Synthesis, crystal structure, spectroscopic properties, and thermal behavior of rare-earth oxide selenates, Ln2O2SeO4 (Ln = La, Pr, Nd): The new perspectives of solid-state double-exchange synthesis

Charkin, Dmitri O.; Karpov, Andrey; Kazakov, Sergey M.; Plokhikh, Igor V.; Zadoya, Anastasiya I.; Kuznetsov, A. N.; Maslakov, K. I.; Teterin, A. Yu.; Teterin, Yury A.; Zaloga, A. N.; Siidra, Oleg I.

doi:10.1016/j.jssc.2019.06.007

Cited by 4 publications

(4 citation statements)

References 24 publications

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“…Figure 3e shows XPS spectra of Se 3d, two peaks located at 55.87 eV and 55.01 eV are clearly observed, which can be related to the 3d 5/2 and 3d 3/2 signals of Se (Figure S3), [30] indicating the presence of Se on the surface of Se‐NCM sample. As present in Figure.3e, two peaks located at 60.58 eV and 61.78 eV are clearly observed, which can be related to the 3d 5/2 and 3d 3/2 signals of Se 6+ in Li 2 SeO 4 , indicating the formation of a uniform Li 2 SeO 4 coating on the external surfaces of Ni‐rich secondary particles [31] . Next, as the calcination temperature is increased and calcination time is prolonged, gas‐phase Se tends to penetrate the secondary particles, thereby the precoated Se will initially substitute some lattice oxygen to anchored Se as SeO 2 [32] .…”

Section: Resultsmentioning

confidence: 71%

Sublimated Se‐Induced Formation of Dual‐Conductive Surface Layers for High‐Performance Ni‐Rich Layered Cathodes

et al. 2021

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Ni‐rich layered oxide cathode materials for Li‐ion batteries have received widespread attention owing to their high specific capacity and comparatively low cost. However, owing to Li‐containing surface residues, side reactions with the electrolyte and structural rearrangement after long‐term cycling leads to severe degradation of the cathode performance. Here, Se coating serves as a novel and simple sublimation‐inducing gas reaction method to modify the Ni‐rich layered material, resulting in capacity retention and rate performance improvement. The sublimed gaseous Se reacts with residual Li compounds to form a Li2SeO4 coating on the surface of the secondary particles, which simultaneously promotes the transmission of Li ions and reduces electrode‐electrolyte side reactions. Moreover, gaseous Se penetrates between the primary particles within the secondary particles to promote electron transmission. This dual‐conductive surface layer facilitates superior capacity and voltage retentions. Significantly, the proposed method is scalable and applicable to all Ni‐rich cathode materials.

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Section: Resultsmentioning

confidence: 71%

Sublimated Se‐Induced Formation of Dual‐Conductive Surface Layers for High‐Performance Ni‐Rich Layered Cathodes

et al. 2021

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“…Synthetic analogs of [Ba 2 F 2 ]S 2 O 3 were found among [Ln 2 O 2 ]CrO 4 oxychromates (Ln = Pr-Tb [33]). Synthetic analogs of the grandreefite structure are observed also among selenates ([Pb 2 F 2 ]SeO 4 [34] and [Ln 2 O 2 ]SeO 4 , Ln = La, Pr, Nd [35]) and chromates ([La 2 O 2 ]CrO 4 [32]). The same structure was also established for [Bi 2 O 2 ]SO 4 [36] and some rare-earth oxysulfates [Ln 2 O 2 ]SO 4 (La [29], Sm [30] and Eu [31]).…”

Section: Introductionmentioning

confidence: 92%

“…The product consisted of grass-green transparent [Bi 2 CuO 3 ]SO 4 crystals in association with unreacted BiOCl. [35]. Rare-earth oxychlorides, LnOCl, prepared by thermal hydrolysis of LnCl 3 •6H 2 O, were mixed with potassium sulfate (pre-dried at 140 • C for 6 h) in 2:1.1 ratio, thoroughly ground and placed in silica-jacketed alumina crucibles.…”

Section: Synthesismentioning

confidence: 99%

“…Structurally related architectures occur when the interlayer gallery hosts various molecular anions (linear triatomic [20,21], trigonal [22][23][24][25][26], or tetrahedral [27][28][29][30][31][32][33][34][35][36][37][38] (Figure 1a-h). There are three possible orientations of tetrahedral anions between the litharge slabs (Figure 1d-f) two of which are represented in nature by the mineral grandreefite [Pb 2 F 2 ]SO 4 [27] and a slag phase [Ba 2 F 2 ]S 2 O 3 [28].…”

Section: Introductionmentioning

confidence: 99%

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Expanding Family of Litharge-Derived Sulfate Minerals and Synthetic Compounds: Preparation and Crystal Structures of [Bi2CuO3]SO4 and [Ln2O2]SO4 (Ln = Dy and Ho)

et al. 2020

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During the last decades, layered structures have attracted particular and increasing interest due to the multitude of outstanding properties exhibited by their representatives. Particularly common among their archetypes, with a significant number of mineral and synthetic species structural derivatives, is that of litharge. In the current paper, we report the structural studies of two later rare-earth oxysulfates, [Ln2O2]SO4 (Ln = Dy, Ho), which belong indeed to the grandreefite family, and a novel compound [Bi2CuO3]SO4, which belongs to a new structure type and demonstrates the second example of Cu2+ incorporation into litharge-type slabs. Crystals of [Bi2CuO3]SO4 were obtained under high-pressure/high-temperature (HP/HT) conditions, whereas polycrystalline samples of [Ln2O2]SO4 (Ln = Dy, Ho) compounds were prepared via an exchange solid-state reaction. The crystal structure of [Bi2CuO3]SO4 is based on alternation of continuous [Bi2CuO3]2+ layers of edge-sharing OBi2Cu2 and OBi3Cu tetrahedra and sheets of sulfate groups. Cu2+ cations are in cis position in O5Bi2Cu2 and O6Bi2Cu2 oxocentered tetrahedra in litharge slab. The crystal structure of [Ln2O2]SO4 (Ln = Dy, Ho) is completely analogous to those of grandreefite and oxysulfates of La, Sm, Eu, and Bi.

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Bi2O2SO4, a new representative of the grandreefite structure type

Charkin

Akimov

Plokhikh

et al. 2020

Journal of Solid State Chemistry

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Synthesis, crystal structure, spectroscopic properties, and thermal behavior of rare-earth oxide selenates, Ln2O2SeO4 (Ln = La, Pr, Nd): The new perspectives of solid-state double-exchange synthesis

Cited by 4 publications

References 24 publications

Sublimated Se‐Induced Formation of Dual‐Conductive Surface Layers for High‐Performance Ni‐Rich Layered Cathodes

Sublimated Se‐Induced Formation of Dual‐Conductive Surface Layers for High‐Performance Ni‐Rich Layered Cathodes

Expanding Family of Litharge-Derived Sulfate Minerals and Synthetic Compounds: Preparation and Crystal Structures of [Bi2CuO3]SO4 and [Ln2O2]SO4 (Ln = Dy and Ho)

Bi2O2SO4, a new representative of the grandreefite structure type

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