离子液体作为电解质在电化学领域中的应用及前景
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摘要
锂离子电池自1991年索尼公司成功商业化以来,由于其具有能量密度大、工作电压高、循环寿命长等优点,成为最受青睐的二次电池。新世纪面临能源短缺和环境污染两大难题,迫切需要发展高功率和大容量的锂离子电池,以满足节能环保型动力汽车或混合动力汽车以及储能电池的要求。研制和开发高比能量、价格便宜、安全可靠的新一代锂离子电池是近几年来化学电源研究领域的焦点之一。经过近二十年的发展,锂离子电池已在移动电话、笔记本电脑、数码相机等便携式电子设备上得到广泛应用。但迄今为止,锂离子电池还不能满足动力锂离子电池的要求,主要存在安全性和稳定性问题,因为在有机电解质中含有挥发性溶剂,这些溶剂分解挥发,可以使电池的内部压力急剧增加,导致电解液分解,电解液泄漏,引起爆炸燃烧,造成极大的安全隐患。因此,使用新的体系来代替易挥发和可燃的电解质就显得尤为重要。
离子液体应用于锂离子电池电解质,其最吸引人的特点是:较宽的液体范围、较强的溶解能力、较低的蒸气压、较合适的黏度、较高的导电性、较宽的电化学窗口等等。以上这些优点使其存在广阔的应用前景,近年来,离子液体的合成及应用已经成为一个研究热点。离子液体发展到现在已经有两个世纪的历史,关于离子液体的合成及工业化方面的综述也很多,但是离子液体作为电解质在电化学领域应用文献的综述极少,本文就近十年来离子液体作为电解质在电化学领域的应用及前景做了相关的综述。
Lithium-ion batteries become the most widely used secondary batteries, oweing to its high energy density, high voltage and long cycling life, since it has been developed successfully by SONY corporation in 1991. It is well known that there are two major problems of energy crisis and environmental pollution in the new century. So the urgent need is to develop high power and high-capacity lithium-ion batteries to meet the requirements of the energy saving environmental electric vehicles or hybrid vehicles and energy storage battery. It is the focus research that develop the high specific energy, cheap, safe and reliable lithium-ion battery as a new generation of chemical power in recent years. After nearly two decades development, lithium-ion batteries are used in mobile phones, laptop computers, digital cameras and other portable electronic devices widely. But until now, lithium-ion batteries can not meet the requirements of lithium-ion power battery, it’s main issue is lack of security and stability, exothermic reactions of lithium-ion batteries containing organic electrolyte include the decomposition of electrolyte and electrolyte and Electrode reaction, in the initial stage of thermal runaway. the accelerating of exothermic have accelerated the increasing of heat, These solvents can make pressure increase dramatically in battery of internal as a result of containing volatile dissolvent in organic electrolytes. It can lead to explosion of battery Therefore, it is particularly important that the new system replace volatile and combustible electrolytes.Ionic liquid can be used as the ideal battery electrolyte.
The most attractive features are: wide range of liquid stable, strong solvency, lower vapor pressure, high conductivity, strong catalytic activity, etc. The existence of these advantages make their broad application prospects .In recent years, synthesis and application of ionic liquids have become a hot topic. Until now, there are two centuries in the development of ionic liquids. There are also many synthesis and industrialization of ionic liquids But the article of application of the ionic liquids as electrolytes in electrochemical synthesis were very few. This article is review article about the field of the ionic liquids as electrolytes in electrochemical applications and prospects.
