High valence Mo-doped Na3V2(PO4)3/C as a high rate and stable cycle-life cathode for sodium battery

Li, Xiang; Huang, Yangyang; Wang, Jingsong; Miao, Ling; Li, Yuyu; Liu, Yi; Qiu, Yuegang; Fang, Chun; Han, Jiantao; Huang, Yunhui

doi:10.1039/c7ta08970h

Cited by 130 publications

(64 citation statements)

References 58 publications

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“…A possible activation of the V 4+/5+ redox couple at higher voltages may also contribute to the increasing of the energy density of NVP‐based materials, as demonstrated in a series of works by using a metal substitution of a part of V 3+ in the structure of NVP. In recent years, several elements have been chosen for the partial substitution of V into the crystal structure of this promising material (such as Ni, Al, Fe 3+ , Zr 4+ , Mn 3+ , Mn 2+ , Cr 3+ , Ti 4+ , Mo 6+ , and Mg 2+ ).…”

Section: Introductionmentioning

confidence: 99%

A NASICON‐Type Positive Electrode for Na Batteries with High Energy Density: Na₄MnV(PO₄)₃

et al. 2018

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Among them, Na 3 V 2 (PO 4 ) 3 (NVP) has been identified so far as the most interesting one as it possesses satisfactory energy density and high power for extended cycle life. Its crystal structure can be described as a 3D framework of VO 6 octahedra and PO 4 tetrahedra connected to each other by common corners forming so-called "lantern units" along the c direction of the commonly used hexagonal cell. Sodium cations were described as randomly disordered over two sodium sites (Na(1), 6b and Na(2), 18e) [18] until Chotard et al. discovered that below 280 K, the so called α-NVP form crystallized in a monoclinic superstructure due to a fully ordered distribution of Na +[19] similar to the ordering previously reported in α-Na 3 Ti 2 (PO 4 ) 3 . [51] The synthesis of Na 3 V 2 (PO 4 ) 3 was first reported by Delmas. [20] Gopalakrishnan [21] later on reported on the possible extraction of three Na + toward the novel sodium-free V IV V V (PO 4 ) 3 composition. Afterward, the electrochemical extraction of Na + from Na 3 V 2 (PO 4 ) 3 to NaV 2 (PO 4 ) 3 (with a theoretical capacity of 117.6 mAh g −1 at 3.4 V vs Na/Na) was extensively investigated. [22][23][24][25][26] A large number of special treatments (e.g., carbon coating, particle shape controlling) was also proposed to improve battery performances. [27][28][29][30][31] It is important to note that only 2Na formula unit −1 have been completely removed from the structure during charging up to now. A possible activation of the V 4+/5+ redox couple at higher voltages may also contribute to the increasing of the energy density of NVP-based materials, as demonstrated in a series of works by using a metal substitution of a part of V 3+ in the structure of NVP. In recent years, several elements have been chosen for the partial substitution of V into the crystal structure of this promising material (such as Ni, [32][33][34] Al, [35,36] Fe 3+ , [34,37] Zr 4+ , [38] Mn 3+ , [39] Mn 2+ , [34,40] Cr 3+ , [41][42][43] Ti 4+ , [44][45][46] Mo 6+ , [47] and Mg 2+[48] ).In this work, Mn 2+ was used as a substituting ion to enhance the capacity of the Na 3 V 2 (PO 4 ) 3 cathode material. Inspired by the recent work of Zhou et al., [34] nearly single-phase Na 4 MnV(PO 4 ) 3 (98.5 wt%) powders were synthesized and studied structurally and electrochemically in details. In operando X-ray diffraction (XRD) studies during electrochemical operation show for the first time that Na 4 MnV(PO 4 ) 3 can deliver 156 mAh g −1 toward the new composition NaMnV(PO 4 ) 3 . Results and DiscussionThe crystal structure of Na 4 MnV(PO 4 ) 3 has been fully determined using high-resolution synchrotron powder XRD (SXRD) dataThe mixed Mn 2+ /V 3+ Na-super-ionic-conductor (NASICON) cathode material Na 4 MnV(PO 4 ) 3 is prepared by solid-state reaction at 800 °C under argon. When used as a positive electrode in Na batteries, this material can exchange three electrons for two transition metals, that is, yielding a high gravimetric capacity of 156 mAh g −1 on charge when the upper cutoff voltage is set to 4.3 V...

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Section: Introductionmentioning

confidence: 99%

A NASICON‐Type Positive Electrode for Na Batteries with High Energy Density: Na₄MnV(PO₄)₃

et al. 2018

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“…), which contributes shortened ion/electron diffusion paths to improve the rate performance. Despite many achievements, single morphology control on NVP still cannot meet the requirement of ultrahigh electron transport rate at high current density . Additionally, conventional NVP‐based cathode inevitably used insulating binders which impaired the whole electronic conductivity and had no contribution to capacity .…”

Section: Introductionmentioning

confidence: 99%

Boosting High‐Rate Sodium Storage Performance of N‐Doped Carbon‐Encapsulated Na₃V₂(PO₄)₃ Nanoparticles Anchoring on Carbon Cloth

Yao

Zhou

et al. 2019

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The further development of high‐power sodium‐ion batteries faces the severe challenge of achieving high‐rate cathode materials. Here, an integrated flexible electrode is constructed by smart combination of a conductive carbon cloth fiber skeleton and N‐doped carbon (NC) shell on Na3V2(PO4)3 (NVP) nanoparticles via a simple impregnation method. In addition to the great electronic conductivity and high flexibility of carbon cloth, the NC shell also promotes ion/electron transport in the electrode. The flexible NVP@NC electrode renders preeminent rate capacities (80.7 mAh g−1 at 50 C for cathode; 48 mAh g−1 at 30 C for anode) and superior cycle performance. A flexible symmetric NVP@NC//NVP@NC full cell is endowed with fairly excellent rate performance as well as good cycle stability. The results demonstrate a powerful polybasic strategy design for fabricating electrodes with optimal performance.

