提高锂离子电池安全性能新型材料的合成及应用研究
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摘要
本论文研究了提高锂离子电池安全性能的两种有效途径,主要内容如下：
1.高密度磷阻燃添加剂的合成、表征及应用研究
磷杂菲是一种新型、高效、无烟、无毒、环保的有机磷系阻燃剂中间体。本文以DOPO与对苯醌和甲醛的反应制得中间体,然后和磷酰氯反应合成了两个系列的含有高密度磷的新型磷杂菲衍生物。通过1H NNR、13C NMR、31P NMR、 FT-IR、HR-MS和ESI-MS对目标产物进行了结构表征；目标产物的TGA和DSC测试结果表明材料具有良好的热稳定性；循环伏安测试结果表明产物具有优良的电化学稳定性。另外,测试了化合物a5在电解液中的燃烧实验,根据其电导率、自熄时间、燃料燃烧率和消耗率的数据,表明a5在不影响电解质电导率的条件下对锂离子电池具有显著的阻燃作用。
2.丙烯酸酯类凝胶聚合物电解质的合成及性能表征
丙烯酸酯类化合物与电解液有很好的相容性,对锂电极有较好的界面稳定性；聚丙烯酸酯的较低的玻璃化转变温度可以增强聚合物链段的运动能力,提高凝胶电解质的离子导电率。丙烯酸酯类凝胶聚合物电解质在室温下为高弹态,机械性能得到了较大的提高。
本论文以丙烯酸酯类化合物作为凝胶单体,加入液体电解液、交联剂、引发剂及其它共聚单体,采用现场热聚合工艺合成新型的交联共聚凝胶聚合物电解质。对丙烯酸酯类凝胶电解质的导电性和机械性能做了详尽的研究,发现丙烯酸酯类共聚凝胶电解质具有良好的机械性能和较高的离子电导率(高于5mS/cm)。 TGA和DSC结果表明丙烯酸酯类凝胶聚合物具有很好的热稳定性,循环伏安测试结果表明丙烯酸酯类凝胶具有良好的电化学稳定性。利用SEM研究了交联聚丙烯酸酯类凝胶的表面形貌表明他们具备了三维的孔状结构。在合成工艺方面,对现场热聚合制备交联网状的凝胶聚合物电解质的制各工艺进行了探索。由于丙烯酸酯类凝胶聚合物电解质具有导电率高、安全稳定、操作方便等优点,在结构和性能上较好的改善了锂离子液体电解质易燃易爆、漏液等安全性问题。
In this thesis, two effective ways to improve the safety performance of the lithium-ion batteries were studied. The results are as follows:
1. Synthesis, characterization and application of hight-content organic phosphorus flame retardants:
We prepared the intermediates by the reaction of DOPO with p-benzoquinone and formaldehyde, then the intermediates reacted with dialkyl phosphoryl chloride produced two series of high density phosphorus derivatives. The structures of target compounds were identified by1H NMR,13C NMR,31P NMR, FT-IR, HR-MS and ESI-MS. Take the TGA, DSC and cyclic voltammetry tests of the representative compounds al and a5, the results showed that they all have excellent thermal and electrochemical stabilities. Furthermore, we carried out the combustion experiments of compound a5, found that the lithium-ion electrolyte with compound a5displayed excellent flame retardant effect, namely have both small additive amount and high flame retardant properties.
2. Synthesis and characterization of alkyl acrylates gel polymer electrolytes for Li-ion batteries:
The polymers of alkyl acrylates have good compatibility with the electrodes, wide electrochemical window, good thermal stability and sufficient mechanical strength enabling its easy handling, etc. The lower glass transition temperature can increase the movement ability of the polymer chain, and enhance the ionic conductivity of the gel polymer electrolytes.
The gel polymer electrolytes containing alkyl acrylates, other monomers, TEGDMA and liquid electrolyte were prepared by the in-situ radical polymerization. The ionic conductivity and mechanical properties of the gel polymer electrolytes were studied in detail. The results showed that the gel copolymer electrolytes have good mechanical properties and high ionic conductivity (exceed5mS/cm). The TGA and DSC results displayed the polymers and copolymers of alkyl acrylates have excellent thermal stability. The cyclic voltammetry tests showed that they have wide electrochemical window. The dimensional network structures of the host polymer matrix of the cross-linking gel polymer electrolytes were studied using the scanning electron microscopy, and the results showed that they have three-dimensional porous structures. In the synthesis process, the in-situ thermal polymerization method was explored and studied. In a word, the alkyl acrylates gel copolymer electrolytes have high ionic conductivity, excellent stability and good mechanical property, and have the ability to enhance the safety of Li-ion batteries.
