NaFe3(HPO3)2((H,F)PO2OH)6: A Potential Cathode Material and a Novel Ferrimagnet

Munao, Irene; Zvereva, E.A.; Волкова, О. С.; Vasiliev, A. N.; Armstrong, A. Robert; Lightfoot, Philip

doi:10.1021/acs.inorgchem.5b02922

Cited by 11 publications

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References 51 publications

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“…Indeed, the structure optimization resulted in realistic O-H distances of 1.0 Å in contrast to 0.73 − 0.78 Å reported experimentally [14]. Likewise, the uniform P-H distances of 1.40 Å in the HPO 3 groups were found, whereas the minor substitution of H atoms by F was neglected in the present calculations.…”

Section: First-principles Calculationscontrasting

confidence: 53%

“…Pink air-stable prismatic crystals were recovered by filtration. The material was found to adopt a triclinic structure in the centrosymmetric space group, P−1, with crystal lattice parameters a = 7.5302 Å, b = 9.1696 Å, c = 9.4732 Å, α = 118.063°, β = 101.274°, γ = 101.192° [14]. The experimental pattern obtained by the single crystal X-ray measurement fits well with the experimental powder pattern, revealing that the synthesized sample has a good level of purity.…”

Section: Methodsmentioning

confidence: 99%

Section: Introductionmentioning

confidence: 99%

“…The crystal structure of NaFP [14] comprises two nonequivalent positions of S = 5/2 Fe 3+ ions, both octahedrally coordinated. These FeO 6 octahedra are linked into a three-dimensional network via tetrahedral phosphite groups.…”

Section: Introductionmentioning

confidence: 99%

“…The true composition, which incorporates a very small amount of fluorine, has been discussed previously (14) but for simplicity in the present work we use an idealized composition NaFe 3 (HPO 3 ) 2 (H 2 PO 3 ) 6 , abbreviated NaFP. This approximation has no bearing on the interpretation of physical properties in the present work.The crystal structure of NaFP [14] comprises two nonequivalent positions of S = 5/2 Fe 3+ ions, both octahedrally coordinated. These FeO 6 octahedra are linked into a three-dimensional network via tetrahedral phosphite groups.…”

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1/3 magnetization plateau and frustrated ferrimagnetism in a sodium iron phosphite

et al. 2016

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The sodium-iron phosphite NaFe 3 (HPO 3 ) 2 (H 2 PO 3 ) 6 is studied by ac-magnetic susceptibility, pulsed-field magnetization, specific heat, and high-frequency electron spin resonance (HF-ESR) measurements combined with Mössbauer spectroscopy and density-functional calculations. We show that this compound develops ferrimagnetic order below T C = 9.5 K and reveals a magnetization plateau at 1/3-saturation. The plateau extends to B c ~ 8 T, whereas above B c the magnetization increases linearly until reaching saturation at B s ~ 27 T. The Mössbauer spectroscopy reveals two magnetically non-equivalent iron sites with the 2:1 ratio. The HF-ESR spectra are consistent with a two-sublattice ferrimagnet and additionally pinpoint weak magnetic anisotropy as well as short-range spin order that persists well above T C . The ferrimagnetic order in the title compound is stabilized by a network of purely antiferromagnetic exchange interactions. The spin lattice comprises layers coinciding with the crystallographic (10-1) planes, with stronger couplings J i ~ 1.5 K within the layers and weaker couplings J i = 0.3−0.4 K between the layers. Both intralayer and interlayer couplings are frustrated. The ensuing ferrimagnetic order arises from a subtle interplay of the frustrated but nonequivalent exchange couplings. IntroductionThe magnetization of conventional isotropic antiferromagnets increases monotonically in an applied magnetic field. Fewer systems will, however, show a more complex magnetization process with flat or nearly flat regions of the magnetization curve that are known as magnetization plateaus [1]. These plateaus will normally appear at integer fractions of the total (saturation) magnetization and manifest ferrimagnetic order induced by the magnetic field. The stabilization of ferrimagnetic phases is strongly linked to the presence of magnetic frustration. For example, triangular antiferromagnets reveal a 1/3-plateau that is most pronounced in the quantum spin-1/2 regime, where the collinear ferrimagnetic phase is stabilized by quantum fluctuations [2][3][4]. It does, however, persist in the classical regime as well, thanks to the stabilization by thermal fluctuations [5,6], as in the extensively studied spin-5/2 triangular multiferroic RbFe(MoO 4 ) 2 [7][8][9]. On the other hand, even classical spin systems can show magnetization plateaus of putatively quantum nature, such as the 1/3-plateau recently observed in the spin-trimer compound SrMn 3 P 4 O 12 [10][11][12][13].In the following we report a detailed investigation of a novel iron fluorophosphite showing a pronounced magnetization plateau at 1/3-saturation. The true composition, which incorporates a very small amount of fluorine, has been discussed previously (14) but for simplicity in the present work we use an idealized composition NaFe 3 (HPO 3 ) 2 (H 2 PO 3 ) 6 , abbreviated NaFP. This approximation has no bearing on the interpretation of physical properties in the present work.The crystal structure of NaFP [14] comprises two nonequivalent positions of S...