离子液体应用于锂离子电池电解质,其最吸引人的特点是:较宽的液体范围、较强的溶解能力、较低的蒸气压、较合适的黏度、较高的导电性、较宽的电化学窗口等等。以上这些优点使其存在广阔的应用前景,近年来,离子液体的合成及应用已经成为一个研究热点。离子液体发展到现在已经有两个世纪的历史,关于离子液体的合成及工业化方面的综述也很多,但是离子液体作为电解质在电化学领域应用文献的综述极少,本文就近十年来离子液体作为电解质在电化学领域的应用及前景做了相关的综述。
Lithium-ion batteries become the most widely used secondary batteries, oweing to its high energy density, high voltage and long cycling life, since it has been developed successfully by SONY corporation in 1991. It is well known that there are two major problems of energy crisis and environmental pollution in the new century. So the urgent need is to develop high power and high-capacity lithium-ion batteries to meet the requirements of the energy saving environmental electric vehicles or hybrid vehicles and energy storage battery. It is the focus research that develop the high specific energy, cheap, safe and reliable lithium-ion battery as a new generation of chemical power in recent years. After nearly two decades development, lithium-ion batteries are used in mobile phones, laptop computers, digital cameras and other portable electronic devices widely. But until now, lithium-ion batteries can not meet the requirements of lithium-ion power battery, it’s main issue is lack of security and stability, exothermic reactions of lithium-ion batteries containing organic electrolyte include the decomposition of electrolyte and electrolyte and Electrode reaction, in the initial stage of thermal runaway. the accelerating of exothermic have accelerated the increasing of heat, These solvents can make pressure increase dramatically in battery of internal as a result of containing volatile dissolvent in organic electrolytes. It can lead to explosion of battery Therefore, it is particularly important that the new system replace volatile and combustible electrolytes.Ionic liquid can be used as the ideal battery electrolyte.
The most attractive features are: wide range of liquid stable, strong solvency, lower vapor pressure, high conductivity, strong catalytic activity, etc. The existence of these advantages make their broad application prospects .In recent years, synthesis and application of ionic liquids have become a hot topic. Until now, there are two centuries in the development of ionic liquids. There are also many synthesis and industrialization of ionic liquids But the article of application of the ionic liquids as electrolytes in electrochemical synthesis were very few. This article is review article about the field of the ionic liquids as electrolytes in electrochemical applications and prospects.
引文
[1]张金生,边鲁宁,李丽华,离子液体的合成研究与应用进展,化学与生物工程,2007,1:7-9。
[2]万辉,黄德英,蔡源等,[omim]BF4离子液体萃取酚类化合物的研究,高校化学工程学报,2008,1:162-165。.
[3]关卫省,李宇亮,茹静等,12丁基232甲基咪唑六氟磷酸盐离子液体合成,.应用化工,2010,6:818-826。
[4]肖峰,王冠楠,吴有庭等,低熔点低粘度的季铵盐类离子液体的合成与表征,南京大学学报(自然科学),2010,2:179-185。
[5]尹建军,孙华雨,朱颖等,含氮手性离子液体的合成及应用研究进展,兰州理工大学学报,2008,6:66-73。
[6]刘鹰,离子液体在催化过程中的应用,北京:化学工业出版社,2008。
[7]王军,离子液体的性能及其应用,北京:中国纺织出版社,2007。
[8]张庆华,王瑞峰,李作鹏,离子液体在绿色催化和清洁合成中应用的进展,.石油化工,2007,10:975-984。
[9]张锁江,李兴梅,离子液体从基础研究到工业应用,北京:科学出版社,2006。
[10]范杰平,曹婧,孔涛等,离子液体的合成、纯化及回收方法研究进展,南昌大学学报(工科版),2009,4:334-338。
[11]闵江马,付时雨,离子液体的合成与功能化设计,广州化学,2005,3:39-45。
[12]陈双平,王寿武,汪守建,离子液体的性质和制备方法,精细化工中间体,2004,5:10-12。
[13] Meng Hong,Li Hui, Li Chunxi et al. Synthesis of ionic liquid using a four-compartment configuration electrodialyzer,Journal of Membrane Science,2008,318:1-4。
