新型多孔合金与金属氧化物锂离子电池负极材料的制备与性能研究
发布时间：2018-10-14 15:28
【摘要】：从1990年起,以碳材料为负极的锂离子电池便进入了产业化,经过近25年的发展,锂离子电池由于其高的能量密度、小的自放电、以及小的记忆效应等优点已成为最重要的可充式二次电池。然而,由于嵌锂容量小和溶剂共嵌入现象严重等缺点,以碳材料作为锂离子负极材料已经满足不了人们对高性能电池日益增长的需求。在过去的几十年中,大量的其他材料如金属、非金属和金属氧化物等被作为替代碳作为负极的材料而得到广泛研究。在这些新型材料中,锡基材料和过渡金属氧化物材料由于具有好的电化学性能和独特的嵌锂机理等特点引起广泛关注。但是它们也存在一些缺点,如这两种材料在充放电循环过程中均存在体积效应,导致材料粉化失活,另外过渡金属氧化物普遍存在导电性差的缺点。为了克服这些缺点,人们探究了许多方法。最常用的方法有纳米化、多孔化、合金化、碳复合以及结合使用以上多种方法等。本文以锡基合金和过渡金属氧化物四氧化三铁为研究对象,通过使用综合使用多孔化、合金化、碳复合等方法,成功地改善了材料的性能。第一章为绪论部分,阐述了锂离子电池的原理、应用和急需解决的问题。另外还对锂离子电池负极材料的种类及其研究进展做了全面的总结。将负极材料分为了碳材料、金属和合金材料、金属氧化物材料和非金属材料,阐述了每种材料的优缺点,并总结了改善各种材料性能所使用的方法。此部分还对本文中使用到的多孔法和碳掺杂法进行了详细的论述,介绍了这两种方法改善材料性能的原理以及应用实例。第二章介绍了实验中使用的仪器与试剂,详细阐明了制备实验材料以及对材料进行表征与测试的方法。第三章以三元锡锑基合金为研究对象,探索了改善Sn-Sb-Cu和Sn-Sb-Co这两种三元合金性能的方法。本文使用电化学溶解法处理两种样品,并以其作为锂离子电池负极材料进行了一系列的表征和测试。研究发现,经过电化学处理后的样品,其电化学性能明显高于处理前的样品,并且此种方法对Sn-Sb-Co合金性能的改善程度高于对Sn-Sb-Cu合金的改善。第四章以锡镍合金为研究对象,使用复合电化学沉积的方法制备多壁碳纳米管掺杂的锡镍合金。发现碳纳米管掺杂可以改变合金沉积形貌,提高材料导电性能和结构稳定性,对提高高锡含量合金的性能非常有益。第五章主要围绕提高过渡金属氧化物四氧化三铁的电化学性能展开。使用了多孔化与碳复合相结合的方法。首先使用氢气泡作为模板化学沉积制备了多孔铜材料,之后使用共沉积法将四氧化三铁与多壁碳纳米管沉积于多孔铜上。多孔结构为体积膨胀提供了空间,而且以多孔铜作为集流体以及掺杂多壁碳纳米管很好的提高了材料的导电性。以此材料作为锂电池负极材料,表现出了较好的循环性能与倍率性能。
[Abstract]:Since 1990, lithium ion battery with carbon material as negative electrode has entered industrialization. After nearly 25 years of development, lithium ion battery has low self-discharge due to its high energy density. And small memory effect has become the most important rechargeable secondary battery. However, because of the disadvantages of small lithium intercalation capacity and serious solvent-co-intercalation phenomenon, the increasing demand for high-performance batteries can not be met by using carbon materials as lithium ion anode materials. In the past few decades, a large number of other materials, such as metal, nonmetallic and metal oxides, have been widely studied as substitutes for carbon as negative electrode materials. Among these new materials, tin based materials and transition metal oxide materials have attracted wide attention due to their good electrochemical properties and unique lithium intercalation mechanism. However, they also have some disadvantages, such as the volume effect in charge and discharge cycle, which leads to the material powdering inactivation, and the poor conductivity of transition metal oxides. In order to overcome these shortcomings, many methods have been explored. The most commonly used methods are nanocrystalline, porous, alloying, carbon compounding and combined use. In this paper, the properties of tin based alloys and transition metal oxide ferric tetroxide have been successfully improved by comprehensive use of porous, alloying and carbon compounding methods. In the first chapter, the principle, application and urgent problems of lithium ion battery are described. In addition, the kinds of anode materials for lithium ion batteries and their research progress are summarized. The negative electrode materials are divided into carbon materials, metal and alloy materials, metal oxide materials and nonmetallic materials. The advantages and disadvantages of each material are described, and the methods used to improve the properties of various materials are summarized. In this part, the porous method and carbon doping method used in this paper are discussed in detail, and the principle and application of these two methods to improve the properties of materials are introduced. In the second chapter, the instruments and reagents used in the experiment are introduced, and the methods of preparation, characterization and measurement of the materials are described in detail. In chapter 3, the methods of improving the properties of Sn-Sb-Cu and Sn-Sb-Co ternary alloys are studied. In this paper, two kinds of samples were treated by electrochemical dissolution method, and they were used as anode materials for lithium ion batteries for a series of characterization and measurement. It is found that the electrochemical properties of the samples treated by electrochemical treatment are obviously higher than those of the samples before treatment, and the improvement of the properties of Sn-Sb-Co alloys by this method is higher than that of Sn-Sb-Cu alloys. In chapter 4, tin-nickel alloy doped with multi-wall carbon nanotubes was prepared by composite electrochemical deposition. It is found that the doping of carbon nanotubes can change the deposition morphology of the alloy and improve the conductivity and structural stability of the alloy, which is beneficial to the improvement of the properties of the alloy with high tin content. The fifth chapter focuses on improving the electrochemical performance of transition metal oxide ferric oxide. The method of combination of porous and carbon was used. Firstly, porous copper was prepared by hydrogen bubble as template, and then Fe _ 2O _ 3 and multi-walled carbon nanotubes were deposited on porous copper by co-deposition. Porous structure provides space for volume expansion, and porous copper as a fluid collector and doped multi-walled carbon nanotubes can improve the conductivity of the materials. This material is used as cathode material for lithium battery, which shows good cycling performance and rate performance.
