1,2-二（氰氨基）-3-羰基-4-环戊烯-4,5-二醇锂硼盐系列电解质的合成及性能研究
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摘要
二次锂离子电池作为一种环保、节约的新型能源,自问世以来一直倍受关注。随着社会的发展,人们的需求越来越多,然而各种资源短缺及能源匮乏,迫使人们去寻找能够满足自身发展的新型能源。二次锂离子电池与其它二次电池(如镍-氢、镍铬电池)相比,具有质量轻、工作电压高、自放电小、无记忆效应、循环寿命长、对环境污染小等优势,这便使它的应用前景更加广阔。因此,二次锂离子电池的快速、全面发展已经成为不可逆转的趋势,电化学研究者对于锂离子电池的研究也是层出不穷,尤其是最近几年中,报道出许多新型的二次锂离子电池材料。合成新型的电解质锂盐,也是锂离子电池创新的一个重要方向。作为锂离子电池中不可或缺的材料之一,电解质承载了锂离子在正、负电极间的传输工作,它的性能的优劣直接关系到锂离子电池的各项性能。所以,研制出具有高的电导率、良好的电化学及热力学稳定性、而且安全无毒的锂离子电池电解质,是开发新型锂离子电池最有效的途径之一。
本论文的主要工作,就是合成了三种含有克酮酸衍生物的锂硼盐,并对其性能进行了实验性的研究。此三种锂硼盐中的阴离子,均是以B为中心的大的螯合体系,形成了大的共轭结构,有利于阴离子的稳定,而且其中引入了强的吸电子基-NCN,更加使中心离子上的负电荷得到分散,增强了阴离子的稳定性,增大了锂硼盐在有机溶剂中的溶解度。Li+与此类阴离子结合后,更容易以离子的状态在电解液中存在,从而提高了锂硼盐的电导率。
在本论文中,研究工作主要分四步展开：首先,合成了三种含克酮酸衍生物的锂盐——1,2-二(氰氨基)-3-羰基-4-环戊烯-4,5-二醇-二氟螯合锂硼盐(DFLNBC)、1,2-二(氰氨基)-3-羰基-4-环戊烯-4,5-二醇-邻苯二酚螯合锂硼盐(BLNBC)、1,2-二(氰氨基)-3-羰基-4-环戊烯-4,5-二醇-四氟邻苯二酚螯合锂硼盐(PFLNBC)、并通过红外光谱(IR)、元素分析、电感耦合等离子体发射光谱(ICP)等方法对它们的结构分别进行了表征,其结果与目标产物基本一致。其次,分别对其热力学性质及电化学性质进行了测试,并做了初步分析。热力学性质主要是从其热稳定性、在混合有机溶剂中的溶解性来探究,电化学性质主要从其在有机溶剂中的电导率、氧化电位来探究。第三,根据测试数据,比较它们的
各项性能的优劣,得出结论,从而进一步认识该类锂硼盐的性能与其结构的关系。最后,对本文的不足之处做了分析,对锂离子电池电解质未来的发展趋势做了展望。
测试结果表明,本文成功合成了三种新型锂盐,并且它们具有较强的热力学稳定性及电化学稳定性,在几种混合有机溶剂中的溶解性较好,电导率较高,可以为该系列锂硼盐的在二次锂离子电池中的实用性作进一步研究。
As a new type of environmental protection and saving energy, the lithium-ion secondary batteries attract much attention since their appearance. People's needs become more and more with the development of the society, and becaus e the various resources shortages and energy poverty, people have to seek rene w-able energies what can meet their development needs. Compare the lithiumi-on secondary batteries with other secondary batteries (such as nickel-hydrogen battery, nickel-chromium battery), they have favorable advantages of light quali-ty, low self-discharge rate, non memory effect, long cycle life and non-pollutio-n and so on, that make them have a good prospect in application. So rapidly and all-round development of the lithium-ion secondary batteries has already become the irreversible trend. The study on the lithium-ion battery by electroc-hemical researchers is emerging in an endless way. Synthesis of novel electrol-yte lithium salt has become a new direction of development for lithium-ion ba-tteries. Electrolyte is one of the essential parts of lithium-ion battery, carrying lithium-ion transfer between positive and negative terminals. Its performance directly affects their performances. So, development of the electrolyte lithium salt which has high electric conductivity, good electrochemical stability and int-ermal domain thermal stability, and non-toxic is one of the effective ways to develop new type lithium-ion battery.
