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.

Claims

1. An ionic liquid of the general formula I
K.sup.+A.sup.(I) in which: K.sup.+ denotes a cation of the general formulae IV ##STR00429## where X denotes CH.sub.2, O, S or NW; R denotes (CH.sub.2).sub.nCN, C.sub.1- to C.sub.16-alkyl, H; R denotes C.sub.1- to C.sub.16-alkyl; R.sub.5 denotes (CH.sub.2).sub.NC(O)OR, R denotes C.sub.1- to C.sub.16-alkyl; where n=2 to 8; and A.sup. denotes an anion selected from the group [F.sub.yP(C.sub.mF.sub.2m+1).sub.6-y].sup.; (C.sub.mF.sub.2m+1).sub.2P(O)O.sup.; (C.sub.mF.sub.2m+1)P(O)O.sub.2.sup.2; OC(O)C.sub.mF.sub.2m+1; OS(O).sub.2C.sub.mF.sub.2m+1; N(C(O)C.sub.mF.sub.2m+1).sub.2; N(S(O).sub.2C.sub.mF.sub.2m+1).sub.2; N(C(O)C.sub.mF.sub.2m+1)(S(O).sub.2C.sub.mF.sub.2m+1); N(C(O)C.sub.mF.sub.2m+1)(C(O)F); N(S(O).sub.2C.sub.mF.sub.2m+1)(S(O).sub.2F); N(S(O).sub.2F).sub.2; C(C(O)C.sub.mF.sub.2m+1).sub.3; C(S(O).sub.2C.sub.mF.sub.2m+1).sub.3; ##STR00430## where y=1, 2, 3, 4 or 5 and m=1 to 8, where some of the CF.sub.2 groups may be replaced by O, S(O).sub.2, NR or CH), and where ##STR00431## 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; R.sub.1 to R.sub.4 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, such as LiPF.sub.6, LiN(SO.sub.2CF.sub.3).sub.2, LiN(SO.sub.2C.sub.2F.sub.5).sub.2, LiF.sub.3P(C.sub.2F.sub.5).sub.3, LiF.sub.3P(C.sub.4F.sub.9).sub.3, LiB(C.sub.2O.sub.4).sub.2 or LiF.sub.2B(C.sub.2O.sub.4).sub.2.

4. Electrolyte according to claim 2, characterized in that the conductive salt is selected from the following compounds: N(C.sub.2H.sub.5).sub.4BF.sub.4, N(C.sub.2H.sub.5).sub.4PF.sub.6, N(C.sub.2H.sub.5).sub.3(CH.sub.3)BF.sub.4, N(C.sub.2H.sub.5).sub.3(CH.sub.3)PF.sub.6, N(C.sub.2H.sub.5).sub.4N(SO.sub.2CF.sub.3).sub.2, N(C.sub.2H.sub.5).sub.3(CH.sub.3)N(SO.sub.2CF.sub.3).sub.2, N(C.sub.2H.sub.5).sub.4F.sub.3P(C.sub.2F.sub.5).sub.3, N(C.sub.2H.sub.5).sub.3(CH.sub.3)F.sub.3P(C.sub.2F.sub.5).sub.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. A process for the preparation of an ionic liquid of the formula I according to claim 1, comprising the following steps: Preparation of heterocyclic cations K.sup.+ 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 Reaction of these cationic onium chlorides or bromides the corresponding anionic potassium and/or, sodium fluoroalkylphosphates and/or, potassium and/or, sodium bis(fluoroalkyl)phosphinates and/or, potassium and/or, sodium fluoroalkylphosphonates and/or, fluoroalkylphosphoric acids and/or, bis(fluoroalkyl)phosphinic acids and/or, fluoroalkylphosphonic acids and/or, alkyl, in particular methyl, bis(fluoroalkyl)phosphinates or lithium imides or methides and/or, trifluoromethanesulfonic acid or potassium or lithium trifluoroacetates or triflates or alkyl triflates or trimethylsilyl triflates and/or, trifluoromethanesulfonic anhydride or trifluoroacetic anhydride or 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 it is at least one 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 cell comprising an ionic liquid of the formula I according to claim 1.

10. A battery comprising an ionic liquid of the formula I according to claim 1.

11. A secondary lithium battery comprising an ionic liquid of the formula I according to claim 1.

12. A double-layer capacitor or supercapacitor or lithium capacitor comprising an ionic liquid of the formula I according to claim 1.

13. A lithium or lithium ion battery comprising the electrolyte according to claim 2.

14. A double-layer capacitor or supercapacitor or lithium capacitor comprising the electrolyte according to claim 2.

15. The ionic liquid according to claim 1, where X denotes CH.sub.2.

16. The ionic liquid according to claim 1, where X denotes CH.sub.2 or O.

17. The ionic liquid according to claim 1, where X denotes CH.sub.2, O or NR.

Description

EXAMPLES

Preparation of the Cations

Example 1

Preparation of Heterocyclic Cations Containing Allyl Side Chains

(1) General Procedure

(2) 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.Math.10.sup.3 mbar). The product yield is virtually quantitative.