[14]邵媛,邓宇,离子液体的合成及其在萃取分离中的应用,精细石油化工进展,2005,11:48-51。
[15] Luo Shichun,Zhang Zhengxi,Li Yang et al,Lithium secondary batteries using an asymmetric sulfonium-based room temperature ionic liquid as a potential electrolyte,Chinese Science Bulletin,2008,9:1337-1342。
[16] Jean-Michel,Andanson Fabian,Jutz Alfons Baiker et al,Purification of ionic liquids by supercritical CO2 monitored by infrared spectroscopy,The Journal of Supercritical Fluids,2010,55:395-400。
[17]张青山,刘爱霞,郭炳南,离子液体相关电解质研究进展,化学世界,2006,6:375-377。
[18] Han Hongbo , Guo Jun , Zhang Daijun et al , Lithium (fluorosulfonyl)(nonafluorobutanesulfonyl)imide (LiFNFSI) as conducting salt to improve the high-temperature resilience of lithiumion cells , Electrochemistry Communications:2011,13:265-268。
[19]黄晓玲,白金泉,陈秋月,离子液体的设计合成,化工新型材料,2005,1:39-42。
[20] Han Hongbo,Liu Kai,Feng Shaowei et al,Ionic liquid electrolytes based on multimethoxyethyl substituted ammoniums and perfluorinated sulfonimides : Preparation,characterization,and properties,Electrochimica Acta,2010,55:7134-7144。
[21] Andrzej Lewandowski,Polymer Electrolytes Based on Ionic Liquids,Journal of Fudan University ( Natural Science),2007,5。
[22]刘卉,陶国宏,邵元华,功能化的离子液体在电化学中的应用,化学通报,2004,11:795-801。
[23]聂进,周志彬,周宜宣,徐冰,刘凯,郭鹏,合成全氟烷基磺酰亚胺碱金属盐的方法和由该类盐合成的离子液体,中国发明专利,专利申请号:200810236672.7。
[24]周志彬,韩洪波,聂进,刘凯,郭鹏,周宜宣,由双(氟磺酰)亚胺和(全氟烷基磺酰基)亚胺碱金属盐制备的离子液体,中国发明专利,专利申请号:200810197928.8。
[25]周志彬,韩洪波,聂进,一种制备含氟磺酰(磷酰)亚胺及其碱金属盐的方法,中国国家专利,专利申请号:200910063820.4。
[26] Han Hongbo , Zhou Yixuan , Liu Kai et al. Efficient Preparation of (Fluorosulfonyl)(pentafluoroethanesulfonyl)imide and Its Alkali Salts, The Chemical Society of Japan,2010,39:472-474。
[27] Liu Kai , Zhou Yixuan , Han Hongbo et al. Ionic liquids based on (fluorosulfonyl)(p-entafluoroethanesulfonyl)imide with various oniums, Electrochimica Acta,2010,55:7145-7151。
[28] Han Hongbo,Nie Jin,Liu Kai et al. Ionic liquids and plastic crystals based on ter-tiary sulfonium and bis(fluorosulfonyl)imide,Electrochimica Acta,2010,55:1221-1226。
[29] Han Hongbo,Zhou Sisi,Zhang Daijun et al,Lithium bis(fluorosulfonyl)imide (LiFSI) as conducting salt for nonaqueous liquid electrolytes for lithium ion batteries:Physicochemical and electrochemical properties,Journal of Power Sources,2011。
[30] Hayashi K,Nemoto Y,Akuto K et al,Alkylated imidazolium salt electrolyte for lithium cells,J Power Sources,2005,2:689-692。
[31] Garcia B,Lavalle S,Perron Get al,Room temperature molten salts as lithium battery electrolyte,Electrochimica Acta,2004,26:4583-4588。
[32]张青山,刘爱霞,郭炳南等,离子液体相关电解质研究进展,化学世界,2004,6:375-377。
[33] Ishikawa M,Morita M,Ihara Met al,EDLC composed of activated carbon fiber cloth electrodes and solid polymer electrolytes containing alkylammonium salt , J. Electrochem. Soc,1994,141:1730-1734。
[34] Honghe Z , Hucheng Z , Yanbao F et al. Temperature dependence of the electrochemical behavior of LiMn2O4 in quaternary ammonium-based ionic liquid electrolyte,J Physchem B,2005, 28:13676-13684。
[35] Egashira M,Okada S,Yamaki J,The preparation of quaternary ammonium based ionic liquid containing a cyano group and its properties in a lithium battery electrolyte,J Power Sources,2004,(1-2):240– 244。
[36]张青山,刘爱霞,郭炳南等,离子液体相关电解质研究进展,化学世界,2004,6:375-377。.