The main objective of this thesis is to synthesize three lithium borates lit-hium with croconic acid, and their properties were investigated, anions of these lithium borates salts which form large conjugated structure are B-centric large chelating anions, this structure is conducive to the stability of the anions, and we introduce strong electron-withdrawing group-NCN into the anions, that can more scatter the negative charge on the central ion, enhance the stability of the anions, and increase the solubility of lithium boron salt in organic solvents. When lithium-ion binds to this anion, it is more likely to exist in the state of ion in the electrolyte, thus the conductivity of the lithium boron salt can be improved
In the present thesis, research work mainly includes four steps:First, synt-hetic three lithium borates salt with croconic acid-Lithium difluoro [1,2-di(cy-anoamino)-3-oxo-4-cyclopentene-4,5-diol croconato] borate (DFLNBC), Lithium[1,2-benzenediolato(2)-O,O'-1,2-di(cyanoamino)-3-oxo-4-cyclopentene-4,5-diol croco-nato] borate (BLNBC), Lithium [3,4,5,6-Tetrafluorocatechol-O,O'-1,2-di(cyanoa mino)-3-oxo-4-cyclopentene-4,5-diol croconato] borate (PFLNBC). The ligands and complexes were characterized by IR, elemental analysis, ICP, and the resu-Its were roughly identical to the target products. Second, the properties of the thermodynamic and electrochemical are tested and preliminary analysized, and the properties of the thermodynamic are explored thermostability, solubility in mixed organic solvent, the properties of the electrochemical are explored from electrical conductivity in organic solvent, and its oxidative potential. Three var-ied performances of the three kinds of lithium boron salts are compared on the basis of numeral results, and some conclusions are obtained, thus further realizes relationship between the properties and structure. At last, the deficien-cy of this subject and the future of the lithium-ion secondary batteries were described.
Our test results show that three new lithium salts can be synthesized and have good thermal stability and electrochemical stability, good solubleness in some kinds of mixed organic solvents, and high conductivity, it makes sense to do further research on this series of lithium boron salts for their practical application.
本论文的主要工作,就是合成了三种含有克酮酸衍生物的锂硼盐,并对其性能进行了实验性的研究。此三种锂硼盐中的阴离子,均是以B为中心的大的螯合体系,形成了大的共轭结构,有利于阴离子的稳定,而且其中引入了强的吸电子基-NCN,更加使中心离子上的负电荷得到分散,增强了阴离子的稳定性,增大了锂硼盐在有机溶剂中的溶解度。Li+与此类阴离子结合后,更容易以离子的状态在电解液中存在,从而提高了锂硼盐的电导率。
在本论文中,研究工作主要分四步展开：首先,合成了三种含克酮酸衍生物的锂盐——1,2-二(氰氨基)-3-羰基-4-环戊烯-4,5-二醇-二氟螯合锂硼盐(DFLNBC)、1,2-二(氰氨基)-3-羰基-4-环戊烯-4,5-二醇-邻苯二酚螯合锂硼盐(BLNBC)、1,2-二(氰氨基)-3-羰基-4-环戊烯-4,5-二醇-四氟邻苯二酚螯合锂硼盐(PFLNBC)、并通过红外光谱(IR)、元素分析、电感耦合等离子体发射光谱(ICP)等方法对它们的结构分别进行了表征,其结果与目标产物基本一致。其次,分别对其热力学性质及电化学性质进行了测试,并做了初步分析。热力学性质主要是从其热稳定性、在混合有机溶剂中的溶解性来探究,电化学性质主要从其在有机溶剂中的电导率、氧化电位来探究。第三,根据测试数据,比较它们的
各项性能的优劣,得出结论,从而进一步认识该类锂硼盐的性能与其结构的关系。最后,对本文的不足之处做了分析,对锂离子电池电解质未来的发展趋势做了展望。
测试结果表明,本文成功合成了三种新型锂盐,并且它们具有较强的热力学稳定性及电化学稳定性,在几种混合有机溶剂中的溶解性较好,电导率较高,可以为该系列锂硼盐的在二次锂离子电池中的实用性作进一步研究。
