray diffractogram was found to consist predominantly of o-Li 3−z Fe z P 1−z Si z O 4 compared to LFP can be rationalized with the differences in the local environment surrounding the phosphate anions (Figure S12). The phosphate ions in LFP are connected to an additional iron site (named "Fe1" in Figure S12) compared to Li 2 FeSiO 4 , and thus five instead of four iron ions are bonded to the anion.…”

Section: Powder X-ray Diffraction (Pxrd)mentioning

confidence: 99%

“…In the literature, two solid solutions between LFP and structurally related iron silicates have been reported: LiFe-PO 4 −Fe 2 SiO 4 24 and LiFePO 4 −Li 2 FeSiO 4 . 25 Considering the first, an "Fe-rich" complete solid solution (olivine-Li 1−y Fe 1+y P 1−y Si y O 4 ) between LFP and Fe 2 SiO 4 was described by Recham et al, 24 which can be rationalized by the homeotypic crystal structures of the compounds (Figure 1). Substitution of all lithium positions in the LFP crystal structure with iron atoms and those of the phosphorus atoms by silicon atoms leads to the Fe 2 SiO 4 (olivine) crystal structure.…”

Section: Introductionmentioning

confidence: 96%

“…The second, "Li-rich" solid solution was introduced by Arachi et al, who reported partial substitution of Li 2 FeSiO 4 with phosphorus by direct SPS synthesis to form "monoclinic m-Li 2−z′ FeSi 1−z′ P z′ O 4 " with z′ ≤ 0.2. 25 However, they did not discuss the so-formed crystal structure in detail. The parent phase Li 2 FeSiO 4 features several closely related orthorhombic and monoclinic polymorphs, depending on the synthesis conditions.…”

Section: Introductionmentioning

confidence: 99%

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Interface Instability in LiFePO₄–Li_3+xP_1–xSi_xO₄ All-Solid-State Batteries

et al. 2018

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All-solid-state batteries (ASSBs) based on noncombustible solid electrolytes are promising candidates for safe and high energy storage systems, but it remains a challenge to prepare systems with stable interfaces between the various solid components that survive both the synthesis conditions and electrochemical cycling. We have investigated cathode mixtures based on a carbon-coated LiFePO 4 active material and Li 3+x P 1−x Si x O 4 solid electrolyte for potential use in all-solid-state batteries. Half-cells were constructed by combining both compounds into pellets by spark plasma sintering (SPS). We report the fast and quantitative formation of two solid solutions (LiFePO 4 −Fe 2 SiO 4 and Li 3 PO 4 − Li 2 FeSiO 4 ) for different compositions and ratios of the pristine compounds, as tracked by powder X-ray diffraction and solid-state nuclear magnetic resonance; X-ray absorption near-edge spectroscopy confirms the formation of iron silicates similar to Fe 2 SiO 4 . Scanning electron microscopy and energy dispersive Xray spectroscopy reveal diffusion of iron cations up to 40 μm into the solid electrolyte even in the short processing times accessible by SPS. Electrochemical cycling of the SPS-treated cathode mixtures demonstrates a substantial decrease in capacity following the formation of the solid solutions during sintering. Consequently, all-solid-state batteries based on LiFePO 4 and Li 3+x P 1−x Si x O 4 would necessitate iron ion blocking layers. More generally, this study highlights the importance of systematic studies on the fundamental reactions at the active material−solid electrolyte interfaces to enable the introduction of protective layers for commercially successful ASSBs.

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Section: Introductionmentioning

confidence: 88%

Section: Methodsmentioning

confidence: 99%

Section: Powder X-ray Diffraction (Pxrd)mentioning

confidence: 99%

Section: Introductionmentioning

confidence: 96%

Section: Introductionmentioning

confidence: 99%

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Interface Instability in LiFePO₄–Li_3+xP_1–xSi_xO₄ All-Solid-State Batteries

et al. 2018

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Facile Synthesis of a Common Na‐Ion Battery Cathode Material Na₃V₂(PO₄)₂F₃ by Spark Plasma Sintering

2020

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ln the pursuit of facile, fast, and efficient methods for the synthesis of various compounds for a variety of applications, spark plasma sintering (SPS) technique is considered to be a powerful and simple tool. Using this technique, a po pular cathode material for Na-ion batteries Na 3 V 2 (P0 4) 2 F 3 is synthesized and char acterized with X-ray diffraction and scanning electron microscopy (SEM), and is electrochemically tested in Swagelok-type cells in a galvanostatic mode. The matter, a lot of research eff ort has already been put into developing new, safe, high performance electrode materials for SIBs. Na 3 V 2 (PO 4) i F 3 (NVPF) has been consid ered as one of the very prornising cathode materials for SIB due to its high electro chemical stability, good electrochernical per formance (theoretical capacity: 128 mAh g-1 for 2Na + intercalation), and fast ion trans port propertiesP1 Since the discovery of its crystal structure in 1999 by Le Meins etaJ.,121 many synthetic routes of ptrre NVPF and its composites have been proposed and realized,13-81 including carbothermal redue tion, solid state, hydrothermal, and sol gel (followed by heat treatrnent) syntheses. Although these methods seem to be rather facile, their dtrration varies from 8 to 65 h obtained material is compared with the conventionally synthesized (via a solid state route) sample. SEM analysis shows 2 times smaller particles in the case of SPS-synthesized material compared with the solid-state-synthesized material which is to be expected from the fast (40 min in totaQ SPS synthesis tha t practically excludes grain/particle growth and promotes much faster diffusion, thereby drastically enhancing the reaction kinetics. Electrochemical perfor mance of the SPS-obtained material shows an improvement in decreasing the overpotential and reducing the capacity loss at high Crates (SC).

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Synthesis and electrochemical properties of Li2FeSiO4/C/Ag composite as a cathode material for Li-ion battery

Tang

Liu

Huang

et al. 2019

J. Cent. South Univ.

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Synthesis and electrical property of Li2−FeSi1−P O4 as positive electrodes by spark-plasma-sintering process

Cited by 9 publications

References 18 publications

Interface Instability in LiFePO₄–Li_3+xP_1–xSi_xO₄ All-Solid-State Batteries

Interface Instability in LiFePO₄–Li_3+xP_1–xSi_xO₄ All-Solid-State Batteries

Facile Synthesis of a Common Na‐Ion Battery Cathode Material Na₃V₂(PO₄)₂F₃ by Spark Plasma Sintering

Synthesis and electrochemical properties of Li2FeSiO4/C/Ag composite as a cathode material for Li-ion battery

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Synthesis and electrical property of Li2−FeSi1−P O4 as positive electrodes by spark-plasma-sintering process

Cited by 9 publications

References 18 publications

Interface Instability in LiFePO4–Li3+xP1–xSixO4 All-Solid-State Batteries

Interface Instability in LiFePO4–Li3+xP1–xSixO4 All-Solid-State Batteries

Facile Synthesis of a Common Na‐Ion Battery Cathode Material Na3V2(PO4)2F3 by Spark Plasma Sintering

Synthesis and electrochemical properties of Li2FeSiO4/C/Ag composite as a cathode material for Li-ion battery

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Interface Instability in LiFePO₄–Li_3+xP_1–xSi_xO₄ All-Solid-State Batteries

Interface Instability in LiFePO₄–Li_3+xP_1–xSi_xO₄ All-Solid-State Batteries

Facile Synthesis of a Common Na‐Ion Battery Cathode Material Na₃V₂(PO₄)₂F₃ by Spark Plasma Sintering