Rhombohedral Form of Li3V2(PO4)3 as a Cathode in Li-Ion Batteries

Gaubicher, Joël; Wurm, Cǎlin; Goward, Gillian R.; Masquelier, Christian; Nazar, Linda F.

doi:10.1021/cm000345g

Cited by 266 publications

(241 citation statements)

References 23 publications

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“…Stability of NASICON structures. In agreement with previous experimental and theoretical work, the Na 3 V 2 (PO 4 ) 3 NASICON is predicted to be stable in the rhombohedral phase, 54 while the Li 3 V 2 (PO 4 ) 3 NASICON is predicted to be stable in the monoclinic phase. 56 Diffusion barriers From Figure 3, we may observe that the nature of the host structure has a significant impact on the relative difference between the Na and Li migration barriers.…”

Section: Voltagessupporting

confidence: 90%

“…[52][53][54][55][56][57] They are of the general formula A x MM'(XO 4 ) 3 and comprise a three-dimensional framework of MO 6 and M'O 6 octahedra sharing corners with XO 4 tetrahedra. This framework forms large interstitial channels, which can accommodate alkali cations.…”

Section: Structure Selectionmentioning

confidence: 99%

“…This framework forms large interstitial channels, which can accommodate alkali cations. In this work, we studied both the rhombohedral R3c structure preferred by Na 3 V 2 (PO 4 ) 3 , 54 and the monoclinic P1121/n structure preferred by Li 3 V 2 (PO 4 ) 3 . 56,58 A notable exclusion from the materials investigated is the popular spinel LiMn 2 O 4 material.…”

Section: Structure Selectionmentioning

confidence: 99%

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Voltage, stability and diffusion barrier differences between sodium-ion and lithium-ion intercalation materials

Ong

Chevrier

Hautier

et al. 2011

Energy Environ. Sci.

1,310

1,046

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To evaluate the potential of Na-ion batteries, we contrast in this work the difference between Na-ion and Li-ion based intercalation chemistries in terms of three key battery properties -voltage, phase stability and diffusion barriers. The compounds investigated comprise the layered AMO 2 and AMS 2 structures, the olivine and maricite AMPO 4 structures, and the NA-SICON A 3 V 2 (PO 4 ) 3 structures. The calculated Na voltages for the compounds investigated are 0.18-0.57 V lower than that of the corresponding Li voltages, in agreement with previous experimental data. We believe the observed lower voltages for Na compounds are predominantly a cathodic effect related to the much smaller energy gain from inserting Na into the host structure compared to inserting Li. We also found a relatively strong dependence of battery properties with structural features. In general, the difference between the Na and Li voltage of the same compound, ∆V Na-Li , is less negative for the maricite structures preferred by Na, and * To whom correspondence should be addressed 1 more negative for the olivine structures preferred by Li. The layered compounds have the most negative ∆V Na-Li . In terms of phase stability, we found that open structures, such as the layered and NASICON structures that are better able to accommodate the larger Na + ion generally have both Na and Li versions of the same compound. For the close-packed AMPO 4 structures, our results show that Na generally prefers the maricite structure, while Li prefers the olivine structure, in agreement with previous experimental work. We also found surprising evidence that the barriers for Na + migration can potentially be lower than that for Li + migration in the layered structures. Overall, our findings indicate that Na-ion systems can be competitive with Li-ion systems.

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Section: Voltagessupporting

confidence: 90%

Section: Structure Selectionmentioning

confidence: 99%

Section: Structure Selectionmentioning

confidence: 99%

See 1 more Smart Citation

Voltage, stability and diffusion barrier differences between sodium-ion and lithium-ion intercalation materials

Ong

Chevrier

Hautier

et al. 2011

Energy Environ. Sci.

1,310

1,046

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“…93 Compared to rhombohedral LVP, monoclinic LVP (space group: P2 1 /n, a = 8.605 Å, b = 8.591 Å, c = 12.038 Å, and β = 90.600) is more thermodynamically stable. Its VO 6 octahedra and PO 4 tetrahedra are connected through oxygen vertices, where three crystallographic interstitial voids are available for the occupancy of lithium.…”