As a new type of environmental protection and saving energy, the lithium-ion secondary batteries attract much attention since their appearance. People's needs become more and more with the development of the society, and becaus e the various resources shortages and energy poverty, people have to seek rene w-able energies what can meet their development needs. Compare the lithiumi-on secondary batteries with other secondary batteries (such as nickel-hydrogen battery, nickel-chromium battery), they have favorable advantages of light quali-ty, low self-discharge rate, non memory effect, long cycle life and non-pollutio-n and so on, that make them have a good prospect in application. So rapidly and all-round development of the lithium-ion secondary batteries has already become the irreversible trend. The study on the lithium-ion battery by electroc-hemical researchers is emerging in an endless way. Synthesis of novel electrol-yte lithium salt has become a new direction of development for lithium-ion ba-tteries. Electrolyte is one of the essential parts of lithium-ion battery, carrying lithium-ion transfer between positive and negative terminals. Its performance directly affects their performances. So, development of the electrolyte lithium salt which has high electric conductivity, good electrochemical stability and int-ermal domain thermal stability, and non-toxic is one of the effective ways to develop new type lithium-ion battery.
The main objective of this thesis is to synthesize three lithium borates lit-hium with croconic acid, and their properties were investigated, anions of these lithium borates salts which form large conjugated structure are B-centric large chelating anions, this structure is conducive to the stability of the anions, and we introduce strong electron-withdrawing group-NCN into the anions, that can more scatter the negative charge on the central ion, enhance the stability of the anions, and increase the solubility of lithium boron salt in organic solvents. When lithium-ion binds to this anion, it is more likely to exist in the state of ion in the electrolyte, thus the conductivity of the lithium boron salt can be improved
In the present thesis, research work mainly includes four steps:First, synt-hetic three lithium borates salt with croconic acid-Lithium difluoro [1,2-di(cy-anoamino)-3-oxo-4-cyclopentene-4,5-diol croconato] borate (DFLNBC), Lithium[1,2-benzenediolato(2)-O,O'-1,2-di(cyanoamino)-3-oxo-4-cyclopentene-4,5-diol croco-nato] borate (BLNBC), Lithium [3,4,5,6-Tetrafluorocatechol-O,O'-1,2-di(cyanoa mino)-3-oxo-4-cyclopentene-4,5-diol croconato] borate (PFLNBC). The ligands and complexes were characterized by IR, elemental analysis, ICP, and the resu-Its were roughly identical to the target products. Second, the properties of the thermodynamic and electrochemical are tested and preliminary analysized, and the properties of the thermodynamic are explored thermostability, solubility in mixed organic solvent, the properties of the electrochemical are explored from electrical conductivity in organic solvent, and its oxidative potential. Three var-ied performances of the three kinds of lithium boron salts are compared on the basis of numeral results, and some conclusions are obtained, thus further realizes relationship between the properties and structure. At last, the deficien-cy of this subject and the future of the lithium-ion secondary batteries were described.
Our test results show that three new lithium salts can be synthesized and have good thermal stability and electrochemical stability, good solubleness in some kinds of mixed organic solvents, and high conductivity, it makes sense to do further research on this series of lithium boron salts for their practical application.
引文
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