Reversible lithium charge–discharge property of bi-capped Keggin-type polyoxovanadates

Uematsu, Shinya; Quan, Zhen; Suganuma, Yoshiaki; Sonoyama, Noriyuki

doi:10.1016/j.jpowsour.2012.05.096

Cited by 55 publications

(48 citation statements)

References 29 publications

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“…The XRD pattern of Na 7 [H 2 PV 14 O 42 ]·24H 2 O crystals simulated from single‐crystal XRD data is shown in Figure a and the powder XRD pattern of precipitated Na 7 [H 2 PV 14 O 42 ]·15H 2 O powders is similar to crystals. The slightly different intensities of these two patterns between 26° and 30° might due to the different amount of crystal water in the precipitated powder and crystal as reported in literature . The amount of crystal water in the molecule can be measured by thermogravimetric analysis (TGA) as shown in Figure b, and the precipitated powders contain around 15H 2 O per molecule (n = 15).…”

Section: Resultsmentioning

confidence: 67%

“…Polyoxometalates (POMs) are transition metal oxide clusters with unique structures, and they are able to provide multi‐electron‐transfer processes during charging/discharging processes. Thus, POMs have been employed as cathode and anode materials for LIBs and most of them exhibited high capacity . Besides, POMs undergo redox reactions as a molecular cluster not as a continuum, so the stability of their crystal structure is less important as compared to other oxide materials .…”

Section: Introductionmentioning

confidence: 99%

“…Therefore, different molecular structures might influence the ability of redox reactions as well as cycling stability. For example, Li 6 [V 10 O 28 ], (KH) 9 [PV 14 O 42 ], K 7 [NiV 13 O 38 ], and K 7 [MnV 13 O 38 ] have been used as cathodes for LIBs, but their capacities and cycling stabilities are totally different. We synthesized Na 7 [H 2 PV 14 O 42 ]·nH 2 O through a facile solution process under low temperature (≤ 50 °C).…”

Section: Introductionmentioning

confidence: 99%

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Mechanism of Sodium Ion Storage in Na₇[H₂PV₁₄O₄₂] Anode for Sodium‐Ion Batteries

Lin

Huang

et al. 2018

Adv Materials Inter

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In this work, the authors explore the sodium salt of the 14‐vanado(V)phosphate, Na7[H2PV14O42], as a potential anode material for sodium‐ion batteries (NIBs). The multi‐electron redox activity of the polyoxovanadate [H2PV14O42]7‐leads to high capacity. This polyanion is synthesized by a simple aqueous solution procedure and isolate as a sodium salt with different numbers of crystal waters, Na7[H2PV14O42]·nH2O (n = 15–24). Na7[H2PV14O42] as anode in NIBs exhibits a high and reversible capacity of 322 mA h g−1 at 25 mA g−1 with a high cycling stability (with capacity retention of 87% after 120 cycles). Some of the V5+ ions in [H2PV14O42]7‐ can be reduced to V3+ after being discharged to 0.01 V versus Na/Na+, resulting in an average oxidation state of V3.7+, as based on ex situ X‐ray photoelectron spectroscopy and in situ synchrotron X‐ray absorption near edge structure studies. The crystalline material becomes amorphous during the charge/discharge processes, which can be observed by in situ synchrotron X‐ray diffraction, indicating that functionality does not require crystallinity. The authors propose that the charge storage mechanism of Na7[H2PV14O42] anodes mainly involves redox reactions of V accompanied by insertion/extraction of Na ions in‐between polyoxo‐14‐vanadate ions and adsorption/desorption of Na ions on the surface of the vanadate material.

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Section: Resultsmentioning

confidence: 67%

Section: Introductionmentioning

confidence: 99%

Section: Introductionmentioning

confidence: 99%

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Mechanism of Sodium Ion Storage in Na₇[H₂PV₁₄O₄₂] Anode for Sodium‐Ion Batteries

Lin

Huang

et al. 2018

Adv Materials Inter

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“…Actually, we have reported many POMs reacting with lithium as a molecular cluster ion which is free from the host crystal structure. [17][18][19] Furthermore, high capacity can be obtained, because POMs can provide reversible multi-electron redox reactions during the discharge-charge process. Many of the POMs, reported by our group, [17][18][19] show not only very high capacity but also very stable cycle performance except for Keggin type KPM.…”