Section: Vo 2 (B) Nanostructures For Libsmentioning

confidence: 99%

Vanadium-based nanostructure materials for secondary lithium battery applications

et al. 2015

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Vanadium-based materials, such as V2O5, LiV3O8, VO2(B) and Li3V2(PO4)3 are compounds that share the characteristic of intercalation chemistry. Their layered or open frameworks allow facile ion movement through the interspaces, making them promising cathodes for LIB applications. To bypass bottlenecks occurring in the electrochemical performances of vanadium-based cathodes that derive from their intrinsic low electrical conductivity and ion diffusion coefficients, nano-engineering strategies have been implemented to "create" newly emerging properties that are unattainable at the bulk solid level. Integrating this concept into vanadiumbased cathodes represents a promising way to circumvent the aforementioned problems as nanostructuring offers potential improvements in electrochemical performances by providing shorter mass transport distances, higher electrode/electrolyte contact interfaces, and better accommodation of strain upon lithium uptake/ release. The significance of nanoscopic architectures has been exemplified in the literature, showing that the idea of developing vanadium-based nanostructures is an exciting prospect to be explored. In this review, we will be casting light on the recent advances in the synthesis of nanostructured vanadium-based cathodes. Furthermore, efficient strategies such as hybridization with foreign matrices and elemental doping are introduced as a possible way to boost their electrochemical performances (e.g., rate capability, cycling stability) to a higher level. Finally, some suggestions relating to the perspectives for the future developments of vanadium-based cathodes are made to provide insight into their commercialization. through the interspaces, making them promising cathodes for LIB applications. To bypass bottlenecks occurring in the electrochemical performances of vanadium-based cathodes that derive from their intrinsic low electrical conductivity and ion diffusion coefficients, nano-engineering strategies have been implemented to "create" newly emerging properties that are unattainable at the bulk solid level. Integrating this concept into vanadium-based cathodes represents a promising way to circumvent the aforementioned problems as nanostructuring offers potential improvements in electrochemical performances by providing shorter mass transport distances, higher electrode/electrolyte contact interfaces, and better accommodation of strain upon lithium uptake/release. The significance of nanoscopic architectures has been exemplified in the literature, showing that the idea of developing vanadium-based nanostructures is an exciting prospect to be explored. In this review, we will be casting light on the recent advances in the synthesis of nanostructured vanadium-based cathodes. Furthermore, efficient strategies such as hybridization with foreign matrices and elemental doping are introduced as a possible way to boost their electrochemical performances (e.g., rate capability, cycling stability) to a higher level. Finally, some suggestions relating to the perspective...

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“…Among the optimized conditions, the sample prepared with 0.15 molar ratio of adipic acid to total metal ions at the calcination temperature of 900 0 C showed a better electrochemical performance compared to other samples. [8][9][10][11][12][13][14] have been focus of candidate as cathode materials. Among the phosphates above, monoclinic Li 3 V 2 (PO 4 ) 3 is a highly promising material proposed as a cathode for higher voltage rechargeable lithium-ion batteries because of their stable framework, good ion mobility and high reversible capacity.…”

mentioning

confidence: 99%

Influence of Adipic Acid on Electrochemical Properties of Li3V2 (PO4)3 as Cathode Material for Rechargeable Lithium-Ion Batteries

Yuvaraj¹

2018

IJRASET

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Monoclinic Li 3 V 2 (PO 4 ) 3 powders were synthesized with different calcination temperature of 800, 900 and 950 0 C for 8 h in Ar atmosphere by solid state method using adipic acid as a chealting agent. The influence of calcination temperatures of carbon coated Li 3 V 2 (PO 4 ) 3 has been investigated using X-ray diffraction (XRD) and electrochemical methods. The crystalline phase formation was investigated using thermogravimetric-differential thermal analysis (TG-DTA). Among the optimized conditions, the sample prepared with 0.15 molar ratio of adipic acid to total metal ions at the calcination temperature of 900 0 C showed a better electrochemical performance compared to other samples. [8][9][10][11][12][13][14] have been focus of candidate as cathode materials. Among the phosphates above, monoclinic Li 3 V 2 (PO 4 ) 3 is a highly promising material proposed as a cathode for higher voltage rechargeable lithium-ion batteries because of their stable framework, good ion mobility and high reversible capacity. Li 3 V 2 (PO 4 ) 3 contains both mobile Li cations and redox-active metal sites occupied within a rigid phosphate structure. The theoretical capacity for Li 3 V 2 (PO 4 ) 3 is 197 mAh/g, while three Li ions are completely extracted at the voltage of 4.8 V, which is the highest for all phosphate [14]. In the monoclinic Li 3 V 2 (PO 4 ) 3 phase, the first charging an ordered Li phase of intermediate composition [Li 2.5 V 2 (PO 4 ) 3 ]; then the second stage (3.68 to 4.1 V) is related by the removal of Li-ions from the stable tetrahedral sites. Then, the final stage (4.1 to 4.5 V) is due to the change of the V

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Rhombohedral Form of Li₃V₂(PO₄)₃ as a Cathode in Li-Ion Batteries

Cited by 266 publications

References 23 publications

Voltage, stability and diffusion barrier differences between sodium-ion and lithium-ion intercalation materials

Voltage, stability and diffusion barrier differences between sodium-ion and lithium-ion intercalation materials

Vanadium-based nanostructure materials for secondary lithium battery applications

Influence of Adipic Acid on Electrochemical Properties of Li3V2 (PO4)3 as Cathode Material for Rechargeable Lithium-Ion Batteries

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