CN102015666B - 反应性离子液体 - Google Patents

反应性离子液体 Download PDF

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CN102015666B
CN102015666B CN200980115361.8A CN200980115361A CN102015666B CN 102015666 B CN102015666 B CN 102015666B CN 200980115361 A CN200980115361 A CN 200980115361A CN 102015666 B CN102015666 B CN 102015666B
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ionic liquid
lithium
fluoroalkyl
acid
alkyl
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CN102015666A (zh
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M·施密特
N·伊格纳特耶夫
W-R·皮特纳
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National Institute of Technology
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BASF SE
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Abstract

本发明涉及用在电化电池(例如锂离子电池)和双层电容器或锂电容器中的反应性离子液体，其含有有机阳离子和阴离子，所述有机阳离子具有可电化还原的基团或取代基，所述阴离子是氟烷基磷酸根、氟烷基次膦酸根、氟烷基膦酸根、乙酸根、三氟甲磺酸根、酰亚胺、甲基阴离子、硼酸根、磷酸根和/或铝酸根的阴离子。

Description

反应性离子液体
本发明涉及用在电化电池(例如锂离子电池)和双层电容器中的反应性离子液体，其含有有机阳离子和阴离子，所述有机阳离子具有容易电化还原的基团或取代基，所述阴离子获自氟烷基磷酸根、氟烷基次膦酸根、氟烷基膦酸根、乙酸根、三氟甲磺酸根、酰亚胺、甲基阴离子(methides)、硼酸根、磷酸根和/或铝酸根。
离子液体或液体盐是由有机阳离子和阴离子(通常是无机的)构成的离子物质。它们不含任何中性分子并通常具有低于373K的熔点。
“反应性离子液体”用于表示下述离子液体：其在有机阳离子上含有容易电化还原的基团或取代基，例如氰基、酯基团、碳酸根或碳酸酯基团、或含双键的侧链。
近年来，离子液体已引起不断增加的兴趣，大量综述文章已经描述了离子液体(简称为“ILs”)的独特性质和指出各种潜在用途。
特别地，离子液体看起来非常有希望用在能量存储介质中，例如双层电容器和电池中，特别集中于电动和混合动力车。
离子液体的杰出性质包括：
·几乎零挥发性和和因此非常高的闪点
·非常大的液体范围，在一些情况下高于数百K
·非常高的极性和因此对无机和有机盐的通常非常好的溶解度。
尽管离子液体，例如四氟硼酸乙基甲基咪唑鎓(EMIBF4)已在商业上用在双层电容器(超级电容器)中，但仍然难以用在电池、特别是锂离子电池中。
对于电池用途，已经表征了下述包含离子液体的体系：
·与包含Li盐的电解质结合的离子液体
·与包含Li盐以及添加剂的电解质结合的离子液体
在此已经使用了下述离子液体：
·具有AlCl4作为阴离子的离子液体(第0代，极早的著作)
·具有咪唑鎓基阳离子和(全)氟化无机或有机阴离子的离子液体(第1代)
·具有“非咪唑鎓”基阳离子和(全)氟化无机或有机阴离子的离子液体(第2代)
AlCl4基离子液体对水解极敏感并与水反应以释放盐酸。因此，已经终止了电池系统的这种发展。咪唑鎓基ILs表现出不足的还原稳定性，因此被认为不是非常有希望商业应用于高能电池。具有无机阴离子、特别是BF4的离子液体造成电容的显著降低，特别是在第一充/放电周期中。目前看起来最适合Li离子电池的离子液体使用与双(三氟甲基)酰亚胺结合的N，N-二烷基吡咯烷鎓(参见例如JP 2006-260952)。
