Monoclinic Phase Na3Fe2(PO4)3: Synthesis, Structure, and Electrochemical Performance as Cathode Material in Sodium-Ion Batteries

Liu, Yao; Zhou, Yue; Zhang, Junxi; Xia, Yongyao; Chen, Tong; Zhang, Shiming

doi:10.1021/acssuschemeng.6b01536

Cited by 99 publications

(82 citation statements)

References 36 publications

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“…NASICON‐Na 3 Fe 2 (PO 4 ) 3 in the space group C 2/ c can uptake one Na within 1.5–3.5 V, resulting in a capacity of 61 mAh g −1 . Activity of Fe 2+ /Fe 3+ was verified using ex situ XPS . However, the voltage of Fe 3+ /Fe 4+ in phosphates is calculated to be higher than ≈4.8 V .…”

Section: Iron‐based Polyanionic Compoundsmentioning

confidence: 96%

“…There are two Na sites: 6b Na(1) sites that locate between two adjacent V 2 (PO 4 ) 3 lantern units and 18e Na(2) sites that situate between two PO 4 tetrahedra, allowing multiple Na extraction and insertion and a 3D Na diffusion channel (Figure d) . NASICON‐type materials show extremely versatile compounds like Na 3 V 2 (PO 4 ) 3 , Na 3 VCr(PO 4 ) 3 , Na 3 Cr 2 (PO 4 ) 3 , Na 3 Fe 2 (PO 4 ) 3 , NaTi 2 (PO 4 ) 3 , Na 3 V 1.5 Al 0.5 (PO 4 ) 3 , Na 3.5 V 1.5 Fe 0.5 (PO 4 ) 3 , Na 4 VMn(PO 4 ) 3 , Na 3 VFe(PO 4 ) 3 , Na 3 TiMn(PO 4 ) 3 , and so on. Chen et al and Jian et al have published excellent reviews on NASICON‐structured materials for energy storage .…”

Section: Vanadium‐based Polyanionic Compoundsmentioning

confidence: 99%

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Research Progress in Multielectron Reactions in Polyanionic Materials for Sodium‐Ion Batteries

Liang

Gong

et al. 2018

Small Methods

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www.advancedsciencenews.com www.small-methods.com and Co). The opportunities and critical issues in this interesting field have also been proposed and discussed for further investigations. Vanadium-Based Polyanionic CompoundsThe versatile coordinations and oxidation states of V ions enable V-containing polyanionic compositions extreme structural diversity. [22] In addition, multiple oxidation states of V (+2 -+5) in these structures might be accessed in a common voltage range (0-4.5 V). [23] These make V-based polyanionic compounds highly suitable for the realization of multielectron reactions. NASICON-Na 3 V 2 (PO 4 ) 3Na 3 V 2 (PO 4 ) 3 adopts a well-known NASICON structure that has rhombohedral phase with high-temperature R-3c symmetry and monoclinic phase with low-temperature C2/c symmetry resulting from Na-vacancy order/disorder. [24,25] Typically, the NASICON framework is built from V 2 (PO 4 ) 3 "lantern units" constructed by corner-sharing VO 6 octahedra and PO 4 tetrahedra. There are two Na sites: 6b Na(1) sites that locate between two adjacent V 2 (PO 4 ) 3 lantern units and 18e Na(2) sites that situate between two PO 4 tetrahedra, allowing multiple Na extraction and insertion and a 3D Na diffusion channel (Figure 2d). [25,26] NASICON-type materials show extremely versatile compounds like so on. Chen et al. and Jian et al. have published excellent reviews on NASICON-structured materials for energy storage. [34,35] Here, we mainly focus on the multielectron reactions of these materials. Na 3 V 2 (PO 4 ) 3 shows promising electrochemical performances: moderate voltage (3.4 V), decent capacity (117 mAh g −1 ), ultralong cycling life, and excellent rate performance due to robust structure and fast Na + ion transport in NASICON framework. [34] This compound attracts extensive attentions as one of the most promising cathode materials for SIBs. [24,26,30,31,[36][37][38][39][40][41][42][43][44][45][46][47][48] Accessibility of the Third NaThe electrochemical extraction of Na + would result in NaV 2 (PO 4 ) 3 via a two-phase reaction, which is a 1-e reaction per V ion. [38] X-ray absorption near edge structure (XANES) further proved that the valence of vanadium ion is +4 after charging to 4.0 V. [36] However, the third Na + ion in Na 3 V 2 (PO 4 ) 3 is inaccessible even charging the electrode up to 4.6 V (Figure 1a). [48] Recently, Jian et al. have determined that all Na + ions at Na(2) sites can be extracted while those at Na(1) maintain in their positions during chemical oxidation using the NO 2 BF 4 as the oxidant. [37] The seemingly impossible extraction of Na + toward V 2 (PO 4 ) 3 recalls a result reported nearly 30 years ago. [49] All the Na + ions have been chemically extracted from Na 3 V 2 (PO 4 ) 3 using Cl 2 as the oxidant to yield a V 2 (PO 4 ) 3 . It is surprising that NO 2 BF 4 cannot oxidize Na 3 V 2 (PO 4 ) 3 to V 2 (PO 4 ) 3 , since the redox potential of the NO 2 + /NO 2 redox (4.8 V) is much higher than that of the Cl 2 /Cl − redox (4.1 V) although the later one is estimated in the aqueous s...

