A combined first principles and experimental study on Na3V2(PO4)2F3 for rechargeable Na batteries

Shakoor, R. A.; Seo, Dong‐Hwa; Kim, Hyungsub; Park, Young‐Uk; Kim, Jongsoon; Kim, Sung-Wook; Gwon, Hyeokjo; Lee, Seongsu; Kang, Kisuk

doi:10.1039/c2jm33862a

Cited by 323 publications

(300 citation statements)

References 45 publications

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“…However, the high cost and limited resources of lithium have caused some concerns of using lithium-ion batteries in the large-scale energy storage systems [7][8][9][10][11][12][13][14][15] . In this background, room-temperature sodium-ion batteries with lower energy density compared with lithium-ion batteries have been reconsidered particularly for such large-scale applications [16][17][18][19][20][21][22][23][24] , where cycle life and cost are the more essential factors than energy density, in both academic and industrial communities, owing to the abundant sodium resources and potentially low cost as well as the similar 'rocking-chair' sodium storage mechanism to that of lithium.…”

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A zero-strain layered metal oxide as the negative electrode for long-life sodium-ion batteries

et al. 2013

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Room-temperature sodium-ion batteries have shown great promise in large-scale energy storage applications for renewable energy and smart grid because of the abundant sodium resources and low cost. Although many interesting positive electrode materials with acceptable performance have been proposed, suitable negative electrode materials have not been identified and their development is quite challenging. Here we introduce a layered material, P2-Na 0.66 [Li 0.22 Ti 0.78 ]O 2 , as the negative electrode, which exhibits only B0.77% volume change during sodium insertion/extraction. The zero-strain characteristics ensure a potentially long cycle life. The electrode material also exhibits an average storage voltage of 0.75 V, a practical usable capacity of ca. 100 mAh g À 1 , and an apparent Na þ diffusion coefficient of 1 Â 10 À 10 cm À 2 s À 1 as well as the best cyclability for a negative electrode material in a half-cell reported to date. This contribution demonstrates that P2-Na 0.66 [Li 0.22 Ti 0.78 ]O 2 is a promising negative electrode material for the development of rechargeable long-life sodium-ion batteries.

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A zero-strain layered metal oxide as the negative electrode for long-life sodium-ion batteries

et al. 2013

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“…However, they suffer from a substantial capacity decay with cycling, owing to crystal structure collapse and/or unstable electrode-electrolyte interfaces (10). For more stable host frameworks, various polyanion structures have also been studied as SIB cathodes as a natural extension of the success shown in the LIB materials of the same classes, including TM fluorophosphates (11)(12)(13)(14)(15), pyrophosphates (16)(17)(18) and phosphates (19)(20)(21)(22). However, most of these materials still exhibited insufficient cycle lifetimes and large voltage steps that limit their practical capacity.…”

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Role of intermediate phase for stable cycling of Na ₇ V ₄ (P ₂ O ₇ ) ₄ PO ₄ in sodium ion battery

Lim

Kim

Chung

et al. 2013

Proc. Natl. Acad. Sci. U.S.A.

139

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Sodium ion batteries offer promising opportunities in emerging utility grid applications because of the low cost of raw materials, yet low energy density and limited cycle life remain critical drawbacks in their electrochemical operations. Herein, we report a vanadium-based ortho-diphosphate, Na 7 V 4 (P 2 O 7 ) 4 PO 4 , or VODP, that significantly reduces all these drawbacks. Indeed, VODP exhibits single-valued voltage plateaus at 3.88 V vs. Na/Na + while retaining substantial capacity (>78%) over 1,000 cycles. Electronic structure calculations reveal that the remarkable single plateau and cycle life originate from an intermediate phase (a very shallow voltage step) that is similar both in the energy level and lattice parameters to those of fully intercalated and deintercalated states. We propose a theoretical scheme in which the reaction barrier that arises from lattice mismatches can be evaluated by using a simple energetic consideration, suggesting that the presence of intermediate phases is beneficial for cell kinetics by buffering the differences in lattice parameters between initial and final phases. We expect these insights into the role of intermediate phases found for VODP hold in general and thus provide a helpful guideline in the further understanding and design of battery materials.cathode | single voltage | atomic reorganization | ab initio calculation S odium ion batteries (SIBs) provide advantages of unlimited resource, low material cost, and easy worldwide accessibility that could make them the material of choice for grid-scale energy storage systems (1, 2). Unfortunately, the electrochemical performance of current SIBs remains inferior to that of lithium ion batteries (LIBs). In particular, we require SIB cathode materials that give a long cycle life with large capacities and high voltages under fast operating conditions, comparable to the Li counterparts.Numerous layered Na x MO 2 [M = Co, Mn, Fe, Ni, Cr, and multicomponent transition metals (TMs)] have been intensively studied as candidate SIB cathodes because such layer-structured materials typically exhibit higher capacities than other classes of materials (3-10). However, they suffer from a substantial capacity decay with cycling, owing to crystal structure collapse and/or unstable electrode-electrolyte interfaces (10). For more stable host frameworks, various polyanion structures have also been studied as SIB cathodes as a natural extension of the success shown in the LIB materials of the same classes, including TM fluorophosphates (11-15), pyrophosphates (16-18) and phosphates (19)(20)(21)(22). However, most of these materials still exhibited insufficient cycle lifetimes and large voltage steps that limit their practical capacity. The Prussian blue family has also been extensively investigated for both organic (23, 24) and aqueous electrolytes (25) owing to its unique advantages related to low material cost, low temperature synthesis, and decent electrochemical performance from well-developed ionic channel structures. However, the as-syn...