(3) TABLE-US-00004 TABLE 1 Amine/phosphine Allyl chloride employed employed Product N(C.sub.2H.sub.5).sub.3 ClCH.sub.2CHCH.sub.2 [N(C.sub.2H.sub.5).sub.3(CH.sub.2CHCH.sub.2)]Cl N(CH.sub.3)(C.sub.2H.sub.5).sub.2 ClCH.sub.2CHCH.sub.2 [N(CH.sub.3)(C.sub.2H.sub.5).sub.3 (CH.sub.2CHCH.sub.2)]Cl P(C.sub.4H.sub.9).sub.3 ClCH.sub.2CHCH.sub.2 [P(C.sub.4H.sub.9).sub.3(CH.sub.2CHCH.sub.2)]Cl ClCH.sub.2CHCH.sub.2 ClCH.sub.2CHCH.sub.2 ClCH.sub.2CHCH.sub.2 ClCH.sub.2CHCH.sub.2 ClCH.sub.2CHCH.sub.2 0 ClCH.sub.2CHCH.sub.2

Example 2

Preparation of Heterocyclic Cations Containing Carboxylate Side Chains or Carbonate Side Chains

(4) General Procedure

(5) 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.

(6) 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%.

(7) TABLE-US-00005 TABLE 2 Amine/ phosphine Chloro(bromo)- employed alkylcarboxylate Product N(C.sub.2H.sub.5).sub.3 BrCH.sub.2C(O)O [N(C.sub.2H.sub.5).sub.3(CH.sub.2C(O) C.sub.2H.sub.5 OC.sub.2H.sub.5)] Br N(CH.sub.3).sub.2(C.sub.2H.sub.5) BrCH.sub.2CH.sub.2C(O) [N(CH.sub.3).sub.2(C.sub.2H.sub.5) OCH.sub.3 (CH.sub.2CH.sub.2 C(O)OCH.sub.3)] Br N(CH.sub.3).sub.2(C.sub.2H.sub.5) BrCH.sub.2C(O)CH.sub.2 [N(CH.sub.3).sub.2(C.sub.2H.sub.5) C(O)OCH.sub.3 (CH.sub.2C(O) CH.sub.2C(O)OCH.sub.3)] Br N(CH.sub.3).sub.2(C.sub.2H.sub.5) BrCH.sub.2OC(O)O [N(CH.sub.3).sub.2(C.sub.2H.sub.5) (CH.sub.2 CH.sub.3 OC(O) OCH.sub.3)] Br P(C.sub.4H.sub.9).sub.3 BrCH.sub.2C(O)O [P(C.sub.4H.sub.9).sub.3(CH.sub.2C(O) C.sub.2H.sub.5 OC.sub.2H.sub.5)]Br BrCH.sub.2CH.sub.2C(O) OCH.sub.3 BrCH.sub.2C(O)CH.sub.2 C(O)OCH.sub.3 BrCH.sub.2OC(O)O CH.sub.3 BrCH.sub.2CH.sub.2C(O) OCH.sub.3 0 BrCH.sub.2CH.sub.2C(O) OCH.sub.3 ClCH.sub.2OC(O)O CH.sub.3 ClCH.sub.2C(O)CH.sub.2 C(O)OCH.sub.3 ClCH.sub.2CH.sub.2C(O) OCH.sub.3 ClCH.sub.2CH.sub.2C(O) OCH.sub.3 0 ClCH.sub.2CH.sub.2C(O) OCH.sub.3

Example 3

Preparation of Heterocyclic Cations Containing Cyano-Containing Side Chains

(8) General Procedure

(9) 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.Math.10.sup.3 mbar). The product yield is virtually quantitative.

(10) TABLE-US-00006 TABLE 3 Amine/phosphine Chloroalkyl employed nitrite Product N(C.sub.2H.sub.5).sub.3 ClCH.sub.2CH.sub.2CN [N(C.sub.2H.sub.5).sub.3(CH.sub.2CH.sub.2CN)] Cl N(CH.sub.3).sub.2(C.sub.2H.sub.5) ClCH.sub.2CH.sub.2CN [N(CH.sub.3).sub.2(C.sub.2H.sub.5) (CH.sub.2 CH.sub.2CN)] Cl P(C.sub.4H.sub.9).sub.3 ClCH.sub.2CH.sub.2CN [P(C.sub.4H.sub.9).sub.3(CH.sub.2CH.sub.2CN)] Cl ClCH.sub.2CH.sub.2CN ClCH.sub.2CH.sub.2CN ClCH.sub.2CH.sub.2CN ClCH.sub.2CH.sub.2CN 0 ClCH.sub.2CH.sub.2CN ClCH.sub.2CH.sub.2CN

Preparation of Fluoroalkylphosphate- and Fluoroalkylphosphinate-Based Reactive Ionic Liquids

Example 4

Preparation of Fluoroalkylphosphate-Based Reactive Ionic Liquids

(11) General Procedure

(12) 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.

(13) 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 Phosphoric Acid

(14) General Procedure

(15) 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.

(16) 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

(17) General Procedure

(18) 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.

(19) 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

(20) 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.

(21) The reaction mixture is stirred at room temperature or with heating up to 100 C. for 1 to 20 h, and CH.sub.3Cl (or CH.sub.3Br) formed and excess methyl bis(fluoroalkyl)phosphinate are removed in vacuo. Bis(fluoroalkyl)phosphinates form in virtually quantitative yield.