[37] Forsyth M,Ogihara W,Sun Jet al Ionic conductivity of polymer gels deriving from alkali metal ionic liquids and negatively charged polyelectrolytes,Electrochimica Acta,2004,11:1797-1801。
[38]李汝雄,绿色溶剂离子液体的合成与应用,北京:化学工业出版社,2004。
[39] Bockris J.O,Reddy A.K.N,Modern Electrochemistry,New York,Plenum Press,1970。
[40] Jae W.C,Kyung I.S,Characterization and properties of hybrid composites prepared from poly(vinylidene fluoride-tetrafluoroethylene) and SiO2,Polymer,2001,2:727-736。
[2]万辉,黄德英,蔡源等,[omim]BF4离子液体萃取酚类化合物的研究,高校化学工程学报,2008,1:162-165。.
[3]关卫省,李宇亮,茹静等,12丁基232甲基咪唑六氟磷酸盐离子液体合成,.应用化工,2010,6:818-826。
[4]肖峰,王冠楠,吴有庭等,低熔点低粘度的季铵盐类离子液体的合成与表征,南京大学学报(自然科学),2010,2:179-185。
[5]尹建军,孙华雨,朱颖等,含氮手性离子液体的合成及应用研究进展,兰州理工大学学报,2008,6:66-73。
[6]刘鹰,离子液体在催化过程中的应用,北京:化学工业出版社,2008。
[7]王军,离子液体的性能及其应用,北京:中国纺织出版社,2007。
[8]张庆华,王瑞峰,李作鹏,离子液体在绿色催化和清洁合成中应用的进展,.石油化工,2007,10:975-984。
[9]张锁江,李兴梅,离子液体从基础研究到工业应用,北京:科学出版社,2006。
[10]范杰平,曹婧,孔涛等,离子液体的合成、纯化及回收方法研究进展,南昌大学学报(工科版),2009,4:334-338。
[11]闵江马,付时雨,离子液体的合成与功能化设计,广州化学,2005,3:39-45。
[12]陈双平,王寿武,汪守建,离子液体的性质和制备方法,精细化工中间体,2004,5:10-12。
[13] Meng Hong,Li Hui, Li Chunxi et al. Synthesis of ionic liquid using a four-compartment configuration electrodialyzer,Journal of Membrane Science,2008,318:1-4。
[14]邵媛,邓宇,离子液体的合成及其在萃取分离中的应用,精细石油化工进展,2005,11:48-51。
[15] Luo Shichun,Zhang Zhengxi,Li Yang et al,Lithium secondary batteries using an asymmetric sulfonium-based room temperature ionic liquid as a potential electrolyte,Chinese Science Bulletin,2008,9:1337-1342。
[16] Jean-Michel,Andanson Fabian,Jutz Alfons Baiker et al,Purification of ionic liquids by supercritical CO2 monitored by infrared spectroscopy,The Journal of Supercritical Fluids,2010,55:395-400。
[17]张青山,刘爱霞,郭炳南,离子液体相关电解质研究进展,化学世界,2006,6:375-377。
[18] Han Hongbo , Guo Jun , Zhang Daijun et al , Lithium (fluorosulfonyl)(nonafluorobutanesulfonyl)imide (LiFNFSI) as conducting salt to improve the high-temperature resilience of lithiumion cells , Electrochemistry Communications:2011,13:265-268。
[19]黄晓玲,白金泉,陈秋月,离子液体的设计合成,化工新型材料,2005,1:39-42。
[20] Han Hongbo,Liu Kai,Feng Shaowei et al,Ionic liquid electrolytes based on multimethoxyethyl substituted ammoniums and perfluorinated sulfonimides : Preparation,characterization,and properties,Electrochimica Acta,2010,55:7134-7144。
[21] Andrzej Lewandowski,Polymer Electrolytes Based on Ionic Liquids,Journal of Fudan University ( Natural Science),2007,5。
[22]刘卉,陶国宏,邵元华,功能化的离子液体在电化学中的应用,化学通报,2004,11:795-801。
