纳米空间限域热解法制备窄分散非聚集笼状中空碳微球及其结构调控

Hollow carbon spheres (HCSs)have attracted a great deal of attention because of their special structures and amazing application prospects.However, previous reports on HCSs have the sole aim of obtaining hollow structure units,and little attention has been paid to addressing the issue of varying the inner diameter, the shell thickness and pore structure,and the particle conglutination of HCSs.Especially, to the best of our knowledge, no feasible solution has been reported to introduce large through-holes (＞10nm)with controllable pore size and amount across the shell of HCSs, which restrict the research and application of HCSs in some areas.To solve this problem, we propose a novel strategy for the preparation of discrete cage-like hollow carbon microspheres with narrow size distribution through confined nanospace pyrolysing raspberry -like composite particles,and further try to achieve the goal of effectively controlling the morphology,the inner diameter, the shell thickness, pore size，pore amount,and the particle conglutination of HCSs. The inner diameter and shell thickness of HCSs are dominated by the central microspheres of the raspberry-like composite particles.The small inorganic "satellite" particles not only determine the pore size and amount across the shell of HCSs,which also could act as confined nanospace to prevent the aggregation of HCSs during carbonization process.Consequently,the controllable preparation and structure control of discrete cage-like hollow carbon microspheres with narrow size distribution will be realized.

中空碳球(HCSs)由于其特殊的结构和诱人的应用前景而引起了人们的极大关注,但是之前的工作主要集中于中空结构单元的制备，而有关HCSs内腔尺寸、壳层厚度、孔结构、以及聚集状态方面的研究很少。尤其是在HCSs壳层引入数量及尺寸可控的直通大孔（大于10nm）而形成笼状HCSs方面的研究迄今为止还未见报道。这使得HCSs在某些方面的研究和应用受到了限制。为此，本项目设计和提出了通过纳米空间限域热解树莓状复合胶体粒子来制备窄分散非聚集笼状HCSs的新思路，并力图实现对笼状HCSs形态、内腔尺寸、壳厚、表面孔尺寸、孔数量以及聚集状态的有效调控。树莓状微球内的中心聚合物微球决定了HCSs的内腔尺寸和壁厚，而"卫星"无机颗粒则不仅控制着HCSs表面的孔尺寸及孔数量，还产生了纳米空间限域效应，有效阻止了微球在碳化过程中的聚集，进而实现了窄分散非聚集笼状中空碳球的可控制备与结构调控。

中空碳球(HCSs)由于其特殊的结构和诱人的应用前景而引起了人们的极大关注,但是之前的工作主要集中于中空结构单元的制备，而有关HCSs 内腔尺寸、壳层厚度、孔结构、以及聚集状态方面的研究很少。尤其是在HCSs 壳层引入数量及尺寸可控的直通大孔（大于10nm）而形成笼状HCSs 方面的研究迄今为止还未见报道。这使得HCSs 在某些方面的 研究和应用受到了限制。为此，本项目设计和提出了通过纳米空间限域热解树莓状复合胶体 粒子来制备窄分散非聚集笼状HCSs 的新思路，并实现了对单层和双层笼状HCSs 形态、内腔尺寸、壳厚、表面孔尺寸、孔数量以及聚集状态的有效调控。树莓状微球内的中心聚合物微球决定了 HCSs 的内腔尺寸和壁厚，而“卫星”无机颗粒则不仅控制着HCSs 表面的孔尺寸及孔数量，还产生了纳米空间限域效应，有效阻止了微球在碳化过程中的聚集，进而实现了窄分散非聚集笼状中空碳球的可控制备与结构调控。同时，还进一步研究了这些微球在超级电容器、锂硫电池、锂离子电池、电解水以及氨硼烷水解方面的应用。