鈦基鈉離子電池負(fù)極材料的合成與表征
發(fā)布時(shí)間：2019-01-08 17:41
【摘要】：得益于較高的能量密度和轉(zhuǎn)化效率,鋰離子電池已經(jīng)被廣泛地應(yīng)用于便攜式電子設(shè)備和電動(dòng)交通工具中。近年來(lái),可再生清潔能源的迅猛發(fā)展,推動(dòng)了儲(chǔ)能技術(shù)的革新。與鋰離子電池相比,鈉離子電池能量密度略低,但由于其擁有更豐富的資源儲(chǔ)量和更低的成本,成為了當(dāng)下儲(chǔ)能技術(shù)領(lǐng)域研究的熱點(diǎn)。若實(shí)現(xiàn)循環(huán)壽命的突破,它將成為新一代儲(chǔ)能電池的有力競(jìng)爭(zhēng)者。在鈉離子電池負(fù)極體系中,鈦基鈉離子電池負(fù)極材料多為嵌入式反應(yīng)機(jī)理,擁有結(jié)構(gòu)穩(wěn)定、體積變化較小、種類繁多等優(yōu)勢(shì),但此類材料通常本征電導(dǎo)率較低,循環(huán)和倍率性能仍有待提高。本論文重點(diǎn)圍繞鈦基鈉離子電池負(fù)極材料中的Na2Ti307和P2型Na0.66[Li0.22Ti0.78]O2進(jìn)行了制備與改性的研究。第一章首先介紹了鈉離子電池的發(fā)展歷程、工作原理和關(guān)鍵組成部分。另外,還對(duì)鈉離子電池的正負(fù)極材料進(jìn)行了詳細(xì)的介紹。重點(diǎn)介紹了幾類脫嵌反應(yīng)機(jī)理的正負(fù)極材料,并結(jié)合其發(fā)展近況論述了本文的研究背景與選題思路。第二章介紹了本論文中所使用的試劑材料以及儀器設(shè)備,并詳細(xì)說(shuō)明了鋰/鈉鋰離子電池的組裝方法及電化學(xué)性能測(cè)試。第三章采用一種簡(jiǎn)單的濕化學(xué)工藝路線,成功地制備出了鈦基鈉離子電池負(fù)極材料:原位碳網(wǎng)絡(luò)復(fù)合的Na2Ti307。與傳統(tǒng)的水熱法和固相反應(yīng)法相比,該方法條件更加溫和,并能充分利用原料鈦酸四丁酯中的有機(jī)官能團(tuán),無(wú)需添加額外的碳源,即可在材料表面獲得均勻的原位碳網(wǎng)絡(luò)。原位碳網(wǎng)絡(luò)的存在,顯著提高了材料的循環(huán)和倍率性能。第四章采用第三章的方法,成功地制備出了另一種鈦基鈉離子電池負(fù)極材料:原位碳網(wǎng)絡(luò)復(fù)合的Na0.66[Li0.22Ti0.78]O2。通過(guò)優(yōu)化通氣速率與煅燒溫度,解決了由于管式爐在高溫下漏氣而導(dǎo)致產(chǎn)物無(wú)法殘?zhí)嫉膯?wèn)題,成功在材料表面獲得了原位碳網(wǎng)絡(luò)。此外,本章還對(duì)該材料首次放電容量的構(gòu)成進(jìn)行了分析。最后,為了進(jìn)一步提高材料電子導(dǎo)電性,我們對(duì)材料開展了碳包覆以及與碳納米管的復(fù)合探索,發(fā)現(xiàn)改性后樣品在首次庫(kù)倫效率維持不變,但其倍率性能顯著提高,各倍率下比容量均提高了 10 mAh g-1以上。第五章首次利用丙烯酸熱聚合方法制備了高容量鋰離子電池負(fù)極材料Li2MoO4,并采用了一種簡(jiǎn)單的方法對(duì)其進(jìn)行了均勻的碳包覆,改性后材料循環(huán)和倍率性能明顯提高。第六章總結(jié)歸納了本論文的創(chuàng)新和不足,并對(duì)未來(lái)研究工作進(jìn)行了展望。
[Abstract]:Lithium ion batteries have been widely used in portable electronic devices and electric vehicles due to their high energy density and conversion efficiency. In recent years, the rapid development of renewable clean energy has promoted the innovation of energy storage technology. Compared with lithium-ion batteries, the energy density of sodium ion batteries is slightly lower, but it has become a hot spot in the field of energy storage technology because of its abundant resource reserves and lower cost. If the cycle life breakthrough is realized, it will become a powerful competitor of the new generation energy storage battery. In the negative electrode system of sodium ion battery, titanium based sodium ion battery anode materials are embedded reaction mechanism, have the advantages of stable structure, small volume change, various kinds of materials, but the intrinsic conductivity of such materials is usually low. Cycle and rate performance still need to be improved. In this thesis, the preparation and modification of Na2Ti307 and P2 type Na0.66 [Li0.22Ti0.78] O2 in anode materials of titanium-based sodium ion batteries were studied. In the first chapter, the development, working principle and key components of sodium ion battery are introduced. In addition, the anode and negative materials of sodium ion battery are introduced in detail. Several kinds of positive and negative materials for deintercalation reaction mechanism are introduced, and the research background and topics of this paper are discussed in the light of their recent development. In the second chapter, the reagents and equipments used in this thesis are introduced, and the assembly method and electrochemical performance test of lithium / sodium lithium ion battery are described in detail. In chapter 3, a simple wet chemical process was used to successfully prepare the anode material of titanium based sodium ion battery: in situ carbon network composite Na2Ti307.. Compared with the traditional hydrothermal method and solid state reaction method, the conditions of this method are more mild, and the organic functional groups in tetrabutyl titanate can be fully utilized, and a homogeneous in-situ carbon network can be obtained on the material surface without adding additional carbon sources. The existence of in situ carbon network improves the cycling and rate performance of the material. In chapter 4, we successfully fabricate another kind of anode material of titanium-based sodium ion battery, Na0.66 [Li0.22Ti0.78] O2, which is composed of in situ carbon network. By optimizing the ventilation rate and calcination temperature, the problem that the product can not remain carbon due to the leakage of gas in the tube furnace at high temperature was solved, and the in-situ carbon network was successfully obtained on the surface of the material. In addition, the composition of the first discharge capacity of the material is analyzed in this chapter. Finally, in order to further improve the electronic conductivity of the materials, we explored the carbon coating and the composite with carbon nanotubes. It was found that the first Coulomb efficiency of the modified samples remained unchanged, but the rate performance of the modified samples was significantly improved. The specific capacity was increased by more than 10 mAh g ~ (-1). In chapter 5, the high capacity lithium ion battery anode material Li2MoO4, was prepared by thermal polymerization of acrylic acid for the first time, and a simple method was used to cover it uniformly. The cyclic and rate properties of the modified materials were improved obviously. The sixth chapter summarizes the innovation and deficiency of this paper, and prospects the future research work.
