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Superior performance of Na₇V₄(P₂O₇)₄PO₄ in sodium ion batteries.

ABSTRACT: A novel synthetic method has been investigated to fabricate a 1D nanostructure Na₇V₄(P₂O₇)₄PO₄. Mixed polyanion materials with a well-defined 3D framework channel can improve the electrochemical performance of sodium reversible insertion/extraction reactions, and can be especially beneficial for high rate performance and cycling capability. It approaches an initial reversible electrochemical capacity of 92.0 mA h g^-1 with a high discharge potential over 3.85 V (vs. Na/Na⁺) and good cycling properties with a capacity retention of 81.4% after 300 cycles at a 0.5C rate in sodium systems. Taking into consideration the superior electrochemical characteristics, the phase-pure composite is considered to have a promising high rate capability as well as being a high capacity electrode material for advanced energy storage applications.

SUBMITTER: Fang W

PROVIDER: S-EPMC9080845 | biostudies-literature | 2018 Jun

REPOSITORIES: biostudies-literature

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Superior performance of Na7V4(P2O7)4PO4 in sodium ion batteries.

Fang Wenying W An Zhongxun Z Xu Jiaqiang J Zhao Hongbin H Zhang Jiujun J

RSC advances 20180611 38

A novel synthetic method has been investigated to fabricate a 1D nanostructure Na7V4(P2O7)4PO4. Mixed polyanion materials with a well-defined 3D framework channel can improve the electrochemical performance of sodium reversible insertion/extraction reactions, and can be especially beneficial for high rate performance and cycling capability. It approaches an initial reversible electrochemical capacity of 92.0 mA h g-1 wi ...[more]

PMID: 35539956

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High power Na3V2(PO4)3 symmetric full cell for sodium-ion batteries.

Project description:Sodium-ion batteries (SIBs) are a viable substitute for lithium-ion batteries due to the low cost and wide availability of sodium. However, practical applications require the development of fast charging sodium-ion-based full-cells with high power densities. Na3V2(PO4)3 (NVP) is a bipolar material with excellent characteristics as both a cathode and an anode material in SIBs. Designing symmetric cells with NVP results in a single voltage plateau with significant specific capacity which is ideal for a full cell. Here we demonstrate for the first time a tremendous improvement in the performance of NVP symmetric full cells by introducing an ether-based electrolyte which favors fast reaction kinetics. In a symmetric full cell configuration, 75.5% of the initial capacity was retained even after 4000 cycles at 2 A g-1, revealing ultra-long cyclability. Excellent rate performances were obtained at current densities as high as 1000C, based on the cathode mass, revealing ultrafast Na+ transfer. The power density obtained for this NVP symmetric cell (48 250 W kg-1) is the best among those of all the sodium-ion-based full cells reported to date.

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Microstructure tuned Na3V2(PO4)3@C electrodes toward ultra-long-life sodium-ion batteries.

Project description:Sodium-ion batteries (SIBs) are emerging as the best replacement for Li-ion batteries. In this regard, research on developing a reliable cathode material for SIBs is burgeoning. Rhombohedral Na3V2(PO4)3 (NVP), is a typical sodium super ionic conductor (NASICON) type material having prominent usage as a cathode material for SIBs. In this study, we prepared an NVP@C composite using a one-step hydrothermal method (at 180 °C) and consecutively calcined at different temperatures (750, 800, 850, and 900 °C). All the samples were thoroughly characterized and the changes in the crystal structure and particle size distribution were investigated using a Rietveld refinement method. NVP calcined at 850 °C exhibits the best battery performance with a discharge capacity of 94 mA h g-1 and retention up to 90% after 250 cycles at 2C. It also exhibits remarkable cycling stability with 94% (63 mA h g-1) retention after 2000 cycles at high-rate endurance (10C). The observed electrochemical performances of the samples were correlated with improved electrical conductivity due to the conductive carbon mixing with Na3V2(PO4)3 and enhancement in the crystallinity.

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Porous NaTi2(PO4)3 Nanocubes Anchored on Porous Carbon Nanosheets for High Performance Sodium-Ion Batteries.

Project description:NaTi2(PO4)3 has attracted great interest as anode material for sodium ion batteries owing to its open three-dimensional framework structure and limited volume changes during the charge and discharge process. However, the poor intrinsic electronic conductivity of NaTi2(PO4)3 needs to be improved for high rate capability. In this work, porous NaTi2(PO4)3 nanocubes anchored on porous carbon nanosheets (NaTi2(PO4)3/C) are designed and developed. This material exhibits a large discharge capacity and good rate capacity including a first discharge capacity of 485 mAh g-1 at a current density of 0.1 A g-1, and 98 mAh g-1 retained at a high rate of 4 A g-1 even after 2,000 cycles. These results suggest that NaTi2(PO4)3/C is a promising anode material for sodium-ion batteries.

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Assembly of Na3V2(PO4)2F3@C nanoparticles in reduced graphene oxide enabling superior Na+ storage for symmetric sodium batteries.

