CN100413873C - 离子型液体ⅱ - Google Patents

离子型液体ⅱ Download PDF

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CN100413873C
CN100413873C CNB011228059A CN01122805A CN100413873C CN 100413873 C CN100413873 C CN 100413873C CN B011228059 A CNB011228059 A CN B011228059A CN 01122805 A CN01122805 A CN 01122805A CN 100413873 C CN100413873 C CN 100413873C
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ionic liquid
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CN1327986A (zh
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M·施米特
U·海德
W·盖斯勒
N·伊格纳蒂夫
V·希拉里斯
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Merck Patent GmbH
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Abstract

本发明涉及用于电化学电池和有机合成的离子型液体。

Description

离子型液体Ⅱ
本发明涉及用于电化学电池和有机合成中的离子型液体。
美国专利US 2446331中第一次描述了无溶剂的离子型液体或“在室温下熔化的盐类”。这些强路易斯酸存在的问题是与大气中的潮气接触易形成有毒气体。
人们对涉及AlCl3和1-乙基-3-甲基咪唑(EMI)氯化物的化合物进行了长期研究。Wilkes和Zaworotko于1992年发现了新型无溶剂的离子型液体,EMI BF4和EMI O2CCH3,见J.Chem.Soc.,Chem.Commun.,第965页。但是,这些化合物不适宜在电化学电池中用做电解质,因为BF4和CH3CO2阴离子甚至在相对低的电位下也易被氧化.
德国专利DE 196 41138中描述了一种新型导电盐,氟代烷基磷酸锂。这些盐具有十分突出的高电化学稳定性和低水解倾向。(M.Schmidt et al.10thInternational Meeting on Lithium Batteries,Como 2000)。在循环实验中,这些化合物显示特别好的结果,且被证明是特别稳定的。
美国专利US 5827602描述了离子型液体的用途,该组离子型液体选自包含吡啶,哒嗪,嘧啶,吡嗪,咪唑,吡唑,噻唑,噁唑,和三唑盐的一组,在电化学电池中含有亚氨盐和甲烷盐(Methanide)作为阴离子。这些离子型液体由于具有良好的导电性特别适合于这种用途。其重要的缺点在于原材料特别是阴离子的昂贵合成。
本发明的目的在于提供具有大的液体范围,高热稳定性,低腐蚀性及较低合成造价的阴离子的离子型液体。
本发明的目的通过通式为下式的离子型液体实现:
K+A-(I)
其中,K+为阳离子,选自:
Figure C0112280500051
其中R1到R5相同或不同,可选择地通过一单键或双键彼此直接键合,且每个单独或一起具有以下的意义:
-H,
-卤素,
