Magnetic Structures of NaFePO<sub>4</sub> Maricite and Triphylite Polymorphs for Sodium-Ion Batteries

Avdeev, Maxim; Mohamed, Zakiah; Ling, Chris D.; Lu, Jiechen; Tamaru, Mao; Yamada, Atsuo; Barpanda, Prabeer

doi:10.1021/ic400870x

Cited by 147 publications

(129 citation statements)

References 45 publications

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“…In the triphylite form, the sodium (Na) occupies M1 (4a) site while Ni occupies M2 (4c) site which is analogous to olivine structure. 25 When the temperature is increased to 550°C for 6 h, the pattern closely matches that of maricite NaNiPO 4 . In the maricite form, the distribution arrangement is reversed, with Ni occupying M1 (4a) site and Na occupying M2 (4c) site, as illustrated in the crystal structure shown in Fig.…”

Section: Resultsmentioning

confidence: 55%

Synthesis, structural and electrochemical properties of sodium nickel phosphate for energy storage devices

et al. 2016

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fElectrochemical energy production and storage at large scale and low cost, is a critical bottleneck in renewable energy systems. Oxides and lithium transition metal phosphates have been researched for over two decades and many technologies based on them exist. Much less work has been done investigating the use of sodium phosphates for energy storage. In this work, the synthesis of sodium nickel phosphate at different temperatures is performed and its performance evaluated for supercapacitor applications. The electronic properties of polycrystalline NaNiPO 4 polymorphs, triphylite and maricite, t-and m-NaNiPO 4 are calculated by means of first-principle calculations based on spin-polarized Density Functional Theory (DFT). The structure and morphology of the polymorphs were characterized and validated experimentally and it is shown that the sodium nickel phosphate (NaNiPO 4 ) exists in two different forms (triphylite and maricite), depending on the synthetic temperature (300-550°C). The as-prepared and triphylite forms of NaNiPO 4 vs. activated carbon in 2 M NaOH exhibit the maximum specific capacitance of 125 F g −1 and 85 F g −1 respectively, at 1 A g −1 ; both having excellent cycling stability with retention of 99% capacity up to 2000 cycles. The maricite form showed 70 F g −1 with a significant drop in capacity after just 50 cycles.These results reveal that the synthesized triphylite showed a high performance energy density of 44 Wh kg −1 which is attributed to the hierarchical structure of the porous NaNiPO 4 nanosheets. At a higher temperature (>400°C) the maricite form of NaNiPO 4 possesses a nanoplate-like (coarse and blocky) structure with a large skewing at the intermediate frequency that is not tolerant of cycling. Computed results for the sodium nickel phosphate polymorphs and the electrochemical experimental results are in good agreement.

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Section: Resultsmentioning

confidence: 55%

Synthesis, structural and electrochemical properties of sodium nickel phosphate for energy storage devices

et al. 2016

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“…solution at various scan rates; (f) Galvanostatic curves of maricite NaFePO 4 over 200 cycles at C/20 in a Na cell, inset: discharge curves of maricite NaFePO 4 as a function of the C rate from C/20 to 3 C (charging under CCCV mode (C/20 rate and 5 hour holding at 4.5 V)), during the first charge of CV, 20 mAh g –1 of capacity was recovered. (a) Reproduced with permission 55. Copyright 2013, American Chemical Society.…”

Section: Single‐phosphate Materials For Na Storagementioning

confidence: 99%

“…The magnetic structures of maricite and olivine NaFePO 4 were well studied through experimental test and theoretical computation 55, 56. However, maricite NaFePO 4 was recently proved to enable excellent Na storage performance and all Na ions can be extracted from the nano‐sized maricite NaFePO 4 with simultaneous transformation of the maricite structure to amorphous FePO 4 57.…”

Section: Single‐phosphate Materials For Na Storagementioning

confidence: 99%

Phosphate Framework Electrode Materials for Sodium Ion Batteries

et al. 2017

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Sodium ion batteries (SIBs) have been considered as a promising alternative for the next generation of electric storage systems due to their similar electrochemistry to Li‐ion batteries and the low cost of sodium resources. Exploring appropriate electrode materials with decent electrochemical performance is the key issue for development of sodium ion batteries. Due to the high structural stability, facile reaction mechanism and rich structural diversity, phosphate framework materials have attracted increasing attention as promising electrode materials for sodium ion batteries. Herein, we review the latest advances and progresses in the exploration of phosphate framework materials especially related to single‐phosphates, pyrophosphates and mixed‐phosphates. We provide the detailed and comprehensive understanding of structure–composition–performance relationship of materials and try to show the advantages and disadvantages of the materials for use in SIBs. In addition, some new perspectives about phosphate framework materials for SIBs are also discussed. Phosphate framework materials will be a competitive and attractive choice for use as electrodes in the next‐generation of energy storage devices.

