【作者】 张海礁；

【导师】 叶枫；

【作者基本信息】 哈尔滨工业大学 ， 材料学， 2010， 博士

【摘要】 本文以间苯二酚（R）-甲醛（F）为炭前驱体及模板,采用反相悬浮法和水热法制备了炭空心微球,氧化物空心微球,及氧化物/炭复合微球。进一步利用RF凝胶特性,结合模板技术制备了Sn-In₂O₃/炭（ITO/C）一维复合纳米材料,验证了以RF为前驱体制备空心微纳米材料的结构可控性。采用X-射线衍射（XRD）、扫描电子显微镜（SEM）、透射电子显微镜（TEM、HRTEM）、傅立叶变换红外光谱（FT-IR）、氮气吸附等分析手段,系统研究了材料微观组织结构,分析了结构形成机理。探索了RF炭微球及ZnO/C复合微球在锂离子电池和超级电容器材料方面的应用,研究了RF炭微球结构、形态对电性能的影响。讨论了ITO/C一维复合纳米材料在气敏元件中的应用。首次以RF为炭前驱体,通过反相悬浮法,制备了形态可控的RF炭微球。实验结果表明,RF前驱体溶液的初始pH值、催化剂和表面活性剂类型是获得RF炭空心球结构,“碗状”结构和胶囊等结构的重要反应参数。分析了不同形态的RF炭微球的形成机制,研究了RF炭微球的电学性能。电化学分析结果表明,以Na₂CO₃为催化剂所制备的RF炭微球电极材料具有理想的电容行为,循环伏安性能稳定、可逆,适用于大电流下充放电。以K₂CO₃为催化剂制备的RF炭胶囊作为锂离子电池阴极材料,充放电、循环特性测试结果表明,其初始放电电容量可达1059mAh/g,且电性能稳定,循环效率可达99%,是理想的锂离子电池阴极材料。以表面功能化修饰的RF凝胶微球为模板,制备了结构完整、粒径分布均匀的氧化物空心微球。研究了不同表面修饰剂对RF凝胶微球表面改性的作用机理,分析了RF表面改性对氧化物空心微球结构的影响。通过炭化Zn²⁺负载的RF凝胶微球,制备了ZnO/C复合微球。其稳定的循环伏安特性和法拉第氧化-还原反应效应表明,ZnO/C复合微球可作为理想的超级电容器材料。首次将ITO溶液和RF溶液组成复合前驱体,并结合多孔氧化铝（AAO）模板技术,制备了ITO/C一维复合纳米材料。讨论了ITO/RF复合前驱体中ITO浓度对ITO/C一维复合纳米结构的影响。结果表明,通过ITO与RF前驱体溶液的同步溶胶-凝胶化过程,有效地将ITO纳米颗粒复合到RF凝胶网络中形成一维纳米复合材料。气敏性测试表明,所制备的ITO/C一维复合纳米材料具有较高氢气灵敏度和较短的响应时间,可作为氢气气敏材料。以葡萄糖溶液为前驱体,利用水热法制备了结构完整、粒径分布均匀的炭微球。通过加入不同添加剂可对炭微球结构进行有效控制。以所制备的炭微球为模板,制备了多种氧化物空心微球。利用ZnCl₂/RF/葡萄糖复合体系的水热反应过程制备了结构完整的Zn/炭复合前驱体微球,通过热处理除去炭模板,并调控热处理条件,控制得到了多种形态的ZnO空心微球,为RF凝胶微球的水热制备及其在生物单糖方面的应用奠定了基础。更多还原

【Abstract】 Resorcinol-formaldehyde （RF） was used as carbon precursor and templates to fabricate carbon hollow spheres, oxide hollow spheres and oxide/carbon composite microspheres. Further, the ITO/C one-dimensional composite nanotubes （nanowires） were synthesized by using RF as carbon precursor, indicating the controllability of RF in fabricating various structures of nanomaterials. The morphologies, microstructures and formation mechanism of the obtained samples were analysed by XRD, SEM, TEM, HRTEM, FT-IR and nitrogen absorption, etc. The influences of morphologies and microstructures of the carbon microspheres on the electrochemical properties were studied. The possibility and advantage of the carbon microspheres applied in supercapacitor and Li-ion battery were discussed. The application of ITO/C one-dimensional composite nanomaterials in gas sensor was discussed.It is the first time to synthesize the morphology-controlled RF carbon microspheres by inverse phase suspension method. The results indicated that the pH values, catalysts and surfactants are crucial in preparing the various RF carbon microspheres such as hollow spheres, bowl-like structures and microcapsules. The formation mechanism of RF carbon microspheres was proposed and the electrochemical properties were studied. The results showed that the RF carbon microspheres prepared with Na₂CO₃ as catalyst exhibited excellent capacity characters. The cyclic voltammetry revealed that the electrochemical properties of prepared carbon microspheres were stable, reversible and were available for charge/discharge under high current. The charge/discharge capacity and cyclic properties of RF carbon microcapsules prepared with K₂CO₃ as catalyst, as anode materials in Lithium-ion batteries, showed that the electrochemical property was stable with the efficiency of 99% and had a maximum value of 1059mAh/g.The intact metal oxide hollow microspheres with even particle size were synthesized by using surface-modified RF gel microspheres as templates. The mechansim of surface modification on RF gel microspheres by different surfactants were studied. The influences of surface modification on structure of metal oxide hollow microspheres were investigated. The ZnO/C composite microspheres were obtained by carbonization of Zn²⁺ loading RF composite microspheres. ZnO/C composite microspheres had stable cyclic voltammetry characters and faradic redox reaction effection, indicating that ZnO/C composite microspheres could be used as ideal supercapacitor materials.It is the first time to prepare ITO/C one-dimensional composite nanomaterials by using ITO and RF mixed solutions as composite precursors. The influence of ITO concentration on the structure of ITO/C one-dimensional nanocomposites was discussed. The results showed that ITO nanoparticles could be well dispersed in RF carbon gel networks by using ITO and RF composite sol-gel precursors. The H2 gas sensitivity indicated that the prepared ITO/C one-dimensional nanocomposites exhibited high sensibility and low response time.The intact carbohydrate microspheres were prepared by hydrothermal reaction of glucose solution. The morphologies and microstructures of carbohydrate microspheres could be tailored with addition of different additives. The various oxide hollow microspheres were prepared by using the obtained carbohydrate microspheres as templates. The zinc/carbon composite precursor microspheres were obtained by hydrothermal process of ZnCl2/RF/glucose system. ZnO hollow microspheres with various morphologies were formed by controlling the thermal treatment conditions during removal of carbon templates. The study provides background for application of RF in the fields of hydrothermal strategy and glucose.更多还原