Coupled X-ray diffraction and electrochemical studies of the mixed Ti/V-containing NASICON: Na<sub>2</sub>TiV(PO<sub>4</sub>)<sub>3</sub>

Lalère, Fabien; Seznéc, Vincent; Courty, Matthieu; Chotard, Jean Noël; Masquelier, Christian

doi:10.1039/c7ta10689k

Cited by 47 publications

(59 citation statements)

References 25 publications

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“…[52] The NaxTiV(PO4)3 convex hull (Figure 4a) displays a minimum at x = 3, analogous to the observed minima in the NaxM2(PO4)3 systems (Figure 2a); this also provides the largest step in the corresponding voltage profile of Figure 4c. In particular, the Na extraction from Na4Ti III V II (PO4)3 takes place through the redox [51], [52] ), Ti IV /Ti III 2.50 V (~2.1 V), and…”

Section: Na + Ion Intercalation In Naxmm'(po4)3 Nasicon Structuressupporting

confidence: 54%

“…We extend our analysis to the reversible extraction of Na from mixed Na4MM Among the NaxTiM'(PO4)3 systems, only NaxTi2(PO4)3, NaxTiV(PO4)3 and NaxTiMn(PO4)3 have been experimentally investigated over the entire Na composition range (1 ≤ x ≤ 4), [29], [51], [52], [53], [54] while NaxTiCr(PO4)3 [55], [65] and NaxTiFe(PO4)3 [55] have been studied in limited ranges of 1 ≤ x ≤ 3 and 2 ≤ x ≤ 4, respectively. NaxTiCo(PO4)3 x = 1.5 and x = 1, the oxidation state of Fe would have to be +4, which may not be experimentally accessible in a reversible manner.…”

Section: Na + Ion Intercalation In Naxmm'(po4)3 Nasicon Structuresmentioning

confidence: 99%

“…Importantly, Yamada et al [49] reported a voltage of ~4.5 V vs. Na/Na + when Na + is extracted from Na3Cr III Cr III (PO4)3, which corresponds to the highest voltage ever The high voltage delivered by the Cr IV /Cr III redox couple offers scope for exploring new high-voltage and high-capacity materials using more than one transition metal, e.g., Na4Cr III Mn II (PO4)3. [31], [37] Other NaSICON materials, such as Na3V III Cr III (PO4)3, [50] Na2Ti IV V III (PO4)3, [51], [52] Na3Ti IV Mn II (PO4)3, [53], [54] Na2Ti IV Fe III (PO4)3, [55] Na4V III Mn II (PO4)3, [35], [36], [56], [57] Na3V III Fe III (PO4)3 [30,36] and Na4V III Ni II (PO4)3, [36] have also been studied to enable high reversible capacity, longevity and as anode and cathode electrodes.…”

Section: Introductionmentioning

confidence: 99%

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A Chemical Map of NaSiCON Electrode Materials for Sodium-ion Batteries

Gill¹,

Wang²,

Park³

et al. 2020

Preprint

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<div><div><div><p>Na-ion batteries are promising devices for smart grids and electric vehicles due to cost effectiveness arising from the overall abundance of sodium (Na) and its even geographical distribution. Among other factors, the energy density of Na-ion batteries is limited by the positive electrode chemistry. NaSICON-based positive electrode materials are known for their wide range of electrochemical potentials,[1],[2],[3] high ionic conductivity, and most importantly their structural and thermal stabilities. Using first- principles calculations, we chart the chemical space of 3d transition metal-based NaSICON phosphates of formula NaxMM’(PO4)3 (with M and M’= Ti, V, Cr, Mn, Fe, Co and Ni), to analyze their thermodynamic stabilities and the intercalation voltages for Na+ ions. Specifically, we computed the Na insertion voltages and related properties of 28 distinct NaSICON compositions. We investigated the thermodynamic stability of Na-intercalation in previously unreported NaxMn2(PO4)3 and NaxVCo(PO4)3. The calculated quaternary phase diagrams of the Na-P-O-Co and Na-P-O-Ni chemical systems explain the origin of the suspected instability of Ni and Co-based NaSICON compositions. From our analysis, we are also able to rationalize anomalies in previously reported experimental data in this diverse and important chemical space.</p></div></div></div>

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Section: Na + Ion Intercalation In Naxmm'(po4)3 Nasicon Structuressupporting

confidence: 54%

Section: Na + Ion Intercalation In Naxmm'(po4)3 Nasicon Structuresmentioning

confidence: 99%

Section: Introductionmentioning

confidence: 99%

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A Chemical Map of NaSiCON Electrode Materials for Sodium-ion Batteries

Gill¹,

Wang²,

Park³

et al. 2020

Preprint

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“…However, the aqueous Na‐ion battery has a narrow voltage range, which limits the capacity of the battery to some extent. Moreover, vanadium has multiple valence states, and titanium has a lower voltage plateau, which are good for full battery . Based on these inspirations, we turned our attention to Na 3 TiV(PO 4 ) 3 , which has the characteristics of cathode and anode materials, and can be used to assemble symmetrical full batteries.…”

Section: Introductionmentioning

confidence: 99%

“…Moreover, vanadium has multiple valence states, and titanium has a lower voltage plateau, which are good for full battery. 25 Based on these inspirations, we turned our attention to Na 3 TiV(PO 4 ) 3 , which has the characteristics of cathode and anode materials, and can be used to assemble symmetrical full batteries. For the above reasons, Na 3 TiV(PO 4 ) 3 /C nanoparticles were prepared by a simple ball-milling method as cathode and anode material for Na-ion batteries.…”

Section: Introductionmentioning

confidence: 99%

Na₃TiV(PO₄)₃/C nanoparticles for sodium‐ion symmetrical and full batteries

et al. 2019

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Na3TiV(PO4)3/C nanoparticles are synthesized by a simple ball‐milling method and studied for sodium‐ion symmetrical and full batteries. Symmetrical battery assembled with Na3TiV(PO4)3/C nanoparticles shows good structural stability and acceptable capacity. Sodium‐ion full battery exhibits an initial capacity of 200 mA h g−1 and maintains 90 mA h g−1 after 100 cycles when the presodiated commercial hard carbon is chosen as the anode. Moreover, the wide sources of raw materials and low environmental pollution mean that Na3TiV(PO4)3/C nanoparticles may have certain industrial prospects.

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