-烷基(C1到C8),它可部分或全部被进一步的基团,优选F,Cl,N(CnF(2n+1-x)Hx)2,O(CnF(2n+1-x)Hx),SO2(CnF(2n+1-x)Hx)或CnF(2n+1-x)Hx取代,其中1<n<6且0<x≤2n+1
且A-为阴离子,选自:
[PFx(CyF2y+1-zHz)6-x]-
其中1≤x<6
1≤y≤8,以及
0≤z≤2y+1。
优选的是,本发明的目的是通过通式为下式的离子型液体实现:
K+A-(I)
其中:
K+为阳离子,选自:
其中R1到R5相同或不同,任意选择地通过一单键或双键彼此直接键合,且每个单独或一起具有以下的意义:
-H,
-卤素,
-具有1-8个碳原子的烷基基团,
且A-为选自如下的阴离子:
[PFx(CyF2y+1-zHz)6-x]-
其中1≤x<6
1≤y≤8
0≤z≤2y+1,
而且上述阴离子不包括[(CF3)2PF4]-、[(CF3)3PF3]-、[(CF3)4PF2]-、[(CF3)5PF]-和[(CF3)6P]-
这些离子型液体适合作为有机合成的溶剂,但也可以用于电化学电池。另外,这些离子型液体还适合于用作有机反应的催化剂。另外,它们还适用于作为高反应活性的化学品的惰性溶剂。还可以用于液压液体领域。
已发现本发明化合物由于使用了全氟烷烃链,优选使用相对长链的全氟烷烃因而是疏水的。而且无水合成最大限度地减少了不希望带入反应体系的水分。
令人惊奇的发现离子型液体是不腐蚀的,但比通常用于电化学电池的铝电流集电器更钝化。这使得循环稳定性增加。另外,通过使用离子型液体可观察到体系的热稳定性的改善。
人们发现加入低粘度的溶剂可提高导电性。低粘度和高导电性是用于电化学电池的先决条件。本发明的化合物具有大的液体范围,使得它们特别适合这种应用。
用于双层电容器的先决条件是高导电性。本发明的化合物满足这一标准,因此可单独使用或以与其它溶剂或导电盐的混合物的形式使用。这些适合的溶剂选自有机碳酸酯(例如,碳酸亚乙酯,碳酸亚丙酯,及其衍生物,碳酸亚丁酯,碳酸二甲酯,碳酸二乙酯,碳酸乙基甲基酯,等),有机羧酸酯(例如,γ-丁内酯,甲酸甲酯,乙酸甲酯,乙酸乙酯,丙酸乙酯,丙酸甲酯,丁酸甲酯,丁酸乙酯,等),有机羧酸酰胺(例如,二甲基甲酰胺,甲基甲酰胺,甲酰胺等),有机醚(例如,1,2-二甲氧基乙烷,四氢呋喃,2-甲基四氢呋喃,四氢呋喃衍生物,1,3-二氧环戊烷,二氧杂环己烷,二氧杂环戊烷衍生物等)或其它对质子惰性的溶剂(例如乙腈,环丁砜。二甲亚砜。硝基甲烷,磷酸三酯,三甲氧基甲烷,3-甲基-2-噁唑烷二酮等)。同样的也可以使用溶剂的混合物,例如碳酸亚乙酯/碳酸二甲酯(ECIDMC)。
本发明的化合物可与常规导电性盐一起用于惯常的电解质中。它们可以1-99%存在于混合物中。适合的电解质的例子为带有选自如下的导电盐的电解质:LiPF6,LiBF4,LiClO4,LiAsF6,LiCF3SO3,LiN(CF3SO2)2和LiC(CF3SO2)3及其混合物。
该电解质也包含有机异氰酸酯(DE 199 44 603)以减少水含量。
也提供了通式(DE 199 51 804)如下的复合盐:
Mx+[EZ]y- x/y
其中:
x和y为1,2或3,
Mx+为金属离子,
E为一种Lewis酸,选自:
BR1R2R3,AlR1R2R3,PR1R2R3R4R5,AsR1R2R3R4R5和VR1R2R3R4R5
R1到R5可相同或不同,可选择地直接与另一个基团通过一单键或双键键合,且每个单独或一起为:
卤素(F,Cl或Br),
烷基或烷氧基(C1到C8),它们可被部分或全部被F,Cl或Br取代,
