# Patent

## Title
Reactive ionic liquids

## Abstract

The invention relates to reactive ionic liquids containing organic cations with groups or substituents which are susceptible to electrochemical reduction and anions obtained from fluoroalkyl phosphates, fluoroalkyl phosphinates, fluoroalkyl phosphonates, acetates, triflates, imides, methides, borates, phosphates and/or aluminates, for use in electrochemical cells, such as lithium ion batteries and double-layer capacitors.

## Background
The invention relates to reactive ionic liquids containing organic cations with groups or substituents which are susceptible to electrochemical reduction and anions obtained from fluoroalkyl phosphates, fluoroalkyl phosphinates, fluoroalkyl phosphonates, acetates, triflates, methides, borates, phosphates and aluminates, for use in electrochemical cells, such as lithium ion batteries and double-layer capacitors.
Ionic liquids or liquid salts are ionic species which consist of an organic cation and a generally inorganic anion. They do not contain any neutral molecules and usually have melting points below 373 K.
“Reactive ionic liquids” are taken to mean ionic liquids which contain, on the organic cation, groups or substituents which are susceptible to electrochemical reduction, such as cyano groups, ester groups, carbonate groups or side chains with double bonds.
In recent years, ionic liquids have attracted ever increasing interest, and a large number of review articles have described unique properties of ionic liquids (“ILs” for short) and indicated various potential uses.
In particular, ionic liquids appear to be highly promising for use in energy-storage media, such as double-layer capacitors and batteries, with a particular focus on electric and hybrid vehicles.
Outstanding properties of ionic liquids include:

    
    
        virtually zero volatility and thus very high flash points
        a very large liquid range, in some cases above several 100 K
        very high polarity and thus generally very good solubility for inorganic and organic salts.
    
    


Whereas ionic liquids, such as, for example, ethylmethylimidazolium tetrafluoroborate (EMIBF4), are already being employed commercially in double-layer capacitors (super- or ultracapacitors), use in batteries, in particular lithium ion batteries, continues to be difficult.
For battery applications, the following systems comprising ionic liquids have been characterised:

    
    
        ionic liquids in combination with electrolytes comprising an Li salt
        ionic liquids in combination with electrolytes comprising an Li salt plus additives
    
    


The following ionic liquids have been used here:

    
    
        ionic liquids having AlCl4 as anion (generation 0, very early work)
        ionic liquids having imidazolium-based cations and (per)fluorinated inorganic or organic anions (generation 1)
        ionic liquids having “non-imidazolium”-based cations and (per)fluorinated inorganic or organic anions (generation 2)
    
    


AlCl4-based ionic liquids are extremely sensitive to hydrolysis and react with water with liberation of hydrochloric acid HCl. The development for battery systems has been stopped because of this. Imidazolium-based ILs exhibit inadequate reductive stability and are therefore not regarded as very promising for commercial application in high-energy batteries. Ionic liquids having inorganic anions, in particular BF4, cause a significant reduction in capacitance, in particular in the first charge/discharge cycle. The ionic liquids which currently appear to be the most suitable for Li ion batteries use N,N-dialkylpyrrolidinium in combination with bis(trifluoromethyl)imides (see, for example, JP 2006-260952).
However, even these ionic liquids still cause a significant drop in the power densities of lithium ion batteries.
The reason for this is, in particular, the high viscosity of electrochemically stable ionic liquids. This results in significantly lower lithium ion conductivity of the IL-based electrolyte compared with standard electrolyte systems with no ionic liquids (O. Borodin et al., J. of Physical Chemistry B, 2006, 110 (34), pp. 16879-16886). Accordingly, lithium ion batteries comprising IL-based electrolytes still today exhibit a significantly lower power density and charge-carrying capacity compared with lithium ion batteries comprising standard electrolytes.
The latter in particular must be regarded as very critical for applications in electric and hybrid vehicles and prevents—in spite of an increase in safety—the use of IL-based electrolytes.
Lee et al. (Electrochem. Comm. 8 (2006) 460) have been able to show that the use of imidazolium-based ILs having ester ligands on the nitrogen in battery electrolytes results in an improvement in the lithium conductivity and diffusion coefficient of Li ions.
However, these imidazolium-based ionic liquids are not sufficiently electrochemically stable.
The object of the present invention was therefore to develop ionic liquids which have high thermal stability, very good oxidation stability and low corrosiveness, and have anions which have been synthesised inexpensively, and do not have the above-mentioned disadvantages.
The present object is achieved by ionic liquids of the general formula I

K+A−  (I)

    
    
        in which:
        K+ denotes a cation, preferably reduction-stable, selected from the group of the general formulae II to IX
    
    






    
    
        where
        
            X denotes CH2, O, S or NR′
            R′ denotes —(CH2)n—CN, C1- to C16-alkyl, preferably methyl, ethyl, propyl, H
            R denotes H, C1- to C16-alkyl, preferably methyl, ethyl, propyl
            R5 denotes —(CH2)n—O—C(O)—R, —(CH2)n—C(O)—OR, —(CH2)n—O—C(O)—OR, —(CH2)n—HC═CH—R or —(CH2)n—CN, where individual CH2 groups are replaced by O, S or NR,
            
                where n 1 to 8,
            
            
            and
            A− denotes an anion selected from the group
            
                [FyP(CmF2m+1)6−y]−
                (CmF2m+1)2P(O)O−
                CmF2m+1P(O)O22−
                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
            
            
        
        
    
    






    
    
        
        
            
            
                where y=1, 2, 3, 4 or 5, and m=1 to 8, preferably 1 to 4,
                where some of the CF2 groups may be replaced by O, S(O)2, NR or CH2, and
            
            
        
        
        where
    
    






    
    
        
        
            denotes a 1,2- or 1,3-diol, a 1,2- or 1,3-dicarboxylic acid or a 1,2- or 1,3-hydroxycarboxylic acid
        
        
        X denotes B or Al
        R1 to R4 denote halogen, in particular F, and/or a fluorinated or non-fluorinated alkoxy or carboxyl radical.
    
    


Compared with conventional ionic liquids, the reactive ionic liquids according to the invention are distinguished by the fact that they contain, on the organic cation, groups/substituents or side chains which are susceptible to electrochemical reduction. These are, in particular,

    
    
        cyano groups —CN
        ester groups —R—C(O)—OR or —R—O—C(O)—R
        carbonate functions —R—O—C(O)—OR
        double bonds in the side chains —R—CH═CH—R
    
    


Surprisingly, the reactive ionic liquids according to the invention form a passivating cover layer at potentials between about 2 V and 0.9 V against Li/Li+ significantly sooner than ethylene carbonate (0.7 to 0.8 V against Li/Li+). This cover layer is electronically passivating, but permeable to lithium ions. A further advantage consists in the excellent oxidation stability of >5 V against Li/Li+. In contrast to many other additives employed at present, some of which are highly toxic (for example propane sultone), the reactive ionic liquids according to the invention are non-volatile and have no measurable vapour pressure.
The cations K+ of the ionic liquids according to the invention are preferably cations selected from the general formula IV




    
    
        where
        X denotes CH2, O, S or NR′
        R′ denotes —(CH2)n—CN, methyl, ethyl, propyl, butyl, H
        R denotes H, methyl, ethyl, propyl, butyl
        R5 denotes —(CH2)n—O—C(O)—R, —(CH2)n—C(O)—OR, —(CH2)n—O—C(O)—OR, —(CH2)n—HC═CH—R or —(CH2)n—CN, where individual CH2 groups may be replaced by O, S or NR,
        
            where n=1 to 8.
        
