On the Effect of Silicon Substitution in Na3V2(PO4)3 on the Electrochemical Behavior as Cathode for Sodium‐Ion Batteries

Aragón, M.J.; Lavela, Pedro; Alcántara, Ricardo; Ortiz, Gregório F.

doi:10.1002/celc.201700933

Cited by 36 publications

(31 citation statements)

References 43 publications

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“…Due to large ion size difference between Si (0.26 Å) and P (0.17 Å), the amount of Si doping is limited in Na 3+ x V 2 (PO 4 ) 3− x ‐ x (SiO 4 ) (N 3 VPS). [ 125 ] At high doping level, the capacity is greatly reduced due to presence of impurities.…”

Section: Modification Of Electronic Structurementioning

confidence: 99%

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Polyanion Sodium Vanadium Phosphate for Next Generation of Sodium‐Ion Batteries—A Review

Chen

Huang

et al. 2020

Adv Funct Materials

113

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Polyanion‐type sodium (Na) vanadium phosphate in the form of Na3V2(PO4)3 has demonstrated reasonably high capacity, good rate capability, and excellent cyclability. Two of three Na ions per formula can be deintercalated at a potential 3.4 V versus Na+/Na with oxidation of V3+/4+. In the reversible process, two Na ions intercalate back resulting in a discharge capacity of 117.6 mAh g−1. Further intercalation is possible but at a low potential of 1.4 V versus Na+/Na accompanied by vanadium reduction V3+/2+, leading to a capacity of 60 mAh g−1. Due to its marvelous electrochemical performance, it has attracted a lot of attention since its discovery in the 1990s. To develop truly useable polyanion‐type vanadium phosphate, better understanding of its crystal configuration, sodium ions' transportation, and electronic structure is essential. Therefore, this review only focuses on the inside of crystal configuration and electronic structure of polyanion‐type vanadium phosphate, Na3V2(PO4)3, since there are a few good reviews on various processing technologies.

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Section: Modification Of Electronic Structurementioning

confidence: 99%

Section: Figure 11mentioning

confidence: 99%

Polyanion Sodium Vanadium Phosphate for Next Generation of Sodium‐Ion Batteries—A Review

Chen

Huang

et al. 2020

Adv Funct Materials

113

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“…Appropriate amounts of citric acid (Sigma-Aldrich, 99%), NH 4 VO 3 (Alfa Aesar, 98%), Na 2 CO 3 (Sigma-Aldrich, 99%), NaH 2 PO 4 .2H 2 O (Alfa Aesar, 98%), and tetraethyl orthosilicate (Sigma-Aldrich, 99%) were weighed and dissolved in deionized water. The molar ratio between citric acid and vanadium was kept as 3:2 to ensure adequate metal cation chelation . The solution was gently stirred for at least 1 h to promote the chelating reaction.…”

Section: Experimental Proceduresmentioning

confidence: 99%

“…Aragón et al. studied the Na 3+ x V 2 (PO 4 ) 3– x (SiO 4 ) x (0 < x < 0.5) series as the positive electrode for NIBs. Although charge capacity improved in a composition with a low Si content ( x = 0.05), vanadium ions were detected to exist in the mixed oxidation states of 3+ and 4+ in all the Si-containing compounds.…”

Section: Introductionmentioning

confidence: 99%

Improving the Electrochemical Performance of Na₃V₂(PO₄)₃ Cathode in Na-Ion Batteries by Si-Doping

Pal

Thirupathi

Chakrabarty

et al. 2020

ACS Appl. Energy Mater.