芳香环,任意选择地通过氧键合,选自:苯基,萘基,蒽基和菲基,这些基团可以是来取代的,或被烷基(C1至C8)或F,Cl或Br单取代到多取代,
芳香杂环,任意选择地通过氧键合,选自:吡啶基,吡唑基和嘧啶基,这些基团可以是未取代的,或被烷基(C1至C8)或F,Cl或Br单取代到多取代,
Z为OR6,NR6R7,CR6R7R8,OSO2R6,N(SO2R6)(SO2R7),C(SO2R6)-(SO2R7)(SO2R8)或OCOR6,其中
R6到R8相同或不同,可选择地直接与另一个基团通过一单键或双键键合,且每个单独或一起为:
氢或如R1到R5的定义,
通过相应的硼或磷Lewis酸/溶剂加合物与亚氨化锂或四烷基铵,methanide或三氟甲磺酸盐反应制备。
也提供了通式如下的硼酸盐(DE 199 59 722):
Figure C0112280500081
其中:
M为金属离子或四烷基铵离子,
x和y为1,2或3,
R1到R4相同或不同,为烷氧基或羧基(C1-C8),它们任意选择地直接与另外的基团通过单键或双键键合。这些硼酸盐可如下制备,使四烷氧基硼酸锂或烷氧基锂与硼酸的1∶1混合物,与适合的羟基或羧基化合物在对质子惰性的溶剂中按2∶1或4∶1的比例反应
也可以存在添加剂,例如通式如下的硅烷化合物:
SiR1R2R3R4
其中R1到R4
H
CyF2y+1-zHz
OC(O)CyF2y+1-zHz
OSO2CyF2y+1-zHz
且1<x<6
1<y<8
0<z<2y+1
R1-R4可相同或不同,为选自苯基和萘基的芳香环,而苯基或萘基可以是非取代的或被下面基团单取代或多取代:F,CyF2y+1-zHz,OCyF2y+1-zHz,OC(O)CyF2y+1-zHz,OSO2CyF2y+1-zHz或N(CyF2y+1-zHz)2,或为选自吡啶基,吡唑基,或嘧啶基的杂芳环,该这些基团中的每一个可被下面基团单取代或多取代:F,CyF2y+1- zHz,OCyF2y+1-zHz,OC(O)CyF2y+1-zHz,OSO2 CyF2y+1-zHz或N(CyF2y+1-zHz)2(DE 100 27626)。
本发明的化合物也可以用于含有下式表示的氟烷基磷酸锂电解质:
Li+[PFx(CyF2y+1-zHz)6-x]-
其中1≤x≤5
3≤y≤8
0≤z≤2y+1
配体(CyF2y+1-zHz)可以相同或不同,只是以下通式化合物除外:
Li+[PFa(CHbFC(CF3)d)c]-
其中,a为2-5的整数,b=0或1,c=0或1,d=2,e为1-4的整数,前提是b和c不能同时分别为0,且a+e的和等于6,配体(CHbFC(CF3)d)可以相同或不同(DE 100 089 55)。
制备氟烷基磷酸锂的方法,其特征在于至少一种通式为下式的化合物:
HmP(CnH2n+1)3-m
OP(CnH2n+1)3
ClmP(CnH2n+1)3-m
FmP(CnH2n+1)3-m
CloP(CnH2n+1)5-o
FoP(CnH2n+1)5-o
其中,0<m<2,1<n<8且0<o<4,
通过在氟化氢中电解氟化,得到的氟化产物的混合物通过提取,相分离和/或蒸馏加以分离,得到的氟化的烷基膦(phosphorane)在质子惰性的溶剂混合物中,在除去水分的条件下与氟化锂反应,得到的盐提纯并用常规方法分离。
本发明的化合物也可以用于含有下式的盐的电解质:
Li[P(OR1)a(OR2)b(OR3)c(OR4)dFe]
其中0<a+b+c+d≤5且a+b+c+d+e=6,R1到R4,各自独立的为烷基,芳基或杂芳基基团,其中R1到R4至少两个可与另外一个通过单键或双键直接键合(DE 100 16 801)。该化合物可通过下面制备:将通式如下的磷(V)化合物:
Li[P(OR1)a(OR2)b(OR3)c(OR4)dFe]
其中0<a+b+c+d≤5且a+b+c+d+e=5,R1到R4的定义如上,与氟化锂在有机溶剂存在下反应。
电解质中也可存在下面通式的离子型液体:
K+A-
其中,K+为选自如下的阳离子:
Figure C0112280500101
其中R1到R5相同或不同,可选择地直接与另一个基团通过一单键或双键键合,且每个单独或一起具有以下的意义:
-H,
-卤素,
-烷基(C1到C8),可被部分或全部被进一步的下列基团取代:F,Cl,N(CnF(2n+1-x)HX)2,O(CnF(2n+1-x)HX),SO2(CnF(2n+1-X)HX)或CnF(2n+1-X)HX,其中1<n<6且0<x≤2n+1
且A-为选自如下的阴离子:
[B(OR1)n(OR2)m(OR3)o(OR4)p]-
其中0<n,m,o,p≤4,且
m+n+o+p=4,
其中,R1到R4不同或成对的相同,可选择地直接与另一个基团通过一单键或双键键合,且每个单独或一起为:
芳环,选自:苯基,萘基,蒽基和菲基,这些基团可以是未取代的,或被下列基团单取代到多取代;CnF(2n+1-x)HX,其中1<n<6且0<x≤13,或卤素(F,Cl或Br),
芳杂环,选自:吡啶基,吡唑基和嘧啶基,这些基团可以是未取代的,或被下列基团单取代到多取代;CnF(2n+1-x)HX,其中1<n<6且0<x≤13,或卤素(F,Cl或Br),
烷基(C1到C8),可部分或全部被进一步的基团、优选F,Cl,N(CnF(2n+1-x)HX)2,O(CnF(2n+1-x)HX),SO2(CnF(2n+1-x)HX或CnF(2n+1-x)HX,其中1<n<6和0<x≤13,取代
或OR1到OR4
单独或一起为芳香或脂肪羧基,二羧基,氧代磺酰基,或氧代羰基基团,这些基团可部分或全部被进一步的基团、优选F,Cl,N(CnF(2n+1-x)HX)2,O(CnF(2n+1-x)HX),SO2(CnF(2n+1-x)HX)或CnF(2n+1-x)HX,其中1<n<6和0<x≤13取代(DE 10026565)。
根据本发明的化合物也可以用在包含下面通式的化合物的电解质中:
NR1R2R3
其中,R1和R2为H,CyF(2y+1-z)Hz或(CnF2n-mHm)X,其中X为芳香的或杂环的基团,
R3为(CnF2n-mHm)Y,其中Y为杂环基团,或(CoF2o-pHp)Z,其中Z为芳香基团,
且其中n,m,o,p,y和z满足下列条件:
0≤n≤6
0≤m≤2n
2≤o≤6
0≤p≤2o,
1≤y≤8且
0≤z≤2y+1,
用于在电化学电池中减少对质子惰性的电解质体系的酸含量。
也可以使用通式如下的氟烷基磷酸盐:
Mn+[PFx(CyF2y+1-zHz)6-x]-
其中:
1≤x≤6
1≤y≤8
0≤z≤2y+1
1≤n≤3,且
Mn+为单价或三价阳离子,特别是:
NR1R2R3R4
PR1R2R3R4
P(NR1R2)kR3 mR4 4-k-m(基中k=1-4,m=0-3且k+m≤4),
C(NR1R2)(NR3R4)(NR5R6),
C(烷基)3,Rb或托品基(tropylium),
其中R1到R8为H,烷基或芳基(C1-C8),可被F,Cl或Br部分取代,
其中,排除Mn+=Li+,Na+,Cs+,K+和Ag+的情况。这些氟烷基磷酸盐通过将正磷与氟化物,或金属氟烷基磷酸盐与氟化物或氯化物在有机非质子溶剂中反应得到(DE 100 388 58)。