但是，即便这些离子液体也仍造成锂离子电池的功率密度的显著降低。
其原因特别在于电化学稳定的离子液体的高粘度。这造成该IL基电解质与不含离子液体的标准电解质体系相比明显更低的锂离子电导率(O.Borodin等人，J.of Physical Chemistry B，2006，110(34)，第16879-16886页)。相应地，包含IL基电解质的锂离子电池如今仍表现出与包含标准电解质的锂离子电池相比明显较低的功率密度和电荷载流容量。
后者特别必须被视为对于在电动和混合动力车中应用而言非常关键，并阻碍——尽管安全性提高——IL基电解质的应用。
Lee等人(Electrochem.Comm.8(2006)460)已表明，在电池电解质中使用在氮上具有酯配体的咪唑鎓基ILs改进了Li离子的锂电导率和扩散系数。
但是，这些咪唑鎓基离子液体不够电化学稳定。
本发明的目的因此是开发具有高的热稳定性、非常好的氧化稳定性和低腐蚀性并具有已廉价合成的阴离子且没有上述缺点的离子液体。
通过通式I的离子液体实现了本发明的目的
K+A-    (I)
其中：
K+是指选自通式II至IX的的阳离子，优选还原稳定的阳离子：
其中
X是指CH2、O、S或NR′，
R′是指-(CH2)n-CN、C1-至C16-烷基，优选甲基、乙基、丙基、H，
R是指H、C1-至C16-烷基，优选甲基、乙基、丙基，
R5是指-(CH2)n-O-C(O)-R、-(CH2)n-C(O)-OR、-(CH2)n-O-C(O)-OR、-(CH2)n-HC＝CH-R或-(CH2)n-CN，其中各个CH2基团可被O、S或NR替代，
其中n＝1至8，
且
A-是指阴离子，其选自：
[FyP(CmF2m+1)6-y]-
(CmF2m+1)2P(O)O-
CmF2m+1P(O)O2 2-
O-C(O)-CmF2m+1，
O-S(O)2-CmF2m+1
N(C(O)-CmF2m+1)2
N(S(O)2-CmF2m+1)2
N(C(O)-CmF2m+1)(S(O)2-CmF2m+1)
N(C(O)-CmF2m+1)(C(O)F)
N(S(O)2-CmF2m+1)(S(O)2F)
N(S(O)2F)2
C(C(O)-CmF2m+1)3
C(S(O)2-CmF2m+1)3
其中y＝1、2、3、4或5，且m＝1至8，优选1至4，
其中一些CF2基团可以被O、S(O)2、NR或CH2替代，且
其中
是指1，2-或1，3-二醇、1，2-或1，3-二羧酸或1，2-或1，3-羟基羧酸，
X是指B或Al，
R1至R4是指卤素，特别是F，和/或氟化或非氟化的烷氧基或羧基。
与传统离子液体相比，本发明的反应性离子液体特征在于下述事实：它们在有机阳离子上含有容易电化还原的基团/取代基或侧链。这些特别是：
·氰基-CN
·酯基团-R-C(O)-OR或-R-O-C(O)-R
·碳酸根或碳酸酯官能-R-O-C(O)-OR
·侧链中的双键-R-CH＝CH-R
令人惊讶地，本发明的反应性离子液体在相对Li/Li+大约2V至0.9V的电位形成钝化覆盖层，这明显快于碳酸亚乙酯(相对Li/Li+0.7至0.8V)。这种覆盖层是电子钝化的，但可透锂离子。另一优点在于对于Li/Li+＞5V的优异氧化稳定性。与目前使用的许多其它添加剂(其中一些高度有毒，例如丙烷磺内酯)相比，本发明的反应性离子液体是非挥发性的，并且没有可测得的蒸气压。
本发明的离子液体的阳离子K+优选是选自通式IV的阳离子：
其中
X是指CH2、O、S或NR′，
R′是指-(CH2)n-CN、甲基、乙基、丙基、丁基、H，
R是指H、甲基、乙基、丙基、丁基，
R5是指-(CH2)n-O-C(O)-R、-(CH2)n-C(O)-OR、-(CH2)n-O-C(O)-OR、-(CH2)n-HC＝CH-R或-(CH2)n-CN，其中各个CH2基团可被O、S或NR替代，
其中n＝1至8。