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“…Recently, Na ion batteries (NIBs) have been considered as a promising alternative to LIBs since the underlying electrochemical reaction is similar to that of LIBs, but is based on the unlimited resources of Na from seawater. [13][14][15][16][17][18][19][20] The use of redox chemistry using earth abundant transition metals would provide the optimal combination with Na electrochemistry further highlighting the advantage of NIBs.In recent years, considerable research has been carried out on Fe-based electrode materials for use in NIBs. …”

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Unexpected discovery of low-cost maricite NaFePO₄as a high-performance electrode for Na-ion batteries

Kim

Seo

Kim

et al. 2015

Energy Environ. Sci.

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328

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Battery chemistry based on earth-abundant elements has great potential for the development of cost-effective, large-scale energy storage systems. Herein, we report, for the first time, that maricite NaFePO 4 can function as an excellent cathode material for Na ion batteries, an unexpected result since it has been regarded as an electrochemically inactive electrode for rechargeable batteries. Our investigation of the Na re-(de)intercalation mechanism reveals that all Na ions can be deintercalated from the nano-sized maricite NaFePO 4 with simultaneous transformation into amorphous FePO 4 . Our quantum mechanics calculations show that the underlying reason for the remarkable electrochemical activity of NaFePO 4 is the significantly enhanced Na mobility in the transformed phase, which is $one fourth of the hopping activation barrier. Maricite NaFePO 4 , fully sodiated amorphous FePO 4 , delivered a capacity of 142 mA h g À1 (92% of the theoretical value) at the first cycle, and showed outstanding cyclability with a negligible capacity fade after 200 cycles (95% retention of the initial cycle).The demand for large-scale energy storage systems (EESs) has prompted considerable effort in the development of new types of batteries with cost-effective and sustainable properties. While the high cost of current Li ion batteries (LIBs) remains one of the major hurdles towards large-scale energy storage applications, 1-12 battery chemistry based on earth-abundant elements offers a feasible solution. Recently, Na ion batteries (NIBs) have been considered as a promising alternative to LIBs since the underlying electrochemical reaction is similar to that of LIBs, but is based on the unlimited resources of Na from seawater. [13][14][15][16][17][18][19][20] The use of redox chemistry using earth abundant transition metals would provide the optimal combination with Na electrochemistry further highlighting the advantage of NIBs.In recent years, considerable research has been carried out on Fe-based electrode materials for use in NIBs. Broader contextWe report, for the rst time, that maricite NaFePO 4 can function as an excellent cathode material for Na ion batteries, an unexpected result since it has been regarded as an electrochemically inactive electrode for rechargeable batteries. Our investigation of the Na re-(de)intercalation mechanism reveals that all Na ions can be deintercalated from the nanosized maricite NaFePO 4 with simultaneous transformation into amorphous FePO 4 . Our quantum mechanics calculations show that the underlying reason for the remarkable electrochemical activity of NaFePO 4 is the signicantly enhanced Na mobility in the transformed phase, which is $one fourth of the hopping activation barrier. Maricite NaFePO 4 , fully sodiated amorphous FePO 4 , delivered a capacity of 142 mA h g À1 (92% of the theoretical value) at the rst cycle, and showed outstanding cyclability with a negligible capacity fade aer 200 cycles (95% retention of the initial cycle).540 | Energy Environ. Sci., 2015, 8, 540-545This jour...

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A combined first principles and experimental study on Na3V2(PO4)2F3 for rechargeable Na batteries

Cited by 323 publications

References 45 publications

A zero-strain layered metal oxide as the negative electrode for long-life sodium-ion batteries

A zero-strain layered metal oxide as the negative electrode for long-life sodium-ion batteries

Role of intermediate phase for stable cycling of Na ₇ V ₄ (P ₂ O ₇ ) ₄ PO ₄ in sodium ion battery

Unexpected discovery of low-cost maricite NaFePO₄as a high-performance electrode for Na-ion batteries

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A combined first principles and experimental study on Na3V2(PO4)2F3 for rechargeable Na batteries

Cited by 323 publications

References 45 publications

A zero-strain layered metal oxide as the negative electrode for long-life sodium-ion batteries

A zero-strain layered metal oxide as the negative electrode for long-life sodium-ion batteries

Role of intermediate phase for stable cycling of Na 7 V 4 (P 2 O 7 ) 4 PO 4 in sodium ion battery

Unexpected discovery of low-cost maricite NaFePO4as a high-performance electrode for Na-ion batteries

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Role of intermediate phase for stable cycling of Na ₇ V ₄ (P ₂ O ₇ ) ₄ PO ₄ in sodium ion battery

Unexpected discovery of low-cost maricite NaFePO₄as a high-performance electrode for Na-ion batteries