锂离子超级电容器的研究
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(2) To improve solid phase method get Li4Ti5O12 materials as the foundation, study the TiN surface modification on the electrochemical performance influence. The results show that surface modification TiN can obviously improve the conductivity of the Li4Ti5O12 materials, rate of performance and circle life
硕士学位论文
论文题目
锂离子超级电容器的研究
研究生姓名 指导教师姓名 专业名称 研究方向 论文提交日期
刘旭 郑军伟 高分子化学与物理 超级电容器 2012-04-01
锂离子超级电容器的研究
中文摘要
中Baidu Nhomakorabea摘要
超级电容器是一种高功率密度的无源储能元件，随着它的问世，如何应用好超级
电容器，是科技工作者的一个热门话题。超级电容器具有充放电速度快、效率高、循
参考文献 ·······················································································51 总结 ···································································································53 致 谢································································································54
第四章 Li4Ti5O12/Graphite 混合型电容器的充放电研究 ································44 4-1 前 言 ····················································································44 4-2 实验部分 ·················································································45 4-3 结果与讨论 ··············································································46 4-4 小 结 ····················································································51
Abstract
Supercapacitor is a kind of high power density of passive energy storage devices, along with its coming out, how to apply supercapacitor well is a hot topic for the workers. Supercapacitor with charge and discharge speed, high efficiency and long cycling life, wide working temperature range, good reliability, and many other advantages, but with the traditional secondary battery than such as lithium ion battery, supercapacitor energy density is lower.
（3）以 Li4Ti5O12 为负极，以石墨为正极，探究出了一种性能更好的体系，得到 了比较理想的超级电容器。
关键词：超级电容器；活性炭；锂离子二次电池； Li4Ti5O12
作者：刘 旭
指导老师：郑军伟 教授
I
Abstract
锂离子超级电容器的研究
The performance research of Lithium-ion supercapacitors
(3) To Li4Ti5O12 for negative with graphite as positive, explore a performance with better system, obtained the ideal supercapacitors.
Key words: Supercapacitors；Active carbon；Li-ion battery; Li4Ti5O12
(1) The active carbon electrode for symmetry, with 1 mol/L LiPF6 / EC + DEC (volume ratio of 1 to 1) for the electrolyte, with different positive and negative electrode than quality, get the best capacitors
第二章 有机体系碳基双电层电容器的性能研究···········································24 2-1 前 言 ····················································································24 2-2 实验部分 ·················································································26 2-3 结果与讨论 ··············································································26 2-4 小 结 ····················································································29 参考文献 ·······················································································29
（1）采用活性炭为对称性电极，以 1mol/L LiPF6/EC+DEC(体积比 1:1)为电解液， 用不同的正负电极质量比，获得最佳的电容器
（2）以改进的固相法得到的 Li4Ti5O12 材料为基础，研究了 TiN 表面修饰对其电 化学性能的影响。结果表明：表面修饰 TiN 能够显著提高 Li4Ti5O12 材料的导电性， 倍率性能和循环寿命。
Written by Xu Liu Supervised by Prof. Junwei Zheng
II
目录
第一章 绪 论 ·····················································································1 1-1 超级电容器概述 ········································································1 1-2 超级电容器的介绍 ·····································································4 1-3 混合型超级电容器研究进展 ·························································10 1-4 锂离子电池简介 ········································································14 1-5 锂离子电池的组成及工作原理·······················································16 1-6 锂离子电池主要材料的研究现状····················································17 1-7 本论文的研究目的及设想 ····························································19 参考文献 ·······················································································20