本发明离子液体的阴离子A-优选是下述阴离子：[F2P(C2F5)4]-、[F3P(C2F5)3]-、[F4P(C2F5)2]-、[F2P(C3F7)4]-、[F3P(C3F7)3]-、[F4P(C3F7)2]-、[F2P(C4F9)4]-、[F3P(C4F9)3]-、[F4P(C4F9)2]-、全氟烷基羧酸根、全氟烷基磺酸根、双(全氟烷基磺酰基)酰亚胺、(全氟烷基磺酰基)(全氟烷基羧基)酰亚胺、三(全氟烷基磺酰基)甲基阴离子(methide)，特别优选为三氟乙酸根、三氟甲磺酸根、双(三氟甲基磺酰基)酰亚胺和三(三氟甲基磺酰基)甲基阴离子。优选的还有螺-氧代硼酸根和螺-氧代磷酸根，特别优选的是螺-氧代硼酸根。
本发明还涉及电解质，其包含至少一种导电盐、非质子溶剂或溶剂混合物、至少一种根据本发明的上述式I的离子液体和任选地其它添加剂。
在一个优选实施方案(例如在该电解质用在锂或锂离子电池中时)中，所述导电盐是锂导电盐，例如LiPF6、LiN(SO2CF3)2、LiN(SO2C2F5)2、LiF3P(C2F5)3、LiF3P(C4F9)3、LiB(C2O4)2或LiF2B(C2O4)2。
在另一优选实施方案(例如在该电解质用在双层电容器或超级电容器中时)中，该导电盐是选自N(C2H5)4BF4、N(C2H5)4PF6、N(C2H5)3(CH3)BF4、N(C2H5)3(CH3)PF6、N(C2H5)4N(SO2CF3)2、N(C2H5)3(CH3)N(SO2CF3)2、N(C2H5)4F3P(C2F5)3、N(C2H5)3(CH3)F3P(C2F5)3的化合物。
该电解质的非质子溶剂优选由有机开链或环状碳酸酯、羧酸酯、腈、醚或内酯或其混合物构成。优选使用腈、特别是乙腈作为双层电容器中的溶剂。
本发明还涉及式I的离子液体的制备方法：
·通过传统湿化学法，由相应的胺、膦、卤代羧酸盐/酯、卤代碳酸盐/酯、卤代烷基腈或烷基卤制备氯化鎓或溴化鎓形式的根据权利要求1的杂环阳离子K+，该杂环阳离子K+具有含烷基、羧酸根或羧酸酯基团、碳酸根或碳酸酯基团、或氰基的侧链，
·在水性和/或醇类介质或有机溶剂中，或在无溶剂的情况下，使这些阳离子型氯化鎓或溴化鎓与相应的阴离子型下述物质反应：
-氟烷基磷酸钾和/或氟烷基磷酸钠，或双(氟烷基)次膦酸钾和/或双(氟烷基)次膦酸钠，或氟烷基膦酸钾和/或氟烷基膦酸钠，或氟烷基磷酸，或双(氟烷基)次膦酸，或氟烷基膦酸，或双(氟烷基)次膦酸烷基酯、特别是甲基酯，或
-酰亚胺锂或甲基化锂，或三氟甲磺酸，或三氟乙酸钾或三氟乙酸锂，或三氟甲磺酸钾或三氟甲磺酸锂，或三氟甲磺酸烷基酯，或三氟甲磺酸三甲硅烷基酯，或三氟甲磺酸酐，或三氟乙酸酐，或
-硼酸锂或硼酸钾，磷酸锂或磷酸钾，或铝酸锂或铝酸钾。
阳离子的制备是本领域技术人员已知的，并可以通过如下述文献中所述的方法进行：总述，P.Wasserscheid和T.Welton(Eds.)″Ionic Liquids inSynthesis″，Wiley-VCH，2003，第7-40页，或关于咪唑鎓阳离子，N.Gathergood，P.J.Scammells，Aust.J.Chem，55(2002)，No.9，第557-560页；E.Alcalde，M.Gisbert，L.Perez-Garcia，Heterocycles，43(1996)，No.3，第567-580页；Z.Fei，D.Zhao，T.J.Geldbach，R.Scopelliti，P.J.Dyson，Chem.Europ.J.，10(2004)，No.19，第4886-4893页；D.Liu，Ji.Gui，X.Zhu，L.Song，Z.Sun，Synth.Commun.，37(2007)，No.5，第759-765页；Ya.Peng，F.Yi，G.Song，Yi.Zhang，Monatsh.Chem.，136(2005)，No.10，第1751-1755页；J.F.Dubreuil，J.P.Bazureau，Tetrahedron Lett，41(2000)，No.38，第7351-7356页；S.-K.Fu，Sh.-T.Liu，Synth.Commun.，36(2006)，No.14，第2059-2067页；M.Yoshizawa，A.Narita，H.Ohno，Aust.J.Chem.