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Section: First-principles Calculationscontrasting

confidence: 53%

Section: Methodsmentioning

confidence: 99%

Section: Introductionmentioning

confidence: 99%

Section: Introductionmentioning

confidence: 99%

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confidence: 99%

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1/3 magnetization plateau and frustrated ferrimagnetism in a sodium iron phosphite

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Excellent Comprehensive Performance of Na‐Based Layered Oxide Benefiting from the Synergetic Contributions of Multimetal Ions

Yao

Wang

et al. 2017

Advanced Energy Materials

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Na‐ion batteries are promising for large‐scale energy storage applications, but few cathode materials can be practically used because of the significant difficulty in synthesizing an electrode material with superior comprehensive performance. Herein, an effective strategy based on synergetic contributions of rationally selected metal ions is applied to design layered oxides with excellent electrochemical performances. The power of this strategy is demonstrated by the superior properties of as‐obtained NaFe0.45Co0.5Mg0.05O2 with 139.9 mA h g−1 of reversible capacity, 3.1 V of average voltage, 96.6% of initial Coulombic efficiency, and 73.9 mA h g−1 of capacity at 10 C rate, which benefit from the synergetic effect of Fe3+ (high redox potential), Co3+ (good kinetics), and inactive Mg2+ with compatible radii (stabilizing structure). Moreover, it is clarified that the superior property is not the simple superposition of performance for layered oxides with single metal ions. With the assistance of density functional theory calculations, it is evidenced that the wide capacity range (>70%) of prismatic Na+‐occupied sites during sodiation/desodiation is responsible for its high rate performance. This rational strategy of designing high‐performance cathodes based on the synergetic effect of various metal ions might be a powerful step forward in the development of new Na‐ion‐insertion cathodes.

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ChemInform Abstract: NaFe₃(HPO₃)₂( (H,F)PO₂OH)₆: A Potential Cathode Material and a Novel Ferrimagnet.

et al. 2016

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NaFe 3(HPO3)2((H,F)PO2OH)6: A Potential Cathode Material and a Novel Ferrimagnet. -The title compound is prepared by hydrothermal reaction of a 1:1:0.122 molar mixture of NaF, Fe 2O3, and H3PO3 (autoclave, 140 C, 3 d). NaFe3(HPO3)2((H,F)PO2OH)6 crystallizes in the triclinic space group P1 with Z = 1 (single crystal XRD). The three-dimensional structure consists of FeO 6 octahedra sharing corners with HPO 3 and HPO2OH tetrahedra. The phase allows for reversible electrochemical Na + insertion at an average discharge voltage of 2.5 V and an experimental capacity at low rates of 90 mAh/g. Low-cost and simple preparation, excellent capacity retention, and efficiency suggest the material is competitive as a cathode material for Na batteries. Magnetization, specific heat, and electron spin resonance measurements confirm the presence of two magnetically nonequivalent Fe 3+ sites. The compound orders magnetically at 9.4 K into a state with spontaneous magnetization. -(MUNAO, I.; ZVEREVA, E. A.; VOLKOVA, O. S.; VASILIEV, A. N.; ARMSTRONG, A. R.; LIGHTFOOT*, P.; Inorg. Chem. 55 (2016) 5, 2558-2564, http://dx.doi.org/10.1021/acs.inorgchem.5b02922 ; Sch. Chem., Univ. St. Andrews, St. Andrews, Fife KY16 9ST, UK; Eng.) -J. Schramke 20-015

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NaFe₃(HPO₃)₂((H,F)PO₂OH)₆: A Potential Cathode Material and a Novel Ferrimagnet

Cited by 11 publications

References 51 publications

1/3 magnetization plateau and frustrated ferrimagnetism in a sodium iron phosphite

1/3 magnetization plateau and frustrated ferrimagnetism in a sodium iron phosphite

Excellent Comprehensive Performance of Na‐Based Layered Oxide Benefiting from the Synergetic Contributions of Multimetal Ions

ChemInform Abstract: NaFe₃(HPO₃)₂( (H,F)PO₂OH)₆: A Potential Cathode Material and a Novel Ferrimagnet.

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NaFe3(HPO3)2((H,F)PO2OH)6: A Potential Cathode Material and a Novel Ferrimagnet

Cited by 11 publications

References 51 publications

1/3 magnetization plateau and frustrated ferrimagnetism in a sodium iron phosphite

1/3 magnetization plateau and frustrated ferrimagnetism in a sodium iron phosphite

Excellent Comprehensive Performance of Na‐Based Layered Oxide Benefiting from the Synergetic Contributions of Multimetal Ions

ChemInform Abstract: NaFe3(HPO3)2( (H,F)PO2OH)6: A Potential Cathode Material and a Novel Ferrimagnet.

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NaFe₃(HPO₃)₂((H,F)PO₂OH)₆: A Potential Cathode Material and a Novel Ferrimagnet

ChemInform Abstract: NaFe₃(HPO₃)₂( (H,F)PO₂OH)₆: A Potential Cathode Material and a Novel Ferrimagnet.