This research mainly by using traditional methods to make it to the symmetry of activated carbon electrode capacitor, and with graphite, Li4Ti5O12 replace an activated carbon electrode asymmetry of the capacitor made the contrast, try to get higher energy density, circle life better super capacitors. The main contents are as follows:
环寿命长、工作温度范围宽、可靠性好等诸多优点，但是与传统的二次电池如锂离子
电池相比，超级电容器的能量密度较低。
本研究主要通过用传统方法做成了以活性碳为电极的对称性电容器，和以石墨、
Li4Ti5O12取代一个活性炭电极的非对称性电容器做了对比，尝试得到能量密度更高、 循环寿命更好的超级电容器。主要研究内容如下：
第三章 锂离子电池负极材料 Li4Ti5O12 的合成及性能研究 ····························31 3-1 尖晶石型 Li4Ti5O12 负极材料的研究现状··········································31 3-2 实验部分 ··················································································35 3-3 结果与讨论 ···············································································36 3-4 小 结 ·····················································································41 参考文献 ·······················································································42
锂离子超级电容器的研究
第一章
第一章 绪 论
1.1 超级电容器概述 能源是人类社会生存和发展的基础，发展新能源、研究新材料是 21 世纪亟待解 决的重大课题。由于石油资源日益短缺，并且燃烧石油的内燃机尾气排放对环境的污 染越来越严重（尤其是在大、中城市），人们都在研究各种类型的新型储能装置。已 经进行了混合动力、燃料电池、化学电池产品的应用及研究与开发，取得了一定的成 效。随着微电子技术的迅猛发展，各种计算机和微型数码产品有关的电子设备、医疗 设备、家用电器及移动通讯设备的逐渐普及，对高性能存储设备用电源的需求越来越 严格。但是由于它们固有的使用寿命短、温度特性差、化学电池环境污染、系统复杂、 造价高昂等致命弱点，一直没有很好的解决办法。而超级电容器以其优异的特性扬长 避短，可以部分或全部替代传统的化学电池用于车辆的牵引电源和启动能源，并且具 有比传统的化学电池更加广泛的用途。这些储能装置除对能源密度有一定要求外，对 功率密度的要求越来越高。传统电容器虽然可以提供非常大的功率，但其功率密度极 其有限，不能满足实际需要。同时随着科技和社会的发展，许多场合如电动汽车等对 电源功率的要求越来越高，也远远超出了当今电池的承受能力。在此背景下，超级电 容器以其自身的优势引起了越来越多研究人员的关注。 电容器是一种能够储蓄电能的设备与器件，由于它的使用能避免电子仪器与设备 因电源瞬间切断或电压偶尔降低而产生的错误动作，所以它作为备用电源被广泛应用 于电子仪器设备:调谐器、电话机、传真机及计算机等通讯设备和家用电器中。电容 器的研究是从 20 世纪 30 年代开始的，随着电子业的发展，先后经历了电解电容器、 瓷介电容器、有机薄膜电容器、铝电解电容器、担电解电容器和电化学电容器的发展。 电容器的发展可以分为下面几个重要的阶段：（1）1879 年 Helmholz 发现了电极/电 解质界面的双电层电容性质，双电层电容器是最先出现的电化学电容器。（2）自从 1954 年 Becker 申请了活性炭作电极材料的双电层电容器专利[1]到现在，超级电容器 己有近 50 多年的发展历史。由经典电化学电极界面双电层原理可知，在一定浓度电 解液中的电极/电解液界面形成的双电层厚度是非常小的，而双电层电容远远高于普
硕士学位论文
论文题目
锂离子超级电容器的研究
研究生姓名 指导教师姓名 专业名称 研究方向 论文提交日期
刘旭 郑军伟 高分子化学与物理 超级电容器 2012-04-01
锂离子超级电容器的研究
中文摘要
中Baidu Nhomakorabea摘要
超级电容器是一种高功率密度的无源储能元件，随着它的问世，如何应用好超级
电容器，是科技工作者的一个热门话题。超级电容器具有充放电速度快、效率高、循
参考文献 ·······················································································51 总结 ···································································································53 致 谢································································································54
第四章 Li4Ti5O12/Graphite 混合型电容器的充放电研究 ································44 4-1 前 言 ····················································································44 4-2 实验部分 ·················································································45 4-3 结果与讨论 ··············································································46 4-4 小 结 ····················································································51
Abstract
Supercapacitor is a kind of high power density of passive energy storage devices, along with its coming out, how to apply supercapacitor well is a hot topic for the workers. Supercapacitor with charge and discharge speed, high efficiency and long cycling life, wide working temperature range, good reliability, and many other advantages, but with the traditional secondary battery than such as lithium ion battery, supercapacitor energy density is lower.
（3）以 Li4Ti5O12 为负极，以石墨为正极，探究出了一种性能更好的体系，得到 了比较理想的超级电容器。
关键词：超级电容器；活性炭；锂离子二次电池； Li4Ti5O12
作者：刘 旭
指导老师：郑军伟 教授
I
Abstract
锂离子超级电容器的研究
The performance research of Lithium-ion supercapacitors
(3) To Li4Ti5O12 for negative with graphite as positive, explore a performance with better system, obtained the ideal supercapacitors.