，57(2004)，No.2，第139-144页；A.Narita，W.Shibayama，H.Ohno，J.Mater.Chem.，16(2006)，No.15，第1475-1482页；T.Mizumo，E.Marwanta，N.Matsumi，H.Ohno，Chem.Lett.，33(2004)，No.10，第1360-1361页；D.Zhao，Zh.Fei，T.J.Geldbach，R.Scopelliti，G.Laurenczy，P.J.Dyson，Hel.Chlm.Ada.，88(2005)，No.3，第665-675页；A.Horvath，Synthesis，1994，第102-106页；或关于吡咯烷鎓阳离子，L.Horner，A.Mentrup，Justus Liebigs Ann.Chem.646(1961)，第49-64页；Bates等人，J.Chem.Soc.1956，第388-395页，v.Braun Chem.Ber.70(1937)，第983页；Z.Dega-Szafran，R.Przybylak，J.Mol.Struct，436(1997)，No.1，第107-122页；或关于哌啶鎓阳离子，Walther等人，Chem.Ber.，89(1956)，第60-65页；或关于吗啉鎓阳离子，Gresham等人，J.Am.Chem.Soc，73(1951)，第3168-3171页；D.Le Berre，Bull.Soc.Chlm.Fn，1973，第2404-2407页；O.A.Kazantsev，S.A.Kazakov，K.V.Shirshin，S.M.Danov，Russ.J.Org.Chem.，36(2000)，No.3，第343-349页；或关于哌嗪鎓阳离子，Z.Dega-Szafran，M.Jaskol-ski，I.Kurzyca，P.Barczynski，M.Szafran，J.Mol.Struct，614(2002)，No.1-3，第23-32页。
如从表1.1至1.3中可以看出，本发明的阴离子是氧化稳定的。
表1.1：
具有三(五氟乙基)三氟磷酸根阴离子(FAP阴离子)和双(五氟乙基)次膦酸根阴离子(C2F5)2P(O)O-的反应性离子液体与具有三氟磺酸根和四氟硼酸根阴离子的类似离子液体相比的电化学稳定性
  反应性离子液体   E(ox)，V   E(red)，V   电化学窗
  1-乙基-3-甲基-咪唑鎓FAP   3.9   -2.5   6.4
  1-乙基-3-甲基-咪唑鎓(C2F5)2P(O)O-   3.6   -2.6   6.2
  三氟甲磺酸1-乙基-3-甲基-咪唑鎓   2.8   -2.5   5.3
  1-乙基-3-甲基-咪唑鎓BF4 -   2.6   -2.6   5.2
表1.2：
具有双(三氟甲基磺酰基)酰亚胺阴离子和三氟甲磺酸根阴离子的反应性离子液体与具有四氟硼酸根阴离子的离子液体相比的电化学稳定性
表1.3：
具有硼酸根、磷酸根和铝酸根阴离子的离子液体的电化学稳定性
通过相应的阳离子型氯化鎓或溴化鎓与相应的氟烷基磷酸钾或氟烷基磷酸钠、或氟烷基磷酸(HFAP)在水性介质中的反应来制备氟烷基磷酸根基反应性离子液体。
通过三种不同方法制备双(氟烷基)次膦酸根基离子液体：
·借助次膦酸制备这些离子液体(参见实施例5.1)
·经由相应的钾盐(例如氟烷基次膦酸钾)制备这些离子液体(参见实施例5.2)
·经由相应的双-(氟烷基)次膦酸烷基酯、优选次膦酸甲酯制备这些离子液体(参见实施例5.3)。
在此优选经由次膦酸和次膦酸甲酯制备双(氟烷基)次膦酸根基离子液体。
通过相应的阳离子型氯化鎓或溴化鎓与相应锂盐在水性介质中的反应制备酰亚胺基和甲基阴离子基离子液体。
通过三种不同方法制备三氟乙酸根基和三氟甲磺酸根基离子液体：
·借助三氟甲磺酸制备三氟甲磺酸根基离子液体(参见实施例5.1)
·经由相应的三氟乙酸钾或锂、或三氟甲磺酸钾或锂制备该离子液体(参见实施例5.2)
·经由相应的三氟甲磺酸甲酯、三氟甲磺酸三甲硅烷基酯、三氟甲磺酸酐或三氟乙酸酐制备该离子液体(参见实施例5.3)。