Project description:Reduced graphene oxide (rGO) was used to encapsulate Na3V2(PO4)2F3@Carbon nanoparticles to overcome its inherent low electronic conductivity and achieve superior sodium storage performance. This as-prepared cathode delivers a remarkable rate performance with a discharge capacity of ca. 64 mA h g-1 at 70C and an ultra-long-term cyclability over 4000 cycles with great capacity retention of 81% at 30C. This excellent performance can be attributed to the favorable combination of fast ionic conductivity of the NASICON structure and the interpenetrating conductive carbon framework; thus bringing a good pseudocapacitive quality to this material. Furthermore, thanks to the good sodium storage properties at low potential, a symmetric full cell can be assembled using Na3V2(PO4)2F3@C@rGO as both cathode and anode. The full cell delivers a high discharge capacity of 53 mA h g-1 at 20C rate, further demonstrating the feasibility of this hybrid material for smart grids.

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Controllable synthesis of a Na-enriched Na4V2(PO4)3 cathode for high-energy sodium-ion batteries: a redox-potential-matched chemical sodiation approach.

Project description:Exploring a sodium-enriched cathode (i.e. Na4V2(PO4)3, which differs from its traditional stoichiometric counterpart Na3V2(PO4)3 that can provide extra endogenous sodium reserves to mitigate the irreversible capacity loss of the anode material (i.e. hard carbon), is an intriguing presodiation method for the development of high energy sodium-ion batteries. To meet this challenge, herein, we first propose a redox-potential-matched chemical sodiation approach, utilizing phenazine-sodium (PNZ-Na) as the optimal reagent to sodiate the Na3V2(PO4)3 precursor into Na-enriched Na4V2(PO4)3. The spontaneous sodiation reaction enables a fast reduction of one-half V ions from V3+ to V2+, followed by the insertion of one Na+ ion into the NASICON framework, which only takes 90 s to obtain the phase-pure Na4V2(PO4)3 product. When paired with a hard carbon anode, the resulting Na4VP‖HC full cell exhibits a high energy density of 251 W h kg-1, which is 58% higher than that of 159 W h kg-1 for the Na3VP‖HC control cell. Our chemical sodiation methodology provides an innovative approach for designing sodium-rich cathode materials and could serve as an impetus to the development of advanced sodium-ion batteries.

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Project description:Conventional sodium-based layered oxide cathodes are extremely air sensitive and possess poor electrochemical performance along with safety concerns when operating at high voltage. The polyanion phosphate, Na3 V2 (PO4 )3 stands out as an excellent candidate due to its high nominal voltage, ambient air stability, and long cycle life. The caveat is that Na3 V2 (PO4 )3 can only exhibit reversible capacities in the range of 100 mAh g-1 , 20% below its theoretical capacity. Here, the synthesis and characterizations are reported for the first time of the sodium-rich vanadium oxyfluorophosphate, Na3.2 Ni0.2 V1.8 (PO4 )2 F2 O, a tailored derivative compound of Na3 V2 (PO4 )3 , with extensive electrochemical and structural analyses. Na3.2 Ni0.2 V1.8 (PO4 )2 F2 O delivers an initial reversible capacity of 117 mAh g-1 between 2.5 and 4.5 V under the 1C rate at room temperature, with 85% capacity retention after 900 cycles. The cycling stability is further improved when the material is cycled at 50 °C within 2.8-4.3 V for 100 cycles. When paired with a presodiated hard carbon, Na3.2 Ni0.2 V1.8 (PO4 )2 F2 O cycled with a capacity retention of 85% after 500 cycles. Cosubstitution of the transition metal and fluorine in Na3.2 Ni0.2 V1.8 (PO4 )2 F2 O as well as the sodium-rich structure are the major factors behind the improvement of specific capacity and cycling stability, which paves the way for this cathode in sodium-ion batteries.

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Off-stoichiometric Na3-3x V2+x (PO4)3/C nanocomposites as cathode materials for high-performance sodium-ion batteries prepared by high-energy ball milling.

Project description:Na3V2(PO4)3 (NVP) is regarded as a promising cathode material for sustainable energy storage applications. Here we present an efficient method to synthesize off-stoichiometric Na3-3x V2+x (PO4)3/C (x = 0-0.10) nanocomposites with excellent high-rate and long-life performance for sodium-ion batteries by high-energy ball milling. It is found that Na3-3x V2+x (PO4)3/C nanocomposites with x = 0.05 (NVP-0.05) exhibit the most excellent performance. When cycled at a rate of 1C in the range of 2.3-3.9 V, the initial discharge capacity of NVP-0.05 is 112.4 mA h g-1, which is about 96% of its theoretical value (117.6 mA h g-1). Even at 20C, it still delivers a discharge capacity of 92.3 mA h g-1 (79% of the theoretical capacity). The specific capacity of NVP-0.05 is as high as 100.7 mA h g-1 after 500 cycles at 5C, which maintains 95% of its initial value (106 mA h g-1). The significantly improved electrochemical performance of NVP-0.05 is attributed to the decrease of internal resistance and increase of the Na+ ion diffusion coefficient.

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