Sodium iron pyrophosphate: A novel 3.0 V iron-based cathode for sodium-ion batteries

Barpanda, Prabeer; Tian, Ye; Nishimura, Shin Ichi; Chung, Sai Cheong; Yamada, Yuki; Okubo, Masashi; Zhou, Haoshen; Yamada, Atsuo

doi:10.1016/j.elecom.2012.08.028

Cited by 333 publications

(243 citation statements)

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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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confidence: 99%

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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“…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 [17][18][19][20][21][22]26 maricite, the thermodynamically stable phase of NaFePO 4 , has been regarded as electrochemically inactive in rechargeable batteries. 20 The NaFePO 4 composition also exhibits an olivine structure; however, the olivine structure is not stable and cannot be synthesized by conventional synthetic routes.…”

Section: Broader Contextmentioning

confidence: 99%

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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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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“…In this pursuit, many ³3 V Fe-based phosphate PO 4 3¹ insertion compounds other than the olivine phase have been reported. These include Na 2 FePO 4 F (3.06 V), 23 Na 2 Fe-P 2 O 7 (2.9 V), 33 and Na 4 Fe 3 (PO 4 ) 2 (P 2 O 7 ) (3.2 V). 34 Among these, Na 2 FeP 2 O 7 shows high current-rate performance and extreme thermal stability.…”

Section: /Fementioning

confidence: 99%

Systematic Studies on “Abundant” Battery Materials: Identification and Reaction Mechanisms

Yamada

2016

Electrochemistry

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"Abundance" is an important keyword in materials development. This is particularly the case for the energy storage sector, where materials themselves function as a storage host. The amount of materials is directly linked to the amount of energy stored in the device. In rechargeable batteries, transition metal elements are necessary to accommodate a large number of electrons/holes in a reversible redox reaction. Iron, as the fourth most abundant element in the earth's crust, is an ideal redox center, but practical storage electrodes with Fe redox have long been the "holy grail" of the lithium-ion battery since its commercialization in 1991. In this review article, the history of replacing Co with Mn and/or Fe in lithium battery electrodes is briefly reviewed followed by recent technical achievements toward more sustainable batteries using Na + as a guest ion, where the goal would be to discover a high voltage electrode material composed of Na and Fe without compromising the energy density. Further, our ultimate destination is set to high energy density aqueous lithium/sodium ion batteries, where the hydrate-melt electrolyte enables surprisingly high-voltage operation over 3 V. During materials identification and optimization, reaction mechanisms should be understood in a systematic way to provide a firm direction for strategic design. With this regards, important physicochemical properties of key materials will be introduced.

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Sodium iron pyrophosphate: A novel 3.0 V iron-based cathode for sodium-ion batteries

Cited by 333 publications

References 20 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

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

Systematic Studies on “Abundant” Battery Materials: Identification and Reaction Mechanisms

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Sodium iron pyrophosphate: A novel 3.0 V iron-based cathode for sodium-ion batteries

Cited by 333 publications

References 20 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

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

Systematic Studies on &ldquo;Abundant&rdquo; Battery Materials: Identification and Reaction Mechanisms

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

Systematic Studies on “Abundant” Battery Materials: Identification and Reaction Mechanisms