Integrated Carbon/Red Phosphorus/Graphene Aerogel 3D Architecture via Advanced Vapor-Redistribution for High-Energy Sodium-Ion Batteries
Integrated Carbon/Red Phosphorus/Graphene Aerogel 3D Architecture via Advanced Vapor-Redistribution for High-Energy Sodium-Ion Batteries
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DOI：
10.1002/aenm.201601037
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发表时间：
2016-11-01
影响因子：
27.8
通讯作者：
Guo, Zaiping
中科院分区：
文献类型：
--
作者：
Gao, Hong;Zhou, Tengfei;Guo, Zaiping
DOI: 10.1002 / aenm。201601037通过耦合集成碳层来提高p基杂化纳米结构的导电性，保持磷与导电基体的密切接触，减小粒径来控制磷的体积变化，缩短离子扩散路径，并结合高导电性网络，可能是进一步提高电化学性能的一种很有前途的方法。石墨烯气凝胶（GA）是一种新型的三维多孔石墨烯结构，具有较高的比表面积和丰富的活性位点，其相互连接的三维多孔结构被认为是循环过程中电子和离子转移的理想电极结构。[11-13]在此，我们通过先进的蒸汽再分配策略制备了三维集成碳/红磷/石墨烯气凝胶复合材料（C@ P/GA），以实现磷纳米颗粒（NPs）在三维石墨烯结构中的均匀分布。我们开发的蒸汽再分配策略包括两个步骤：(i)磷微粒（MPs）并入和（ii）局部磷（NPs）蒸汽再分配过程。与传统的蒸发-冷凝策略不同，首先，通过原位自组装方法将红色pmp纳入石墨烯水凝胶中，然后通过聚吡咯（PPy）的气相聚合，将红色pmp封装成具有明确孔隙度的结构。在接下来的高温蒸汽再分配过程中，聚吡啶薄膜的涂层/沉积对于保持红磷加载水平至关重要。最后，引入局部气相再分布过程获得均匀沉积的红色P NPs，从而得到C@ P/GA。制备的C@ P/GA复合材料的红色P NPs均匀分布在碳包覆的GA基体（C@ GA）中，并集成成三维多孔结构。这种独特的结构结合了以下优点：首先，红色P np被封装在矩阵中，可以适应红色P在循环过程中的体积膨胀。其次，集成的三维导电网络可以有效地促进电子转移，并使导电框架充分浸入电解质中。据我们所知，这是合成集成三维多孔C@ P/GA复合材料的第一份报告，其中P NPs （10-20 nm）被密封在C@ GA矩阵中。这样，在随后的蒸汽再分布过程中可以有效地保持复合材料中的P含量，并且由于设计的独特结构，P NPs均匀分布并密封在C@ GA基体中，从而降低了P颗粒在基体上的迁移率，极大地防止了P颗粒在电化学循环过程中作为sib负极材料时的聚集。制备的C@ P/GA电极提供容量
DOI: 10.1002/aenm. 201601037 developing a novel P-based hybrid nanostructure by coupling the integrated carbon layer so as to enhance the conductivity and maintain the intimate contact between phosphorus and the conducting matrix, minimizing the particle size to control the phosphorus volume change, and shorten the ion diffusion path together with highly conductive networks might be a promising approach to further improve the electrochemical performance. Graphene aerogel (GA), a novel type of 3D porous graphene architecture, has a high surface area and ample active sites, and the interconnected 3D porous structure is regarded as an ideal electrode structure for both electron and ion transfer during cycling.[11–13] Herein, we fabricated a 3D integrated carbon/red phosphorus/graphene aerogel composite (C@ P/GA) via an advanced vapor-redistribution strategy to achieve a uniform distribution of phosphorus nanoparticles (NPs) within the 3D graphene-based architecture. The vapor-redistribution strategy that we developed includes two steps:(i) phosphorus microparticles (MPs) incorporation and (ii) localized phosphorus (NPs) vapor-redistribution processes. In contrast to the traditional vaporization–condensation strategy, first, the red P MPs were incorporated into the graphene hydrogel via an in situ selfassembly approach, followed by vapor-phase polymerization of polypyrrole (PPy) in order to encapsulate the red P MPs into structure with well-defined porosity. The coating/deposition of PPy film is critical for maintaining the red P loading level during the following high-temperature vapor-redistribution process. Finally, a localized vapor-redistribution process was introduced to obtain uniformly deposited red P NPs, resulting in the C@ P/GA.The as-prepared C@ P/GA composite features red P NPs uniformly distributed in the carbon covered GA matrix (C@ GA), which integrated into 3D porous structure. The unique construction combines the following merits: first, the red P NPs are encapsulated in the matrix, which can accommodate the volume expansion of red P during cycling. Second, the integrated 3D conductive network could efficiently facilitate electron transfer and enable the conductive framework to be sufficiently immersed in the electrolyte. To the best of our knowledge, this is the first report on the synthesis of an integrated 3D porous C@ P/GA composite with P NPs (10–20 nm) that are sealed in the C@ GA matrix. In this way, the P content in the composite can be effectively maintained during the following vapor-redistribution process, and due to the designed unique structure, P NPs were uniformly distributed and sealed in the C@ GA matrix, so that the mobility of P particles on matrix was reduced, which greatly prevents the aggregation of P particles during electrochemical cycling when it is used as an anode material for SIBs. The as-prepared C@ P/GA electrode delivers a capacity