【學(xué)位授予單位】：中國(guó)科學(xué)技術(shù)大學(xué)
【學(xué)位級(jí)別】：碩士
【學(xué)位授予年份】：2017
【分類號(hào)】：TM912
本文編號(hào)：2404922
[Abstract]:Lithium ion batteries have been widely used in portable electronic devices and electric vehicles due to their high energy density and conversion efficiency. In recent years, the rapid development of renewable clean energy has promoted the innovation of energy storage technology. Compared with lithium-ion batteries, the energy density of sodium ion batteries is slightly lower, but it has become a hot spot in the field of energy storage technology because of its abundant resource reserves and lower cost. If the cycle life breakthrough is realized, it will become a powerful competitor of the new generation energy storage battery. In the negative electrode system of sodium ion battery, titanium based sodium ion battery anode materials are embedded reaction mechanism, have the advantages of stable structure, small volume change, various kinds of materials, but the intrinsic conductivity of such materials is usually low. Cycle and rate performance still need to be improved. In this thesis, the preparation and modification of Na2Ti307 and P2 type Na0.66 [Li0.22Ti0.78] O2 in anode materials of titanium-based sodium ion batteries were studied. In the first chapter, the development, working principle and key components of sodium ion battery are introduced. In addition, the anode and negative materials of sodium ion battery are introduced in detail. Several kinds of positive and negative materials for deintercalation reaction mechanism are introduced, and the research background and topics of this paper are discussed in the light of their recent development. In the second chapter, the reagents and equipments used in this thesis are introduced, and the assembly method and electrochemical performance test of lithium / sodium lithium ion battery are described in detail. In chapter 3, a simple wet chemical process was used to successfully prepare the anode material of titanium based sodium ion battery: in situ carbon network composite Na2Ti307.. Compared with the traditional hydrothermal method and solid state reaction method, the conditions of this method are more mild, and the organic functional groups in tetrabutyl titanate can be fully utilized, and a homogeneous in-situ carbon network can be obtained on the material surface without adding additional carbon sources. The existence of in situ carbon network improves the cycling and rate performance of the material. In chapter 4, we successfully fabricate another kind of anode material of titanium-based sodium ion battery, Na0.66 [Li0.22Ti0.78] O2, which is composed of in situ carbon network. By optimizing the ventilation rate and calcination temperature, the problem that the product can not remain carbon due to the leakage of gas in the tube furnace at high temperature was solved, and the in-situ carbon network was successfully obtained on the surface of the material. In addition, the composition of the first discharge capacity of the material is analyzed in this chapter. Finally, in order to further improve the electronic conductivity of the materials, we explored the carbon coating and the composite with carbon nanotubes. It was found that the first Coulomb efficiency of the modified samples remained unchanged, but the rate performance of the modified samples was significantly improved. The specific capacity was increased by more than 10 mAh g ~ (-1). In chapter 5, the high capacity lithium ion battery anode material Li2MoO4, was prepared by thermal polymerization of acrylic acid for the first time, and a simple method was used to cover it uniformly. The cyclic and rate properties of the modified materials were improved obviously. The sixth chapter summarizes the innovation and deficiency of this paper, and prospects the future research work.
【學(xué)位授予單位】：中國(guó)科學(xué)技術(shù)大學(xué)
【學(xué)位級(jí)別】：碩士
【學(xué)位授予年份】：2017
【分類號(hào)】：TM912
【參考文獻(xiàn)】
相關(guān)期刊論文 前1條
1 張晶晶;余愛(ài)水;;納米結(jié)構(gòu)過(guò)渡金屬氧化物作為鋰離子電池負(fù)極材料（英文）[J];Science Bulletin;2015年09期
，本文編號(hào)：2404922
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