CN101616898A - 环状胍离子液体 - Google Patents

环状胍离子液体 Download PDF

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CN101616898A
CN101616898A CN200880005670A CN200880005670A CN101616898A CN 101616898 A CN101616898 A CN 101616898A CN 200880005670 A CN200880005670 A CN 200880005670A CN 200880005670 A CN200880005670 A CN 200880005670A CN 101616898 A CN101616898 A CN 101616898A
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川田敦志
田代亚矢
熊谷逸裕
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Nippon Steel Chemical and Materials Co Ltd
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Abstract

本发明提供一种在更宽的电位范围内稳定的具有高离子电导率的离子液体。所述离子液体包含下述式(1)所示的环状胍盐。式中，R1和R2独立地表示烷基或烷氧基烷基，X表示亚甲基、氧原子、硫原子或R3N。R3表示烷基、烷氧基烷基或酰基。l、m、n表示1以上6以下的整数。Y－表示(R4SO2)2N－、R4SO3 －、R4COO－、BF4 －、PF6 －、NO3 －、(CN)2N－、(CHO)2N－、NCS－、R4OSO3 －、R4SO2S－和卤离子等一价的阴离子。所述离子液体作为各种电解质是有效的，特别是作为电化学电池的电解质是有效的。

Description

环状胍离子液体
技术领域
本发明涉及一种具有作为电化学器件中的电解质有用的环状胍阳离子的新型离子液体。
背景技术
作为锂电池、双电层电容器、电致变色元件、色素敏化太阳能电池等电化学器件中使用的非水系电解液，可使用使电解质溶解在碳酸亚丙酯、γ-丁内酯、乙腈等有机溶剂中而成的溶液。但是，由于这些电解质溶液中使用的有机溶剂易挥发，其自身为危险品，因此有可能存在长期可靠性、耐久性、安全性的问题。
因此，作为解决上述问题的方法之一，可列举电解质使用离子液体的方法。离子液体是包含阴离子和阳离子的组合的熔点在100℃以下的化合物的总称，据报告，可通过根据目的的离子的组合来显示必要的特性(非专利文献1)。
对于电化学器件中使用的电解质，也提出了几种方案。例如、可以例示：烷基取代咪唑鎓盐(例如专利文献1～4)、烷基季铵盐(例如专利文献5～8)。
虽然据报告这些离子液体可如上所述通过根据目的的离子的组合来显示必要的特性，但现状是，大部分开发中使用季咪唑鎓、脂环式季铵、烷基季铵等，需要采用新型骨架的突破。
因此，本发明人等进行了以电化学器件中使用的电解质为目的的新型骨架的探索，结果，着眼于胍类化合物具有的化学结构上的特异性、即电子的离域结构。但是，迄今为止的胍类化合物的用途为医药品原料、染料·涂料·摄影药品原料、高分子材料的添加剂原料等。作为关于胍类化合物的电化学特性的报告，有作为非环状胍化合物的四甲基胍和布朗斯台德酸的盐(专利文献9、非专利文献2)，但所得到的盐均限于质子性化合物。作为关于季胍(4級グアニジン)化合物的报道，有使六烷基胍形成阳离子的报告(专利文献3)，但在该报告中限于关于非环状季胍化合物在色素敏化太阳能电池中利用的内容。