电解质也可以包含下面的混合物:
a)至少一种下面通式的氟烷基磷酸锂:
Li+[PFx(CyF2y+1-zHz)6-x]-
其中:
1≤x≤5
1≤y≤8且
0≤z≤2y+1
在每中情况下配体CyF2y+1-zHz可相同或不同,及
b)至少一种聚合物(DE 100 58 264)。
电解质还可以包括下面通式的四氟烷基硼酸盐:
Mn+([BR4]-)n
其中,Mn+为单价,二价或三价阳离子,
在每种情况下配体R相同,为(CxF2x+1),其中1≤x≤8,且n=1,2或3(DE100 558 11)。制备四氟烷基硼酸盐的方法,其特征在于至少有一种通式为Mn+([B(CN)4]-)n的化合物,其中Mn+和n的定义如上,通过与至少一种氟化试剂在至少一种溶剂中氟化,得到的被氟化的化合物通过常规方法提纯和分离。
电解质还可以包括下面通式的硼酸盐:
Mn+[BFx(CyF2y+1-zHz)4-x]n -
其中
1<x<3,1≤y≤8且0≤z≤2y+1,
M为除了钾和钡之外的单价到三价阳离子(1≤n≤3),
特别是:
Li,
NR1R2R3R4,PR5R6R7R8,P(NR5R6)kR7 mR8 4k-m(其中k=1-4,m=0-3且k+m≤4),或
C(NR5R6)(NR7R8)(NR9R10),其中
R1到R4为CyF2y+1-zHz
R5到R10为H或CyF2y+1-zHz,或
芳香杂环阳离子,优选含氮和/或氧和/或硫的芳香杂环阳离子(DE 101 03189)。制备这些化合物的特征在于:
a)1∶1的BF3/溶剂复合物与烷基锂在冷却下反应,缓慢升温下除去大部分的溶剂,而后过滤得到的固体,用适当的溶剂洗涤,
b)在适当的溶剂中锂盐与B(CF3)F3盐1∶1的反应,混合物升温搅拌,除去溶剂,向反应混合物中加入非质子非水溶剂,优选那些用于电化学电池中的溶剂,将反应混合物干燥,或
c)B(CF3)F3盐与锂盐按1∶1到1∶1.5的比例在水中在升温下反应,在沸点下加热0.5到2小时,除去水,向反应混合物中加入非质子非水溶剂,优选那些用于电化学电池中的溶剂,将反应混合物干燥。
电解质也可以包含下面通式的氟烷基磷酸盐:
Mn+[PFx(CyF2y+1-zHz)6-x]n -
Mn+为单价,二价或三价阳离子,
1≤x≤5
1≤y≤8且
0≤z≤2y+1,n=1,2或3,在每种情况下配体(CyF2y+1-zHz)可以相同或不同,其中氟烷基磷酸盐中
Mn+为锂阳离子,且盐
M+([PF4(CF3)2]-)中M+=Cs+,Ag+或K+
M+([PF4(C2F5)2]-)中M+=Cs+
M+([PF3(C2F5)3]-)中M+=Cs+,K+,Na+或对-Cl(C6H4)N2 +
M+([PF3(C3F7)3]-)中M+=Cs+,K+,Na+,对-Cl(C6H4)N2 +或对-O2N(C6H4)N2 +,被排除(DE 100 558 12)。制备这些氟烷基磷酸盐的特征在于:至少一种下面通式的化合物:
HrP(CsH2s+1)3-r
OP(CsH2s+1)3
ClrP(CsH2s+1)3-r
FrP(CsH2s+1)3-r
CltP(CsH2s+1)5-t和/或
FtP(CsH2s+1)5-t
其中,在每种情况下:
0≤r≤2
3≤s≤8且
0≤t≤4,
通过在氟化氢中电解被氟化,得到的氟化产物混合物分离,将得到的氟化的烷基磷酸在非质子溶剂或在除去水分的溶剂的混合物中与下面的通式的化合物反应:
Mn+(F-)n,其中Mn+和n如上述所定义,
得到的氟烷基磷酸盐通过常规方法提纯和分离。
本发明的化合物也可以用于含有下式的氟烷基磷酸盐(DE 10109032)电解质中:
(Ma+)b[(CnF2n+1-mHm)yPF5-y(CR1R2)xPF5-y(CnF2n+1-mHm)y](2-) (a+b/2)
其中,
Ma+为单价,二价或三价阳离子,
a=1,2或3,b=2对应于a=1,b=2对应于a=3,b=1对应于a=2,且在每种情况下:
1≤n≤8,
0≤m≤2对应于n=1或2,
0≤m≤4对应于3≤n≤8
1≤x≤12,
0≤y≤2
其中在每种情况下R1和R2相同或不同,选自:氟,氢,烷基,氟烷基和全氟烷基取代基,且
在其中每种情况下,取代基(CnF2n+1-mHm)相同或不同。这些化合物如下制备:将至少一种氟-α,ω-双(烷基氟代磷酰)烷烃与至少一种通式为(Ma+)[F-]a,其中(Ma+)和a的定义同上的氟盐在溶液中反应,得到氟烷基磷酸盐,并在必要时用常规方法对后者加以提纯和/或分离。
本发明的化合物可用于下面的电化学电池的电解质,其阳极材料由涂覆的金属核构成。金属选自Sb,Bi,Cd,In,Pb,Ga和锡或它们的合金(DE 100 16 024)。制备这种阳极材料的方法的特征在于:
a)制备一种金属或合金核在乌洛脱品中的悬浊液或溶液,
b)将该悬浊液在的C5-C12-烷烃中乳化,
c)将乳化液沉淀在金属或合金核上,
d)通过加热体系将金属氧化物或过氧化物转化为相应的氧化物。
本发明的化合物还可用于下面的电化学电池的电解质,其阴极材料由通常的锂嵌入或插入化合物制成。阴极材料也可以由用一种或多种金属氧化物涂覆的混合金属氧化物锂颗粒构成(DE 199 22 522)。它们也可以由用一种或多种聚合物涂覆的混合金属氧化物锂颗粒构成(DE 199 46 066)。本发明的化合物同样可以用于下面的阴极体系,其阴极由用一种或多种碱金属化合物和金属氧化物涂覆的混合金属锂颗粒构成(DE 100 14 884)。制备这些材料的特征在于:将颗粒悬浮于有机溶剂中,加入悬浮于有机溶剂中的碱金属盐化合物,加入溶于有机溶剂的金属氧化物,向悬浊液中加入水解溶液,随后过滤被涂覆的颗粒,干燥并煅烧。本发明的化合物也可以用于含有浸渍了氧化锡的阳极材料的体系(DE 100 25761)。这些阳极材料可按下面方法制备:
a)向氯化锡溶液中加入尿素,
b)向溶液中加入乌洛脱品和适宜的浸渍化合物,
c)得到的溶液在石油醚中乳化,
d)洗涤得到的凝胶,抽滤除去溶剂,
e)干燥并加热该凝胶。
本发明的化合物还可以用于含有用还原的锡氧化物制成的阳极材料的体系(DE 100 257 62)。阳极材料如下制备:
a)向氯化锡溶液中加入尿素,
b)向溶液中加入乌洛脱品,
c)得到的溶液在石油醚中乳化,
d)洗涤得到的凝胶,抽滤除去溶剂,
e)干燥并加热该凝胶。
f)将得到的SnO2暴露在一可通空气的反应炉中暴露在还原气蒸汽中。
下面将对本发明的一般实施例加以详细解释。
阴离子选自由下式构成的一组:
[PFx(CyF2y+1-zHz)6-x]-
其中1≤x≤6
1≤y≤8且
0≤z≤2y+1
按照DE 196 411 38所使用的方法制备。
阳离子选自下面构成的一组:
Figure C0112280500171
由已知的US 5827602中的方法制备。将起始原料在对质子惰性的有机溶剂中,在溶剂为液体范围的温度下反应0.5到12小时,优选1-4小时。
为除去副产物,将混合物冷却至-30℃,例如在LiCl为副产物的情况下,冷却至-10℃到-20℃,将沉淀的副产物过滤除去,优选在真空下过滤。
溶剂/产物的混合物可以直接用于电解质中。在必要时,可蒸馏除去溶剂,将得到的产物干燥以用于所述是用途。
