All-climate and air-stable NASICON-Na2TiV(PO4)3 cathode with three-electron reaction toward high-performance sodium-ion batteries

Zhang, Wei; Xu, Zhenming; Xu, Ming; Wang, Sha; Zheng, Li; Wang, Aonan; Zhang, Liuyun; Liang, Huihui; Li, Shihao; Zhu, Bin; Zhang, Zhian; Lai, Yanqing

doi:10.1016/j.cej.2021.133542

Cited by 33 publications

(50 citation statements)

References 61 publications

Supporting

Mentioning

Contrasting

Order By: Relevance

“…From Figure 5f, the well-interconnected 3D pathways contribute to relatively low energy barriers no more than 0.396 eV, which are lower than those of the well-studied Na 3 V 2 (PO 4 ) 3 and other NASICONs. [21,31,35,36] It offers valid evidence for the high Na + diffusion coefficient as discussed in Figure 3a and therefore accounts for the activated V 5+ /V 4+ from a kinetics perspective.…”

Section: Dft Calculationsmentioning

confidence: 68%

“…[53] When charged to 3.72 V, it shifted to 517.00 eV (V 4+ ). [21,54] Subsequently, when it was subjected to 4.2 V, the peak of V 2p 3/2 further experienced a right shift to 517.40 eV (V 5+ ). [55] As discharging proceeds to 3.60 and 2.30 V, valence states of V returned to V 4+ and V 3+ , respectively.…”

Section: Sodium-ion Storage Mechanismmentioning

confidence: 99%

“…[55] As discharging proceeds to 3.60 and 2.30 V, valence states of V returned to V 4+ and V 3+ , respectively. [21,[53][54] After that, the peak of V 2p 3/2 further shifted to 516.50 eV (V 2+ ). [56] On the other hand, the peaks of Cr 2p 3/2 were kept invariant (577.71 eV, signal of Cr 3+ ) throughout the whole process.…”

Section: Sodium-ion Storage Mechanismmentioning

confidence: 99%

“…[1,2] PO bonds), excellent air tolerance and higher redox potential (inductive effect between transition metal and phosphates). [18] Due to the ease of redox tunability, diverse NASI-CONs have been identified, including Na 3 V 2 (PO 4 ) 3 , [19] Na 2 CrTi(PO 4 ) 3 , [20] Na 2 TiV(PO 4 ) 3 , [21,22] Na 4 NiV(PO 4 ) 3 , [23] Na 3 Mn Ti(PO 4 ) 3 , [24,25] Na 3 FeV(PO 4 ) 3 , [23] Na 3 MnZr(PO 4 ) 3 , [26] Na 4 Mn V(PO 4 ) 3 , [23,27,28] Na 4 MnAl(PO 4 ) 3 , [29] Na 4 MnCr(PO 4 ) 3 , [30][31][32] and Na 4 VMn 0.5 Fe 0.5 (PO 4 ) 3 , [33] etc. Nevertheless, most NASICONs suffer from low capacity (<120 mAh g −1 ) as a result of limited (i.e., one to two) electron transfer per chemical formula unit, which reduces the overall energy density and impedes further practical application.…”

Section: Introductionmentioning

confidence: 99%

See 3 more Smart Citations

Rationally Designed Sodium Chromium Vanadium Phosphate Cathodes with Multi‐Electron Reaction for Fast‐Charging Sodium‐Ion Batteries

Zhang

et al. 2022

Advanced Energy Materials

Self Cite

View full text Add to dashboard Cite

Lithium-ion batteries (LIBs) have changed modern life-enabling mobile communication and electric vehicles. They are the most widespread energy storage devices but they are not totally suitable for sustainable development due to the limited lithium resources in countries often with underlying political disputes. [3][4][5] As alternative candidates, sodium-ion batteries (SIBs) have drawn increasing attention by both academic and industrial communities on account of the high abundance of sodium resources. [6,7] Of great promise are inexpensive, high-energy, long-lifespan, and fast-charging SIBs in order to improve on LIBs. [8] However, a key bottleneck in commercializing SIBs is to identify competitive cathodes with long lifespan, negligible volume change, cost-effectiveness, as well as high capacity. [9][10][11] Until now, several families of cathode materials have been developed for use such as layered oxides, [12,13] Prussian blues analogs, [14] and polyanion oxides. [15][16][17] Among these, sodium superionic conductor (NASICON)-structured Na x MeMe′(PO 4 ) 3 (Me/Me′ refers to transition metals) are capable of satisfying the above requirements in terms of high ionic conductivity (3D open frameworks), limited volume change (strong Sodium super-ionic conductor (NASICON)-structured phosphates are emerging as rising stars as cathodes for sodium-ion batteries. However, they usually suffer from a relatively low capacity due to the limited activated redox couples and low intrinsic electronic conductivity. Herein, a reduced graphene oxide supported NASICON Na 3 Cr 0.5 V 1.5 (PO 4 ) 3 cathode (VC/C-G) is designed, which displays ultrafast (up to 50 C) and ultrastable (1 000 cycles at 20 C) Na + storage properties. The VC/C-G can reach a high energy density of ≈470 W h kg −1 at 0.2 C with a specific capacity of 176 mAh g −1 (equivalent to the theoretical value); this corresponds to a three-electron transfer reaction based on fully activated V 5+ /V 4+ , V 4+ /V 3+ , V 3+ /V 2+ couples. In situ X-ray diffraction (XRD) results disclose a combination of solid-solution reaction and biphasic reaction mechanisms upon cycling. Density functional theory calculations reveal a narrow forbiddenband gap of 1.41 eV and a low Na + diffusion energy barrier of 0.194 eV. Furthermore, VC/C-G shows excellent fast-charging performance by only taking ≈11 min to reach 80% state of charge. The work provides a widely applicable strategy for realizing multi-electron cathode design for high-performance SIBs.