在此优选经由三氟甲磺酸或三氟乙酸、和/或三氟甲磺酸甲酯或乙酯、或三氟乙酸甲酯或乙酯、或三氟甲磺酸三甲硅烷基酯、三氟甲磺酸酐或三氟乙酸酐法制备三氟乙酸根基和三氟甲磺酸根基离子液体。
通过相应的阳离子型氯化鎓或溴化鎓与相应的阴离子型硼酸钾或锂、磷酸钾或锂、或铝酸钾或锂在水性或有机介质中的反应制备硼酸根基、磷酸根基或铝酸根基反应性离子液体。
本发明的阳离子与阴离子的反应可以在0至150℃的温度、优选在0至50℃、特别是在室温进行，以产生最终产物。
合适的溶剂或溶剂混合物是水或去离子水、醇、二氧杂环己烷、乙腈和丙酮。所用醇优选是甲醇或异丙醇。在使用次膦酸甲酯的情况下，通常不需要溶剂。
本发明还涉及含有至少一种电解质的电化学和/或光电器件，所述电解质包含至少一种通式I的离子液体。该器件可优选是太阳能电池、锂或锂离子电池、双层电容器或超级电容器、锂电容器、发光器件、电化学传感器和/或生物传感器。
本发明还涉及所述通式I的反应性离子液体的用途，用作电化学或光电电池所用的电解质中的导电盐或添加剂。
在另一优选实施方案中，本发明的反应性离子液体用作电池、二次锂电池、双层电容器和超级电容器或锂电容器所用的电解质中的导电盐或添加剂。
本发明还涉及本发明的电解质在电化学和/或光电器件中的用途。这些器件优选是锂或锂离子电池、双层电容器、超级电容器或锂电容器。
下述实施例旨在例证本发明。但是，它们无论如何不应被视为限制。该组合物中可用的所有化合物或组分是已知和可购得的，或可通过已知方法合成。实施例中所示的温度始终以℃计。在说明书和实施例中，组合物中组分的添加量始终合计为总共100％。所给出的百分比数据始终在所给上下文中考虑。但是，它们通常总是涉及所示部分量或总量的重量。
实施例
阳离子的制备
实施例1：含烯丙基侧链的杂环阳离子的制备
通用程序：
将1.1摩尔烯丙基氯逐滴添加到1摩尔相应的胺或膦中。在此必须确保温度保持在30至35℃之间。然后将反应混合物在40℃至50℃搅拌3小时至48小时(在形成固体产物的情况下，用二氯甲烷或乙腈稀释该反应混合物)，然后在真空(2·10-3毫巴)馏出过量烯丙基氯和溶剂。产物收率几乎定量。
表1
实施例2：含羧酸酯基团侧链或碳酸酯基团侧链的杂环阳离子的制备
通用程序：
先将在300毫升乙腈中的1摩尔相应的胺或膦引入带有精密玻璃搅拌器的2升多颈圆底烧瓶中，并达到80℃。然后经1.5小时缓慢地逐滴加入1.1摩尔相应的卤代羧酸酯或卤代碳酸酯(优选溴代羧酸酯或溴代碳酸酯)。
然后使反应混合物在此温度下进一步反应0.5至48小时，并搅拌到1升乙酸乙酯中，由此产物以白色固体形式沉淀。抽吸滤出产物，用乙酸乙酯漂洗并干燥(带有在大约30℃的水浴的旋转蒸发器)。收率为90至95％。
表2
实施例3：含有含氰基的侧链的杂环阳离子的制备
通用程序：
将1.1摩尔氯烷基腈(或溴烷基腈或碘烷基腈)逐滴添加到1摩尔相应的胺或膦中。在此必须确保温度保持在30至35℃之间。然后将反应混合物在50℃至80℃搅拌3小时至48小时(在形成固体产物的情况下，用乙腈稀释该反应混合物)，然后在真空(2·10-3毫巴)下馏出过量氯烷基腈和溶剂。产物收率几乎定量。
表3
氟烷基磷酸根基和氟烷基次膦酸根基反应性离子液体的制备
实施例4：氟烷基磷酸盐基反应性离子液体的制备
通用程序：
在带有磁搅拌棒的烧瓶中将1摩尔相应的氯化鎓或溴化鎓(来自上述实施例)溶解在200毫升去离子水中，然后缓慢加入1摩尔相应的氟烷基磷酸钾(或钠)。立即形成2相。
将这两个相在室温下再搅拌1小时。然后分离出有机相，并用每次100毫升去离子水洗涤5次直至脱除氯化物(验证：1摩尔硝酸银溶液)，并在80℃-90℃真空干燥。
实施例5.1：借助次膦酸制备双(氟烷基)次膦酸根基反应性离子液体
通用程序
在带有磁搅拌棒的烧瓶中，将1摩尔相应的氯化鎓(来自上述实施例)溶解在200毫升去离子水中，然后缓慢加入1摩尔相应的双(氟烷基)次膦酸。
将反应混合物在室温下再搅拌1小时，将水与形成的盐酸一起馏出。为了实现盐酸的完全除去，可以用二氧杂环己烷和水反复共沸蒸馏(直至用硝酸银溶液的阴性试验结果)。在80℃-90℃的真空干燥以几乎定量收率产生双(氟烷基)-次膦酸盐。
实施例5.2：经由相应的钾盐制备双(氟烷基)次膦酸根基反应性离子液体
通用程序
