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用于高可逆锂存储的合成均匀介孔 TiO2/石墨烯/介孔 TiO2 三明治状纳米片的通用策略。

General strategy to synthesize uniform mesoporous TiO2/graphene/mesoporous TiO2 sandwich-like nanosheets for highly reversible lithium storage.

机构信息

Department of Chemistry, Laboratory of Advanced Materials, Shanghai Key Lab of Molecular Catalysis and Innovative Materials, and State Key Laboratory of Molecular Engineering of Polymers, Fudan University , Shanghai 200433, P. R. China.

出版信息

Nano Lett. 2015 Mar 11;15(3):2186-93. doi: 10.1021/acs.nanolett.5b00291. Epub 2015 Feb 26.

Abstract

Uniform oxide deposition on graphene to form a sandwich-like configuration is a well-known challenge mainly due to their large lattice mismatches and poor affinities. Herein, we report a general strategy to synthesize uniform mesoporous TiO2/graphene/mesoporous TiO2 sandwich-like nanosheets (denoted as G@mTiO2), which cannot be achieved by conventional one-pot synthetic methods. We show that by rational control of hydrolysis and condensation of Ti precursors in a slow way, GO sheets can be conformably coated by amorphous TiO2 shells, which then can be facilely transformed into the well-defined G@mTiO2 nanosheets by annealing. This amorphous-to-crystalline strategy conveniently allows bypassing strain fields that would inevitably arise if direct growth of mesoporous anatase shells on graphene. As distinct from the most common structures of graphene-based composites (mixed, wrapped, or anchored models), the resultant materials display a uniform sandwich-like configuration: few-layer graphene conformably encapsulated by mesoporous TiO2 shells. This new G@mTiO2 nanosheet exhibits ultrathin nature (∼34 nm), small size and high crystalline nanocrystals (∼6 nm), high surface areas (∼252 m(2)/g) and uniform mesopores (∼3.4 nm). We further show that the thickness of mesoporous TiO2 shells can be facilely adjusted as desired by controlling the ammonia content, and this facile strategy can be easily extended to design other oxide/graphene/oxide sandwich-like materials. More importantly, we showcase the benefits of the resultant G@mTiO2 nanosheets as anodes in lithium ion batteries: they deliver an extra high capacity, an excellent high-rate capability, and long cycle life.

摘要

在石墨烯上形成均匀的氧化物沉积以形成三明治状结构是一个众所周知的挑战,主要是由于它们的大晶格失配和较差的亲和力。在此,我们报告了一种通用策略,用于合成均匀的介孔 TiO2/石墨烯/介孔 TiO2 三明治状纳米片(表示为 G@mTiO2),这是传统的一锅合成方法无法实现的。我们表明,通过合理控制 Ti 前体的水解和缩合速度,可以使 GO 片通过无定形 TiO2 壳层进行共形涂覆,然后通过退火可以容易地转化为具有良好定义的 G@mTiO2 纳米片。这种非晶态到晶态的策略方便地避免了如果直接在石墨烯上生长介孔锐钛矿壳层必然会出现的应变场。与最常见的基于石墨烯复合材料的结构(混合、包裹或锚定模型)不同,所得材料显示出均匀的三明治状结构:少层石墨烯通过介孔 TiO2 壳层共形封装。这种新的 G@mTiO2 纳米片具有超薄的性质(约 34nm)、小尺寸和高结晶纳米晶(约 6nm)、高比表面积(约 252m2/g)和均匀的介孔(约 3.4nm)。我们进一步表明,通过控制氨含量,可以轻松地调整介孔 TiO2 壳层的厚度,并且这种简便的策略可以很容易地扩展到设计其他氧化物/石墨烯/氧化物三明治状材料。更重要的是,我们展示了所得 G@mTiO2 纳米片作为锂离子电池阳极的优势:它们提供了额外的高容量、优异的高倍率性能和长循环寿命。

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