溶剂热法合成三氧化四铜和复合铜氧化物微球及其应用的研究
文献类型：学位论文
| 作者 | 赵丽润 |
| 学位类别 | 硕士 |
| 答辩日期 | 2012-05-23 |
| 授予单位 | 中国科学院研究生院 |
| 导师 | 苏发兵 |
| 关键词 | 铜氧化物 锂电池 Rochow Cu4O3 |
| 其他题名 | Solvothermal Synthesis of Cu4O3 and Copper Oxide Composite Microspheres and their Applications |
| 学位专业 | 化学工程 |
| 中文摘要 | 微纳米铜氧化物材料由于其优越的物理、化学性能一直是研究的重点之一。作为无机材料，微纳米氧化铜、氧化亚铜在工业生产中都有着非常广泛的用途。铜氧化物除了氧化铜、氧化亚铜，还有一种氧化物是Cu4O3。Cu4O3是一种亚稳态物质，一般与CuO，Cu2O共存，难以合成纯相产物，限制了对其性能及应用的研究，因此对Cu4O3的制备及其应用研究有着非常重要的科学意义和应用前景。本论文首次用溶剂热方法合成出纯相Cu4O3微球及空心Cu4O3/Cu2O复合物微球，分别对纯相Cu4O3微球的合成机理及空心Cu4O3/Cu2O形成机理进行了讨论，并进一步对纯相Cu4O3微球作为锂电池负极材料，以及纯相Cu4O3微球及空心Cu4O3/Cu2O复合物微球分别作为Rochow反应的催化剂进行了探索性研究。论文的主要研究内容及创新性成果如下： 1. 以硝酸铜为原料，在二甲基甲酰胺（DMF）和乙醇的混合溶剂中通过溶剂热反应合成出粒径为2-10μm的纯相Cu4O3微球。通过调整反应物初始浓度、混合溶剂比例、反应温度及反应时间等条件得到了纯相Cu4O3微球的最佳合成条件，并研究了纯相Cu4O3微球的形成机理和热稳定性。 2. 以硝酸铜为原料，在DMF和乙醇的混合溶剂中通过溶剂热反应制备出粒径为500nm-5μm的空心Cu4O3/Cu2O复合物微球。实验发现随着反应时间的延长，Cu4O3/Cu2O复合物微球由实心变为空心，提出Ostwald ripening是形成Cu4O3/Cu2O微米空心球的主要原因。研究还发现Cu4O3在空心Cu4O3/Cu2O复合物微球的含量随着反应时间的延长而减少。 3. 研究了纯相Cu4O3微球作为锂电池负极材料的电化学性能。分别研究了纯相Cu4O3微球和CuO/Cu2O复合物的首次充放电曲线，循环伏安曲线，循环性能及电化学阻抗谱。研究结果表明，纯相Cu4O3微球的充电量及循环性能明显优于CuO/Cu2O，具有高可逆循环容量，良好的循环性能和较强的电极反应动力，表现出良好的电化学性能。 4. 研究了纯相Cu4O3微球及Cu4O3/Cu2O微米空心球复合物作为Rochow反应的催化剂性能。实验结果表明纯相Cu4O3微球作为催化Rochow反应的催化剂，表现出良好的二甲选择性（86.4%）。空心Cu4O3/Cu2O复合物作为Rochow反应的催化剂，表现出良好的硅粉转化率（32.0%）。 |
| 英文摘要 | Copper oxides nano/microspheres have been widely studied owing to their excellent photo-electrochemical properties, solar-thermal conversion performances, catalytic applications and electrochromic properties. Besides Cu2O and CuO in the binary Cu-O system, a third defined compound Cu4O3 (paramelaconite) has also been reported. The pure paramelaconite is difficult to be synthesized due to the fact that both Cu(Ι) and Cu(ΙΙ) atoms exit in this material. It will be quite interesting and important to explore the feasibility of developing an alternative potential approach to obtain pure or composite Cu4O3 powders, thereby ensuring studies for their corresponding properties and various promising applications. In this study, pure Cu4O3 and its composites with controllable morphology and size were prepared by solvothermal method in the absence of template and additives. The formation mechanisms for pure Cu4O3 and hollow Cu4O3/Cu2O composite microspheres are proposed. The obtained pure Cu4O3 microspheres exhibit unique lithium storage behaviors and superior electrochemical properties as anode materials for Li-ion batteries. In addition, Cu4O3/Cu2O composite microspheres exhibit higher catalytic activity for the Rochow reaction. The major work and innovative results for this dissertation are as follows: 1. Pure Cu4O3 microspheres with controllable morphology and size are prepared by solvothermal method with Cu(NO3)2?H2O as a precursor in DMF and ethanol mixed solvents in the absence of template and additives. The optimum synthesis conditions were determined based on systematic studies of the effects of precursor concentration, volume ratio of DMF to ethanol, temperature and time. A possible formation mechanism was proposed to account for the evolving process of the morphology and component of the product. Moreover, the thermal stability of pure of Cu4O3 was also studied. 2. A promising method for the fabrication of hollow Cu4O3/Cu2O composite microspheres was proposed. Increasing the reaction time from 2h to 6h, the product structures changed from solid to hollow. Ostwald ripening was believed to play a key role in the formation of hollow Cu4O3/Cu2O composite microspheres. Moreover, the content of Cu4O3 in the composite microspheres decreased with increasing the reaction time. 3. The electrochemical properties of pure Cu4O3 microspheres as anode materials for Li-ion batteries were investigated. Compared to CuO/Cu2O composite microspheres, the as-prepared Cu4O3 exhibited unique lithium storage behaviors at low voltage range and superior electrochemical performance as anode materials for Li-ion batteries. 4. Catalytic performance of the obtained Cu4O3 and CuO/Cu2O composite hollow microspheres as copper-based catalyst in the Rochow reaction was investigated for the production of dimethyldichlorosilane (DMDCS). It was found that the pure Cu4O3 microspheres exhibited an excellent DMDCS selective (86.4%). And the hollow CuO/Cu2O composite microspheres exhibited an excellent Si conversion of 32.0wt%. |
| 语种 | 中文 |
| 公开日期 | 2013-09-25 |
| 源URL | [http://ir.ipe.ac.cn/handle/122111/1839]  |
| 专题 | 过程工程研究所_研究所（批量导入） |
| 推荐引用方式 GB/T 7714 | 赵丽润. 溶剂热法合成三氧化四铜和复合铜氧化物微球及其应用的研究[D]. 中国科学院研究生院. 2012. |
入库方式： OAI收割
来源：过程工程研究所
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