在带有磁搅拌棒的烧瓶中，将1摩尔相应的氯化鎓(来自上述实施例)溶解在异丙醇(或甲醇或乙腈)中，然后缓慢加入1摩尔相应的氟烷基次膦酸钾。
将反应混合物在室温下再搅拌1小时，滤出形成的KCl。借助旋转蒸发器在真空中除去异丙醇(或甲醇或乙腈)，以几乎定量收率产生双(氟烷基)-次膦酸盐。
实施例5.3：经由相应的次膦酸甲酯制备双(氟烷基)次膦酸根基反应性离子液体
在带有磁搅拌棒的烧瓶中，将1至1.1摩尔相应的双(氟烷基)次膦酸甲酯添加到1摩尔相应的氯化鎓(或溴化鎓)(来自上述实施例)中。
将该反应混合物在室温下或在加热最高达100℃下搅拌1至20小时，并真空除去形成的CH3Cl(或CH3Br)和过量双-(氟烷基)次膦酸甲酯。以几乎定量收率形成双(氟烷基)次膦酸盐。
表4
表5
表6
乙酸根基、三氟甲磺酸根基、酰亚胺基和甲基阴离子基反应性离子液体的制备
实施例5：酰亚胺基和甲基阴离子基离子液体的制备
通用程序
在带有磁搅拌棒的1升烧瓶中，将1摩尔相应的氯化鎓或溴化鎓(来自上述实施例)溶解或部分悬浮在200-500毫升去离子水中，然后缓慢加入1摩尔相应的锂盐或钾盐或1摩尔双(三氟甲基磺酰基)酰亚胺(N-H酸)或三(三氟甲基磺酰基)甲基化物(C-H酸)。立即形成2相。
将这两个相在室温再搅拌1至10小时。然后通过用每次50毫升二氯甲烷摇振3次来萃取该乳状液。然后用每次100毫升去离子水洗涤5次有机相，直至脱除氯化物(验证：1摩尔硝酸银溶液)。
向该有机溶液中加入10克Al2O3和1.4克活性炭，在大约1小时后再过滤该混合物，并在带有在大约80℃的水浴的旋转蒸发器中蒸发。
表7
表8
表9
三氟乙酸根基或三氟甲磺酸根基离子液体的制备
实施例6.1：借助三氟甲磺酸制备三氟甲磺酸根基离子液体
通用程序
在带有磁搅拌棒的烧瓶中，将1摩尔相应的氯化鎓(来自上述实施例)溶解在200-500毫升去离子水中，然后缓慢加入1摩尔三氟甲磺酸。
将反应混合物在室温再搅拌1小时，将水与形成的HCl一起馏出。为了实现HCl的完全除去，可以用二氧杂环己烷和水反复共沸蒸馏(直至用硝酸银溶液的阴性试验结果)。在80℃-90℃的真空干燥以几乎定量收率产生三氟甲磺酸盐。
实施例6.2：经由相应的钾或锂盐制备三氟乙酸根基或三氟甲磺酸根基离子液体
通用程序
在带有磁搅拌棒的烧瓶中，将1摩尔相应的氯化鎓(来自上述实施例)溶解在异丙醇(或甲醇或乙腈)中，然后缓慢加入1摩尔相应的三氟乙酸钾(或锂)或三氟甲磺酸钾(或锂)。
将反应混合物在室温再搅拌1小时，滤出形成的KCl(或LiCl)。借助旋转蒸发器在真空中除去异丙醇(或甲醇或乙腈)，以几乎定量收率产生三氟乙酸盐或三氟甲磺酸盐。
实施例6.3：经由相应的三氟甲磺酸甲酯、三氟甲磺酸三甲硅烷基酯、三氟甲磺酸酐或三氟乙酸酐制备三氟乙酸根基和三氟甲磺酸根基离子液体
在带有磁搅拌棒的烧瓶中，将1至1.1摩尔相应的三氟甲磺酸甲酯、三氟甲磺酸三甲硅烷基酯、三氟甲磺酸酐或三氟乙酸酐添加到1摩尔相应的氯化鎓(或溴化鎓)(来自上述实施例)中。
该反应混合物在室温下或在加热最高达100℃下再搅拌1至48小时，并真空除去形成的CH3Cl(或CH3Br或(CH3)3SiCl或CF3SO2Cl或CF3COCl或CF3COBr)和过量三氟甲磺酸甲酯或三氟甲磺酸三甲硅烷基酯或酐。以几乎定量收率形成三氟乙酸盐或三氟甲磺酸盐。
表10
表11
实施例7：硼酸根基、磷酸根基和铝酸根基离子液体的制备
通用程序
在带有磁搅拌棒的3升烧瓶中，将1摩尔相应的氯化鎓或溴化鎓(来自上述实施例)溶解在2升二氯甲烷中，然后缓慢加入1摩尔相应的钾或锂盐。在添加后，将反应混合物搅拌5天。然后向该批料中加入500毫升去离子水。形成2相。分离出有机相，用300毫升二氯甲烷洗涤水相，合并所有有机相。将有机相用每次250毫升去离子水再洗涤两次，然后蒸发至1/3，然后搅拌到1升正庚烷中。
形成2相。分离出包含该离子液体的正庚烷整夜，并在带有在60至70℃的水浴的旋转蒸发器中蒸发。
表12
表13
表14
实施例8：在石墨上的研究
在每种情况下，在带有石墨阳极(含PVDF粘合剂的SFG 44)、锂对电极和锂参比电极的测量电池中相继记录5个循环伏安图。为此，首先将电位从静止电位开始以0.1mV/s的速率降至相对于Li/Li+的0V，然后恢复至该静止电位。