(22) TABLE-US-00007 TABLE 4 Potassium salt or phosphinic acid or methyl phosphinate Onium salt employed employed Ionic liquid [N(C.sub.2H.sub.5).sub.3(CH.sub.2 K F.sub.3P(C.sub.2F.sub.5).sub.3 [N(C.sub.2H.sub.5).sub.3(CH.sub.2CHCH.sub.2)] CHCH.sub.2)] Cl F.sub.3P(C.sub.2F.sub.5).sub.3 [N(C.sub.2H.sub.5).sub.3(CH.sub.2 K F.sub.3P(C.sub.4F.sub.9).sub.3 [N(C.sub.2H.sub.5).sub.3(CH.sub.2CHCH.sub.2)] CHCH.sub.2)] Cl F.sub.3P(C.sub.4F.sub.9).sub.3 [N(C.sub.2H.sub.5).sub.3(CH.sub.2 K OP(O)(C.sub.2F.sub.5).sub.2 [N(C.sub.2H.sub.5).sub.3(CH.sub.2CHCH.sub.2)] CHCH.sub.2)] Cl HOP(O)(C.sub.2F.sub.5).sub.2 OP(O)(C.sub.2F.sub.5).sub.2 CH.sub.3OP(O)(C.sub.2F.sub.5).sub.2 [N(C.sub.2H.sub.5).sub.3(CH.sub.2 K OP(O)(C.sub.4F.sub.9).sub.2 [N(C.sub.2H.sub.5).sub.3(CH.sub.2CHCH.sub.2)] CHCH.sub.2)] Cl HOP(O)(C.sub.4F.sub.9).sub.2 OP(O)(C.sub.4F.sub.9).sub.2 CH.sub.3OP(O)(C.sub.4F.sub.9).sub.2 [N(CH.sub.3)(C.sub.2H.sub.5).sub.3(CH.sub.2 K F.sub.3P(C.sub.2F.sub.5).sub.3 [N(CH.sub.3)(C.sub.2H.sub.5).sub.3(CH.sub.2 CHCH.sub.2)] Cl CHCH.sub.2)] F.sub.3P(C.sub.2F.sub.5).sub.3 [P(C.sub.4H.sub.9).sub.3(CH.sub.2 K F.sub.3P(C.sub.2F.sub.5).sub.3 [P(C.sub.4H.sub.9).sub.3(CH.sub.2CHCH.sub.2)] CHCH.sub.2)] Cl F.sub.3P(C.sub.2F.sub.5).sub.3 K F.sub.3P(C.sub.2F.sub.5).sub.3 K F.sub.3P(C.sub.4F.sub.9).sub.3 K OP(O)(C.sub.2F.sub.5).sub.2 HOP(O)(C.sub.2F.sub.5).sub.2 CH.sub.3OP(O)(C.sub.2F.sub.5).sub.2 0 K OP(O)(C.sub.4F.sub.9).sub.2 HOP(O)(C.sub.4F.sub.9).sub.2 CH.sub.3OP(O)(C.sub.4F.sub.9).sub.2 K F.sub.3P(C.sub.2F.sub.5).sub.3 K F.sub.3P(C.sub.2F.sub.5).sub.3 K F.sub.3P(C.sub.2F.sub.5).sub.3

