The effect of chemically preintercalated alkali ion on structure of layered titanates and their electrochemistry in aqueous energy storage systems.
The effect of chemically preintercalated alkali ion on structure of layered titanates and their electrochemistry in aqueous energy storage systems.
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DOI：
10.1039/d0ta04545d
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发表时间：
2020-09-21
期刊：
影响因子：
--
通讯作者：
Pomerantseva E
中科院分区：
文献类型：
--
作者：
Mukherjee S;Quilty CD;Yao S;Stackhouse CA;Wang L;Takeuchi KJ;Takeuchi ES;Wang F;Marschilok AC;Pomerantseva E
介绍了一种基于过氧化氢诱导的溶胶-凝胶法的化学预插层法制备含碱离子的三元层状钛酸盐(MTO)，其中M=Li，Na，K。报告了导致形成元素分布均匀的单相材料的每个预嵌插离子的合成参数。分析表明，随着水合预嵌离子半径的增大，层状钛酸盐结构中的层间距增大。扫描和透射电子显微镜图像显示了形貌的多样性：LTO相结晶为以牡丹状球形团聚的纳米片状，而NTO和KTO粒子呈现一维纳米带或线状形貌，KTO纳米带比NTO纳米带更短和更聚集。电子衍射和高分辨电子显微镜的结构细化表明，LTO相的结构是由含有单一直层相连的TiO6八面体的TiO层堆积而成的。NTO和KTO结构中的层形成不同的形式，由两排钛的TiO6八面体组成的单元排列不规则的双层Ti-O层组成。在含1M Na2SO4电解液的电池中，NTO电极表现出最高的电化学性能，KTO电极次之，LTO电极次之，并且在不同的扫描速率下保持这一趋势。已建立的结构与电化学性能之间的关系表明，除了层间距和层间区域的化学成分外，层的结构对层状氧化物电极的电荷存储性能也有重要影响。与LTO电极相比，NTO和KTO相结构中的双层Ti-O层提供了更多的氧化还原中心，这可能有助于获得更好的电化学性能。我们的研究结果表明，含有双过渡金属氧化层的层状材料很有可能成为剥离和组装电子导电层的候选材料，目的是创造出具有高电化学性能的2D异质结构。
We introduce a novel chemical preintercalation based synthesis technique based on hydrogen peroxide induced sol-gel process to obtain alkali ion containing ternary layered titanates (MTO, where M = Li, Na, K). Synthesis parameters leading to the formation of single-phase materials with homogeneous elemental distribution are reported for each of the preintercalated ion. Our analyses indicate that the interlayer spacing in the structure of the layered titanates increases with the increase of the radius of the hydrated preintercalated ion. Scanning and transmission electron microscopy imaging revealed morphological diversity: the LTO phase crystallized as nanoplates assembled in “peony-like” spherical agglomerates while NTO and KTO particles exhibited one-dimensional nanobelt or wire-like morphology, with the KTO nanobelts being shorter and more aggregated than the NTO nanobelts. Structural refinement corroborated by electron diffraction and high-resolution transmission electron microscopy revealed that the structure of the LTO phase is built by stacking Ti-O layers containing a single straight layer of connected TiO6 octahedra. The layers in NTO and KTO structures form differently and consist of double Ti-O layers with ragged arrangement of units built by TiO6 octahedra with two titanium rows. The NTO electrodes exhibited the highest electrochemical performance in cells with aqueous 1 M Na2SO4 electrolyte, followed by the KTO electrodes and then LTO electrodes, and this trend is maintained at various scan rates. The established relationships between the structure and electrochemical performance reveal that, in addition to interlayer distance and chemistry of the interlayer region, the structure of the layers can play an important role in charge storage properties of layered oxide electrodes. The double Ti-O layers in the structure of NTO and KTO phases provide a larger number of redox centers which could contribute to the superior electrochemical performance as compared to the LTO electrodes. Our findings indicate that layered materials containing double transition metal oxide layers are promising candidates for exfoliation and assembly with electronically conductive layers with the aim to create 2D heterostructures with high electrochemical performance.
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影响因子：
3.3
作者：
WATANABE, M;BANDO, Y;TSUTSUMI, M
通讯作者：
TSUTSUMI, M
影响因子：
3.5
作者：
Reyes-Coronado, D.;Rodriguez-Gattorno, G.;Oskam, G.
通讯作者：
Oskam, G.
DOI：
10.1107/s0108768111014534
发表时间：
2011-06-01
影响因子：
1.9
作者：
Andrusenko, Iryna;Mugnaioli, Enrico;Kolb, Ute
通讯作者：
Kolb, Ute
影响因子：
6.7
作者：
Rogelj, Joeri;Schaeffer, Michiel;Hare, William
通讯作者：
Hare, William
影响因子：
56.7
作者：
Pomerantseva, Ekaterina;Gogotsi, Yury
通讯作者：
Gogotsi, Yury