Key words: Supercapacitors；Active carbon；Li-ion battery; Li4Ti5O12
(1) The active carbon electrode for symmetry, with 1 mol/L LiPF6 / EC + DEC (volume ratio of 1 to 1) for the electrolyte, with different positive and negative electrode than quality, get the best capacitors
第二章 有机体系碳基双电层电容器的性能研究···········································24 2-1 前 言 ····················································································24 2-2 实验部分 ·················································································26 2-3 结果与讨论 ··············································································26 2-4 小 结 ····················································································29 参考文献 ·······················································································29
（1）采用活性炭为对称性电极，以 1mol/L LiPF6/EC+DEC(体积比 1:1)为电解液， 用不同的正负电极质量比，获得最佳的电容器
（2）以改进的固相法得到的 Li4Ti5O12 材料为基础，研究了 TiN 表面修饰对其电 化学性能的影响。结果表明：表面修饰 TiN 能够显著提高 Li4Ti5O12 材料的导电性， 倍率性能和循环寿命。
Written by Xu Liu Supervised by Prof. Junwei Zheng
II
目录
第一章 绪 论 ·····················································································1 1-1 超级电容器概述 ········································································1 1-2 超级电容器的介绍 ·····································································4 1-3 混合型超级电容器研究进展 ·························································10 1-4 锂离子电池简介 ········································································14 1-5 锂离子电池的组成及工作原理·······················································16 1-6 锂离子电池主要材料的研究现状····················································17 1-7 本论文的研究目的及设想 ····························································19 参考文献 ·······················································································20
This research mainly by using traditional methods to make it to the symmetry of activated carbon electrode capacitor, and with graphite, Li4Ti5O12 replace an activated carbon electrode asymmetry of the capacitor made the contrast, try to get higher energy density, circle life better super capacitors. The main contents are as follows:
环寿命长、工作温度范围宽、可靠性好等诸多优点，但是与传统的二次电池如锂离子
电池相比，超级电容器的能量密度较低。
本研究主要通过用传统方法做成了以活性碳为电极的对称性电容器，和以石墨、
Li4Ti5O12取代一个活性炭电极的非对称性电容器做了对比，尝试得到能量密度更高、 循环寿命更好的超级电容器。主要研究内容如下：
第三章 锂离子电池负极材料 Li4Ti5O12 的合成及性能研究 ····························31 3-1 尖晶石型 Li4Ti5O12 负极材料的研究现状··········································31 3-2 实验部分 ··················································································35 3-3 结果与讨论 ···············································································36 3-4 小 结 ·····················································································41 参考文献 ·······················································································42
锂离子超级电容器的研究
第一章
第一章 绪 论
1.1 超级电容器概述 能源是人类社会生存和发展的基础，发展新能源、研究新材料是 21 世纪亟待解 决的重大课题。由于石油资源日益短缺，并且燃烧石油的内燃机尾气排放对环境的污 染越来越严重（尤其是在大、中城市），人们都在研究各种类型的新型储能装置。已 经进行了混合动力、燃料电池、化学电池产品的应用及研究与开发，取得了一定的成 效。随着微电子技术的迅猛发展，各种计算机和微型数码产品有关的电子设备、医疗 设备、家用电器及移动通讯设备的逐渐普及，对高性能存储设备用电源的需求越来越 严格。但是由于它们固有的使用寿命短、温度特性差、化学电池环境污染、系统复杂、 造价高昂等致命弱点，一直没有很好的解决办法。而超级电容器以其优异的特性扬长 避短，可以部分或全部替代传统的化学电池用于车辆的牵引电源和启动能源，并且具 有比传统的化学电池更加广泛的用途。这些储能装置除对能源密度有一定要求外，对 功率密度的要求越来越高。传统电容器虽然可以提供非常大的功率，但其功率密度极 其有限，不能满足实际需要。同时随着科技和社会的发展，许多场合如电动汽车等对 电源功率的要求越来越高，也远远超出了当今电池的承受能力。在此背景下，超级电 容器以其自身的优势引起了越来越多研究人员的关注。 电容器是一种能够储蓄电能的设备与器件，由于它的使用能避免电子仪器与设备 因电源瞬间切断或电压偶尔降低而产生的错误动作，所以它作为备用电源被广泛应用 于电子仪器设备:调谐器、电话机、传真机及计算机等通讯设备和家用电器中。电容 器的研究是从 20 世纪 30 年代开始的，随着电子业的发展，先后经历了电解电容器、 瓷介电容器、有机薄膜电容器、铝电解电容器、担电解电容器和电化学电容器的发展。 电容器的发展可以分为下面几个重要的阶段：（1）1879 年 Helmholz 发现了电极/电 解质界面的双电层电容性质，双电层电容器是最先出现的电化学电容器。（2）自从 1954 年 Becker 申请了活性炭作电极材料的双电层电容器专利[1]到现在，超级电容器 己有近 50 多年的发展历史。由经典电化学电极界面双电层原理可知，在一定浓度电 解液中的电极/电解液界面形成的双电层厚度是非常小的，而双电层电容远远高于普