        
    
    


The anions A− of the ionic liquids according to the invention are preferably the following anions: [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]−, perfluoroalkylcarboxylate, perfluoroalkylsulfonate, bis(perfluoroalkylsulfonyl)imide, (perfluoroalkylsulfonyl)(perfluoroalkylcarboxyl)-imide, tris(perfluoroalkylsulfonyl)methide, particularly preferably trifluoroacetate, trifluoromethanesulfonate (triflate), bis(trifluoromethylsulfonyl)imide and tris(trifluoromethylsulfonyl)methide.
Preference is also given to spiro-oxo borates and spiro-oxo phosphates, particularly preferably spiro-oxo borates.
The invention furthermore relates to an electrolyte comprising at least one conductive salt, an aprotic solvent or solvent mixture, at least one, ionic liquid of the above-mentioned formula I according to the invention, and optionally further additives.
In a preferred embodiment (for example on use of the electrolyte in lithium or lithium ion batteries), the conductive salt is a lithium conductive salt, such as LiPF6, LiN(SO2CF3)2, LiN(SO2C2F5)2, LiF3P(C2F5)3, LiF3P(C4F9)3, LiB(C2O4)2 or LiF2B(C2O4)2.
In a further preferred embodiment (for example on use of the electrolyte in double-layer capacitors or supercapacitors), the conductive salt is a compound from the group N(C2H5)4BF4N(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.
The aprotic solvent of the electrolyte preferably consists of organic open-chain or cyclic carbonates, carboxylic acid esters, nitriles, ethers or lactones or a mixture thereof. Nitriles, in particular acetonitrile, are preferably employed as solvent in double-layer capacitors.
The present invention furthermore relates to a process for the preparation of ionic liquids of the formula I:

    
    
        Preparation of heterocyclic cations K+ containing alkyl-, carboxylate-, carbonate- or cyano-containing side chains according to Claim 1 as onium chlorides or bromides from the corresponding amines, phosphines, halocarboxylates, halocarbonates, haloalkyl-nitriles or alkyl halides by conventional wet-chemical methods,
        Reaction of these cationic onium chlorides or bromides with the corresponding anionic
        
            potassium and/or sodium fluoroalkylphosphates or potassium and/or sodium bis(fluoroalkyl)phosphinates or potassium and/or sodium fluoroalkylphosphonates or fluoroalkylphosphoric acids or bis(fluoroalkyl)phosphinic acids or fluoroalkylphosphonic acids or alkyl, in particular methyl, bis(fluoroalkyl)-phosphinates or
            lithium imides or methides or trifluoromethanesulfonic acid or potassium or lithium trifluoroacetates or triflates or alkyl triflates or trimethylsilyl triflates or trifluoromethanesulfonic anhydride or trifluoroacetic anhydride or
            lithium or potassium borates, phosphates or aluminates in an aqueous and/or alcoholic medium or an organic solvent or without a solvent.
        
        
    
    


The preparation of the cations is known to the person skilled in the art and can be carried out by processes as described, for example, in P. Wasserscheid and T. Welton (Eds.) “Ionic Liquids in Synthesis”, Wiley-VCH, 2003, pp. 7-40 in general or for imidazolium cations in N. Gathergood, P. J. Scammells, Aust. J. Chem, 55 (2002), No. 9, pp. 557-560; E. Alcalde, M. Gisbert, L. Perez-Garcia, Heterocycles, 43 (1996), No. 3, pp. 567-580; Z. Fei, D. Zhao, T. J. Geldbach, R. Scopelliti, P. J. Dyson, Chem. Europ. J., 10 (2004), No. 19, pp. 4886-4893; D. Liu, Ji. Gui, X. Zhu, L. Song, Z. Sun, Synth. Commun., 37 (2007), No. 5, pp. 759-765; Ya. Peng, F. Yi, G. Song, Yi. Zhang, Monatsh. Chem., 136 (2005), No. 10, pp. 1751-1755; J. F. Dubreuil, J. P. Bazureau, Tetrahedron Lett., 41 (2000), No. 38, pp. 7351-7356; S.-K. Fu, Sh.-T. Liu, Synth. Commun., 36 (2006), No. 14, pp. 2059-2067; M. Yoshizawa, A. Narita, H. Ohno, Aust. J. Chem.; 57 (2004), No. 2, pp. 139-144; A. Narita, W. Shibayama, H. Ohno, J. Mater. Chem., 16 (2006), No. 15, pp. 1475-1482; T. Mizumo, E. Marwanta, N. Matsumi, H. Ohno, Chem. Lett., 33 (2004), No. 10, pp. 1360-1361; D. Zhao, Zh. Fei, T. J. Geldbach, R. Scopelliti, G. Laurenczy, P. J. Dyson, Hel. Chim. Acta., 88 (2005), No. 3, pp. 665-675; A. Horvath, Synthesis, 1994, pp. 102-106; or for pyrrolidinium cations in L. Horner, A. Mentrup, Justus Liebigs Ann. Chem. 646 (1961), pp. 49-64; Bates et al., J. Chem. Soc. 1956, pp. 388-395, v. Braun Chem. Ber. 70 (1937), p. 983; Z. Dega-Szafran, R. Przybylak, J. Mol. Struct., 436 (1997), No. 1, pp. 107-122; or for piperidinium cations in Walther et al., Chem. Ber., 89 (1956), pp. 60-65; or for morpholinium cations in Gresham et al., J. Am, Chem. Soc., 73 (1951), pp. 3168-3171; D. Le Berre, Bull. Soc. Chim. Fr., 1973, pp. 2404-2407; O. A. Kazantsev, Kazakov, K. V. Shirshin, S. M. Danov, Russ. J. Org. Chem., 36 (2000), No. 3, pp. 343-349; or for piperazinium cations in Z. Dega-Szafran, M. Jaskolski, I. Kurzyca, P. Barczynski, M. Szafran, J. Mol. Struct., 614 (2002), No. 1-3, pp. 23-32.
The anions according to the invention are oxidation-stable, as can be seen from Tables 1.1 to 1.3.







TABLE 1.1







Electrochemical stability of reactive ionic liquids having


a tris(pentafluoroethyl)trifluorophosphate anion (FAP


anion) and a bis(pentafluoroethyl)phosphinate anion,


(C2F5)2P(O)O−, compared with similar ionic liquids


having triflate and tetrafluoroborate anions













Electrochem.


Reactive ionic liquid
E(ox), V
E(red), V
window













1-Ethyl-3-methyl-
3.9
−2.5
6.4


imidazolium FAP


1-Ethyl-3-methyl-
3.6
−2.6
6.2


imidazolium (C2F5)2P(O)O−


1-Ethyl-3-methyl-
2.8
−2.5
5.3


imidazolium triflate


1-Ethyl-3-methylimidazolium
2.6
−2.6
5.2


BF4−
















TABLE 1.2







Electrochemical stability of reactive ionic liquids having a bis(trifluoro-


methylsulfonyl)imide anion and a triflate anion compared with


the ionic liquid having a tetrafluoroborate anion













Electrochem.


Reactive ionic liquid
E(ox), V
E(red), V
window













1-Butyl-1-methylpyrrolidinium
−3.5
−3.3
6.8


bis(trifluoromethylsulfonyl)imide


Trihexyl(tetradecyl)phos-

−3.4
6.5


phontum bis(trifluoromethyl-


sulfonyl)imide


1-Hexyl-3-methylimidazolium
3.7
−2.6
6.3


bis(trifluoromethylsulfonyl)imide


1-Ethyl-3-methylimidazolium
2.8
−2.5
5.3


triflate


1-Ethyl-3-methylimidazolium
2.6
−2.6
5.2


BF4−
















TABLE 1.3







Electrochemical stability of ionic liquids having borate, phosphate and


aluminate anions











E(ox), vs. Li/Li+


















4.7-4.8 
V


 







4.8-5.0 
V


 







4.8-5.0 
V


 







4.7-4.8 
V


 







4.8-5.0 
V


 







>5 
V









The fluoroalkylphosphate-based reactive ionic liquids are prepared by reaction of the corresponding cationic onium chlorides or onium bromides with the corresponding potassium or sodium fluoroalkylphosphates or fluoroalkylphosphoric acid (HFAP) in an aqueous medium.
The bis(fluoroalkyl)phosphinate-based ionic liquids are prepared by three different methods:

    
    
        preparation of these ionic liquids by means of phosphinic acid (see Example 5.1)
        preparation of these ionic liquids via the corresponding potassium salts (such as potassium fluoroalkylphosphinate) (see Example 5.2)
        preparation of these ionic liquids via the corresponding alkyl bis-(fluoroalkyl)phosphinates, preferably methyl phosphinates (see Example 5.3).
    