(23) TABLE-US-00008 TABLE 5 Potassium salt or methyl phosphin- Onium salt employed ate employed Ionic liquid [N(C.sub.2H.sub.5).sub.3(CH.sub.2C(O)O K F.sub.3P(C.sub.2F.sub.5).sub.3 [N(C.sub.2H.sub.5).sub.3(CH.sub.2C(O)O C.sub.2H.sub.5)] Br C.sub.2H.sub.5)] F.sub.3P(C.sub.2F.sub.5).sub.3 [N(C.sub.2H.sub.5).sub.3(CH.sub.2C(O)O K F.sub.3P(C.sub.4F.sub.9).sub.3 [N(C.sub.2H.sub.5).sub.3(CH.sub.2C(O)O C.sub.2H.sub.5)] Br C.sub.2H.sub.5)] F.sub.3P(C.sub.4F.sub.9).sub.3 [N(C.sub.2H.sub.5).sub.3(CH.sub.2C(O)O K OP(O)(C.sub.2F.sub.5).sub.2 [N(C.sub.2H.sub.5).sub.3(CH.sub.2C(O)O C.sub.2H.sub.5)] Br C.sub.2H.sub.5)] OP(O)(C.sub.2F.sub.5).sub.2 [N(C.sub.2H.sub.5).sub.3(CH.sub.2C(O)O K OP(O)(C.sub.4F.sub.9).sub.2 [N(C.sub.2H.sub.5).sub.3(CH.sub.2C(O)O C.sub.2H.sub.5)] Br CH.sub.3OP(O)(C.sub.4F.sub.9).sub.2 C.sub.2H.sub.5)] OP(O)(C.sub.4F.sub.9).sub.2 [N(CH.sub.3).sub.2(C.sub.2H.sub.5) (CH.sub.2 K F.sub.3P(C.sub.2F.sub.5).sub.3 [N(CH.sub.3).sub.2(C.sub.2H.sub.5) (CH.sub.2 CH.sub.2C(O)OCH.sub.3)] Br CH.sub.2-C(O)-O-CH.sub.3)] F.sub.3P(C.sub.2F.sub.5).sub.3 [N(CH.sub.3).sub.2(C.sub.2H.sub.5) (CH.sub.2 K F.sub.3P(C.sub.2F.sub.5).sub.3 [N(CH.sub.3).sub.2(C.sub.2H.sub.5) (CH.sub.2 C(O)CH.sub.2C(O)OCH.sub.3)] C(O)CH.sub.2C(O)OCH.sub.3)] Br F.sub.3P(C.sub.2F.sub.5).sub.3 [N(CH.sub.3).sub.2(C.sub.2H.sub.5) (CH.sub.2O K F.sub.3P(C.sub.2F.sub.5).sub.3 [N(CH.sub.3).sub.2(C.sub.2H.sub.5) (CH.sub.2O C(O)OCH.sub.3)] Br C(O)OCH.sub.3)] F.sub.3P(C.sub.2F.sub.5).sub.3 [P(C.sub.4H.sub.9).sub.3(CH.sub.2C(O)O K F.sub.3P(C.sub.2F.sub.5).sub.3 [P(C.sub.4H.sub.9).sub.3(CH.sub.2C(O)O C.sub.2H.sub.5)] Br C.sub.2H.sub.5)] F.sub.3P(C.sub.2F.sub.5).sub.3 K F.sub.3P(C.sub.2F.sub.5).sub.3 0 K F.sub.3P(C.sub.4F.sub.9).sub.3 K OP(O)(C.sub.2F.sub.5).sub.2 CH.sub.3OP(O)(C.sub.2F.sub.5).sub.2 K OP(O)(C.sub.4F.sub.9).sub.2 CH.sub.3OP(O)(C.sub.4F.sub.9).sub.2 K F.sub.3P(C.sub.2F.sub.5).sub.3 K F.sub.3P(C.sub.2F.sub.5).sub.3 0 K F.sub.3P(C.sub.2F.sub.5).sub.3 K F.sub.3P(C.sub.2F.sub.5).sub.3 K F.sub.3P(C.sub.2F.sub.5).sub.3 K F.sub.3P(C.sub.2F.sub.5).sub.3 K F.sub.3P(C.sub.2F.sub.5).sub.3 0 K F.sub.3P(C.sub.2F.sub.5).sub.3 K F.sub.3P(C.sub.2F.sub.5).sub.3

(24) TABLE-US-00009 TABLE 6 Potassium salt or phosphinic acid or methyl Onium salt phosphinate employed employed Ionic liquid [N(C.sub.2H.sub.5).sub.3(CH.sub.2CH.sub.2 K F.sub.3P(C.sub.2F.sub.5).sub.3 [N(C.sub.2H.sub.5).sub.3 CN)] Cl (CH.sub.2CH.sub.2CN)] F.sub.3P(C.sub.2F.sub.5).sub.3 N(C.sub.2H.sub.5).sub.3(CH.sub.2CH.sub.2 K F.sub.3P(C.sub.4F.sub.9).sub.3 N(C.sub.2H.sub.5).sub.3(CH.sub.2CH.sub.2CN)] CN)] Cl F.sub.3P(C.sub.4F.sub.9).sub.3 N(C.sub.2H.sub.5).sub.3(CH.sub.2CH.sub.2 K OP(O)(C.sub.2F.sub.5).sub.2 N(C.sub.2H.sub.5).sub.3(CH.sub.2CH.sub.2CN)] CN)] Cl HOP(O)(C.sub.2F.sub.5).sub.2 OP(O)(C.sub.2F.sub.5).sub.2 CH.sub.3OP(O)(C.sub.2F.sub.5).sub.2 N(C.sub.2H.sub.5).sub.3(CH.sub.2CH.sub.2 K OP(O)(C.sub.4F.sub.9).sub.2 N(C.sub.2H.sub.5).sub.3(CH.sub.2CH.sub.2CN)] CN)] Cl HOP(O)(C.sub.4F.sub.9).sub.2 OP(O)(C.sub.4F.sub.9).sub.2 CH.sub.3OP(O)(C.sub.4F.sub.9).sub.2 [N(CH.sub.3).sub.2(C.sub.2H.sub.5) (CH.sub.2 K F.sub.3P(C.sub.2F.sub.5).sub.3 [N(CH.sub.3).sub.2(C.sub.2H.sub.5) CH.sub.2CN)] Cl (CH.sub.2CH.sub.2CN)] F.sub.3P(C.sub.2F.sub.5).sub.3 [P(C.sub.4H.sub.9).sub.3(CH.sub.2CH.sub.2 K F.sub.3P(C.sub.2F.sub.5).sub.3 [P(C.sub.4H.sub.9).sub.3(CH.sub.2CH.sub.2CN)] CN)] Cl F.sub.3P(C.sub.2F.sub.5).sub.3 K F.sub.3P(C.sub.2F.sub.5).sub.3 K F.sub.3P(C.sub.4F.sub.9).sub.3 K OP(O)(C.sub.2F.sub.5).sub.2 HOP(O)(C.sub.2F.sub.5).sub.2 CH.sub.3OP(O)(C.sub.2F.sub.5).sub.2 00 01 K OP(O)(C.sub.4F.sub.9).sub.2 HOP(O)(C.sub.4F.sub.9).sub.2 CH.sub.3OP(O)(C.sub.4F.sub.9).sub.2 02 03 K F.sub.3P(C.sub.2F.sub.5).sub.3 04 05 K F.sub.3P(C.sub.2F.sub.5).sub.3 06 07 K F.sub.3P(C.sub.2F.sub.5).sub.3 08 09 K F.sub.3P(C.sub.2F.sub.5).sub.3 0 K F.sub.3P(C.sub.2F.sub.5).sub.3