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“…19 Unlike LiMPO 4 , the NaMPO 4 thermodynamically stable phase obtained under the conventional synthesis conditions is the maricite phase that is known to be electrochemically inactive with respect to the olivine phase. 20,21 Among the polyanionic frameworks, pyrophosphate compounds offer a stable three-dimensional (P 2 O 7 ) 4 − framework with multiple sites for Na ions. Fe-based pyrophosphates have been reported to exhibit enhanced rate capability performance most likely because of the presence of open diffusion pathways for Na ions.…”

Section: Introductionmentioning

confidence: 99%

Exploring the Ni redox activity in polyanionic compounds as conceivable high potential cathodes for Na rechargeable batteries

et al. 2017

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Although nickel-based polyanionic compounds are expected to exhibit a high operating voltage for batteries based on the Ni 2+/3+ redox couple activity, some rare experimental studies on the electrochemical performance of these materials are reported, resulting from the poor kinetics of the bulk materials in both Li and Na nonaqueous systems. Herein, the electrochemical activity of the Ni 2+/3+ redox couple in the mixed-polyanionic framework Na 4 Ni 3 (PO 4 ) 2 (P 2 O 7 ) is reported for the first time. This novel material exhibits a remarkably high operating voltage when cycled in sodium cells in both carbonate-and ionic liquid-based electrolytes. The application of a carbon coating and the use of an ionic liquid-based electrolyte enable the reversible sodium ion (de-)insertion in the host structure accompanied by the redox activity of Ni 2+/3+ at operating voltages as high as 4.8 V vs Na/Na + . These results present the realization of Ni-based mixed polyanionic compounds with improved electrochemical activity and pave the way for the discovery of new Na-based high potential cathode materials. NPG Asia Materials (2017) 9, e370; doi:10.1038/am.2017.41; published online 31 March 2017 INTRODUCTION Lithium-ion batteries have been largely recognized as the most efficient electrochemical energy storage devices for both portable electronics and electric vehicle applications. 1,2 However, the growth and diversification of the energy storage market trigger interest in low-cost and environmentally friendly alternative systems. In addition, recent concerns over the cost and future availability of lithium highlight the urgent need to exploit alternative energy storage systems. 3 In these terms, sodium (Na)-ion batteries are attractive candidates because of the electrochemistry that is similar to the well-established lithium-ion technology. 4 To date, the LiFePO 4 olivine with (PO 4 ) 3 − polyanionic framework, owing to its superior thermal stability and low cost, is considered to be one of the best electrode materials for lithium-ion batteries, mostly in view of its stable operating voltage and satisfactory specific capacity. However, the intrinsic tunability of the operating voltage of polyanionic compounds because of the presence of different transition metals such as Mn, Co and Ni 5-7 has triggered interest in alternative frameworks exhibiting higher cell voltages. According to theoretical prediction, lithium nickel phosphate has a remarkably high working potential (~5.1 V vs Li + /Li) because of the Ni 2+/3+ redox activity. 8 Unfortunately, several studies have demonstrated that the implementation of this material is restricted by several drawbacks such as the intrinsic sluggish kinetics attributable to the low electronic conductivity, the poor lithium transport in commonly used electrolyte systems and the structural

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Magnetic Structures of NaFePO₄ Maricite and Triphylite Polymorphs for Sodium-Ion Batteries

Cited by 147 publications

References 45 publications

Synthesis, structural and electrochemical properties of sodium nickel phosphate for energy storage devices

Synthesis, structural and electrochemical properties of sodium nickel phosphate for energy storage devices

Phosphate Framework Electrode Materials for Sodium Ion Batteries

Exploring the Ni redox activity in polyanionic compounds as conceivable high potential cathodes for Na rechargeable batteries

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Magnetic Structures of NaFePO4 Maricite and Triphylite Polymorphs for Sodium-Ion Batteries

Cited by 147 publications

References 45 publications

Synthesis, structural and electrochemical properties of sodium nickel phosphate for energy storage devices

Synthesis, structural and electrochemical properties of sodium nickel phosphate for energy storage devices

Phosphate Framework Electrode Materials for Sodium Ion Batteries

Exploring the Ni redox activity in polyanionic compounds as conceivable high potential cathodes for Na rechargeable batteries

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Magnetic Structures of NaFePO₄ Maricite and Triphylite Polymorphs for Sodium-Ion Batteries