    


The preparation of the bis(fluoroalkyl)phosphinate-based ionic liquids via phosphinic acid and methyl phosphinates is preferred here.
The imide- and methide-based ionic liquids are prepared by reaction of the corresponding, cationic onium chlorides or onium bromides with the corresponding lithium salts in an aqueous medium.
The trifluoroacetate- and triflate-based ionic liquids are prepared by three different methods:

    
    
        preparation of the triflate-based ionic liquids by means of triflic acid (see Example 5.1)
        preparation of the ionic liquids via the corresponding potassium or lithium trifluoroacetates or triflates (see Example 5.2)
        preparation of the ionic liquids via the corresponding methyl triflates, trimethylsilyl triflates, triflic anhydrides or trifluoroacetic anhydrides (see Example 5.3).
    
    


The preparation of the trifluoroacetate- and triflate-based ionic liquids via the triflic acid or trifluoroacetic acid and/or methyl or ethyl triflate or trifluoroacetate or trimethylsilyl triflate, triflic anhydride or trifluoroacetic anhydride method is preferred here.
The borate-, phosphate- or aluminate-based reactive ionic liquids are prepared by reaction of the corresponding, cationic onium chlorides or onium bromides with the corresponding anionic potassium or lithium borates, phosphates or aluminates in an aqueous or organic medium.
The reaction of the cations according to the invention with the anions to give the end product can be carried out at temperatures of 0 to 150° C., preferably at 0 to 50° C. and in particular at room temperature.
Suitable solvents or solvent mixtures are water or deionised water, alcohols, dioxane, acetonitrile and acetone. The alcohol employed is preferably methanol or isopropanol. In the case of the use of methyl phosphinates, a solvent is usually not needed.
The present invention furthermore relates to an electrochemical and/or electro-optical device containing at least one electrolyte which comprises at least one ionic liquid of the general formula I. The device can preferably be a solar cell, a lithium or lithium ion battery, a double-layer capacitor or supercapacitor, a lithium capacitor, a light-emitting device, an electrochemical sensor and/or a biosensor.
The present invention furthermore relates to the use of the said reactive ionic liquids of the general formula I as conductive salt or additive in electrolytes for electrochemical or electro-optical cells.
In a further preferred embodiment, the reactive ionic liquids according to the invention are used as conductive salt or additive in electrolytes for batteries, secondary lithium batteries, double-layer capacitors and supercapacitors or lithium capacitors.
The present invention furthermore relates to the use of the electrolytes according to the invention in electrochemical and/or electro-optical devices. These devices are preferably lithium or lithium ion batteries, double-layer capacitors, supercapacitors or lithium capacitors.
The following examples are intended to illustrate the present invention. However, they should in no way be regarded as limiting. All compounds or components which can be used in the compositions are either known and commercially available or can be synthesised by known methods. The temperatures indicated in the examples are always in ° C. It furthermore goes without saying that, both in the description and in the examples, the added amounts of the components in the compositions always add up to a total of 100%. Percentage data given should always be regarded in the given context. However, they usually always relate to the weight of the part amount or total amount indicated.


EXAMPLES
Preparation of the Cations
Example 1
Preparation of Heterocyclic Cations Containing Allyl Side Chains
General Procedure:
1.1 mol of an allyl chloride are added dropwise to 1 mol of the corresponding amine or phosphine. It must be ensured here that the temperature is held at between 30 and 35° C. The reaction mixture is then stirred at 40° C. to 50° C. for 3 h to 48 h (in the case of the formation of solid products, the reaction mixture is diluted with dichloromethane or acetonitrile), and the excess allyl chloride and solvent are then distilled off in vacuo (2·10−3 mbar). The product yield is virtually quantitative.









TABLE 1





Amine/




phosphine
Allyl chloride



employed
employed
Product







N(C2H5)3
Cl—CH2—CH═CH2
[N(C2H5)3(CH2—CH═CH2)] Cl


N(CH3)(C2H5)2
Cl—CH2—CH═CH2
[N(CH3)(C2H5)3




(CH2—CH═CH2)]Cl


P(C4H9)3
Cl—CH2—CH═CH2
[P(C4H9)3(CH2—CH═CH2)] Cl


 






Cl—CH2—CH═CH2






 






Cl—CH2—CH═CH2






 






Cl—CH2—CH═CH2






 






Cl—CH2—CH═CH2






 






Cl—CH2—CH═CH2






 






Cl—CH2—CH═CH2













Example 2
Preparation of Heterocyclic Cations Containing Carboxylate Side Chains or Carbonate Side Chains
General Procedure:
1 mol of the corresponding amine or phosphine in 300 ml of acetonitrile are initially introduced in a 2 l multinecked round-bottomed flask with precision glass stirrer and brought to 80° C. 1.1 mol of the corresponding halocarboxylate or -carbonate (preferably bromocarboxylate or -carbonate) are subsequently slowly added dropwise over the course of 1.5 h.
The reaction mixture is then allowed to react further at this temperature for 0.5 to 48 hours and stirred into 1 l of ethyl acetate, whereupon the product precipitates as a white solid. The product is filtered off with suction, rinsed with ethyl acetate and dried (rotary evaporator with water bath at about 30° C.). The yield is between 90 and 95%.









TABLE 2





Amine/phosphine
Chloro(bromo)-



employed
alkylcarboxylate
Product







N(C2H5)3
Br—CH2—C(O)—O—C2H5
[N(C2H5)3(CH2—C(O)—O—C2H5)]




Br


N(CH3)2(C2H5)
Br—CH2—CH2—C(O)—O—CH3
[N(CH3)2(C2H5)




(CH2—CH2—C(O)—O—CH3)] Br


N(CH3)2(C2H5)
Br—CH2—C(O)—CH2—C(O)—O—CH3
[N(CH3)2(C2H5)




(CH2—C(O)—CH2—C(O)—O—CH3)] Br


N(CH3)2(C2H5)
Br—CH2—O—C(O)—O—CH3
[N(CH3)2(C2H5)




(CH2—O—C(O)—O—CH3)] Br


P(C4H9)3
Br—CH2—C(O)—O—C2H5
[P(C4H9)3(CH2—C(O)—O—C2H5)]




Br


 






Br—CH2—CH2—C(O)—O—CH3






 






Br—CH2—C(O)—CH2—C(O)—O—CH3






 






Br—CH2—O—C(O)—O—CH3






 






Br—CH2—CH2—C(O)—O—CH3






 






Br—CH2—CH2—C(O)—O—CH3






 






Cl—CH2—O—C(O)—O—CH3






 






Cl—CH2—C(O)—CH2—C(O)—O—CH3






 






Cl—CH2—CH2—C(O)—O—CH3






 






Cl—CH2—CH2—C(O)—O—CH3






 






Cl—CH2—CH2—C(O)—O—CH3













Example 3
Preparation of Heterocyclic Cations Containing Cyano-Containing Side Chains
General Procedure:
1.1 mol of a chloroalkyl nitrile (or bromo- or iodoalkyl nitrile) are added dropwise to 1 mol of the corresponding amine or phosphine. It must be ensured here that the temperature is held at between 30 and 50°. The reaction mixture is then stirred at 50° C. to 80° C. for 3 h to 48 h (in the case of the formation of solid products, the reaction mixture is diluted with acetonitrile), and the excess chloroalkyl nitrile and solvent is then distilled off in vacuo (2·10−3 mbar). The product yield is virtually quantitative.