Preparation of Acetate-, Triflate-, Imide- and Methide-Based Reactive Ionic Liquids

Example 5

Preparation of Imide- and Methide-Based Ionic Liquids

(25) General Procedure

(26) 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(trifluoromethylsulfonyl)imide (NH acid) or tris(trifluoromethylsulfonyl)methide (CH acid) is subsequently added slowly. 2 phases immediately form.

(27) 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).

(28) 10 g of Al.sub.2O.sub.3 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.

(29) TABLE-US-00010 TABLE 7 Lithium salt or bis(trifluoro- methylsulfonyl)- imide or tris(tri- fluoromethyl- sulfonyl)methide Onium salt employed employed Ionic liquid [N(C.sub.2H.sub.5).sub.3(CH.sub.2 Li N(SO.sub.2CF.sub.3).sub.2 [N(C.sub.2H.sub.5).sub.3 CHCH.sub.2)] Cl HN(SO.sub.2CF.sub.3).sub.2 (CH.sub.2CHCH.sub.2)] N(SO.sub.2CF.sub.3).sub.2 [N(C.sub.2H.sub.5).sub.3(CH.sub.2 Li C(SO.sub.2CF.sub.3).sub.3 [N(C.sub.2H.sub.5).sub.3 CHCH.sub.2)] Cl HN(SO.sub.2CF.sub.3).sub.2 (CH.sub.2CHCH.sub.2)] [N(CH.sub.3)(C.sub.2H.sub.5).sub.3(CH.sub.2 Li N(SO.sub.2CF.sub.3).sub.2 [N(CH.sub.3)(C.sub.2H.sub.5).sub.3 CHCH.sub.2)] Cl HN(SO.sub.2CF.sub.3).sub.2 (CH.sub.2CHCH.sub.2)]N(SO.sub.2CF.sub.3).sub.2 [P(C.sub.4H.sub.9).sub.3(CH.sub.2 Li N(SO.sub.2CF.sub.3).sub.2 [P(C.sub.4H.sub.9).sub.3(CH.sub.2CHCH.sub.2)] CHCH.sub.2)] Cl HN(SO.sub.2CF.sub.3).sub.2 N(SO.sub.2CF.sub.3).sub.2 Li N(SO.sub.2CF.sub.3).sub.2 HN(SO.sub.2CF.sub.3).sub.2 Li C(SO.sub.2CF.sub.3).sub.3 HC(SO.sub.2CF.sub.3).sub.3 Li N(SO.sub.2CF.sub.3).sub.2 HN(SO.sub.2CF.sub.3).sub.2 Li N(SO.sub.2CF.sub.3).sub.2 HN(SO.sub.2CF.sub.3).sub.2 0 Li N(SO.sub.2CF.sub.3).sub.2 HN(SO.sub.2CF.sub.3).sub.2 Li N(SO.sub.2CF.sub.3).sub.2 HN(SO.sub.2CF.sub.3).sub.2 Li N(SO.sub.2CF.sub.3).sub.2 HN(SO.sub.2CF.sub.3).sub.2

