【摘要】：從1990年起,以碳材料為負(fù)極的鋰離子電池便進(jìn)入了產(chǎn)業(yè)化,經(jīng)過近25年的發(fā)展,鋰離子電池由于其高的能量密度、小的自放電、以及小的記憶效應(yīng)等優(yōu)點(diǎn)已成為最重要的可充式二次電池。然而,由于嵌鋰容量小和溶劑共嵌入現(xiàn)象嚴(yán)重等缺點(diǎn),以碳材料作為鋰離子負(fù)極材料已經(jīng)滿足不了人們對(duì)高性能電池日益增長(zhǎng)的需求。在過去的幾十年中,大量的其他材料如金屬、非金屬和金屬氧化物等被作為替代碳作為負(fù)極的材料而得到廣泛研究。在這些新型材料中,錫基材料和過渡金屬氧化物材料由于具有好的電化學(xué)性能和獨(dú)特的嵌鋰機(jī)理等特點(diǎn)引起廣泛關(guān)注。但是它們也存在一些缺點(diǎn),如這兩種材料在充放電循環(huán)過程中均存在體積效應(yīng),導(dǎo)致材料粉化失活,另外過渡金屬氧化物普遍存在導(dǎo)電性差的缺點(diǎn)。為了克服這些缺點(diǎn),人們探究了許多方法。最常用的方法有納米化、多孔化、合金化、碳復(fù)合以及結(jié)合使用以上多種方法等。本文以錫基合金和過渡金屬氧化物四氧化三鐵為研究對(duì)象,通過使用綜合使用多孔化、合金化、碳復(fù)合等方法,成功地改善了材料的性能。第一章為緒論部分,闡述了鋰離子電池的原理、應(yīng)用和急需解決的問題。另外還對(duì)鋰離子電池負(fù)極材料的種類及其研究進(jìn)展做了全面的總結(jié)。將負(fù)極材料分為了碳材料、金屬和合金材料、金屬氧化物材料和非金屬材料,闡述了每種材料的優(yōu)缺點(diǎn),并總結(jié)了改善各種材料性能所使用的方法。此部分還對(duì)本文中使用到的多孔法和碳摻雜法進(jìn)行了詳細(xì)的論述,介紹了這兩種方法改善材料性能的原理以及應(yīng)用實(shí)例。第二章介紹了實(shí)驗(yàn)中使用的儀器與試劑,詳細(xì)闡明了制備實(shí)驗(yàn)材料以及對(duì)材料進(jìn)行表征與測(cè)試的方法。第三章以三元錫銻基合金為研究對(duì)象,探索了改善Sn-Sb-Cu和Sn-Sb-Co這兩種三元合金性能的方法。本文使用電化學(xué)溶解法處理兩種樣品,并以其作為鋰離子電池負(fù)極材料進(jìn)行了一系列的表征和測(cè)試。研究發(fā)現(xiàn),經(jīng)過電化學(xué)處理后的樣品,其電化學(xué)性能明顯高于處理前的樣品,并且此種方法對(duì)Sn-Sb-Co合金性能的改善程度高于對(duì)Sn-Sb-Cu合金的改善。第四章以錫鎳合金為研究對(duì)象,使用復(fù)合電化學(xué)沉積的方法制備多壁碳納米管摻雜的錫鎳合金。發(fā)現(xiàn)碳納米管摻雜可以改變合金沉積形貌,提高材料導(dǎo)電性能和結(jié)構(gòu)穩(wěn)定性,對(duì)提高高錫含量合金的性能非常有益。第五章主要圍繞提高過渡金屬氧化物四氧化三鐵的電化學(xué)性能展開。使用了多孔化與碳復(fù)合相結(jié)合的方法。首先使用氫氣泡作為模板化學(xué)沉積制備了多孔銅材料,之后使用共沉積法將四氧化三鐵與多壁碳納米管沉積于多孔銅上。多孔結(jié)構(gòu)為體積膨脹提供了空間,而且以多孔銅作為集流體以及摻雜多壁碳納米管很好的提高了材料的導(dǎo)電性。以此材料作為鋰電池負(fù)極材料,表現(xiàn)出了較好的循環(huán)性能與倍率性能。
[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.
【學(xué)位授予單位】：山東大學(xué)
【學(xué)位級(jí)別】：碩士
【學(xué)位授予年份】：2015
【分類號(hào)】：TM912

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相關(guān)期刊論文 前1條

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本文編號(hào)：2270874