TABLE 3





Amine/




phosphine
Chloroalkyl



employed
nitrile
Product







N(C2H5)3
Cl—CH2—CH2—CN
[N(C2H5)3(CH2—CH2—CN)] Cl


N(CH3)2(C2H5)
Cl—CH2—CH2—CN
[N(CH3)2(C2H5) 




(CH2—CH2—CN)] Cl


P(C4H9)3
Cl—CH2—CH2—CN
[P(C4H9)3(CH2—CH2—CN)] Cl


 






Cl—CH2—CH2—CN






 






Cl—CH2—CH2—CN






 






Cl—CH2—CH2—CN






 






Cl—CH2—CH2—CN






 






Cl—CH2—CH2—CN






 






Cl—CH2—CH2—CN













Preparation of Fluoroalkylphosphate- and Fluoroalkylphosphinate-Based Reactive Ionic Liquids
Example 4
Preparation of Fluoroalkylphosphate-Based Reactive Ionic Liquids
General Procedure
1 mol of the corresponding onium chloride or onium bromide (from the examples described above) are dissolved in 200 ml of deionised water in a flask with magnetic stirrer bar, and 1 mol of the corresponding potassium (or sodium) fluoroalkylphosphate is subsequently added slowly. 2 phases immediately form.
These two phases are stirred at room temperature for a further 1 h. The organic phase is then separated off and washed 5 times with 100 ml of deionised water each time until free from chloride (evidence: 1 molar silver nitrate solution) and dried at 80° C.-90° C. in vacuo.
Example 5.1
Preparation of Bis(Fluoroalkyl)Phosphinate-Based Reactive Ionic Liquids by Means of Phosphonic Acid
General Procedure
1 mol of the corresponding onium chloride (from the examples described above) are dissolved in 200 ml of deionised water in a flask with magnetic stirrer bar, and 1 mol of the corresponding bis(fluoroalkyl)phosphinic acid is subsequently added slowly.
The reaction mixture is stirred at room temperature for a further 1 h, and water is distilled off together with hydrochloric acid formed. In order to achieve complete removal of hydrochloric acid, repeated azeotropic distillation with dioxane and water can be used (until a negative test with silver nitrate solution). Drying at 80° C.-90° C. in vacuo gives the bis(fluoroalkyl)-phosphinates in virtually quantitative yield.
Example 5.2
Preparation of Bis(Fluoroalkyl)Phosphinate-Based Reactive Ionic Liquids Via the Corresponding Potassium Salts
General Procedure
1 mol of the corresponding onium chloride (from the examples described above) is dissolved in isopropanol (or methanol or acetonitrile) in a flask with magnetic stirrer bar, and 1 mol of the corresponding potassium fluoroalkylphosphinate is subsequently added slowly.
The reaction mixture is stirred at room temperature for a further 1 h, and KCl formed is filtered off. Removal of isopropanol (or methanol or acetonitrile) in vacuo with the aid of a rotary evaporator gives the bis(fluoroalkyl)-phosphinates in virtually quantitative yield.
Example 5.3
Preparation of Bis(Fluoroalkyl)Phosphinate-Based Reactive Ionic Liquids Via the Corresponding Methylphosphinates
1 to 1.1 mol of the corresponding methyl bis(fluoroalkyl)phosphinate are added to 1 mol of the corresponding onium chloride (or bromide) (from the examples described above) in a flask with magnetic stirrer bar.
The reaction mixture is stirred at room temperature or with heating up to 100° C. for 1 to 20 h, and CH3Cl (or CH3Br) formed and excess methyl bis-(fluoroalkyl)phosphinate are removed in vacuo. Bis(fluoroalkyl)phosphinates form in virtually quantitative yield.









TABLE 4






Potassium salt or




phosphinic acid or




methyl phosphin-



Onium salt employed
ate employed
Ionic liquid







[N(C2H5)3(CH2—CH═CH2)] Cl
K F3P(C2F5)3
[N(C2H5)3(CH2—CH═CH2)]




F3P(C2H5)3


[N(C2H5)3(CH2—CH═CH2)] Cl
K F3P(C4F9)3
[N(C2H5)3(CH2—CH═CH2)]




F3P(C4H9)3


[N(C2H5)3(CH2—CH═CH2)] Cl
K OP(O)(C2F5)2
[N(C2H5)3(CH2—CH═CH2)]



HOP(O)(C2F5)2
OP(O)(C2F5)2



CH3OP(O)(C2F5)2



[N(C2H5)3(CH2—CH═CH2)] Cl
K OP(O)(C4F9)2
[N(C2H5)3(CH2—CH═CH2)]



HOP(O)(C4F9)2
OP(O)(C4F9)2



CH3OP(O)(C4F9)2



[N(CH3)(C2H5)3(CH2—CH═CH2)]
K F3P(C2F5)3
[N(CH3)(C2H5)3(CH2—CH═CH2)]


Cl

F3P(C2F5)3


[P(C4H9)3(CH2—CH═CH2)] Cl
K F3P(C2F5)3
[P(C4H9)3(CH2—CH═CH2)]




F3P(C2H5)3


 






K F3P(C2F5)3






 






K F3P(C4F9)3






 






K OP(O)(C2F5)2 HOP(O)(C2F5)2 CH3OP(O)(C2F5)2






 






K OP(O)(C4F9)2 HOP(O)(C4F9)2 CH3OP(O)(C4F9)2






 






K F3P(C2F5)3






 






K F3P(C2F5)3






 






K F3P(C2F5)3






















TABLE 5






Potassium salt 




or methyl 



Onium salt employed
phosphinate employed
Ionic liquid







[N(C2H5)3(CH2—C(O)—O—(C2H5)] Br
K F3P(C2F5)3
[N(C2H5)3(CH2—C(O)—O—(C2H5)]




F3P(C2F5)3


[N(C2H5)3(CH2—C(O)—O—(C2H5)] Br
K F3P(C4F9)3
[N(C2H5)3(CH2—C(O)—O—(C2H5)]




F3P(C4F9)3


[N(C2H5)3(CH2—C(O)—O—(C2H5)] Br
K OP(O)(C2F5)3
[N(C2H5)3(CH2—C(O)—O—(C2H5)]




OP(O)(C2F5)2


[N(C2H5)3(CH2—C(O)—O—(C2H5)] Br
K OP(O)(C4F9)2
[N(C2H5)3(CH2—C(O)—O—(C2H5)]



CH3OP(O)(C4F9)2
OP(O)(C4F9)2


[N(CH3)2(C2H5)
K F3P(C2F5)3
[N(CH3)2(C2H5) (CH2—CH2—C(O)—O—(CH3)]


(CH2—CH2—C(O)—O—CH3)] Br

F3P(C2F5)3


[N(CH3)2(C2H5) 
K F3P(C2F5)3
[N(CH3)2(C2H5)


(CH2—C(O)—CH2—C(O)—O—CH3)]

(CH2—C(O)—CH2—C(O)—O—(CH3)]


Br

F3P(C2F5)3


[N(CH3)2(C2H5)
K F3P(C2F5)3
[N(CH3)2(C2H5) (CH2—O—C(O)—O—(CH3)]


(CH2—O—C(O)—O—CH3)] Br

F3P(C2F5)3


[P(C4H9)3(CH2—C(O)—O—(C2H5)] Br
K F3P(C2F5)3
[P(C4H9)3(CH2—C(O)—O—(C2H5)] F3P(C2F5)3


 






K F3P(C2F5)3






 






K F3P(C4F9)3






 






K OP(O)(C2F5)2 CH3OP(O)(C2F5)2






 






K OP(O)(C4F9)2 CH3OP(O)(C4F9)2






 






K F3P(C2F5)3






 






K F3P(C2F5)3






 






K F3P(C2F5)3






 






K F3P(C2F5)3






 






K F3P(C2F5)3






 






K F3P(C2F5)3






 






K F3P(C2F5)3






 






K F3P(C2F5)3






 






K F3P(C2F5)3






















TABLE 6






Potassium salt




or phosphinic




acid or methyl



Onium salt
phosphinate



employed
employed
Ionic liquid







[N(C2H5)3(CH2—CH2—CN)] Cl
K F3P(C2F5)3
[N(C2H5)3(CH2—CH2—CN)]




F3P(C2F5)3


[N(C2H5)3(CH2—CH2—CN)] Cl
K F3P(C4F9)3
[N(C2H5)3(CH2—CH2—CN)]