(30) TABLE-US-00011 TABLE 8 Lithium salt or bis(trifluoro- methylsulfonyl)- imide or tris(tri- fluoromethyl- sulfonyl)methide Onium salt employed employed Ionic liquid [N(C.sub.2H.sub.5).sub.3(CH.sub.2C(O)O Li N(SO.sub.2CF.sub.3).sub.2 [N(C.sub.2H.sub.5).sub.3(CH.sub.2C(O)OC.sub.2H.sub.5)] C.sub.2H.sub.5)] Br HN(SO.sub.2CF.sub.3).sub.2 N(SO.sub.2CF.sub.3).sub.2 [N(C.sub.2H.sub.5).sub.3(CH.sub.2C(O)O Li OSO.sub.2CF.sub.3 [N(C.sub.2H.sub.5).sub.3(CH.sub.2C(O)OC.sub.2H.sub.5)] C.sub.2H.sub.5)] Cl OSO.sub.2CF.sub.3 [N(C.sub.2H.sub.5).sub.3(CH.sub.2C(O)O Li OCOCF.sub.3 [N(C.sub.2H.sub.5).sub.3(CH.sub.2C(O)OC.sub.2H.sub.5)] C.sub.2H.sub.5)) Cl OCOCF.sub.3 [N(C.sub.2H.sub.5).sub.3(CH.sub.2C(O)O Li C(SO.sub.2CF.sub.3).sub.3 [N(C.sub.2H.sub.5).sub.3(CH2C(O)OC.sub.2H.sub.5)] C.sub.2H.sub.5)] Br HC(SO.sub.2CF.sub.3).sub.3 C(SO.sub.2CF.sub.3).sub.3 [N(CH.sub.3).sub.2(C.sub.2H.sub.5) (CH.sub.2 Li N(SO.sub.2CF.sub.3).sub.2 [N(CH.sub.3).sub.2(C.sub.2H.sub.5) (CH.sub.2CH.sub.2C(O) CH.sub.2C(O)OCH.sub.3)] Br HN(SO.sub.2CF.sub.3).sub.2 O-CH.sub.3)] N(SO.sub.2CF.sub.3).sub.2 [N(CH.sub.3).sub.2(C.sub.2H.sub.5) (CH.sub.2 Li N(SO.sub.2CF.sub.3).sub.2 [N(CH.sub.3).sub.2(C.sub.2H.sub.5) (CH.sub.2C(O)CH.sub.2 C(O)CH.sub.2C(O)OCH.sub.3) HN(SO.sub.2CF.sub.3).sub.2 C(O)OCH.sub.3)] N(SO.sub.2CF.sub.3).sub.2 Br [N(CH.sub.3).sub.2(C.sub.2H.sub.5) (CH.sub.2O Li N(SO.sub.2CF.sub.3).sub.2 [N(CH.sub.3).sub.2(C.sub.2H.sub.5) (CH.sub.2OC(O)O C(O)OCH.sub.3)] Br HN(SO.sub.2CF.sub.3).sub.2 CH.sub.3)] N(SO.sub.2CF.sub.3).sub.2 [P(C.sub.4H.sub.9).sub.3(CH.sub.2C(O)O Li N(SO.sub.2CF.sub.3).sub.2 P(C.sub.4H.sub.9).sub.3(CH.sub.2C(O)OC.sub.2H.sub.5)] C.sub.2H.sub.5)] Br HN(SO.sub.2CF.sub.3).sub.2 N(SO.sub.2CF.sub.3).sub.2 Li N(SO.sub.2CF.sub.3).sub.2 HN(SO.sub.2CF.sub.3).sub.2 Li C(SO.sub.2CF.sub.3).sub.3 HC(SO.sub.2CF.sub.3).sub.3 0 Li N(SO.sub.2CF.sub.3).sub.2 HN(SO.sub.2CF.sub.3).sub.2 Li N(SO.sub.2CF.sub.3).sub.2 HN(SO.sub.2CF.sub.3).sub.2 Li N(SO.sub.2CF.sub.3).sub.2 HN(SO.sub.2CF.sub.3).sub.2 Li N(SO.sub.2CF.sub.3).sub.2 HN(SO.sub.2CF.sub.3).sub.2 Li N(SO.sub.2CF.sub.3).sub.2 HN(SO.sub.2CF.sub.3).sub.2 0 Li N(SO.sub.2CF.sub.3).sub.2 HN(SO.sub.2CF.sub.3).sub.2 Li N(SO.sub.2CF.sub.3).sub.2 HN(SO.sub.2CF.sub.3).sub.2 Li N(SO.sub.2CF.sub.3).sub.2 HN(SO.sub.2CF.sub.3).sub.2 Li N(SO.sub.2CF.sub.3).sub.2 HN(SO.sub.2CF.sub.3).sub.2

(31) TABLE-US-00012 TABLE 9 Lithium salt or bis(trifluoro- methyl- sulfonyl)- imide or tris(tri- fluorornethyl- sulfonyl)- methide Onium salt employed employed Ionic liquid [N(C.sub.2H.sub.5).sub.3(CH.sub.2CH.sub.2 Li N(SO.sub.2CF.sub.3).sub.2 [N(C.sub.2H.sub.5).sub.3(CH.sub.2CH.sub.2CN)] CN)] Cl HN(SO.sub.2CF.sub.3).sub.2 N(SO.sub.2CF.sub.3).sub.2 N(C.sub.2H.sub.5).sub.3(CH.sub.2CH.sub.2 Li C(SO.sub.2CF.sub.3).sub.3 N(C.sub.2H.sub.5).sub.3(CH.sub.2CH.sub.2CN)] CN)] Cl HC(SO.sub.2CF.sub.3).sub.3 C(SO.sub.2CF.sub.3).sub.3 [N(CH.sub.3).sub.2(C.sub.2H.sub.5) (CH.sub.2 Li N(SO.sub.2CF.sub.3).sub.2 [N(CH.sub.3).sub.2(C.sub.2H.sub.5) (CH.sub.2CH.sub.2 CH.sub.2CN)] Cl HN(SO.sub.2CF.sub.3).sub.2 CN)] N(SO.sub.2CF.sub.3).sub.2 [P(C.sub.4H.sub.9).sub.3(CH.sub.2CH.sub.2 Li N(SO.sub.2CF.sub.3).sub.2 [P(C.sub.4H.sub.9).sub.3(CH.sub.2CH.sub.2CN)] CN)] Cl HN(SO.sub.2CF.sub.3).sub.2 N(SO.sub.2CF.sub.3).sub.2 Li N(SO.sub.2CF.sub.3).sub.2 HN(SO.sub.2CF.sub.3).sub.2 0 Li C(SO.sub.2CF.sub.3).sub.3 HC(SO.sub.2CF.sub.3).sub.3 Li N(SO.sub.2CF.sub.3).sub.2 HN(SO.sub.2CF.sub.3).sub.2 Li N(SO.sub.2CF.sub.3).sub.2 HN(SO.sub.2CF.sub.3).sub.2 Li N(SO.sub.2CF.sub.3).sub.2 HN(SO.sub.2CF.sub.3).sub.2 Li N(SO.sub.2CF.sub.3).sub.2 HN(SO.sub.2CF.sub.3).sub.2 0 Li N(SO.sub.2CF.sub.3).sub.2 HN(SO.sub.2CF.sub.3).sub.2