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High-performance cathode materials are highly desirable for the realization of commercial Na-ion batteries. Sodium super ion conductor (NASICON)-type Na 3 V 2 (PO 4 ) 3 is one of the most promising cathode materials. In the present study, an improvement in the kinetics of the redox reactions and consequently, the electrochemical performance of Na 3 V 2 (PO 4 ) 3 cathode have been demonstrated by the partial substitution of Si for P. Nano-sized powders of Na 3+x V 2 (PO 4 ) 3−x (SiO 4 ) x (x = 0, 0.1, 0.2 and 0.4) are synthesized using the citric acid-assisted sol-gel route. A thin carbon layer of ∼8−16 nm thickness is formed on the calcined particles of the active material. The vanadium present in Na 3 V 2 (PO 4 ) 3 is shown to retain the trivalent state after the Si substitution. Coin cells are fabricated using an organic electrolyte, carbon nanotubes decorated Na 3+x V 2 (PO 4 ) 3−x (SiO 4 ) x as a cathode, and Na as an anode. Cyclic voltammetry profiles acquired on the half-cells confirmed (1) improved reversibility of the redox reactions, (2) lower polarization losses, and (3) superior sodium-ion diffusivity in the Si-substituted compounds. As a result, cells with these electrodes exhibit an enhanced electrochemical performance with a high specific capacity, excellent rate capability, and stable cycling performance. The electroactive material with Na 3.1 V 2 (PO 4 ) 2.9 (SiO 4 ) 0.1 composition exhibits ∼21% higher specific capacity than that with Na 3 V 2 (PO 4 ) 3 at 5C charging/ discharging rates, furnishing a Coulombic efficiency of >99%. The expansion of the crystal volume and the presence of excess Na-ion for ionic conduction are primarily responsible for the observed superior performance. The exceptional capacity of 85 mA h/g at 1C charging/discharging rates and superior cycling life achieved in Na 3.1 V 2 (PO 4 ) 2.9 (SiO 4 ) 0.1 /carbon nanotubes show that the strategy of expanding the crystal lattice through appropriate doping is an effective way to develop Na 3 V 2 (PO 4 ) 3 cathode for Na-ion batteries. KEYWORDS: sodium-ion battery, cathodes, NASICON, doping, Na 3 V 2 (PO 4 ) 3

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“…Served as a greatly hopeful cathode material of SIBs, NVP crystallizes have trigonal system and belong to R-3c space group. As shown in Figure 2, VO 6 octahedra and PO 4 tetrahedra interlink mutually to construct a 3D [V 2 (PO 4 ) 3 ] frame via sharing corners (Kabbour et al, 2011;Kang et al, 2012;Shen et al, 2015a;Lavela et al, 2018), in which sodium ion occupies two different positions of Na(1) and Na(2), respectively. The desorption process of sodium ion relates to the transformation from Na 3 V 2 (PO 4 ) 3 to NaV 2 (PO 4 ) 3 , it is generally considered that all the outer sodium ions come from the Na(2) position while the Na(1) position is unchanged.…”

Section: Structure Of Na 3 V 2 (Po 4 )mentioning

confidence: 99%

Research Progress on Na3V2(PO4)3 Cathode Material of Sodium Ion Battery

et al. 2020

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Sodium ion batteries (SIBs) are one of the most potential alternative rechargeable batteries because of their low cost, high energy density, high thermal stability, and good structure stability. The cathode materials play a crucial role in the cycling life and safety of SIBs. Among reported cathode candidates, Na 3 V 2 (PO 4) 3 (NVP), a representative electrode material for sodium super ion conductor, has good application prospects due to its good structural stability, high ion conductivity and high platform voltage (∼3.4 V). However, its practical applications are still restricted by comparatively low electronic conductivity. In this review, recent progresses of Na 3 V 2 (PO 4) 3 are well summarized and discussed, including preparation and modification methods, electrochemical properties. Meanwhile, the future research and further development of Na 3 V 2 (PO 4) 3 cathode are also discussed.

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On the Effect of Silicon Substitution in Na₃V₂(PO₄)₃ on the Electrochemical Behavior as Cathode for Sodium‐Ion Batteries

Cited by 36 publications

References 43 publications

Polyanion Sodium Vanadium Phosphate for Next Generation of Sodium‐Ion Batteries—A Review

Polyanion Sodium Vanadium Phosphate for Next Generation of Sodium‐Ion Batteries—A Review

Improving the Electrochemical Performance of Na₃V₂(PO₄)₃ Cathode in Na-Ion Batteries by Si-Doping

Research Progress on Na3V2(PO4)3 Cathode Material of Sodium Ion Battery

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On the Effect of Silicon Substitution in Na3V2(PO4)3 on the Electrochemical Behavior as Cathode for Sodium‐Ion Batteries

Cited by 36 publications

References 43 publications

Polyanion Sodium Vanadium Phosphate for Next Generation of Sodium‐Ion Batteries—A Review

Polyanion Sodium Vanadium Phosphate for Next Generation of Sodium‐Ion Batteries—A Review

Improving the Electrochemical Performance of Na3V2(PO4)3 Cathode in Na-Ion Batteries by Si-Doping

Research Progress on Na3V2(PO4)3 Cathode Material of Sodium Ion Battery

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Product

Resources

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On the Effect of Silicon Substitution in Na₃V₂(PO₄)₃ on the Electrochemical Behavior as Cathode for Sodium‐Ion Batteries

Improving the Electrochemical Performance of Na₃V₂(PO₄)₃ Cathode in Na-Ion Batteries by Si-Doping