所用电解质是在碳酸亚乙酯∶碳酸二亚乙酯(比率3∶7)中的1M LiPF6，在每种情况下向其中加入大约2％选自表7的反应性离子液体。该反应性离子液体在相对Li/Li+大约2V至0.9V的电位形成钝化顶层。从第二循环开始，实现了锂离子在石墨中的包含和提取的95％收率(±5％测量公差)。
不能观察到选自表15的反应性离子液体在石墨中的共嵌入。
表15
*参照物＝LiPF6在EC∶DEC(3∶7)中
实施例9：在石墨上的研究
在每种情况下，在带有石墨阳极(含PVDF粘合剂的SFG 44)、锂对电极和锂参比电极的测量电池中相继记录5个循环伏安图。为此，首先将电位从静止电位开始以0.1mV/s的速率降至相对Li/Li+的0V，然后恢复至该静止电位。
所用电解质是在EC∶DEC(比率3∶7)中的1M LiPF6，在每种情况下向其中加入大约10％选自表8的反应性离子液体。该反应性离子液体在相对Li/Li+大约2V至0.9V的电位形成钝化顶层。从第二循环开始，实现了锂离子在石墨中的包含和提取的大于90％收率(±5％测量公差)。
不能观察到选自表16的反应性离子液体在石墨中的共嵌入。
表16
*参照物＝LiPF6在EC∶DEC(3∶7)中
实施例10：氧化稳定性的研究
在每种情况下，在带有铂工作电极、锂对电极和锂参比电极的测量电池中相继记录5个循环伏安图。为此，首先将电位从静止电位开始以10mV/s的速率提高至相对Li/Li+的6.0V，然后恢复至该静止电位。
所用电解质是在EC∶DEC(比率3∶7)中的1M LiPF6，在每种情况下向其中加入大约2％选自表17的反应性离子液体。测得氧化电位为相对Li/Li+＞5V。
在所研究的任何系统中，没有发现低于参照电解质的氧化稳定性的信号。
表17
*参照物＝LiPF6在EC∶DEC(3∶7)中
实施例11：氧化稳定性的研究
在每种情况下，在带有铂工作电极、锂对电极和锂参比电极的测量电池中相继记录5个循环伏安图。为此，首先将电位从静止电位开始以10mV/s的速率提高至相对Li/Li+的6.0V，然后恢复至该静止电位。
所用电解质是在EC∶DEC(比率3∶7)中的1M LiPF6，在每种情况下向其中加入大约10％选自表18的反应性离子液体。测得氧化电位为相对Li/Li+＞5V。在所研究的任何系统中没有发现低于参照电解质的氧化稳定性的信号。
表18
*参照物＝LiPF6在EC∶DEC(3∶7)中

Claims (26)

1.通式I的离子液体：
K+A-    (I)
其中：
K+是指选自的阳离子，
其中
X是指CH2、O、S或NR′，
R′是指-(CH2)n-CN、C1-至C16-烷基、H，
R是指H、C1-至C16-烷基，
R5是指-(CH2)n-O-C(O)-R、-(CH2)n-C(O)-OR、-(CH2)n-HC＝CH-R或-(CH2)n-CN，其中各个CH2基团可以被S或NR替代，
其中n＝1至8，
且
A-是指阴离子，选自：
其中
是指1，2-或1，3-二醇、1，2-或1，3-二羧酸或1，2-或1，3-羟基羧酸，
X是指B，
R1至R4是指卤素，和/或氟化或非氟化的烷氧基或羧基。
2.根据权利要求1的离子液体，其中关于R′定义的C1-至C16-烷基选自甲基、乙基和丙基。
3.根据权利要求1的离子液体，其中关于R定义的C1-至C16-烷基选自甲基、乙基和丙基。
4.根据权利要求1的离子液体，其中m＝1至4。
5.根据权利要求1的离子液体，其中关于R1至R4定义的卤素是F。
6.根据权利要求1至5任一项的离子液体，其中K+选自：
7.根据权利要求1的离子液体，其特征在于所述阳离子K+是选自通式的化合物，
其中
X是指CH2、O、S或NR′，
R′是指-(CH2)n-CN、C1-至C16-烷基、H，
R是指H、C1-至C16-烷基，
R5是指-(CH2)n-O-C(O)-R、-(CH2)n-C(O)-OR、-(CH2)n-HC＝CH-R或-(CH2)n-CN，其中各个CH2-基团可以被S或NR替代，
其中n＝1至8。
8.根据权利要求7的离子液体，其中关于R′定义的C1-至C16-烷基选自甲基、乙基和丙基。