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Section: Iron‐based Polyanionic Compoundsmentioning

confidence: 96%

Section: Vanadium‐based Polyanionic Compoundsmentioning

confidence: 99%

Research Progress in Multielectron Reactions in Polyanionic Materials for Sodium‐Ion Batteries

Liang

Gong

et al. 2018

Small Methods

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“…However, there is a necessity to find alternatives to Li-ion batteries as energy demand increases rapidly with the world population. In this respect, sodium (Na) batteries are currently being considered mainly due to the high abundance of Na [1][2][3][4]. Batteries based on multivalent cations such as magnesium (Mg 2+ ) and zinc (Zn 2+ ) are also promising, as they can provide high energy density [5][6][7][8][9].…”

Section: Introductionmentioning

confidence: 99%

Defects and Dopants in CaFeSi2O6: Classical and DFT Simulations

Kuganathan

Chroneos

2020

Energies

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Calcium (Ca)-bearing minerals are of interest for the design of electrode materials required for rechargeable Ca-ion batteries. Here we use classical simulations to examine defect, dopant and transport properties of CaFeSi2O6. The formation of Ca-iron (Fe) anti-site defects is found to be the lowest energy process (0.42 eV/defect). The Oxygen and Calcium Frenkel energies are 2.87 eV/defect and 4.96 eV/defect respectively suggesting that these defects are not significant especially the Ca Frenkel. Reaction energy for the loss of CaO via CaO Schottky is 2.97 eV/defect suggesting that this process requires moderate temperature. Calculated activation energy of Ca-ion migration in this material is high (>4 eV), inferring very slow ionic conductivity. However, we suggest a strategy to introduce additional Ca2+ ions in the lattice by doping trivalent dopants on the Si site in order to enhance the capacity and ion diffusion and it is calculated that Al3+ is the favourable dopant for this process. Formation of Ca vacancies required for the CaO Schottky can be facilitated by doping of gallium (Ga) on the Fe site. The electronic structures of favourable dopants were calculated using density functional theory (DFT).

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“…Актуальность настоящей работы связана с тем, что некоторые вещества с ромбоэдрическими кристаллическими каркасами из семейства NASICON обладают практически ценными свойствами и могут применяются, как конструкционные материалы в источниках тока [1][2][3][4][5][6][7]. В частности, ведутся работы над возможностью повышения энергетических параметров аккумуляторов с использованием Na 3 Fe 2 (PO 4 ) 3 в качестве электродного материала [2][3][4][5].…”

Section: Introductionunclassified

Дипольное упорядочение и ионная проводимость в NASICON-подобных структурах типа Na-=SUB=-3-=/SUB=-Fe-=SUB=-2-=/SUB=-(PO-=SUB=-4-=/SUB=-)-=SUB=-3-=/SUB=-

Ногай¹,

Ногай²,

Стефанович³

et al. 2020

Физика Твердого Тела

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Изучены вопросы структурных особенностей, диэлектрических и проводящих свойств поликристалла Na3Fe2(PO4)3, полученного методом горячего прессования. Показано, что исследуемые поликристаллы в alpha- и beta-фазах Na3Fe2(PO4)3, лучше по проводящим свойствам, чем в alpha-, beta-фазах монокристаллов, полученные традиционным раствор-расплавным методом. Уточнены закономерности появления дипольного упорядочения, ионной и суперионной проводимости, связанные фазовыми переходами и со структурными изменениями ромбоэдрического кристаллического каркаса \[Fe2(PO4)3]3-\3бесконечность при полиморфных превращениях. Обсуждены вопросы релаксационной поляризации в alpha- и beta-фазах Na3Fe2(PO4)3. Предложена модель, поясняющая явления дипольного упорядочения и ионной проводимости Na3Fe2(PO4)3. Ключевые слова: поликристалл, ионная проводимость, фазовые переходы, кристаллический каркас, кристаллическая фаза, суперионная фаза.

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Monoclinic Phase Na₃Fe₂(PO₄)₃: Synthesis, Structure, and Electrochemical Performance as Cathode Material in Sodium-Ion Batteries

Cited by 99 publications

References 36 publications

Research Progress in Multielectron Reactions in Polyanionic Materials for Sodium‐Ion Batteries

Research Progress in Multielectron Reactions in Polyanionic Materials for Sodium‐Ion Batteries

Defects and Dopants in CaFeSi2O6: Classical and DFT Simulations

Дипольное упорядочение и ионная проводимость в NASICON-подобных структурах типа Na-=SUB=-3-=/SUB=-Fe-=SUB=-2-=/SUB=-(PO-=SUB=-4-=/SUB=-)-=SUB=-3-=/SUB=-

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