专利文献1：特开8-259543号公报
专利文献2：特开2003-62467号公报
专利文献3：特开平11-86905号公报
专利文献4：特许347213号公报
专利文献5：WO02/076924号公报
专利文献6：特开2003-331918号公报
专利文献7：特许2981545号公报
专利文献8：特开2004-67543号公报
专利文献9：特开2004-253357号公报
非专利文献1：Chem.&Eng.News，2000年5月15日号
非专利文献2：Synthetic Communication，Vol.34，pp3083-3089(2004)
非专利文献3：Appl.Phys.A，79，73-77(2004)
发明内容
发明要解决的课题
本发明的目的在于，提供一种在更宽的电位范围内稳定的、具有高离子电导率的离子液体。
解决课题的手段
因此，本发明人等为了解决这样的问题反复进行了潜心研究，结果发现，具有环状胍作为阳离子的离子液体在宽的电位范围内稳定、具有高的离子电导率，以至完成了本发明。
本发明为特征在于包含下述式(1)所示的环状胍盐的离子液体，
Figure G2008800056705D00031
式中，R1和R2表示烷基或烷氧基烷基，X表示亚甲基、氧原子、硫原子或R3N。R3表示烷基、烷氧基烷基或酰基。l、m、n独立地表示1～6的整数。Y-表示一价的阴离子。
另外，在式(1)中，作为Y-可以例示选自(R4SO2)2N-、R4SO3 -、R4COO-、BF4 -、PF6 -、NO3 -、(CN)2N-、(CHO)2N-、NCS-、R4OSO3 -、R4SO2S-和卤离子中的阴离子。这里，在(R4SO2)2N-、R4SO3 -、R4COO-、R4OSO3 -、R4SO2S-中，R4表示全氟烷基、烷基或芳香族基团。
另外，本发明为式(1)所示的离子液体的制备方法，其特征在于，使用式(2)所示的环状脲和式(3)所示的化合物作为反应原料而使其反应。
(这里，R1、R2和n具有与式(1)相同的含义。)
Figure G2008800056705D00041
(这里，X、l和m具有与式(1)相同的含义。)
这里，如果在使式(2)所示的环状脲和式(3)所示的化合物反应时，存在反应促进剂，或在使式(2)所示的环状脲与反应促进剂反应后，使式(3)所示的化合物反应，则可促进反应。
另外，本发明为一种电解质，其特征在于，其含有式(1)所述的离子液体。而且，本发明为一种电化学电池，其特征在于，其使用含有离子液体的电解质。
具体实施方式
本发明的离子液体包含上述式(1)所示的环状胍盐。本发明的离子液体也由上述式(1)所示。式中，R1和R2表示烷基或烷氧基烷基，R1和R2也可以相同。作为烷基，可优选列举C1～C12的烷基。作为烷氧基烷基，优选C1～C8的低级烷氧基烷基，例如、可以例示：甲氧基甲基、甲氧基乙基、甲氧基丙基、甲氧基丁基、乙氧基乙基、乙氧基丙基、乙氧基丁基、丙氧基乙基、异丙氧基乙基、异丙氧基丙基、丁氧基乙基、丁氧基丙基、丁氧基丁基等。