下面的实施例旨在对本发明加以详细说明,但不限制发明。
实施例
实施例1
三(五氟乙基)三氟磷酸1-乙基-3-甲基咪唑鎓的合成
三(五氟乙基)三氟磷酸锂按照DE 196411 38的方法合成。产物在乙腈中按照下面反应式进行反应:
Figure C0112280500172
反应混合物在冷却下用玻璃漏斗真空过滤,以除去所形成的LiCl副产物。在减压下蒸馏除去溶剂,得到的三(五氟乙基)三氟磷酸1-乙基-3-甲基咪唑鎓在减压下干燥。
实施例2
三(五氟乙基)三氟磷酸1,2-二甲基-3-丙基咪唑鎓
三(五氟乙基)三氟磷酸锂按照DE 196411 38的方法合成。产物在乙腈中按照下面反应式进行反应:
反应混合物在冷却下用玻璃漏斗真空过滤,以除去所形成的LiCl副产物。在减压下蒸馏除去溶剂,得到的三(五氟乙基)三氟磷酸1,2-二甲基-3-丙基咪唑鎓在减压下干燥。
实施例3
三(九氟丁基)三氟磷酸1-乙基-3-甲基咪唑鎓的合成
三(九氟丁基)三氟磷酸锂的合成类似于三(五氟乙基)三氟磷酸锂合成。产物在乙腈中按照下面反应式进行反应:
Figure C0112280500182
反应混合物在冷却下用玻璃漏斗真空过滤,以除去所形成的LiCl副产物。在减压下蒸馏除去溶剂,得到的三(九氟丁基)三氟磷酸1-乙基-3-甲基咪唑鎓在减压下干燥。

Claims (9)

1. 通式为下式的离子型液体:
K+A-(I)
其中:
K+为阳离子,选自:
Figure C011228050002C1
其中R1到R5相同或不同,任意选择地通过一单键或双健彼此直接键合,且每个单独或一起具有以下的意义:
-H,
-卤素,
-具有1-8个碳原子的烷基基团,
且A-为选自如下的阴离子:
[PFx(CyF2y+1-zHz)6-x]-
其中1≤x<6
1≤y≤8
0≤z≤2y+1,
而且上述阴离子不包括[(CF3)2PF4]-、[(CF3)3PF3]-、[(CF3)4PF2]-、[(CF3)5PF]-和[(CF3)6P]-
2. 权利要求1的离子型液体,其中阴离子A-是三(五氟乙基)三氟磷酸根或三(九氟丁基)三氟磷酸根。
3. 权利要求1或2的离子型液体,其中杂环阳离子是
Figure C011228050003C1
其中R1到R5相同或不同,每个单独或一起具有以下意义:
-H,或
具有1-8个碳原子的烷基基团。
4. 如权要求1所定义的离子型液体在对质子惰性的溶制的混合物中的用途。
5. 如权利要求1所定义的离子型液体在与选自LiPF6、LiBF4、LiClO4、LiAsF6、LiCF3SO3、LiN(CF3SO2)2、LiC(CF3SO2)3和其混合物的导电性盐的混合物中的用途。
6. 如权利要求1所定义的离子型液体在电化学电池中的用途。
7. 如权利要求1所定义的离子型液体在超级电容器中的用途。
8. 如权利要求1所定义的离子型液体作为溶剂及在催化化学反应中的用途。
9. 如权利要求1所定义的离子型液体作为液压液的用途。
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DE10027995A1 (de) 2001-12-13
BR0102318A (pt) 2002-02-13
CN1327986A (zh) 2001-12-26
RU2272043C2 (ru) 2006-03-20
JP5236135B2 (ja) 2013-07-17
CA2349903A1 (en) 2001-12-09
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