F3P(C4F9)3


[N(C2H5)3(CH2—CH2—CN)] Cl
K OP(O)(C2F5)2
[N(C2H5)3(CH2—CH2—CN)]



HOP(O)(C2F5)2
OP(O)(C2F5)2



CH3OP(O)(C2F5)2



[N(C2H5)3(CH2—CH2—CN)] Cl
K OP(O)(C4F9)2
[N(C2H5)3(CH2—CH2—CN)]



HOP(O)(C4F9)2
OP(O)(C4F9)2



CH3OP(O)(C4F9)2



[N(CH3)2(C2H5) 
K F3P(C2F5)3
[N(CH3)2(C2H5) (CH2—CH2—CN)] 


(CH2—CH2—CN)] Cl

F3P(C2F5)3


[P(C4H9)3(CH2—CH2—CN)] Cl
K F3P(C2F5)3
[P(C4H9)3(CH2—CH2—CN)]




F3P(C2F5)3


 






K F3P(C2F5)3






 






K F3P(C4F9)3






 






K OP(O)(C2F5)2 HOP(O)(C2F5)2 CH3OP(O)(C2F5)2 






 






K OP(O)(C4F9)2 HOP(O)(C4F9)2 CH3OP(O)(C4F9)2 






 






K F3P(C2F5)3






 






K F3P(C2F5)3






 






K F3P(C2F5)3






 






K F3P(C2F5)3






 






K F3P(C2F5)3













Preparation of Acetate-, Triflate-, Imide- and Methide-Based Reactive Ionic Liquids
Example 5
Preparation of Imide- and Methide-Based Ionic Liquids
General Procedure
1 mol of the corresponding onium chloride or onium bromide (from the examples described above) are dissolved or partially suspended in 200-500 ml of deionised water in a 1 liter flask with magnetic stirrer bar, and 1 mol of the corresponding lithium salt or potassium salt or 1 mol of bis(tri-fluoromethylsulfonyl)imide (N—H acid) or tris(trifluoromethylsulfonyl)methide (C—H acid) is subsequently added slowly. 2 phases immediately form.
These two phases are stirred at room temperature for a further 1 to 10 hours. The emulsion is then extracted by shaking 3 times with 50 ml of dichloromethane each time. The organic phase is then washed 5 times with 100 ml of deionised water each time until free from chloride (evidence: 1 molar silver nitrate solution).
10 g of Al2O3 and 1.4 g of activated carbon are added to the organic solution, and the mixture is filtered again after about 1 h and evaporated in a rotary evaporator with a water bath at about 80° C.









TABLE 7






Lithium salt or




bis(trifluoro-




methylsulfonyl)-




imide or tris(tri-




fluoromethyl-




sulfonyl)methide



Onium salt employed
employed
Ionic liquid







[N(C2H5)3(CH2—CH═CH2)] Cl
Li N(SO2CF3)2
[N(C2H5)3(CH2—CH═CH2)]



HN(SO2CF3)2
N(SO2CF3)2


[N(C2H5)3(CH2—CH═CH2)] Cl
Li C(SO2CF3)2
[N(C2H5)3(CH2—CH═CH2)]



HN(SO2CF3)2



[N(CH3)(C2H5)3(CH2—CH═CH2)]
Li N(SO2CF3)2
[N(CH3)(C2H5)3(CH2—CH═CH2)]


Cl
HN(SO2CF3)2
N(SO2CF3)2


[P(C4H9)3(CH2—CH═CH2)] Cl
Li N(SO2CF3)2
[P(C4H9)3(CH2—CH═CH2)]



HN(SO2CF3)2
N(SO2CF3)2


 






Li N(SO2CF3)2 HN(SO2CF3)2






 






Li C(SO2CF3)2 HC(SO2CF3)2






 






Li N(SO2CF3)2 HN(SO2CF3)2






 






Li N(SO2CF3)2 HN(SO2CF3)2






 






Li N(SO2CF3)2 HN(SO2CF3)2






 






Li N(SO2CF3)2 HN(SO2CF3)2






 






Li N(SO2CF3)2 HN(SO2CF3)2






















TABLE 8






Lithium salt or




bis(trifluoro-




methylsulfonyl)-




imide or tris(tri-




fluoromethyl-




sulfonyl)methide



Onium salt employed
employed
Ionic liquid







[N(C2H5)3(CH2—C(O)—O—(C2H5)] Br
Li N(SO2CF3)2
[N(C2H5)3(CH2—C(O)—O—(C2H5)]



HN(SO2CF3)2
N(SO2CF3)2


[N(C2H5)3(CH2—C(O)—O—(C2H5)] Cl
Li OSO2CF3
[N(C2H5)3(CH2—C(O)—O—(C2H5)]




OSO2CF3


[N(C2H5)3(CH2—C(O)—O—(C2H5)] Cl
Li OCOCF3
[N(C2H5)3(CH2—C(O)—O—(C2H5)]




OCOCF3


[N(C2H5)3(CH2—C(O)—O—(C2H5)] Br
Li C(SO2CF3)2
[N(C2H5)3(CH2—C(O)—O—(C2H5)]



HC(SO2CF3)2
C(SO2CF3)3


[N(CH3)2(C2H5)
Li N(SO2CF3)2
[N(CH3)2(C2H5) (CH2—CH2—C(O)—O—(CH3)]


(CH2—C(O)—O—(CH3)] Br
HN(SO2CF3)2
N(SO2CF3)2


[N(CH3)2(C2H5)
Li N(SO2CF3)2
[N(CH3)2(C2H5)


(CH2—C(O)—CH2—C(O)—O—(CH3)]
HN(SO2CF3)2
(CH2—C(O)—CH2—C(O)—O—(CH3)]


Br

N(SO2CF3)2


[N(CH3)2(C2H5)
Li N(SO2CF3)2
[N(CH3)2(C2H5)


(CH2—O—C(O)—O—(CH3)] Br
HN(SO2CF3)2
(CH2—O—C(O)—O—(CH3)] N(SO2CF3)2


[P(C4H9)3(CH2—C(O)—O—(C2H5)] Br
Li N(SO2CF3)2
[P(C4H9)3(CH2—C(O)—O—(C2H5)]



HN(SO2CF3)2
N(SO2CF3)2


 






Li N(SO2CF3)2 HN(SO2CF3)2






 






Li C(SO2CF3)3 HC(SO2CF3)3






 






Li N(SO2CF3)2 HN(SO2CF3)2






 






Li N(SO2CF3)2 HN(SO2CF3)2






 






Li N(SO2CF3)2 HN(SO2CF3)2






 






Li N(SO2CF3)2 HN(SO2CF3)2






 






Li N(SO2CF3)2 HN(SO2CF3)2






 






Li N(SO2CF3)2 HN(SO2CF3)2






 






Li N(SO2CF3)2 HN(SO2CF3)2






 






Li N(SO2CF3)2 HN(SO2CF3)2






 






Li N(SO2CF3)2 HN(SO2CF3)2






















TABLE 9






Lithium salt or




bis(trifluoro-




methylsulfonyl)-




imide or tris




(trifluoromethyl-




sulfonyl)methide



Onium salt employed
employed
Ionic liquid







[N(C2H5)3(CH2—CH2—CN)] Cl
Li N(SO2CF3)2
[N(C2H5)3(CH2—CH2—CN)]



HN(SO2CF3)2
N(SO2CF3)2


[N(C2H5)3(CH2—CH2—CN)] Cl
Li C(SO2CF3)3
[N(C2H5)3(CH2—CH2—CN)]



HC(SO2CF3)3
C(SO2CF3)2


[N(CH3)2(C2H5) 
Li N(SO2CF3)2
[N(CH3)2(C2H5) 


(CH2—CH2—CN)] Cl
HN(SO2CF3)2
(CH2—CH2—CN)] N(SO2CF3)2


[P(C4H9)3(CH2—CH2—CN)] Cl
Li N(SO2CF3)2
[P(C4H9)3(CH2—CH2—CN)]



HN(SO2CF3)2
N(SO2CF3)2


 






Li N(SO2CF3)2 HN(SO2CF3)2






 