show abstract

Section: Dft Calculationsmentioning

confidence: 68%

Section: Sodium-ion Storage Mechanismmentioning

confidence: 99%

Section: Sodium-ion Storage Mechanismmentioning

confidence: 99%

Section: Introductionmentioning

confidence: 99%

See 2 more Smart Citations

Rationally Designed Sodium Chromium Vanadium Phosphate Cathodes with Multi‐Electron Reaction for Fast‐Charging Sodium‐Ion Batteries

Zhang

et al. 2022

Advanced Energy Materials

Self Cite

View full text Add to dashboard Cite

show abstract

“…The b value can be calculated corresponding to the linear relationship between log(i) and log(v) plots for every peak value according to the equation: log(i) = b log(v) + log(a), where b and a are adjustable parameters. 32,33 When the b value is 0.5, the capacity contribution originates from the diffusion-dominated reaction, and when the b value is 1, the capacity contribution originates from the capacitancedominated process. 34,35 As shown in Fig.…”

Section: Resultsmentioning

confidence: 99%

Electropolymerization reaction-driven 2,6-naphthalenediamine monomers to a multilayered sheet structure for ultralong cycling aqueous zinc-ion batteries

Xie

et al. 2022

New J. Chem.

View full text Add to dashboard Cite

show abstract

Na_2.5VTi_0.5Al_0.5(PO₄)₃ as Long Lifespan Cathode for Fast Charging Sodium‐Ion Batteries

Li,

Sun,

et al. 2024

Adv Funct Materials

View full text Add to dashboard Cite

Vanadium based NASICON‐type cathodes are faced with the exorbitant cost and underdeveloped multi‐electrons reaction of V species. In this work, a strategy of increased covalency of the NASICON framework combined with the reversible activation of V4+/V5+ couple is proposed to improve the electrochemical performance together with energy density of V‐based cathodes. Making full use of V2+/V3+/V4+/V5+ and Ti3+/Ti4+ redox couples, Na2.5VTi0.5Al0.5(PO4)3 exhibits admirable electrochemical performance, including a high specific capacity of 160.9 mAh g−1 at 0.1 C and favorable cycling stability (a capacity retention of 88.3% at 20 C after 1000 cycles). Moreover, this cathode displays outstanding low temperature performance at 0 °C with a capacity retention of 89% after 1200 cycles at 5 C. In situ XRD and EIS analysis are conducted to reveal the Na+ storage mechanism. The cathode reveals a lattice volume variation of 2.16% upon cycling, which is responsible for the high structural stability during the extraction and intercalation process of Na+. Applying Na2.5VTi0.5Al0.5(PO4)3 as both cathode and anode electrode, the symmetric cell is assembled and displays exceptional capacity of 59.8 mAh g−1 at 20 C. The research provides an effective routine to stimulate the electrochemical potential of V‐based electrode materials.

show abstract

All-climate and air-stable NASICON-Na2TiV(PO4)3 cathode with three-electron reaction toward high-performance sodium-ion batteries

Cited by 33 publications

References 61 publications

Rationally Designed Sodium Chromium Vanadium Phosphate Cathodes with Multi‐Electron Reaction for Fast‐Charging Sodium‐Ion Batteries

Rationally Designed Sodium Chromium Vanadium Phosphate Cathodes with Multi‐Electron Reaction for Fast‐Charging Sodium‐Ion Batteries

Electropolymerization reaction-driven 2,6-naphthalenediamine monomers to a multilayered sheet structure for ultralong cycling aqueous zinc-ion batteries

Na_2.5VTi_0.5Al_0.5(PO₄)₃ as Long Lifespan Cathode for Fast Charging Sodium‐Ion Batteries

Contact Info

Product

Resources

About

All-climate and air-stable NASICON-Na2TiV(PO4)3 cathode with three-electron reaction toward high-performance sodium-ion batteries

Cited by 33 publications

References 61 publications

Rationally Designed Sodium Chromium Vanadium Phosphate Cathodes with Multi‐Electron Reaction for Fast‐Charging Sodium‐Ion Batteries

Rationally Designed Sodium Chromium Vanadium Phosphate Cathodes with Multi‐Electron Reaction for Fast‐Charging Sodium‐Ion Batteries

Electropolymerization reaction-driven 2,6-naphthalenediamine monomers to a multilayered sheet structure for ultralong cycling aqueous zinc-ion batteries

Na2.5VTi0.5Al0.5(PO4)3 as Long Lifespan Cathode for Fast Charging Sodium‐Ion Batteries

Contact Info

Product

Resources

About

Na_2.5VTi_0.5Al_0.5(PO₄)₃ as Long Lifespan Cathode for Fast Charging Sodium‐Ion Batteries