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“…Na 3 V 2 (PO 4 ) 3 (NVP) with the NASCION (Na super‐ionic conductor) structure is a very promising cathode material in SIBs . Many works have been done to enhance the cycling life and rate performances of NVP, mainly focusing on the improvement of the electronic conductivity by the NVP/carbon composite, cation doping,, fabricating novel structures to control particle size and morphology, and building a surface conductive layer . For instance, the honeycomb NVP/C microballs with hierarchical porous structure were prepared by in situ carbonization of hexadecyl trimethyl ammonium bromide surfactant, delivering a high reversible capacity of 80.2 mAh g −1 at 20 C corresponding to 71 % of the capacity .…”

Section: Introductionmentioning

confidence: 99%

Na₃V₂(PO₄)₃/N‐doped Carbon Nanocomposites with Sandwich Structure for Cheap, Ultrahigh‐Rate, and Long‐Life Sodium‐Ion Batteries

Yang

Zhang

et al. 2019

ChemElectroChem

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A new nanocomposite composed of ultrathin Na 3 V 2 (PO 4 ) 3 /Ndoped carbon sheets with stable sandwich structure is reported. The material is synthesized using laminar vanadium metalorganic frameworks (V-MOFs) as the precursor and multifunction sodium lignosulfonate (SLS) as the organic ligand for the V-MOFs and the carbon source. The synthetic mechanism and the influence of the SLS and Na contents on the electrochemical properties are investigated, and the Na-ion insertion/ extraction mechanism in the sandwich framework structure is established. The nanocomposite with the molar ratio: V 2 O 5 /SLS/ Na 2 CO 3 = 2 : 1.5 : 1.7, used as a cathode material for sodium-ion batteries, not only exhibits the best discharge capacity (117.3 mA h g À 1 at the 0.1 C rate), but also ultra-high rate performances (82 mAh g À 1 at 100 C, 78 mAh g À 1 at 200 C and 54 mAh g À 1 at 250 C) and a long cycling life (retains 40 mAh g À 1 at 200 C over 6000 cycles) because of its unique nanostructure.

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High valence Mo-doped Na₃V₂(PO₄)₃/C as a high rate and stable cycle-life cathode for sodium battery

Abstract: High valence Mo-doped Na3−5xV2−xMox(PO4)3/C (0 < x < 0.04) has been investigated to promote Na ion diffusion.

Cited by 130 publications

References 58 publications

A NASICON‐Type Positive Electrode for Na Batteries with High Energy Density: Na₄MnV(PO₄)₃

A NASICON‐Type Positive Electrode for Na Batteries with High Energy Density: Na₄MnV(PO₄)₃

Boosting High‐Rate Sodium Storage Performance of N‐Doped Carbon‐Encapsulated Na₃V₂(PO₄)₃ Nanoparticles Anchoring on Carbon Cloth

Na₃V₂(PO₄)₃/N‐doped Carbon Nanocomposites with Sandwich Structure for Cheap, Ultrahigh‐Rate, and Long‐Life Sodium‐Ion Batteries

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High valence Mo-doped Na3V2(PO4)3/C as a high rate and stable cycle-life cathode for sodium battery

Abstract: High valence Mo-doped Na3−5xV2−xMox(PO4)3/C (0 < x < 0.04) has been investigated to promote Na ion diffusion.

Cited by 130 publications

References 58 publications

A NASICON‐Type Positive Electrode for Na Batteries with High Energy Density: Na4MnV(PO4)3

A NASICON‐Type Positive Electrode for Na Batteries with High Energy Density: Na4MnV(PO4)3

Boosting High‐Rate Sodium Storage Performance of N‐Doped Carbon‐Encapsulated Na3V2(PO4)3 Nanoparticles Anchoring on Carbon Cloth

Na3V2(PO4)3/N‐doped Carbon Nanocomposites with Sandwich Structure for Cheap, Ultrahigh‐Rate, and Long‐Life Sodium‐Ion Batteries

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High valence Mo-doped Na₃V₂(PO₄)₃/C as a high rate and stable cycle-life cathode for sodium battery

A NASICON‐Type Positive Electrode for Na Batteries with High Energy Density: Na₄MnV(PO₄)₃

A NASICON‐Type Positive Electrode for Na Batteries with High Energy Density: Na₄MnV(PO₄)₃

Boosting High‐Rate Sodium Storage Performance of N‐Doped Carbon‐Encapsulated Na₃V₂(PO₄)₃ Nanoparticles Anchoring on Carbon Cloth

Na₃V₂(PO₄)₃/N‐doped Carbon Nanocomposites with Sandwich Structure for Cheap, Ultrahigh‐Rate, and Long‐Life Sodium‐Ion Batteries