X表示亚甲基、烷氧基烷基氨基、氧原子、硫原子或R3N。R3表示烷基、烷氧基烷基或酰基。当R3为烷基或烷氧基烷基时，可优选列举和上述相同的烷基或烷氧基烷基。对于为烷氧基烷基氨基的情况，烷氧基烷基也和上述的相同。作为R3可以使用的酰基，优选C1～C8的酰基，可以例示乙酰基、乙基羰基、苯甲酰基等。
l、m及n分别独立地表示1～6的整数，优选1及m为1～3的整数，n为2或3。
Y-表示一价的阴离子。可优选例示选自(R4SO2)2N-、R4SO3 -、R4COO-、BF4 -、PF6 -、NO3 -、(CN)2N-、(CHO)2N-、NCS-、R4OSO3 -、R4SO2S-和卤离子的阴离子。这里，R4表示全氟烷基、烷基或芳香族基团。作为全氟烷基，优选C1～C8的全氟烷基。作为烷基，优选C1～C12的烷基。作为芳香族基团，可以是取代或无取代的芳香族基团，优选取代或无取代的苯基。例如、可以例示：苯基、烷基苯基、烷基氧苯基、卤代苯基、硝基苯基、酰基苯基、烷氧基羰基苯基。
式(1)所示的环状胍盐，虽然可以利用公知的方法来制备，单通过使用以下的反应式所示的方法可以高效率地进行制备。
Figure G2008800056705D00051
即为通过使式(3)所示的化合物对式(2)所示的环状脲化合物进行作用来获得式(1)所示的环状胍盐的方法。式(2)中的R1、R2、n及式(3)中的X、l、m为与式(1)相同的含义。
在通过使用式(2)所示的环状脲化合物和式(3)所示的化合物来获得式(1)所示的环状胍盐的方法中，优选通过使用反应促进剂、在式(2)所示的环状脲化合物的羰基的碳原子上导入离去基团来提高反应性，然后，使式(3)所示的化合物进行作用。作为离去基团，可优选使用氯、溴之类的卤原子。例如可以例示如下的方法，即，通过使式(2)所示的环状脲化合物和作为反应促进剂的氯化剂作用，对式(2)中的羰基碳进行氯化反应，由此可获得式(2)所示的环状脲化合物的氯化物，使该氯化物和式(3)所示的化合物作用。式(2)所示的环状脲化合物的氯化反应，通常在溶剂中、氯化剂存在下进行。作为氯化剂，可以例示磷酰氯、碳酰氯、亚硫酰氯等。作为氯化剂的用量，通常可使用相对于式(2)所示的环状脲化合物的理论量以上。另一方面，在环状脲化合物容易获得的情况下，或根据从氯化剂中除去反应副产物等方面，有时从经济性方面考虑优选在理论摩尔量以下进行。予以说明的是，氯化物可推测为下述式所示的化合物。
Figure G2008800056705D00061
上述反应在溶剂中进行是有利的。作为溶剂，只要不阻碍本反应就没有限制，可以例示：己烷、庚烷、石油醚等脂肪族烃；苯、甲苯、二甲苯等芳香族烃；硝基甲烷、硝基苯等有机硝基化合物；四氢呋喃、二噁烷等环状醚化合物；二氯甲烷、氯仿、四氯乙烷等卤化物等。本氯化反应的反应温度通常为室温～150℃、优选为50℃～100℃。反应时间通常为0.5～24小时、优选为1～10小时。
在对式(2)所示的环状脲化合物进行氯化反应后、使反应混合物与式(3)所示的化合物进行反应时，可以从氯化反应的混合物中分离氯化物，也可以通过在进行了氯化反应的反应液中加入式(3)所示的化合物来进行反应。氯化反应后，有时氯化物不溶解于反应溶剂中而析出或相分离，这时，通过追加反应溶剂来使氯化物溶解。作为此时可以使用的溶剂，可以例示氯化反应时所使用的溶剂。式(3)所示的化合物的用量，可使用相对氯化剂的使用量为等摩尔量以上，优选为1～2.5摩尔量。在进行对式(3)所示的化合物的反应时，为了使反应顺利进行，也可以使用碱催化剂。作为可以使用的碱催化剂，优选三乙胺等烷基叔胺、N-甲基吡咯烷等脂环式叔胺、吡啶、喹啉等含氮芳香族碱。本反应的反应温度通常为室温～100℃、优选为30℃～70℃。反应时间通常为0.5～24小时、优选为1～10小时。