1.高密度磷阻燃添加剂的合成、表征及应用研究
磷杂菲是一种新型、高效、无烟、无毒、环保的有机磷系阻燃剂中间体。本文以DOPO与对苯醌和甲醛的反应制得中间体,然后和磷酰氯反应合成了两个系列的含有高密度磷的新型磷杂菲衍生物。通过1H NNR、13C NMR、31P NMR、 FT-IR、HR-MS和ESI-MS对目标产物进行了结构表征；目标产物的TGA和DSC测试结果表明材料具有良好的热稳定性；循环伏安测试结果表明产物具有优良的电化学稳定性。另外,测试了化合物a5在电解液中的燃烧实验,根据其电导率、自熄时间、燃料燃烧率和消耗率的数据,表明a5在不影响电解质电导率的条件下对锂离子电池具有显著的阻燃作用。
2.丙烯酸酯类凝胶聚合物电解质的合成及性能表征
丙烯酸酯类化合物与电解液有很好的相容性,对锂电极有较好的界面稳定性；聚丙烯酸酯的较低的玻璃化转变温度可以增强聚合物链段的运动能力,提高凝胶电解质的离子导电率。丙烯酸酯类凝胶聚合物电解质在室温下为高弹态,机械性能得到了较大的提高。
本论文以丙烯酸酯类化合物作为凝胶单体,加入液体电解液、交联剂、引发剂及其它共聚单体,采用现场热聚合工艺合成新型的交联共聚凝胶聚合物电解质。对丙烯酸酯类凝胶电解质的导电性和机械性能做了详尽的研究,发现丙烯酸酯类共聚凝胶电解质具有良好的机械性能和较高的离子电导率(高于5mS/cm)。 TGA和DSC结果表明丙烯酸酯类凝胶聚合物具有很好的热稳定性,循环伏安测试结果表明丙烯酸酯类凝胶具有良好的电化学稳定性。利用SEM研究了交联聚丙烯酸酯类凝胶的表面形貌表明他们具备了三维的孔状结构。在合成工艺方面,对现场热聚合制备交联网状的凝胶聚合物电解质的制各工艺进行了探索。由于丙烯酸酯类凝胶聚合物电解质具有导电率高、安全稳定、操作方便等优点,在结构和性能上较好的改善了锂离子液体电解质易燃易爆、漏液等安全性问题。
In this thesis, two effective ways to improve the safety performance of the lithium-ion batteries were studied. The results are as follows:
1. Synthesis, characterization and application of hight-content organic phosphorus flame retardants:
We prepared the intermediates by the reaction of DOPO with p-benzoquinone and formaldehyde, then the intermediates reacted with dialkyl phosphoryl chloride produced two series of high density phosphorus derivatives. The structures of target compounds were identified by1H NMR,13C NMR,31P NMR, FT-IR, HR-MS and ESI-MS. Take the TGA, DSC and cyclic voltammetry tests of the representative compounds al and a5, the results showed that they all have excellent thermal and electrochemical stabilities. Furthermore, we carried out the combustion experiments of compound a5, found that the lithium-ion electrolyte with compound a5displayed excellent flame retardant effect, namely have both small additive amount and high flame retardant properties.
2. Synthesis and characterization of alkyl acrylates gel polymer electrolytes for Li-ion batteries:
The polymers of alkyl acrylates have good compatibility with the electrodes, wide electrochemical window, good thermal stability and sufficient mechanical strength enabling its easy handling, etc. The lower glass transition temperature can increase the movement ability of the polymer chain, and enhance the ionic conductivity of the gel polymer electrolytes.
The gel polymer electrolytes containing alkyl acrylates, other monomers, TEGDMA and liquid electrolyte were prepared by the in-situ radical polymerization. The ionic conductivity and mechanical properties of the gel polymer electrolytes were studied in detail. The results showed that the gel copolymer electrolytes have good mechanical properties and high ionic conductivity (exceed5mS/cm). The TGA and DSC results displayed the polymers and copolymers of alkyl acrylates have excellent thermal stability. The cyclic voltammetry tests showed that they have wide electrochemical window. The dimensional network structures of the host polymer matrix of the cross-linking gel polymer electrolytes were studied using the scanning electron microscopy, and the results showed that they have three-dimensional porous structures. In the synthesis process, the in-situ thermal polymerization method was explored and studied. In a word, the alkyl acrylates gel copolymer electrolytes have high ionic conductivity, excellent stability and good mechanical property, and have the ability to enhance the safety of Li-ion batteries.
引文
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[3]李蔚.“品高成大器”走近佛山金银河机械设备有限公司[J].电源技术,2012,36,933-934。
[4]Karden E, Ploumen S, Fricke B, et aL Energy storage devices for future hybrid electric vehicles [J]. J. Power Sources,2007,168:2-11
[5]WakiharaM. Mater. Sci. Eng. R,2001,33:109～134
[6]Xu K, Chem. Rev.2004,104:4303～4418
[7]Takami, et al. J. Electrochem. Soc,1995,142:371-379
[8]Herstedt M, Rensmo H, Siegbahn H, et al. Electrolyte additives for enhanced thermal stability of the graphite anode interface in a Li-ion battery[J]. Electrochim.Acta,2004,49:2351～2359
[9]Hyung Y E, Vissers D R, Khalil A, J. Power Sources,2003,119:383～387
[10]Gnanaraj J S, Zinigrad E, Asraf L, et al. A Detailed Investigation of Thermal Reactions of LiPF6 Solution in Organic Carbonates Using ARC and DSC [J]. J. Electrochem. Soc,2003, 150:1533-1537
[11]Wang X M, Yamada C, Naito H, et al. J. Electrochem Soc,2006,153:135～139
[12]Ota H, Kominato A, Chun W J, et al. J. Power Sources,2003,119:393～398
[13]周代营,左晓希,谭春林,李伟善,卢雷,刘建生.电源技术[J].2007,31：687-689。
[14]Nam N D, Park I J, Kim J G, Triethyl and tributyl phosphite as flame-retarding additives in Li-ion batteries [J]. Metals and Materials International,2012,18:189～196
[15]Hyung Y E, Vissers D R, Amine K, J. Power Sources,2003,119:383～387
[16]Zhou D Y,Li WH, Tan CL, et al. J. Power Sources,2008,184:589～592
[17]Shim E G, Nam T H, Kim J G, et al. J. Power Sources,2008,175:533-539
[18]Wang Q S, Sun J H, Yao X L, Chen C H, Electrochem Solid-State Lett,2005,8:467～470
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