Preparation of Trifluoroacetate- or Triflate-Based Ionic Liquids

Example 6.1

Preparation of Triflate-Based Ionic Liquids by Means of Triflic Acid

(32) General Procedure

(33) 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.

(34) 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

(35) General Procedure

(36) 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.

(37) 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

(38) 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.

(39) The reaction mixture is stirred at room temperature or with heating up to 100 C. for a further 1 to 48 h, and CH.sub.3Cl (or CH.sub.3Br or (CH.sub.3).sub.3SiCl or CF.sub.3SO.sub.2Cl or CF.sub.3COCl or CF.sub.3COBr) formed and excess methyl or trimethylsilyl triflates or anhydrides are removed in vacuo. Trifluoroacetates or triflates form in virtually quantitative yield.

(40) TABLE-US-00013 TABLE 10 Lithium or potas- sium salt or methyl triflate or anhydride em- Onium salt employed ployed Ionic liquids [N(C.sub.2H.sub.5).sub.3(CH.sub.2 K OSO.sub.2CF.sub.3, [N(C.sub.2H.sub.5).sub.3(CH.sub.2CHCH.sub.2)] CHCH.sub.2)] Cl HOSO.sub.2CF.sub.3, CH.sub.3OSO.sub.2CF.sub.3, (CH.sub.3).sub.3SIOSO.sub.2CF.sub.3, [N(C.sub.2H.sub.5).sub.3(CH.sub.2 Li OCOCF.sub.3, [N(C.sub.2H.sub.5).sub.3(CH.sub.2CHCH.sub.2)] CHCH.sub.2)) Cl (CF.sub.3CO).sub.2O K OSO.sub.2CF.sub.3, HOSO.sub.2CF.sub.3, CH.sub.3OSO.sub.2CF.sub.3, (CH.sub.3).sub.3SiOSO.sub.2CF.sub.3, Li OCOCF.sub.3, (CF.sub.3CO).sub.2O [N(C.sub.2H.sub.5).sub.3(CH.sub.2C(O)O K OSO.sub.2CF.sub.3, [N(C.sub.2H.sub.5).sub.3(CH.sub.2C(O)O C.sub.2H.sub.5)] Br HOSO.sub.2CF.sub.3, C.sub.2H.sub.5)] OSO.sub.2CF.sub.3 CH.sub.3OSO.sub.2CF.sub.3, (CH.sub.3).sub.3SiOSO.sub.2CF.sub.3 [N(C.sub.2H.sub.5).sub.3(CH.sub.2C(O)O K OCOCF.sub.3, [N(C.sub.2H.sub.5).sub.3(CH.sub.2C(O)O C.sub.2H.sub.5)] Br (CF.sub.3CO).sub.2O C.sub.2H.sub.5)] OCOCF.sub.3 K OSO.sub.2CF.sub.3, HOSO.sub.2CF.sub.3, CH.sub.3OSO.sub.2CF.sub.3, (CH.sub.3).sub.3SiOSO.sub.2CF.sub.3 K OCOCF.sub.3, (CF.sub.3CO).sub.2O 0 K OSO.sub.2CF.sub.3, HOSO.sub.2CF.sub.3, CH.sub.3OSO.sub.2CF.sub.3, (CH.sub.3).sub.3SIOSO.sub.2CF.sub.3 K OCOCF.sub.3, (CF.sub.3CO).sub.2O K OSO.sub.2CF.sub.3, HOSO.sub.2CF.sub.3, CH.sub.3OSO.sub.2CF.sub.3, (CH.sub.3).sub.3SiOSO.sub.2CF.sub.3 K OSO.sub.2CF.sub.3, HOSO.sub.2CF.sub.3, CH.sub.3OSO.sub.2CF.sub.3, (CH.sub.3).sub.3SiOSO.sub.2CF.sub.3 K OSO.sub.2CF.sub.3, HOSO.sub.2CF.sub.3, CH.sub.3OSO.sub.2CF.sub.3, (CH.sub.3).sub.3SiOSO.sub.2CF.sub.3 0