Li C(SO2CF3)3 HC(SO2CF3)3






 






Li N(SO2CF3)2 HN(SO2CF3)2






 






Li N(SO2CF3)2 HN(SO2CF3)2






 






Li N(SO2CF3)2 HN(SO2CF3)2






 






Li N(SO2CF3)2 HN(SO2CF3)2






 






Li N(SO2CF3)2 HN(SO2CF3)2













Preparation of Trifluoroacetate- or Triflate-Based Ionic Liquids
Example 6.1
Preparation of Triflate-Based Ionic Liquids by Means of Triflic Acid
General Procedure
1 mol of the corresponding onium chloride (from the examples described above) is dissolved in 200-500 ml of deionised water in a flask with magnetic stirrer bar, and 1 mol of triflic acid (=trifluoromethanesulfonic acid) is subsequently added slowly.
The reaction mixture is stirred at room temperature for a further 1 h, and water is distilled off together with HCl formed. In order to achieve complete removal of HCl, repeated azeotropic distillation with dioxane and water can be used (until a negative test with silver nitrate solution). Drying at 80° C.-90° C. in vacuo gives the corresponding triflates in virtually quantitative yield.
Example 6.2
Preparation of Trifluoroacetate- or Triflate-Based Ionic Liquids Via the Corresponding Potassium or Lithium Salts
General Procedure
1 mol of the corresponding onium chloride (from the examples described above) is dissolved in isopropanol (or methanol or acetonitrile) in a flask with magnetic stirrer bar, and 1 mol of the corresponding potassium (or lithium) trifluoroacetate or triflate is subsequently added slowly.
The reaction mixture is stirred at room temperature for a further 1 h, and KCl (or LiCl) formed is filtered off. Removal of isopropanol (or methanol or acetonitrile) in vacuo with the aid of a rotary evaporator gives the trifluoroacetates or triflates in virtually quantitative yield.
Example 6.3
Preparation of Trifluoroacetate- and Triflate-Based Ionic Liquids Via the Corresponding Methyl Triflates, Trimethylsilyl Triflates, Triflic Anhydrides or Trifluoroacetic Anhydrides
1 to 1.1 mol of the corresponding methyl triflates or trimethylsilyl triflates or triflic anhydrides or trifluoroacetic anhydrides are added to 1 mol of the corresponding onium chloride (or bromide) (from the examples described above) in a flask with magnetic stirrer bar.
The reaction mixture is stirred at room temperature or with heating up to 100° C. for a further 1 to 48 h, and CH3Cl (or CH3Br or (CH3)3SiCl or CF3SO2Cl or CF3COCl or CF3COBr) formed and excess methyl or trimethylsilyl triflates or anhydrides are removed in vacuo. Trifluoroacetates or triflates form in virtually quantitative yield.









TABLE 10






Lithium or potas-




slum salt or




methyl triflate or




anhydride em-



Onium salt employed
ployed
Ionic liquids







[N(C2H5)3(CH2—CH═CH2)] Cl
K OSO2CF3,
[N(C2H5)3(CH2—CH═CH2)]



HOSO2CF3,




CH3OSO2CF3,




(CH3)3SiOSO2CF3,



[N(C2H5)3(CH2—CH═CH2)] Cl
Li OCOCF3,
[N(C2H5)3(CH2—CH═CH2)]



(CF3CO)2O



 






K OSO2CF3, HOSO2CF3, CH3OSO2CF3, (CH3)3SiOSO2CF3,






 






Li OCOCF3, (CF3CO)2O






 


[N(C2H5)3(CH2—C(O)—O—(C2H5)] Br
K OSO2CF3,
[N(C2H5)3(CH2—C(O)—O—(C2H5)]



HOSO2CF3,
OSO2CF3



CH3OSO2CF3,




(CH3)3SiOSO2CF3,



[N(C2H5)3(CH2—C(O)—O—(C2H5)] Br
K OCOCF3,
[N(C2H5)3(CH2—C(O)—O—(C2H5)]



(CF3CO)2O
OCOCF3


 






K OSO2CF3, HOSO2CF3, CH3OSO2CF3, (CH3)3SiOSO2CF3 






 






K OCOCF3, (CF3CO)2O 






 






K OSO2CF3, HOSO2CF3, CH3OSO2CF3, (CH3)3SiOSO2CF3 






 






K OCOCF3, (CF3CO)2O 






 






K OSO2CF3, HOSO2CF3, CH3OSO2CF3, (CH3)3SiOSO2CF3 






 






K OSO2CF3, HOSO2CF3, CH3OSO2CF3, (CH3)3SiOSO2CF3 






 






K OSO2CF3, HOSO2CF3, CH3OSO2CF3, (CH3)3SiOSO2CF3 






















TABLE 11






Lithium or potas-




sium salt or




methyl triflate or




anhydride



Onium salt employed
employed
Ionic liquids







[N(C2H5)3(CH2—CH2—CN)] Cl
K OSO2CF3,
[N(C2H5)3(CH2—CH2—CN)] OSO2CF3



HOSO2CF3,




CH3OSO2CF3,




(CH3)3SiOSO2CF3



[N(C2H5)3(CH2—CH2—CN)] Cl
K OCOCF3,
[N(C2H5)3(CH2—CH2—CN)] OCOCF3



(CF3CO)2O



 






K OSO2CF3, HOSO2CF3, CH3OSO2CF3, (CH3)3SiOSO2CF3 






 






K OCOCF3, (CF3CO)2O 






 






K OSO2CF3, CH3OSO2CF3, (CH3)3SiOSO2CF3 






 






K OSO2CF3, HOSO2CF3, CH3OSO2CF3, (CH3)3SiOSO2CF3 






 






K OSO2CF3, HOSO2CF3, CH3OSO2CF3, (CH3)3SiOSO2CF3 






 






K OSO2CF3, HOSO2CF3, CH3OSO2CF3, (CH3)3SiOSO2CF3 






 






K OSO2CF3, HOSO2CF3, CH3OSO2CF3, (CH3)3SiOSO2CF3 













Example 7
Preparation of Borate-, Phosphate- and Acuminate-Based Ionic Liquids
General Procedure
1 mol of the corresponding onium chloride or onium bromide (from the examples described above) is dissolved in 2 l of dichloromethane in a 3 liter flask with magnetic stirrer bar, and 1 mol of the corresponding potassium or lithium salt is subsequently added slowly. After addition, the reaction mixture is stirred for 5 days. 500 ml of deionised water are then added to the batch. 2 phases form. The organic phase is separated off, the aqueous phase is washed with 300 ml of dichloromethane, and all organic phases are combined. The organic phase is washed further twice with 250 ml of deionised water each time and then evaporated to 1⁄3 and subsequently stirred into 1 l of n-heptane.
Two phases form. The n-heptane phase comprising the ionic liquid is separated off overnight and evaporated in a rotary evaporator with a water bath at 60 to 70° C.









TABLE 12





Onium salt
Potassium or lithium salt



employed
employed
Ionic liquid







[N(C2H5)3(CH2—CH═CH2)] Cl




[N(C2H5)3(CH2—CH═CH2)] BOB


 


[N(C2H5)3(CH2—CH═CH2)] Cl




[N(C2H5)3(CH2—CH═CH2)] DFOB


 


[N(C2H5)3(CH2—CH═CH2)] Cl




[N(C2H5)3(CH2—CH═CH2)] D(Ac)OB


 


[N(C2H5)3(CH2—CH═CH2)] Cl




[N(C2H5)3(CH2—CH═CH2)] DFGB


 


[N(C2H5)3(CH2—CH═CH2)] Cl




[N(C2H5)3(CH2—CH═CH2)] TFOP


 


[N(C2H5)3(CH2—CH═CH2)] Cl




[N(C2H5)3(CH2—CH═CH2)] D(Ac)OAl


 


[N(C2H5)3(CH2—CH═CH2)] Cl




[N(C2H5)3(CH2—CH═CH2)] TOP


 


[N(C2H5)3(CH2—CH═CH2)] Cl




[N(C2H5)3(CH2—CH═CH2)] DFPB


 