9.根据权利要求7的离子液体，其中关于R定义的C1-至C16-烷基选自甲基、乙基和丙基。
10.根据权利要求1至5、7至9任一项的离子液体，其特征在于在R5中一个或多个CH2-基团被S或NR替代。
11.电解质，包含至少一种导电盐、非质子溶剂或溶剂混合物、至少一种根据权利要求1至10任一项的离子液体和任选地其它添加剂，其中所述非质子溶剂或溶剂混合物由有机开链或环状碳酸酯、羧酸酯、腈、醚、内酯或其混合物构成。
12.根据权利要求11的电解质，其特征在于所述导电盐是锂导电盐。
13.根据权利要求12的电解质，其特征在于所述导电盐是LiPF6、LiN(SO2CF3)2、LiN(SO2C2F5)2、LiF3P(C2F5)3、LiF3P(C4F9)3、LiB(C2O4)2或LiF2B(C2O4)2。
14.根据权利要求11的电解质，其特征在于所述导电盐选自下述化合物：
N(C2H5)4BF4、N(C2H5)4PF6、N(C2H5)3(CH3)BF4、N(C2H5)3(CH3)PF6、N(C2H5)4N(SO2CF3)2、N(C2H5)3(CH3)N(SO2CF3)2、N(C2H5)4F3P(C2F5)3、N(C2H5)3(CH3)F3P(C2F5)3。
15.制备根据权利要求1至10任一项的通式I的离子液体的方法，包括下述步骤：
·通过传统湿化学法，由相应的胺、膦、卤代羧酸盐/酯、卤代碳酸盐/酯、卤代烷基腈或烷基卤制备氯化鎓或溴化鎓形式的根据权利要求1的杂环阳离子K+，该杂环阳离子K+具有含烷基、羧酸根或羧酸酯基团、碳酸根或碳酸酯基团、或氰基的侧链，
·在水性和/或醇类介质或有机溶剂中，或在无溶剂的情况下，使这些阳离子型氯化鎓或溴化鎓与相应的阴离子型下述物质反应：
-氟烷基磷酸钾和/或氟烷基磷酸钠，和/或双(氟烷基)次膦酸钾和/或双(氟烷基)次膦酸钠，和/或氟烷基膦酸钾和/或氟烷基膦酸钠，和/或氟烷基磷酸，和/或双(氟烷基)次膦酸，和/或氟烷基膦酸，和/或双(氟烷基)次膦酸烷基酯，或
-酰亚胺锂或甲基化锂，和/或三氟甲磺酸，或三氟乙酸钾或三氟乙酸锂，或三氟甲磺酸钾或三氟甲磺酸锂，或三氟甲磺酸烷基酯，或三氟甲磺酸三甲硅烷基酯，和/或三氟甲磺酸酐，或三氟乙酸酐，或
-硼酸锂或硼酸钾，磷酸锂或磷酸钾，或铝酸锂或铝酸钾。
16.含有至少一种电解质的电化学和/或光电器件，所述电解质包含至少一种根据权利要求1至10任一项的通式I的离子液体。
17.根据权利要求16的电化学和/或光电器件，其特征在于其是至少一种太阳能电池、锂离子电池、锂电池、双层电容器或超级电容器、锂电容器、发光器件、电化学传感器和/或生物传感器。
18.根据权利要求1至10任一项的通式I的离子液体的用途，用作电化学或光电电池用的电解质中的导电盐或添加剂。
19.根据权利要求1至10任一项的通式I的离子液体的用途，用作电池的电解质中的导电盐或添加剂。
20.根据权利要求1至10任一项的通式I的离子液体的用途，用作二次锂电池中的电解质中的导电盐或添加剂。
21.根据权利要求1至10任一项的通式I的离子液体的用途，用于双层电容器和超级电容器或锂电容器中。
22.根据权利要求1至10任一项的通式I的离子液体的用途，用作电化学电池中的形成钝化覆盖层的添加剂。
23.根据权利要求11至14任一项的电解质的用途，用于电化学和/或光电器件中。
24.根据权利要求11至14任一项的电解质的用途，用于锂或锂离子电池中。
25.根据权利要求11至14任一项的电解质的用途，用于双层电容器和超级电容器或锂电容器中。
26.权利要求15的方法，其中所述双(氟烷基)次膦酸烷基酯是甲基酯。
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CN102015666A (zh) 2011-04-13
KR101650207B1 (ko) 2016-08-22
EP2274291A2 (de) 2011-01-19
US9006457B2 (en) 2015-04-14
JP5778575B2 (ja) 2015-09-16

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