反应结束后，按照常规方法进行处理，由此可以得到式(1)所示的环状胍盐。根据处理方法可以得到所希望的Y-，通过使用以下的方法可以简便地得到具有各种Y-的环状胍化合物盐，故优选。即，为以下方法：进行式(2)所示的环状脲的氯化反应后，使其与式(3)所示的化合物作用，然后通过进行反应混合液的硅胶等的吸附处理，除去副产物和未反应的原料，然后，通过蒸馏除去溶剂而得到以Cl-作为阴离子的环状胍化合物盐，然后，根据需要进行盐交换反应。作为盐交换的方法，可以进行在季铵盐等使用的已知的盐交换反应。
式(1)所示的环状胍盐的优选阳离子部分(从环状胍盐中除去了Y-的部分)的例子如下所示，但并不限定于这些。化学式下面所记载的编号为化学式编号。予以说明的是，优选的环状胍盐包含该阳离子部分和Y-。
Figure G2008800056705D00071
由于式(1)所示的环状胍盐一般熔点低、具有高的离子电导率，因此可以作为一次和二次锂离子电池、色素敏化型太阳能电池、双电层电容器、电致变色显示元件等电化学器件的电解质来使用。将本发明的离子液体用于这些用途时，可以使用一种式(1)所示的环状胍盐，也可以混合两种以上使用。将本发明的离子液体用于离子液体的用途时，可以含有不阻碍作为离子液体的功能的成分。例如，在作为电化学器件中的电解质进行使用的情况下，也可以将式(1)所示的环状胍盐和可作为电化学器件中的电解质来使用的其他盐混合使用。另外，也可以将式(1)所示的环状胍盐或该环状胍盐和其他盐的混合物溶解在溶剂中使用。
实施例
以下，通过实施例对本发明进行更详细地说明。
实施例1
在氮气氛下，在具备滴液漏斗和回流管的三口烧瓶中，加入1，3-二甲基-2-咪唑啉酮(170mmol、19.4g)和甲苯(50mL)。加入磷酰氯(85mmol、13.0g)，在65℃进行搅拌。1小时后，停止加热，用冰浴冷却烧瓶，由此得到含有1，3-二甲基-2-咪唑啉酮的氯化物的溶液。在得到的含有1，3-二甲基-2-咪唑啉酮的氯化物的溶液中，加入二氯甲烷(50mL)，接着加入三乙胺(170mmol、23.6mL)。在冰冷下，用约30分钟向该溶液中滴加吡咯烷(170mmol、13.8mL)的二氯甲烷(50mL)溶液。滴加结束后，取下冰浴，在55℃进行搅拌。1小时后，冷却至室温。过滤分离不溶物后，减压蒸馏除去滤液。将得到的残渣用柱色谱法进行精制，由此得到作为淡黄色固体的4，5-二氢-1，3-二甲基-2-(1-吡咯烷基)-1H-咪唑鎓氯化物(包含化学式编号1的阳离子和Cl-的环状胍盐；以下称为环状胍盐1)15.9g。由于该固体的熔点显示49℃，因此得知为形成离子液体的环状胍盐。
将上述得到的环状胍盐1(5.08g、24.9mmol)溶解于100mL的二氯甲烷。向该溶液加入双(三氟甲磺酰)酰亚胺锂(7.30、25.4mmol)，在室温下搅拌1小时。过滤分离生成的白色沉淀，将滤液用离子交换水洗涤后，用旋转蒸发器浓缩。将残渣溶解于甲醇，加入活性炭，在室温下搅拌1小时。通过过滤除去活性炭，对滤液进行浓缩、用柱色谱(活性氧化铝)进行精制，由此得到作为淡黄色油状物的以化学式编号1为阳离子、以双(三氟甲磺酰)酰亚胺为阴离子的环状胍盐。
1H-NMR(CDCl3)；δ3.70(s，4H)，3.63(t，J＝6.58，4H)，3.06(s，6H)，1.96(t，J＝6.58Hz，4H).