[N(CH3)(C2H5)3(CH2—CH═CH2)] Cl
K or Li BOB
[N(CH3)(C2H5)3(CH2—CH═CH2)]




BOB


[N(CH3)(C2H5)3(CH2—CH═CH2)] Cl
K or Li DFOB
[N(CH3)(C2H5)3(CH2—CH═CH2)]




DFOB


[P(C4H9)3(CH2—CH═CH2)] Cl
K or Li BOB
[P(C4H9)3(CH2—CH═CH2)]




BOB


[P(C4H9)3(CH2—CH═CH2)] Cl
K or Li DFOB
[P(C4H9)3(CH2—CH═CH2)]




DFOB


 






K or Li BOB






 






K or Li DFOB






 






K or Li TOP






 






K or Li TFOP






 






K or Li D(Ac)OAl






 






K or Li BOB






 






K or Li DFOB






 






K or Li BOB






 






K or Li DFOB






 






K or Li BOB






 






K or Li DFOB






 






K or Li BOB






 






K or Li DFOB






 






K or Li BOB






 






K or Li DFOB






















TABLE 13






Potassium or




lithium salt



Onium salt employed
employed
Ionic liquid







[N(C2H5)3(CH2—C(O)—O—C2H5)] Br
K or Li BOB
[N(C2H5)3(CH2—C(O)—O—C2H5)] BOB


[N(C2H5)3(CH2—C(O)—O—C2H5)] Br
K or Li DFOB
[N(C2H5)3(CH2—C(O)—O—C2H5)] DFOB


[N(C2H5)3(CH2—C(O)—O—C2H5)] Br
K or Li TOP
[N(C2H5)3(CH2—C(O)—O—C2H5)] TOP


[N(C2H5)3(CH2—C(O)—O—C2H5)] Br
K or Li D(Ac)OAl
[N(C2H5)3(CH2—C(O)—O—C2H5)] D(Ac)Oal


[N(CH3)2(C2H5)(CH2—CH2—C(O)—O—CH3)] Br
K or Li BOB
[N(CH3)2(C2H5)(CH2—CH2—C(O)—O—CH3)] BOB


[N(CH3)2(C2H5)(CH2—CH2—C(O)—O—CH3)] Br
K or Li DFOB
[N(CH3)2(C2H5)(CH2—CH2—C(O)—O—CH3)] DFOB


[N(CH3)2(C2H5)(CH2—C(O)—CH2—C(O)—O—CH3)] Br
K or Li BOB
[N(CH3)2(C2H5)(CH2—C(O)—CH2—C(O)—O—CH3)] BOB


[N(CH3)2(C2H5)(CH2—C(O)—CH2—C(O)—O—CH3)] Br
K or Li DFOB
[N(CH3)2(C2H5)(CH2—C(O)—CH2—C(O)—O—CH3)] BDFOB


[N(CH3)2(C2H5)(CH2—O—C(O)—O—CH3)] Br
K or Li BOB
[N(CH3)2(C2H5)(CH2—O—C(O)—O—CH3)] BOB


[N(CH3)2(C2H5)(CH2—O—C(O)—O—CH3)] Br
K or Li DFOB
[N(CH3)2(C2H5)(CH2—O—C(O)—O—CH3)] DFOB


[P(C4H9)3(CH2—C(O)—O—C2H5)] Br
K or Li BOB
[P(C4H9)3(CH2—C(O)—O—C2H5)] BOB


[P(C4H9)3(CH2—C(O)—O—C2H5)] Br
K or Li DFOB
[P(C4H9)3(CH2—C(O)—O—C2H5)] DFOB


 






K or Li BOB






 






K or Li DFOB






 






K or Li TOP






 






K or Li D(Ac)OAl






 






K or Li BOB






 






K or Li DFOB






 






K or Li BOB






 






K or Li DFOB






 






K or Li BOB






 






K or Li DFOB






 






K or Li BOB






 






K or Li DFOB






 






K or Li BOB






 






K or Li DFOB






 






K or Li BOB






 






K or Li DFOB






 






K or Li BOB






 






K or Li DFOB






 






K or Li BOB






 






K or Li DFOB






 






K or Li BOB






 






K or Li DFOB






















TABLE 14






Lithium or 




potassium salt




or methyl triflate




or anhydride



Onium salt employed
employed
Ionic liquid







N(C2H5)3(CH2—CH2—CN)] Cl
LiBOB or KBOB
N(C2H5)3(CH2—CH2—CN)] BON


N(C2H5)3(CH2—CH2—CN)] Cl
K or Li DFOB
N(C2H5)3(CH2—CH2—CN)] DFOB


 






K or Li DFOB






 






LiBOB or KBOB






 






K or LiTOP






 






K or Li D(Ac)OAl






 






K or Li DFOB






 






LiBOB or KBOB






 






K or Li DFOB






 






K or Li DFOB






 






LiBOB or KBOB






 






K or Li DFOB






 






K or Li DFOB






 






LiBOB or KBOB






 






K or Li DFOB






 






LiBOB or KBOB













Example 8
Investigations on Graphite
In each case, 5 cyclic voltammograms are recorded successively in a measurement cell with graphite anode (SFG 44 with PVDF binder), lithium counterelectrode and lithium reference electrode. To this end, the potential is firstly lowered starting from the rest potential to 0 V against Li/Li+ at a rate of 0.1 mV/s and then returned to the rest potential.
The electrolyte used is 1 M LiPF6 in ethylene carbonate:diethylene carbonate (ratio 3:7) to which about 2% of a reactive ionic liquid selected from Table 7 is added in each case. The reactive ionic liquid forms a passivating top layer at potentials between about 2 V and 0.9 V against Li/Li+. From the second cycle, a 95% yield (±5% measurement tolerance) of the inclusion and extraction of lithium ions in the graphite is achieved.
Co-intercalation of the reactive ionic liquid selected from Table 15 in the graphite cannot be observed.








TABLE 15








Yield in %













Cycle
Cycle
Cycle
Cycle
Cycle


Ionic liquid
1
2
3
4
5















Reference* no IL additive
80
82
90
93
95


 






75
95
98
99
99


 






76
98
99
99
99


 






72
96
98
98
99


 






70
95
98
99
99


 






77
97
99
99
100


 






72
95
97
98
99


 






78
97
99
99
100


 






75
94
96
99
99


 






72
93
94
97
99


 






74
99
95
99
99


 






74
96
98
98
99


 






72
95
98
99
99


 






72
95
98
99
99


 






77
97
99
99
100


 






72
94
97
98
99


 






72
95
98
98
99


 






80
97
99
99
100


 






75
95
97
99
100


 






72
93
97
98
99


 






74
93
95
99
99


 






74
95
96
99
99


 






72
93
95
98
99


 






74
96
98
98
99


 






72
93
96
98
99


 






72
94
96
98
99


 






72
95
98
99
99


 






77
97
99
100
100


 






72
94
97
98
99


 






72
95
98
98
99


 






80
97
99
100
100


 






80
97
99
99
100





*Reference = LiPF6 in EC:DEC (3:7)






Example 9
Investigations on Graphite
In each case, 5 cyclic voltammograms are recorded successively in a measurement cell with graphite anode (SFG 44 with PVDF binder), lithium counterelectrode and lithium reference electrode. To this end, the potential is firstly lowered starting from the rest potential to 0 V against Li/Li+ at a rate of 0.1 mV/s and then returned to the rest potential.
The electrolyte used is 1 M LiPF6 in EC:DEC (3:7) to which about 10% of a reactive ionic liquid selected from Table 8 is added in each case. The reactive ionic liquid forms a passivating top layer at potentials between about 2 V and 0.9 V against Li/Li+. From the second cycle, a greater than 90% yield (±5% measurement tolerance) of the inclusion and extraction of lithium ions in the graphite is achieved.
Co-intercalation of the reactive ionic liquid selected from Table 16 in the graphite cannot be observed.








