Enhanced thermal stability of the lepidocrocite‐type titanates by intercalation of large alkaline ions

Yang, Daoguo; Liu, Ruichao; Líu, Hao; Niu, Chunyao; Cui, Junyan; Jin, Gao; Yuan, Huiyu; Ma, Chengliang; Jia, Quanli; Zhang, Shaowei

doi:10.1111/jace.17566

Cited by 11 publications

(8 citation statements)

References 39 publications

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“…The basal spacings of Li-ILT, Na-ILT, K-ILT, and Cs-ILT are calculated by using the position of the (020) peak, and their values are 0.68, 0.71, 0.76, and 0.85 nm at angles of 12.9, 12.4, 11.6, and 10.4°, respectively. These data are similar to our previous findings . The interlayer distance changes from 0.68 to 0.85 nm as the size of the interlayer ion increases.…”

Section: Resultssupporting

confidence: 92%

“…The interlayer distance changes from 0.68 to 0.85 nm as the size of the interlayer ion increases. The diffraction peak at 10.4° marked by a dot in Na-ILT is due to its swollen phase . Sasaki et al also noticed the swollen phase of Na-ILT and suggested that the swollen phase is responsible for the formation of a bilayer hydrate, as opposed to other monolayer hydrates …”

Section: Resultsmentioning

confidence: 99%

“…(HTO) crystals was conducted following our previous protocol. 32 In simple terms, KLTO material was obtained by simple calcination of a mixture of K 2 CO 3 , Li 2 CO 3 , and TiO 2 , and the obtained KLTO crystals were immersed in HCl solution at room temperature for 72 h with stirring. One gram of KLTO was dissolved in 100 mL of 1 mol/L HCl solution.…”

Section: Introductionmentioning

confidence: 99%

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Altering the Alkaline Metal Ions in Lepidocrocite-Type Layered Titanate for Sodium-Ion Batteries

Ali

Zhang

Yang

et al. 2023

ACS Appl. Mater. Interfaces

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The relatively large ionic radius of the Na ion is one of the primary reasons for the slow diffusion of Na ions compared to that of Li ions in de/intercalation processes in sodium-ion batteries (SIBs). Interlayer expansion of intercalation hosts is one of the effective techniques for facilitating Na-ion diffusion. For most ionic layered compounds, interlayer expansion relies on intercalation of guest ions. It is important to investigate the role of these ions for material development of SIBs. In this study, alkalimetal ions (Li + , Na + , K + , and Cs + ) with different sizes were intercalated into lepidocrocite-type layered titanate by a simple ion-exchange technique to achieve interlayer modulation and those were then evaluated as anode materials for SIBs. By controlling the intercalated alkaline ion species, basal spacings of layered titanates (LTs) in the range of 0.68 to 0.85 nm were obtained. Interestingly, the largest interlayer spacing induced by the large size of Cs did not yield the best performance, while the Na intercalated layered titanate (Na-ILT) demonstrated a superior performance with a specific capacity of 153 mAh g −1 at a current density of 0.1 A g −1 . We found that the phenomena can be explained by the high alkaline metal ion concentration and the efficient utilization of the active sites in Na-ILT. The detailed analysis indicates that large intercalating ions like Cs can hamper sodium-ion diffusion although the interlayer spacing is large. Our work suggests that adopting an appropriate interlayer ion species is key to developing highly efficient layered electrode materials for SIBs.

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Section: Resultssupporting

confidence: 92%

Section: Resultsmentioning

confidence: 99%

Section: Introductionmentioning

confidence: 99%

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Altering the Alkaline Metal Ions in Lepidocrocite-Type Layered Titanate for Sodium-Ion Batteries

Ali

Zhang

Yang

et al. 2023

ACS Appl. Mater. Interfaces

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“…The observed result contrasts with phase transformations in K 2 Ti 4 O 9 , β-Li 2 TiO 3 , and H 2 Ti 3 O 7 , suggesting that the interlayer ion exerts a secondary effect to the Ti–O interactions, which prohibit/catalyze the phase change. This effect is well known for H + where the interlayer OH group leads to lower thermal stability in protonic titanate. ,, After Cs + deintercalation, the system can achieve charge neutrality by (i) H + (or most likely H + ·H 2 O) intercalation, (ii) slight oxidation state increase to Ti 4+δ , and (iii) oxygen vacancy formation. Note that (i) will preserve the SCD, while (ii) and (iii) will decrease the SCD.…”

Section: Resultsmentioning

confidence: 92%

“…This effect is well known for H + where the interlayer OH group leads to lower thermal stability in protonic titanate. 11,29,60 After Cs + deintercalation, the system can achieve charge neutrality by (i) H + (or most likely H + •H 2 O) intercalation, (ii) slight oxidation state increase to Ti 4+δ , and (iii) oxygen vacancy formation. Note that (i) will preserve the SCD, while (ii) and (iii) will decrease the SCD.…”

Section: ■ Results and Discussionmentioning

confidence: 99%

Structural and Compositional Characteristics of Ball-Milled Lepidocrocite Alkali Titanate and the Correlation to Its Surface Acidic–Basic Properties

et al. 2021

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The studies on mechanical treatments of layered alkali metal oxides are limited despite their diverse compositions/ structures and potential for property tuning. In this work, we vibratory mill Cs 0.7 Zn 0.35 Ti 1.65 O 4 , K 0.8 Zn 0.4 Ti 1.6 O 4 , and Cs 2 Ti 6 O 13 for up to 4 h, during which the lepidocrocite-type structure and the plate-like morphology are well preserved. X-ray diffraction (XRD) indicates a tiny (≤0.6 Å) interlayer expansion accompanied by the enhancement of the preferred orientation along the stacking direction. Chemical analyses across multiple length scales suggest Cs deintercalation, elemental redistributions, and bulk-to-surface (or crystal edge) Cs migration. This ball-milling-induced Cs-rich moiety partially blocks the surface acid sites, although the solids still show a dominating acidic character. The ball-milled samples Cs 0.7−p Zn 0.35−q Ti 1.65 O 4−δ contain vacancies between the sheets (p) and at the sheets (q and δ). It is deduced from Sanderson's electronegativity equalization principle and experimentally verified by Xray photoelectron spectroscopy (XPS) that ball milling increases (decreases) the partial charge at the surface acidic Ti 4+ /Zn 2+ (basic O 2− ) sites. These nonporous solids (≤20 m 2 •g −1 ) contain water sorbed on the external surface as high as 1.1 mol•mol −1 , which is comparable to that in a water-intercalated sample. Our work expands the current understanding of the reactivity vs robustness in layered alkali titanates under physically demanding conditions, complementing knowledge gathered via the soft chemistry approach.

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MAX phase-derived woolen ball-like K2Ti8O17 with excellent surface-enhanced Raman scattering property

Sui

Liu

Wang

et al. 2023

Ceramics International

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Enhanced thermal stability of the lepidocrocite‐type titanates by intercalation of large alkaline ions

Cited by 11 publications

References 39 publications

Altering the Alkaline Metal Ions in Lepidocrocite-Type Layered Titanate for Sodium-Ion Batteries

Altering the Alkaline Metal Ions in Lepidocrocite-Type Layered Titanate for Sodium-Ion Batteries

Structural and Compositional Characteristics of Ball-Milled Lepidocrocite Alkali Titanate and the Correlation to Its Surface Acidic–Basic Properties

MAX phase-derived woolen ball-like K2Ti8O17 with excellent surface-enhanced Raman scattering property

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