利用交流阻抗法对得到的环状胍盐的2M碳酸亚丙酯溶液的离子电导率进行了测定，结果示于表1。另外，进行了CV测定，其结果电位窗相对于Ag/Ag+为-2.77～1.63v。
[表1]
  温度(℃)   离子电导率(mS/cm)
  40   13.4
  30   10.5
  20   8.1
  10   6.0
  0   4.3
  -10   2.9
实施例2～5
代替吡咯烷，使用表2所示的化合物作为反应原料，除此以外，与实施例1同样进行操作，由此得到以双(三氟甲磺酰)酰亚胺作为阴离子的环状胍盐。通过交流阻抗法对得到的环状胍盐的2M碳酸亚丙酯溶液在20℃的离子电导率进行了测定，其结果与实施例2～5得到的环状胍盐的1H-NMR(CDCl3)的测定结果示于表2。实施例1-5得到的环状胍盐的任一种均为离子液体。
[表2]
Figure G2008800056705D00091
实施例6
将根据实施例1的操作得到的环状胍盐2.03g(10mmol)溶于20mL二氯甲烷。向该溶液加入二氰胺钠0.89g(10mmol)，在室温下搅拌12小时。过滤分离生成的白色沉淀，将滤液用旋转蒸发器进行浓缩。将残渣用柱色谱(活性氧化铝)进行精制，由此得到作为白色固体的以化学式编号1作为阳离子和以二氰胺作为阴离子的环状胍盐。该环状胍盐是熔点为62℃的离子液体。
实施例7～11
代替二氰胺钠，使用下面所示的原料，除此以外，与实施例6同样进行操作，得到对应的环状胍盐。
实施例7：二甲酰钠(diformyl sodium)
实施例8：硫氰酸钠
实施例9：甲基硫酸钠
实施例10：十二烷磺酸钠
实施例11：乙烷硫代磺酸钠
对实施例6～11得到的环状胍盐的2M碳酸亚丙酯溶液在20℃的离子电导率进行测定，结果示于表3。实例6～11得到的环状胍盐都是离子液体。
[表3]
  实施例   性状   电导率(mS/cm)
6   白色固体m.p.62℃ 20.0
  7   黄色油状物   7.6
8   白色固体m.p.82℃ 17.9
  9   无色油状物   13.0
  10   无色油状物   4.5
  11   褐色油状物   9.5
产业上的可利用性
通过使用本发明的含有包含环状胍盐的离子液体的电解质来构成一次和二次锂离子电池、色素敏化型太阳能电池、双电层电容器、电致变色显示元件等电化学器件，可以获得低温特性和长期稳定性优异的电化学器件。

Claims (7)

1、一种离子液体，其特征在于，该离子液体包含下述式(1)所示的环状胍盐，
Figure A2008800056700002C1
在此，R1和R2独立地表示烷基或烷氧基烷基，X表示亚甲基、氧原子、硫原子或R3N，R3表示烷基、烷氧基烷基或酰基，l、m及n独立地表示1～6的整数，Y-表示一价的阴离子。
2、如权利要求1所述的离子液体，其特征在于，式(1)中，Y-为选自由(R4SO2)2N-、R4SO3 -、R4COO-、BF4 -、PF6 -、NO3 -、(CN)2N-、(CHO)2N-、NCS-、R4OSO3 -、R4SO2S-和卤离子组成的组中的阴离子，其中，所述R4表示全氟烷基、烷基或芳香族基团。
3、一种权利要求1所述的离子液体的制备方法，其特征在于，使用式(2)所示的环状脲和式(3)所示的化合物作为反应原料而使其反应，
Figure A2008800056700002C2
在此，R1和R2独立地表示烷基或烷氧基烷基，n表示1～6的整数，
Figure A2008800056700003C1
在此，X表示亚甲基、氧原子、硫原子或R3N，R3表示烷基、烷氧基烷基、酰基，l及m独立地表示1～6的整数。
4、如权利要求3所述的离子液体的制备方法，其中，在使式(2)所示的环状脲和式(3)所示的化合物反应时，存在反应促进剂。
5、如权利要求3所述的离子液体的制备方法，其中，在使式(2)所示的环状脲与反应促进剂反应后，使式(3)所示的化合物反应。
6、一种电解质，其特征在于，其含有权利要求1所述的离子液体。
7、一种电化学电池，其特征在于，其使用权利要求6所述的电解质作为电化学电池的电解质。
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