A high-energy-density NASICON-type Na3V1.25Ga0.75(PO4)3 cathode with reversible V4+/V5+ redox couple for sodium ion batteries

Chen, Yuxiang; Liao, Xiangyue; Wang, Peng; Chen, Ji; Zhang, Xiaoqin; Wu, Xingqiao; Smith, Sean C.; Lin, Dunmin; Tan, Xin; Zheng, Qiaoji

doi:10.1016/j.jcis.2023.09.057

Cited by 14 publications

(2 citation statements)

References 55 publications

Supporting

Mentioning

Contrasting

Order By: Relevance

“…Similarly, Zheng's group also demonstrated that the reversible activation of V 4+ /V 5+ can be realized by introducing Ga 3+ in NVP. 55 The reason for the different potentials of the V 4+ /V 5+ redox couple in Na 3 VM(PO 4 ) 3 (M = Ga or Al) and Na 3 V 2 (PO 4 ) 3 was investigated by Jin's group. 31 They reveal that the potentials of the V 4+ /V 5+ redox couple were closely related to the crystallographic sites of sodium ion extraction/insertion.…”

Section: Single Metal Substitutionmentioning

confidence: 99%

See 1 more Smart Citation

Emerging high voltage V⁴⁺/V⁵⁺ redox reactions in Na₃V₂(PO₄)₃-based cathodes for sodium-ion batteries

Zhou,

et al. 2024

Chem. Sci.

View full text Add to dashboard Cite

show abstract

Section: Single Metal Substitutionmentioning

confidence: 99%

“…Similarly, Zheng's group also demonstrated that the reversible activation of V 4+ /V 5+ can be realized by introducing Ga 3+ in NVP. 55 …”

Section: Recent Achievement Of Activation Of the V 4+ ...mentioning

confidence: 99%

Emerging high voltage V⁴⁺/V⁵⁺ redox reactions in Na₃V₂(PO₄)₃-based cathodes for sodium-ion batteries

Zhou,

et al. 2024

Chem. Sci.

View full text Add to dashboard Cite

show abstract

Homeostatic Solid Solution Reaction in Phosphate Cathode: Breaking High‐Voltage Barrier to Achieve High Energy Density and Long Life of Sodium‐Ion Batteries

Gu,

Zhao,

et al. 2024

Advanced Materials

View full text Add to dashboard Cite

The stable phase transformation during electrochemical progress drives extensive research on vanadium‐based polyanions in sodium‐ion batteries (SIBs), especially Na3V2(PO4)3 (NVP). And the electron transfer between V3+/4+ redox couple in NVP could be generally achieved, owing to the confined crystal variation during battery service. However, the more favorable V4+/5+ redox couple is still in hard‐to‐access situation due to the high barrier and further bring about the corresponding inefficiency in energy densities. In this work, the multilevel redox in NVP frame (MLNP) alters reaction pathway to undergo homeostatic solid solution process and breaks the high barrier of V4+/5+ at high voltage, taking by progressive transition metal (V, Fe, Ti and Cr) redox couple. The diversified reaction paths across diffusion barriers could be realized by distinctive release/uptake of inactive Na1 site, confirmed by the calculations of density functional theory. Thereby its volume change is merely 1.73% during the multielectron‐transfer process (∼2.77 electrons). MLNP cathode could achieve an impressive energy density of 440 Wh kg−1, driving the leading development of MLNP among other NASICON structure SIBs. The integration of multiple redox couples with low strain modulates the reaction pathway effectively and will open a new avenue for fabricating high‐performance cathodes in SIBs.This article is protected by copyright. All rights reserved

show abstract

Optimizing Interplanar Spacing, Oxygen Vacancies and Micromorphology via Lithium‐Ion Pre‐Insertion into Ammonium Vanadate Nanosheets for Advanced Cathodes in Aqueous Zinc‐Ion Batteries

Chen,

Zhai,

et al. 2024

Small

Self Cite

View full text Add to dashboard Cite

Ammonium vanadates, featuring an N─H···O hydrogen bond network structure between NH4+ and V─O layers, have become popular cathode materials for aqueous zinc‐ion batteries (AZIBs). Their appeal lies in their multi‐electron transfer, high specific capacity, and facile synthesis. However, a major drawback arises as Zn2+ ions tend to form bonds with electronegative oxygen atoms between V─O layers during cycling, leading to irreversible structural collapse. Herein, Li+ pre‐insertion into the intermediate layer of NH4V4O10 is proposed to enhance the electrochemical activity of ammonium vanadate cathodes for AZIBs, which extends the interlayer distance of NH4V4O10 to 9.8 Å and offers large interlaminar channels for Zn2+ (de)intercalation. Moreover, Li+ intercalation weakens the crystallinity, transforms the micromorphology from non‐nanostructured strips to ultrathin nanosheets, and increases the level of oxygen defects, thus exposing more active sites for ion and electron transport, facilitating electrolyte penetration, and improving electrochemical kinetics of electrode. In addition, the introduction of Li+ significantly reduces the bandgap by 0.18 eV, enhancing electron transfer in redox reactions. Leveraging these unique advantages, the Li+ pre‐intercalated NH4V4O10 cathode exhibits a high reversible capacity of 486.1 mAh g−1 at 0.5 A g−1 and an impressive capacity retention rate of 72% after 5,000 cycles at 5 A g−1.

show abstract

A high-energy-density NASICON-type Na3V1.25Ga0.75(PO4)3 cathode with reversible V4+/V5+ redox couple for sodium ion batteries

Cited by 14 publications

References 55 publications

Emerging high voltage V⁴⁺/V⁵⁺ redox reactions in Na₃V₂(PO₄)₃-based cathodes for sodium-ion batteries

Emerging high voltage V⁴⁺/V⁵⁺ redox reactions in Na₃V₂(PO₄)₃-based cathodes for sodium-ion batteries

Homeostatic Solid Solution Reaction in Phosphate Cathode: Breaking High‐Voltage Barrier to Achieve High Energy Density and Long Life of Sodium‐Ion Batteries

Optimizing Interplanar Spacing, Oxygen Vacancies and Micromorphology via Lithium‐Ion Pre‐Insertion into Ammonium Vanadate Nanosheets for Advanced Cathodes in Aqueous Zinc‐Ion Batteries

Contact Info

Product

Resources

About

A high-energy-density NASICON-type Na3V1.25Ga0.75(PO4)3 cathode with reversible V4+/V5+ redox couple for sodium ion batteries

Cited by 14 publications

References 55 publications

Emerging high voltage V4+/V5+ redox reactions in Na3V2(PO4)3-based cathodes for sodium-ion batteries

Emerging high voltage V4+/V5+ redox reactions in Na3V2(PO4)3-based cathodes for sodium-ion batteries

Homeostatic Solid Solution Reaction in Phosphate Cathode: Breaking High‐Voltage Barrier to Achieve High Energy Density and Long Life of Sodium‐Ion Batteries

Optimizing Interplanar Spacing, Oxygen Vacancies and Micromorphology via Lithium‐Ion Pre‐Insertion into Ammonium Vanadate Nanosheets for Advanced Cathodes in Aqueous Zinc‐Ion Batteries

Contact Info

Product

Resources

About

Emerging high voltage V⁴⁺/V⁵⁺ redox reactions in Na₃V₂(PO₄)₃-based cathodes for sodium-ion batteries

Emerging high voltage V⁴⁺/V⁵⁺ redox reactions in Na₃V₂(PO₄)₃-based cathodes for sodium-ion batteries