【学位授予单位】：山东大学
【学位级别】：硕士
【学位授予年份】：2015
【分类号】：TM912
本文编号：2270874
[Abstract]:Since 1990, lithium ion battery with carbon material as negative electrode has entered industrialization. After nearly 25 years of development, lithium ion battery has low self-discharge due to its high energy density. And small memory effect has become the most important rechargeable secondary battery. However, because of the disadvantages of small lithium intercalation capacity and serious solvent-co-intercalation phenomenon, the increasing demand for high-performance batteries can not be met by using carbon materials as lithium ion anode materials. In the past few decades, a large number of other materials, such as metal, nonmetallic and metal oxides, have been widely studied as substitutes for carbon as negative electrode materials. Among these new materials, tin based materials and transition metal oxide materials have attracted wide attention due to their good electrochemical properties and unique lithium intercalation mechanism. However, they also have some disadvantages, such as the volume effect in charge and discharge cycle, which leads to the material powdering inactivation, and the poor conductivity of transition metal oxides. In order to overcome these shortcomings, many methods have been explored. The most commonly used methods are nanocrystalline, porous, alloying, carbon compounding and combined use. In this paper, the properties of tin based alloys and transition metal oxide ferric tetroxide have been successfully improved by comprehensive use of porous, alloying and carbon compounding methods. In the first chapter, the principle, application and urgent problems of lithium ion battery are described. In addition, the kinds of anode materials for lithium ion batteries and their research progress are summarized. The negative electrode materials are divided into carbon materials, metal and alloy materials, metal oxide materials and nonmetallic materials. The advantages and disadvantages of each material are described, and the methods used to improve the properties of various materials are summarized. In this part, the porous method and carbon doping method used in this paper are discussed in detail, and the principle and application of these two methods to improve the properties of materials are introduced. In the second chapter, the instruments and reagents used in the experiment are introduced, and the methods of preparation, characterization and measurement of the materials are described in detail. In chapter 3, the methods of improving the properties of Sn-Sb-Cu and Sn-Sb-Co ternary alloys are studied. In this paper, two kinds of samples were treated by electrochemical dissolution method, and they were used as anode materials for lithium ion batteries for a series of characterization and measurement. It is found that the electrochemical properties of the samples treated by electrochemical treatment are obviously higher than those of the samples before treatment, and the improvement of the properties of Sn-Sb-Co alloys by this method is higher than that of Sn-Sb-Cu alloys. In chapter 4, tin-nickel alloy doped with multi-wall carbon nanotubes was prepared by composite electrochemical deposition. It is found that the doping of carbon nanotubes can change the deposition morphology of the alloy and improve the conductivity and structural stability of the alloy, which is beneficial to the improvement of the properties of the alloy with high tin content. The fifth chapter focuses on improving the electrochemical performance of transition metal oxide ferric oxide. The method of combination of porous and carbon was used. Firstly, porous copper was prepared by hydrogen bubble as template, and then Fe _ 2O _ 3 and multi-walled carbon nanotubes were deposited on porous copper by co-deposition. Porous structure provides space for volume expansion, and porous copper as a fluid collector and doped multi-walled carbon nanotubes can improve the conductivity of the materials. This material is used as cathode material for lithium battery, which shows good cycling performance and rate performance.
【学位授予单位】：山东大学
【学位级别】：硕士
【学位授予年份】：2015
【分类号】：TM912
【参考文献】
相关期刊论文 前1条
1 刘竞;姜睿;;血红素氧合酶在去势大鼠阴茎海绵体的表达[J];中华男科学杂志;2009年03期
，本文编号：2270874
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