Full differentiation and assignment of boron species in the electrolytes Li2B6O9F2 and Li2B3O4F3 by solid-state 11B NMR spectroscopy

Bräuniger, Thomas; Pilz, Thomas; Chandran, C. Vinod; Jansen, Martin

doi:10.1016/j.jssc.2012.05.026

Cited by 22 publications

(6 citation statements)

References 27 publications

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“…The present work again evidences the usefulness of NMR spectroscopy as a complementary analytical tool for investigation of solid electrolytes, another example being recent NMR studies on fluorooxoborates [25][26][27]. The 7 Li and 31 P NMR interaction tensors determined in the current study provide a good starting point for temperature dependent single-crystal NMR of LDP, which possibly could reveal new insights about the diffusion mechanism of the lithium atoms in the crystal structure.…”

Section: Discussionsupporting

confidence: 71%

Single-Crystal 31P and 7Li NMR of the Ionic Conductor LiH2PO4

Zeman

Kainz²,

Bräuniger

2020

Crystals

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The electronic surroundings of phosphorus and lithium atoms in the ionic conductor lithium dihydrogen phosphate (LDP) have been studied by single-crystal nuclear magnetic resonance (NMR) spectroscopy at room temperature. From orientation-dependent NMR spectra of a large homegrown LDP single crystal, the full 31 P chemical shift (CS) and 7 Li quadrupole coupling (QC) tensor was determined, using a global fit over three rotation patterns. The resulting CS tensor is characterized by its three eigenvalues: δ PAS 11 = (67.0 ± 0.6) ppm, δ PAS 22 = (13.9 ± 1.5) ppm, and δ PAS 33 = (−78.7 ± 0.9) ppm. All eigenvalues have also been verified by magic-angle spinning NMR on a polycrystalline sample, using Herzfeld-Berger analysis of the rotational side band pattern. The resulting 7 Li QC tensor is characterized by its quadrupolar coupling constant χ = Q PAS 33 = (−71 ± 1) kHz and the two eigenvalues Q PAS 11 = (22.3 ± 0.9) kHz, and Q PAS 22 = (48.4 ± 0.8) kHz. The initially unknown orientation of the mounted crystal, expressed by the orientation of the rotation axis in the orthorhombic crystal frame, was included in the global data fit as well, thus obtaining it from NMR data only.Crystals 2020, 10, 302 2 of 12 with four formula units per unit cell [6]. The PO 4 tetrahedra build a three-dimensional framework connected by two different types of hydrogen bonds. The LiO 4 coordination tetrahedra are linked by their vertices forming [100] isolated chains and share each edge with the PO 4 units. All atoms in the unit cell are located at Wyckoff position 4a with the general site symmetry 1 − C 1 [7]. As a result, no symmetry constraints affect the algebraic form of the NMR interaction tensors, as will be explained in the following.Abstract: Last thing to be done...

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Section: Discussionsupporting

confidence: 71%

Single-Crystal 31P and 7Li NMR of the Ionic Conductor LiH2PO4

Zeman

Kainz²,

Bräuniger

2020

Crystals

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“…In another class of the fluorine-containing borates, the fluorine atom is directly connected to the boron atom; that is, fluorine is substituted for the oxygen atom. This kind of compound is named a fluorooxoborate, such as Li 2 B 3 O 4 F 3 , Li 2 B 6 O 9 F 2 , LiB 6 O 9 F, etc. − …”

Section: Introductionmentioning

confidence: 99%

A Member of Fluorooxoborates: Li₂Na_0.9K_0.1B₅O₈F₂ with the Fundamental Building Block B₅O₁₀F₂ and a Short Cutoff Edge

et al. 2018

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A new member of fluorooxoborates, LiNaKBOF, was obtained in the sealed system, and single-crystal X-ray diffraction was used to determine its structure. It contains a three-dimensional framework stacking of [BOF] layers extending into the ac plane. Detailed structural comparisons among all of the fluorine-containing alkali-metal borates suggest that the [BOF] layer composed of the new fundamental building blocks BOF represents a new structure type of fluorooxoborate. The IR spectrum verifies its structural validity. The deep-ultraviolet spectral measurement shows that it has no obvious absorption in the range of 180-300 nm, and its cutoff edge is under 180 nm. In addition, theoretical calculations were done to help us understand its electronic structure and optical properties.

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“…Although the assignment and positiono ft he fluorine atomsi s suggested from an electronic point of view,w ev erified the presenceo fc ovalentB ÀFb onds by solid-state NMR spectroscopy.P revious studies provided helpful 11 Bd ata. [32,33] The 11 Band 19 F-MAS NMR spectra of Ba[B 4 O 6 F 2 ]a re shown in Figure 5.…”

Section: Introductionmentioning

confidence: 99%

The First Alkaline‐Earth Fluorooxoborate Ba[B₄O₆F₂]—Characterisation and Doping with Eu²⁺

Jantz

Pielnhofer

Wüllen

et al. 2017

Chemistry A European J

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The very first alkaline-earth fluorooxoborate Ba[B O F ] was synthesised by solid state methods starting from Ba(BF ) , β-BaB O , and B O . The crystal structure derived from single-crystal X-ray diffraction (P2 /n, a=6.6384(2) Å, b=7.6733(3) Å, c=11.3385(4) Å, β=91.281(2)°, Z=4, R =0.0269, R =0.018, wR =0.034) comprises layers of BO F tetrahedra condensed through triangular BO units according to the descriptor 2Δ2□:<Δ2□>Δ. The extraordinary thirteen-fold coordination of barium by oxygen and fluorine leads to interesting optical properties of a sample doped with divalent europium, where a 4f→4f emission was recorded around 359 nm together with a broad emission band of a 5d→4f emission peaking at 366 nm. The compound is further characterised by IR-, Raman-, and solid-state NMR-spectroscopic methods. Moreover, DFT calculations as well as TGA and DSC measurements were performed.

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Full differentiation and assignment of boron species in the electrolytes Li2B6O9F2 and Li2B3O4F3 by solid-state 11B NMR spectroscopy

Cited by 22 publications

References 27 publications

Single-Crystal 31P and 7Li NMR of the Ionic Conductor LiH2PO4

Single-Crystal 31P and 7Li NMR of the Ionic Conductor LiH2PO4

A Member of Fluorooxoborates: Li₂Na_0.9K_0.1B₅O₈F₂ with the Fundamental Building Block B₅O₁₀F₂ and a Short Cutoff Edge

The First Alkaline‐Earth Fluorooxoborate Ba[B₄O₆F₂]—Characterisation and Doping with Eu²⁺

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Full differentiation and assignment of boron species in the electrolytes Li2B6O9F2 and Li2B3O4F3 by solid-state 11B NMR spectroscopy

Cited by 22 publications

References 27 publications

Single-Crystal 31P and 7Li NMR of the Ionic Conductor LiH2PO4

Single-Crystal 31P and 7Li NMR of the Ionic Conductor LiH2PO4

A Member of Fluorooxoborates: Li2Na0.9K0.1B5O8F2 with the Fundamental Building Block B5O10F2 and a Short Cutoff Edge

The First Alkaline‐Earth Fluorooxoborate Ba[B4O6F2]—Characterisation and Doping with Eu2+

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A Member of Fluorooxoborates: Li₂Na_0.9K_0.1B₅O₈F₂ with the Fundamental Building Block B₅O₁₀F₂ and a Short Cutoff Edge

The First Alkaline‐Earth Fluorooxoborate Ba[B₄O₆F₂]—Characterisation and Doping with Eu²⁺