Section: Introductionmentioning

confidence: 99%

Effect of Annealing Treatment on the Electrochemical Properties of Polyoxomolybdate K4[SiMo12O40] as Cathode Material of Lithium Battery

Kume

Uematsu

et al. 2014

Electrochemistry

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Silicon-centered polyoxomolybdate K 4 [SiMo 12 O 40 ] (KSM) with the Keggin type structure was investigated as the cathode material for rechargeable lithium battery. The discharge capacity and cycle performance of KSM mainly depends on the annealing temperature. This material shows improved discharge capacity by the increase of annealing temperature. Rietveld analysis of X-ray powder diffraction data and Raman spectra were used to analyze the effect of annealing treatment on the cycle performance of KSM. The results indicate that the improvement of cycle performance would be caused by the re-oxidation of Mo 5+ ion in KSM reduced during the preparation process. The KSM cathode shows better electrochemical performance than that of the reported phosphorous-centered polyoxomolybdate K 3 [PMo 12 O 40 ] (KPM), indicating that KSM as the cathode material with high discharge capacity and cycle stability is accessible.

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“…One approach that was demonstrated is to replace materials with a defined long-range order with a different class of materials such as POMs. Even though POMs have been shown to work in LIBs [139][140][141][142][143][144] , they had not been employed in NIBs before. POMs consist of polyanionic clusters with cavities between the respective compounds.…”

Section: Resultsmentioning

confidence: 99%

Vanadium-based materials as electrode materials in sodium-ion batteries

Hartung¹

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Natrium-Ionen-Batterien haben Vorteile gegenüber Lithium-Ionen-Batterien hinsichtlich Kosten und Kinetik. Jedoch sind die Identifikation neuer Elektrodenmaterialien sowie ein besseres Verständnis der Ladungsspeicherung notwendig, um die Zyklenstabilität zu verbessern. Diese Arbeit beschreibt die Untersuchung Vanadium-basierter Elektrodenmaterialien. Der beobachtete Kapazitätsverlust von Alkali-Vanadaten während des Zyklisierens wird erklärt und erfolgreich umgesetzte Strategien zur Verbesserung der Zyklenstabilität werden beschrieben. Sodium-ion batteries have advantages over the widespread lithium-ion batteries with regard to cost and kinetics. However, low cycling stability is still a common problem for many electrode materials. Thus, identification of suitable materials and understanding of the respective charge-storage mechanisms are necessary. This work presents investigations on vanadium-based electrode materials in sodium-ion batteries. Reasons for the observed decrease in capacity during cycling are identified and successful strategies to improve cycling stability are presented. This doctoral thesis comprises the scientific publications resulting from my work as a research associate at TUM CREATE. After an introduction to sodium-ion batteries, the main experimental methods employed in this work are described. Subsequently, my four scientific publications, as well as one further publication in which my contribution was crucial, are presented. The thesis is concluded with a discussion of the described results.

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Reversible lithium charge–discharge property of bi-capped Keggin-type polyoxovanadates

Cited by 55 publications

References 29 publications

Mechanism of Sodium Ion Storage in Na₇[H₂PV₁₄O₄₂] Anode for Sodium‐Ion Batteries

Mechanism of Sodium Ion Storage in Na₇[H₂PV₁₄O₄₂] Anode for Sodium‐Ion Batteries

Effect of Annealing Treatment on the Electrochemical Properties of Polyoxomolybdate K<sub>4</sub>[SiMo<sub>12</sub>O<sub>40</sub>] as Cathode Material of Lithium Battery

Vanadium-based materials as electrode materials in sodium-ion batteries

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Reversible lithium charge–discharge property of bi-capped Keggin-type polyoxovanadates

Cited by 55 publications

References 29 publications

Mechanism of Sodium Ion Storage in Na7[H2PV14O42] Anode for Sodium‐Ion Batteries

Mechanism of Sodium Ion Storage in Na7[H2PV14O42] Anode for Sodium‐Ion Batteries

Effect of Annealing Treatment on the Electrochemical Properties of Polyoxomolybdate K<sub>4</sub>[SiMo<sub>12</sub>O<sub>40</sub>] as Cathode Material of Lithium Battery

Vanadium-based materials as electrode materials in sodium-ion batteries

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Mechanism of Sodium Ion Storage in Na₇[H₂PV₁₄O₄₂] Anode for Sodium‐Ion Batteries

Mechanism of Sodium Ion Storage in Na₇[H₂PV₁₄O₄₂] Anode for Sodium‐Ion Batteries