摘要
锂离子电池以其高的比能量、无环境污染、循环使用寿命长以及无记忆效应等诸多优点而受到了人们的广泛关注。目前，它已经普遍应用在我们生活的方方面面，比如手机、笔记本电脑、数码相机以及作为太阳能、风能等的储备电源及储能装置等。锂离子电池的负极材料通常采用石墨材料，已获得很大的进展，而正极材料已成为制约电池性能和价格的重要因素。1997年，Goodenough等首次报道了基于LiFePO_4的锂离子电池正极材料，因为其具有非常好的结构稳定性、高的安全性能以及优异的循环性能，LiFePO_4材料引起了广大科学工作者的高度重视。随后，又陆续涌现出一系列聚阴离子型锂离子电池正极材料，如LiMnPO_4、Li_3V_2(PO_4)_3、Li_2MnSiO_4和Li_2FeSiO_4等。其中LiFePO_4、LiMnPO_4和Li_3V_2(PO_4)_3以其较高的比能量而被认为是理想的动力电池正极材料。但是低的电子电导率和锂离子扩散系数等缺点极大地限制了它们的电化学性能。在本论文中，我们以改善LiFePO_4、LiMnPO_4和Li_3V_2(PO_4)_3的电化学性能为目的对其进行了研究。
首先，我们以酚醛树脂为碳源、六次甲基四胺为均匀沉淀剂，通过原位聚合限制法合成了LiFePO_4/C复合材料，并讨论了不同的烧结温度对其电化学性能的影响。基本原理是六次甲基四胺在酸性条件下水解生成甲醛和铵根离子。这一方面升高了溶液的pH值，利于磷酸铁沉淀的生成；另一方面，水解生成的甲醛可作为酚醛树脂的原材料。同时，酚醛树脂在惰性气氛下裂解生成的碳有助于提高材料表面的电子电导率。通过X-射线衍射和拉曼光谱分析了材料的结构，并分析了烧结温度对其结构的影响；采用热重分析计算了复合材料中碳的含量；通过扫描电子显微镜和透射电子显微镜观察了材料的形貌和颗粒尺寸；通过循环伏安和充放电性能测试分析了材料结构的稳定性和电化学性能。电化学结果表明，当烧结温度为750°C时，所得的LiFePO_4/C复合材料具有最佳的倍率性能和循环性能。10C，20C和50C倍率下，初始放电容量分别为115.6、84.5和67.8mAh/g。电极循环1000次以后，容量的保持率分别为89.5%，90.9%和85.7%。
然后，我们采用一种更为简便的方法来合成LiFePO_4/C复合材料。在酸性条件或者加热状态下，糠醇能够发生聚合反应生成聚糠醇。借助于这个聚合过程，我们采用原位聚合限制法制备出LiFePO_4/C复合材料，并讨论了不同的烧结温度对其电化学性能的影响。通过XRD和Raman图谱分析了材料的结构，并分析了烧结温度对其结构的影响；通过SEM和TEM观察了材料的形貌和颗粒尺寸大小；通过循环伏安和充放电性能测试分析了材料的结构稳定性和电化学性能。电化学性能测试得知，在0.5C倍率下材料初始的放电容量为156.1mAh/g，循环50次以后容量仍能达到145.2mAh/g。在5C，10C，20C和50C倍率下循环500次以后，容量的保持率分别为94.4%，90.6%，87.8%和90.9%。
再者，我们采用一种碳凝胶方法制备了LiFe_(0.4)Mn_(0.6)PO_4/C复合材料。借助于碳凝胶的过程，使得所有的离子均匀分布在碳凝胶中，达到了分子级别的混合，有利于LiFe_(0.4)Mn_(0.6)PO_4的制备。同时Fe~(2+)的掺杂降低了Mn的含量，有助于提高材料的结构稳定性。碳凝胶裂解产生的碳能够改善材料的电子电导率。电化学结果表明，10C时首次放电容量为64.6mAh/g，循环1000次后放电容量为53.8mAh/g。
最后，我们利用燃烧法合成了Li_3V_2(PO_4)_3/C复合材料。采用X射线衍射和Raman光谱分析了材料的结构；通过SEM和TEM观察了材料的形貌、颗粒尺寸和表面包覆碳层的厚度；通过恒流充放电性能测试深入分析了不同碳含量和烧结温度对其电化学性能的影响。充放电性能测试表明适宜的碳含量和烧结温度对材料的电化学性能有着重要影响。
总之，通过本文一系列的研究，我们对LiFePO_4、LiMnPO_4和Li_3V_2(PO_4)_3的结构特征、存在的问题以及电化学性能等有了更深入的认识，为上述材料的实际应用提供了一定的理论基础以及合成指导。
Lithium-ion batteries have attracted extensive attention due to the superiorenergy density, environmental benignity, outstanding cycling performance and nomemory effect, etc. At present, it has been widely used in every aspect of our lives,such as cell phones, laptop computers, digital cameras, and energy storage devices forsolar and wind electricity generation. Usually, the used anode materials of lithium ionbatteries are graphite, and cathode materials have become the important factor for theproperties and price of Li-ion batteries. In1997, Goodenough et al. proposed LiFePO_4as cathode material due to its good structure stability, high safety and excellentcycling performance. Since then, some polyanion materials have been investigated toimprove the electrochemical performance, such as LiMnPO_4, Li_3V_2(PO_4)_3, Li_2MnSiO_4,Li_2FeSiO_4and so on. Among them, LiFePO_4, LiMnPO_4and Li_3V_2(PO_4)_3have highenergy density, and both of them are considered ideal cathode materials of powerbatteries. However, the electrochemical performance is greatly limited by the poorelectronic conductivity and low lithium ion diffusivity. Therefore, this thesis isdevoted to improve the electrochemical performances of the LiFePO_4, LiMnPO_4andLi_3V_2(PO_4)_3materials.