[23]聂进,周志彬,周宜宣,徐冰,刘凯,郭鹏,合成全氟烷基磺酰亚胺碱金属盐的方法和由该类盐合成的离子液体,中国发明专利,专利申请号:200810236672.7。
[24]周志彬,韩洪波,聂进,刘凯,郭鹏,周宜宣,由双(氟磺酰)亚胺和(全氟烷基磺酰基)亚胺碱金属盐制备的离子液体,中国发明专利,专利申请号:200810197928.8。
[25]周志彬,韩洪波,聂进,一种制备含氟磺酰(磷酰)亚胺及其碱金属盐的方法,中国国家专利,专利申请号:200910063820.4。
[26] Han Hongbo , Zhou Yixuan , Liu Kai et al. Efficient Preparation of (Fluorosulfonyl)(pentafluoroethanesulfonyl)imide and Its Alkali Salts, The Chemical Society of Japan,2010,39:472-474。
[27] Liu Kai , Zhou Yixuan , Han Hongbo et al. Ionic liquids based on (fluorosulfonyl)(p-entafluoroethanesulfonyl)imide with various oniums, Electrochimica Acta,2010,55:7145-7151。
[28] Han Hongbo,Nie Jin,Liu Kai et al. Ionic liquids and plastic crystals based on ter-tiary sulfonium and bis(fluorosulfonyl)imide,Electrochimica Acta,2010,55:1221-1226。
[29] Han Hongbo,Zhou Sisi,Zhang Daijun et al,Lithium bis(fluorosulfonyl)imide (LiFSI) as conducting salt for nonaqueous liquid electrolytes for lithium ion batteries:Physicochemical and electrochemical properties,Journal of Power Sources,2011。
[30] Hayashi K,Nemoto Y,Akuto K et al,Alkylated imidazolium salt electrolyte for lithium cells,J Power Sources,2005,2:689-692。
[31] Garcia B,Lavalle S,Perron Get al,Room temperature molten salts as lithium battery electrolyte,Electrochimica Acta,2004,26:4583-4588。
[32]张青山,刘爱霞,郭炳南等,离子液体相关电解质研究进展,化学世界,2004,6:375-377。
[33] Ishikawa M,Morita M,Ihara Met al,EDLC composed of activated carbon fiber cloth electrodes and solid polymer electrolytes containing alkylammonium salt , J. Electrochem. Soc,1994,141:1730-1734。
[34] Honghe Z , Hucheng Z , Yanbao F et al. Temperature dependence of the electrochemical behavior of LiMn2O4 in quaternary ammonium-based ionic liquid electrolyte,J Physchem B,2005, 28:13676-13684。
[35] Egashira M,Okada S,Yamaki J,The preparation of quaternary ammonium based ionic liquid containing a cyano group and its properties in a lithium battery electrolyte,J Power Sources,2004,(1-2):240– 244。
[36]张青山,刘爱霞,郭炳南等,离子液体相关电解质研究进展,化学世界,2004,6:375-377。.
[37] Forsyth M,Ogihara W,Sun Jet al Ionic conductivity of polymer gels deriving from alkali metal ionic liquids and negatively charged polyelectrolytes,Electrochimica Acta,2004,11:1797-1801。
[38]李汝雄,绿色溶剂离子液体的合成与应用,北京:化学工业出版社,2004。
[39] Bockris J.O,Reddy A.K.N,Modern Electrochemistry,New York,Plenum Press,1970。
[40] Jae W.C,Kyung I.S,Characterization and properties of hybrid composites prepared from poly(vinylidene fluoride-tetrafluoroethylene) and SiO2,Polymer,2001,2:727-736。