TABLE 16








Yield in %













Cycle
Cycle
Cycle
Cycle
Cycle


Ionic liquid (IL)
1
2
3
4
5















Reference* no IL additive
80
82
90
93
95


 






70
93
98
99
99


 






72
96
99
99
99


 






69
90
98
98
99


 






69
95
98
99
99


 






72
97
99
99
100


 






70
92
97
98
99


 






75
95
99
99
100


 






70
92
95
98
99


 






69
90
93
97
99


 






72
90
95
99
99


 






70
92
97
98
99


 






72
90
95
99
99


 






72
92
98
99
99


 






73
95
99
99
100


 






70
92
97
98
99


 






73
95
98
98
99


 






75
97
99
99
100


 






70
90
96
98
100


 






69
91
96
97
99


 






71
91
95
98
99


 






72
92
94
99
99


 






70
90
92
97
99


 






71
94
97
98
99


 






70
91
94
97
99


 






69
93
94
98
99


 






69
93
97
98
99


 






75
95
98
198
100


 






71
91
97
98
99


 






70
93
96
98
99


 






78
97
99
100
100


 






78
97
99
99
100





*Reference = LiPF6 in EC:DEC (3:7)






Example 10
Investigations of the Oxidation Stability
In each case, 5 cyclic voltammograms are recorded successively in a measurement cell with platinum working electrode, lithium counterelectrode and lithium reference electrode. To this end, the potential is firstly increased starting from the rest potential to 6.0 V against Li/Li+ at a rate of 10 mV/s and then returned to the rest potential.
The electrolyte used is 1 M LiPF6 in EC:DEC (3:7), to which about 2% of a reactive ionic liquid selected from Table 17 is added in each case. The oxidation potential is determined as >5 V against Li/Li+.
A signal below the oxidation stability of the reference electrolyte is not found in any of the systems investigated.










TABLE 17








Oxidation stability




EOX









Reference* no IL additive
>5 V



 







>5 V 



 







>5 V 



 







>5 V



 







>5 V



 







>5 V



 







>5 V



 







>5 V



 







>5 V



 







>5 V



 







>5 V



 







>5 V



 







>5 V



 







>5 V



 







>5 V



 







>5 V



 







>5 V



 







>5 V



 







>5 V



 







>5 V



 







>5 V



 







>5 V



 







>5 V



 







>5 V



 







>5 V



 







>5 V



 







>5 V



 







>5 V



 







>5 V



 







>5 V



 







>5 V



 







>5 V







*Reference = LiPF6 in EC:DEC (3:7)






Example 11
Investigations of the Oxidation Stability
In each case, 5 cyclic voltammograms are recorded successively in a measurement cell with platinum working electrode, lithium counterelectrode and lithium reference electrode. To this end, the potential is firstly increased starting from the rest potential to 6.0 V against Li/Li+ at a rate of 10 mV/s and then returned to the rest potential.
The electrolyte used is 1 M LiPF6 in EC:DEC to which about 10% of a reactive ionic liquid selected from Table 18 is added in each case. The oxidation potential is determined as >5 V against Li/Lip. A signal below the oxidation stability of the reference electrolyte is not found in any of the systems investigated.










TABLE 18








Oxidation stability



Ionic liquid
EOX









Reference* no IL additive
>5 V



 







>5 V 



 







>5 V



 







>5 V



 







>5 V



 







>5 V



 







>5 V



 







>5 V



 







>5 V



 







4.6-4.8 V



 







4.5-4.7 V



 







>5 V



 







4.6-4.8 V



 







4.7-4.8 V



 







>5 V



 







4.6-4.8 V



 







4.5-4.7 V



 







>5 V



 







4.7-4.8 V



 







4.8-5.0 V



 







4.8-5.0 V



 







4.7-4.8 V



 







>5 V



 







4.7-4.8 V



 







4.8-5.0 V



 







4.7-4.8 V



 







>5 V



 







4.7-4.8 V



 







4.8-5.0 V



 







4.7-4.8 V



 







4.7-4.8 V



 







4.8-5.0 V







*Reference = LiPF6 in EC:DEC (3:7)

## Claims

1. Ionic liquids of the general formula I


K+A−  (I)

in which:
K+ denotes at least one cation selected from the group consisting of the general formula IV




where
X denotes CH2;
R5 denotes —(CH2)n—O—C(O)—R— where n=2; and
R denotes CH3;
and
A− denotes at least one anion selected from the group consisting of
[FyP(CmF2m+1)6−y]−;
(CmF2m+1)2P(O)O−;
(CmF2m+1)P(O)O22−;
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;




where y=1, 2, 3, 4 or 5 and m=1 to 8, where some of the CF2 groups may be replaced by O, S(O)2, NR or CH2, and where




denotes a 1,2- or 1,3-diol, a 1,2- or 1,3-dicarboxylic acid or a 1,2- or 1,3-hydroxycarboxylic acid;
Y denotes B or Al;
R1 to R4 denote halogen, and/or a fluorinated or non-fluorinated alkoxy or carboxyl radical.

2. Electrolyte comprising at least one conductive salt, an aprotic solvent or solvent mixture, at least one ionic liquid according to claim 1 and optionally further additives.

3. Electrolyte according to claim 2, characterized in that the conductive salt is a lithium conductive salt.

4. Electrolyte according to claim 2, characterized in that the conductive salt is at least one conductive salt selected from the following compounds: 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.

5. Electrolyte according to claim 2, characterized in that the aprotic solvent consists of organic open-chain or cyclic carbonates, carboxylic acid esters, nitrites, ethers, lactones or a mixture thereof.

6. Process for the preparation of ionic liquids of the formula I according to claim 1, comprising:
preparing heterocyclic cations K+ having alkyl-, carboxylate-, carbonate- or cyano-containing side chains according to claim 1 as onium chlorides or bromides from the corresponding amines, phosphines, halocarboxylates, halocarbonates, haloalkyl nitriles or alkyl halides by conventional wet-chemical methods
reacting said cationic onium chlorides or bromides with at least one anion selected from the group consisting of the corresponding anionic potassium, sodium fluoroalkylphosphates, potassium, sodium bis(fluoroalkyl)phosphinates, potassium, sodium fluoroalkylphosphonates, fluoroalkylphosphoric acids, bis(fluoroalkyl)phosphinic acids, fluoroalkylphosphonic acids, alkyl, or
with at least one compound selected from the group consisting of lithium imides or methides, trifluoromethanesulfonic acid or potassium or lithium trifluoroacetates or triflates or alkyl triflates or trimethylsilyl triflates, trifluoromethanesulfonic anhydride or trifluoroacetic anhydride or
with at least one compound selected from the group consisting of lithium or potassium borates, phosphates or aluminates in aqueous and/or alcoholic medium or an organic solvent or without a solvent.

7. Electrochemical and/or electro-optical device containing at least one electrolyte which comprises at least one ionic liquid of the general formula I according to claim 1.

8. Electrochemical and/or electro-optical device according to claim 7, characterized in that said device is at least one device selected from the group consisting of solar cell, lithium ion battery, lithium battery, double-layer capacitor or supercapacitor, lithium capacitor, light-emitting device, electrochemical sensor and/or biosensor.

9. An electrochemical or electro-optical cells, comprising an ionic liquid according to claim 1.

10. A battery, comprising an ionic liquid according to claim 1.

11. A secondary lithium battery, comprising an ionic liquid according to claim 1.

12. A double-layer capacitor or supercapacitor or lithium capacitors comprising an ionic liquid according to claim 1.

13. A lithium or lithium ion battery, comprising an ionic liquid according to claim 1.

14. The ionic liquids according to claim 1, wherein m is 1 to 4.

15. The ionic liquids according to claim 1, wherein A− denotes at least one anion selected from the group consisting of



wherein R1 to R4 denote a halogen which is F.

16. The electrolyte according to claim 3 wherein said lithium conductive salt is at least one conductive salt selected from the group consisting of LiPF6, LiN(SO2CF3)2, LiN(SO2C2F5)2, LiF3P(C2F5)3, LiF3P(C4F9)3, LiB(C2O4)2 and LiF2B(C2O4)2.

17. The ionic liquid according to claim 1, wherein A− is bisoxalatoborate.