Firstly, the LiFePO_4/C composite was prepared by an in situ polymerizationrestriction method using resorcinol-formaldehyde (RF) gel as carbon source andhexamethylenetetramine as potential precipitant, and we also discussed the effect ofvarious calcination temperatures for the electrochemical performance of LiFePO_4/C.It is known that hexamethylenetetramine can be cleaved to give formaldehyde andammonium ions under acidic conditions. On the one hand, the pH value of thesolution increases and facilitates the formation of FePO4precipitation; on the other hand, formaldehyde, formed in situ, as one reactant for the raw material of theresorcinol-formaldehyde gel. The residual carbon from the pyrolysis of RF gel caneffectively increase the electron conduction. We studied the structure properties of thematerial using XRD and Raman, and we also discussed the effect of variouscalcination temperatures for the structure of LiFePO_4/C. The carbon content of theLiFePO_4/C was determined by thermogravimetric analysis, and the morphology andparticle size were observed through SEM and TEM. Then we studied the structurestability and electrochemical properties of the material by galvanostaticcharge/discharge tests and cyclic voltammetry (CV). Electrochemical test indicatedthat the obtained LiFePO_4/C at750°C delivered better electrochemical properties.Even at the high rates of10C,20C and50C, the initial discharge capacities of theelectrodes exhibited115.6mAh/g,84.5mAh/g and67.8mAh/g, and the electrodesdelivered capacity retention of89.5%,90.9%and85.7%after1000cycles,respectively.
Then, we developed a more convenient method for the synthesis of LiFePO_4/Ccomposite. Poly(furfuryl alcohol)(PFA) can be easily obtained from FA by heating oracidic catalysis. The mixture of poly(furfuryl alcohol) and FePO4was preparedthrough the polymerization of furfuryl alcohol under heating and acidic conditions.The LiFePO_4/C composite was synthesized by an in situ polymerization restrictionmethod, and we also discussed the effect of various calcination temperatures for theelectrochemical performance. We studied the structure properties of the material usingvaries techniques including XRD, Raman, SEM and TEM. Then we studied theelectrochemical properties of the material by galvanostatic charge/discharge tests andcyclic voltammetry (CV). The material delivered a high discharge capacity of156.1mAh/g in the first cycle at0.5C, and it remained145.2mAh/g after50cycles. Thedischarge capacity retention of sample after500cycles was94.4%,90.6%,87.8%and90.9%at rates of5C,10C,20C and50C, respectively.
Thirdly, the LiFe_(0.4)Mn_(0.6)PO_4/C composite was prepared via a carbon gel process.The carbon gel process between resorcinol and formaldehyde can ensure themolecular-level homogeneity of the chemical product, and the doping of Fe~(2+)can improve the structure stability of the material. The produced carbon can effectivelyimprove the electronic conductivity. The initial discharge capacity of the electrodewas64.6mAh/g, and it remained53.8mAh/g after1000cycles.
Finally, The Li_3V_2(PO_4)_3/C composites were prepared by a combustion method.The structure properties of the material were studied by XRD, Raman, SEM and TEM.It was discussed that the effects of the content of carbon and synthesis temperature forthe electrochemical performances of the Li_3V_2(PO_4)_3/C composites by galvanostaticcharge/discharge tests. The results showed that a suitable carbon content andcalcination temperature had an important influence for the electrochemical propertiesof the material.
In short, these works give us the understanding in depth on the structure of LiFePO_4,LiMnPO_4and Li_3V_2(PO_4)_3materials, as well as their existing problems andelectrochemical properties, and the theoretical and technical guidance for the practicalapplication of the materials.
引文
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