摘要
本论文在综述锂离子电池研究应用概况和国内外金属过渡族氧化物CuO负极材料研究进展的基础上,针对CuO作为锂离子电池负极材料目前存在的循环稳定性差等问题,提出了通过经济简单的对CuO热还原和对Cu热氧化的方法制备CuO/Cu复合电极材料。通过在CuO材料中引入金属Cu,利用Cu良好的导电性和韧性,提高CuO电极的电导率,减低其在循环过程中的粉化以获得循环稳定性良好的高容量CuO/Cu负极材料。采用X射线衍射、场发射扫描电镜、能量分散谱仪、透射电子显微镜和高分辨透射电镜等多种现代材料测试分析手段以及恒电流充放电、循环伏安等电化学测试技术,系统研究了材料制备工艺对合成材料结构和电化学性能的影响,分析探讨了影响CuO负极材料首次不可逆容量和循环稳定性的关键因数。此外,还研究了对CuO进行高能球磨和导电剂添加量对CuO电极电化学性能的影响。
研究结果表明,对纳米商业CuO进行高能球磨能有效减小颗粒尺寸,并在一定程度上使CuO非晶化,这都有利于提高材料的循环稳定性。粘结剂的加入量对电池的容量和稳定性有较大的影响。CuO与PVDF质量比分别为8:1.8:0.18和8：0.47的三种电极中,质量比为8：1的电极具有较高的容量和循环稳定性。
对纳米商业CuO(ca.40-50 nm)在氢气中,80-140℃不同温度下进行部分还原,合成了CuO/Cu复合材料。随还原温度从80℃增加到100℃,复合材料中Cu的含量从0.4wt.%增加到4.5wt.%,但当温度升高到120℃时,Cu含量明显增加到38.4wt.%,而当温度进一步升高到140℃时产物全为金属Cu。经80℃还原样品的首次库伦效率与初始CuO的基本相当(57-58%),当还原温度增加到100℃,样品的首次库伦效率略有增加。经100℃还原的样品表现出最高的首次充电容量,这说明适量还原产物Cu的生成有助于Li2O分解,提高了材料的利用率。经80℃、100℃还原的CuO/Cu样品的首次可逆容量均大于初始纳米CuO但循环稳定性的改善还较有限。经120℃还原的CuO/Cu样品具有良好循环稳定性,100次循环后容量保持率仍为92.2%。非活性的具有良好韧性的Cu在循环过程中对CuO脱嵌锂而产生的体积膨胀起到很好的缓冲作用,提高了其循环稳定性。但由于活性物质量的减低,大大降低了材料的容量。
商业纳米Cu粉(ca.40 nm)在250-500℃的不同温度下,在空气气氛中氧化4h,Cu基本被氧化为CuO,并保持了初始Cu的纳米尺寸。其中250-450℃氧化的产物中有约3-4wt.%Cu,而500℃氧化的产物中未发现有Cu。对材料的电化学性能研究表明,用该方法制备的纳米CuO/Cu材料作为锂离子电池负极材料具有良好的循环稳定性。其中经450℃氧化的材料表现出最高的循环稳定性和较高的容量特性,经约8次循环活化后,容量达到423 mAh/g,经80次循环后,容量为377 mAh/g,容量保持率接近90%。通过初始Cu粉颗粒尺寸相应合成的CuO的颗粒尺寸和氧化时间等因素对材料电化学性能影响的研究表明,减小初始铜粉颗粒尺寸和延长氧化时间都能够有效地提高循环性能和可逆容量。
On the basis of a brief summary of the investigation and application of lithium ion batteries (LIBs) and a review of the investigations and development of copper oxide (CuO), which is one of the promising anode materials for LIBs, the thesis aims to prepare CuO/Cu composites as anode materials by simple and economic methods of thermal oxidation and reduction. By means of the introduction of metallic Cu into CuO, the good electron conductivity and the excellent toughness of Cu plays effective roles in improving the electron conductivity and reducing the pulverization of the CuO anode, respectively, during cycling. Therefore, CuO/Cu anode materials with high capacity and favorable cycle stability are hopefully obtained. The effects of the fabrication technique and its parameters on the structure and electrochemical properties are investigated by XRD, SEM, EDS, TEM and HRTEM etc. and electrochemical testing of galvanostatic charge-discharge, cyclic voltammograms. The key factors that affect the cycle stability as well as the initial irreversible capacity of the composite anodes and the mechanism are also discussed. In addition, effects of high-energy ball-milling on the structure and electrochemical properties of nano-sized CuO and addition amount of PVDF binder on the electrochemical properties of nano-sized CuO are also studied.
The results show that high-energy ball-milling reduces the particle size and results in a tendency of amorphous feature of the CuO particles, which all improve its electrochemical properties. The content of PVDF binder shows visible effect on the cycle stability and capacity of CuO anode. Among the three weight ratios of 8:1, 8:0.18 and 8:0.47 of CuO to PVDF, the first one possesses the best electrochemical properties.
Commercial nano-CuO (ca.40-50 nm) are reduced partially in the atmosphere of H2 at the temperature ranging from 80 to 140℃, forming CuO/Cu composites. The content of Cu of the CuO/Cu composite slightly increases from 0.4 wt.% to 4.5 wt.% with the reduction temperature increasing from 80 to 100℃. Whereas the Cu content increases obviously to 38.4 wt.% when the reduction temperature is increased to 120℃and no Cu is found in the product when the reduction temperature is further increased to 120℃. The initial coulombic efficiency of the product reduced at 80℃shows correspond with the raw CuO (57-58%), and the efficiency increases slightly as the reduction temperature increases to 100℃. The initial charge capacity of the product obtained at 100℃shows the highest initial charge capacity among all the products, indicating that the suitable amount Cu favors the decomposition of Li2O and enhances the utilization efficiency of the CuO active material. The products reduced at 80 and 100℃show higher initial reversible capacity compared with the raw CuO, however, the improvement of the cycle stability is limited. The product reduced at 120℃exhibits good cycle performance, showing a capacity retention of 92% after 80 cycles. The inactive Cu with good toughness buffers the volume change of CuO caused by the lithium extraction and insertion during cycles and hence improves the cycle stability of the composite. However, as the reduction fraction of the active CuO, the capacity is unfavorably decreased.
Commercial nano-Cu powders are mostly oxidized to CuO at the temperature rangeing from 250 to 500℃for 4 hours in air and the content of CuO was higher than 94 wt.% for each product. The nano-morphology of the raw Cu powder is preserved. About 3-4 wt.% Cu remains in the products which prepared by oxidation temperature from 250 to 450℃, whereas no Cu is found for the oxidation temperature of 500℃. The electrochemical study shows that the nano-sized products synthesized by the thermal oxidation method possess favorable cycle stability as anode materials for lithium ion battery. The product prepared at 450℃displays the best cycle stability and a favorable capacity. A capacity of 423 mAh/g is approached after an activation of 8 cycles, and the capacity after 80 cycles maintains as 377 mAh/g, showing a capacity retention of almost 90%. The study of the effect of Cu particle size and oxidation time on the electrochemical properties of oxidized products shows that either reducing Cu particle size or prolonging the oxidation time improves the cycle capability of the oxidized products effectively.
引文
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