(41) TABLE-US-00014 TABLE 11 Lithium or potas- sium salt or methyl triflate or anhydride em- Onium salt employed ployed Ionic liquids N(C.sub.2H.sub.5).sub.3(CH.sub.2CH.sub.2 K OSO.sub.2CF.sub.3, N(C.sub.2H.sub.5).sub.3(CH.sub.2CH.sub.2CN)] CN)] Cl HOSO.sub.2CF.sub.3, OSO.sub.2CF.sub.3 CH.sub.3OSO.sub.2CF.sub.3, (CH.sub.3).sub.3SiOSO.sub.2CF.sub.3 N(C.sub.2H.sub.5).sub.3(CH.sub.2CH.sub.2 K OCOCF.sub.3, N(C.sub.2H.sub.5).sub.3(CH.sub.2 CN)] Cl (CF.sub.3CO).sub.2O CH.sub.2CN)] OCOCF.sub.3 K OSO.sub.2CF.sub.3, HOSO.sub.2CF.sub.3, CH.sub.3OSO.sub.2CF.sub.3, (CH.sub.3).sub.3SiOSO.sub.2CF.sub.3 K OCOCF.sub.3, (CF.sub.3CO).sub.2O K OSO.sub.2CF.sub.3, CH.sub.3OSO.sub.2CF.sub.3, (CH.sub.3).sub.3SiOSO.sub.2CF.sub.3 K OSO.sub.2CF.sub.3, HOSO.sub.2CF.sub.3, CH.sub.3OSO.sub.2CF.sub.3, (CH.sub.3).sub.3SiOSO.sub.2CF.sub.3 K OSO.sub.2CF.sub.3, HOSO.sub.2CF.sub.3, CH.sub.3OSO.sub.2CF.sub.3, (CH.sub.3).sub.3SiOSO.sub.2CF.sub.3 0 K OSO.sub.2CF.sub.3, HOSO.sub.2CF.sub.3, CH.sub.3OSO.sub.2CF.sub.3, (CH.sub.3).sub.3SiOSO.sub.2CF.sub.3 K OSO.sub.2CF.sub.3, HOSO.sub.2CF.sub.3, (CH.sub.3).sub.3SiOSO.sub.2CF.sub.3

Example 7

Preparation of Borate-, Phosphate- and Aluminate-Based Ionic Liquids

(42) General Procedure

(43) 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 nil 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 nil of deionised water each time and then evaporated to and subsequently stirred into 1 l of n-heptane.

(44) 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.

(45) TABLE-US-00015 TABLE 12 Onium salt Potassium or lithium salt employed employed Ionic liquid [N(C.sub.2H.sub.5).sub.3(CH2CHCH.sub.2)] Cl [N(C.sub.2H.sub.5).sub.3(CH.sub.2CHCH.sub.2)] BOB [N(C.sub.2H.sub.5).sub.3(CH2CHCH.sub.2)] Cl [N(C.sub.2H.sub.5).sub.3(CH.sub.2CHCH.sub.2)] DFOB [N(C.sub.2H.sub.5).sub.3(CH2CHCH.sub.2)] Cl [N(C.sub.2H.sub.5).sub.3(CH.sub.2CHCH.sub.2)] D(Ac)OB [N(C.sub.2H.sub.5).sub.3(CH2CHCH.sub.2)] Cl [N(C.sub.2H.sub.5).sub.3(CH.sub.2CHCH.sub.2)] DFGB [N(C.sub.2H.sub.5).sub.3(CH2CHCH.sub.2)] Cl [N(C.sub.2H.sub.5).sub.3(CH.sub.2CHCH.sub.2)] TFOP [N(C.sub.2H.sub.5).sub.3(CH2CHCH.sub.2)] Cl 00 [N(C.sub.2H.sub.5).sub.3(CH.sub.2CHCH.sub.2)] D(Ac)OAl [N(C.sub.2H.sub.5).sub.3(CH2CHCH.sub.2)] Cl 01 [N(C.sub.2H.sub.5).sub.3(CH.sub.2CHCH.sub.2)] TOP [N(C.sub.2H.sub.5).sub.3(CH2CHCH.sub.2)] Cl 02 [N(C.sub.2H.sub.5).sub.3(CH.sub.2CHCH.sub.2)] DFPB [N(CH.sub.3)(C.sub.2H.sub.5).sub.3(CH.sub.2CHCH.sub.2)] K or Li BOB [N(CH.sub.3)(C.sub.2H.sub.5).sub.3(CH.sub.2CHCH.sub.2)] Cl BOB [N(CH.sub.3)(C.sub.2H.sub.5).sub.3(CH.sub.2CHCH.sub.2)] K or Li DFOB [N(CH.sub.3)(C.sub.2H.sub.5).sub.3(CH.sub.2CHCH.sub.2)] Cl DFOB [P(C.sub.4H.sub.9).sub.3(CH.sub.2CHCH.sub.2)] K or Li BOB [P(C.sub.4H.sub.9).sub.3(CH.sub.2CHCH.sub.2)] Cl BOB [P(C.sub.4H.sub.9).sub.3(CH.sub.2CHCH.sub.2)] K or Li DFOB [P(C.sub.4H.sub.9).sub.3(CH.sub.2CHCH.sub.2)] Cl DFOB 03 K or Li BOB 04 05 K or Li DFOB 06 07 K or Li TOP 08 09 K or Li TFOP 0 K or Li D(Ac)OAl K or Li BOB K or Li DFOB K or Li BOB K or Li DFOB 0 K or Li BOB K or Li DFOB K or Li BOB K or Li DFOB K or Li BOB 0 K or Li DFOB

(46) TABLE-US-00016 TABLE 13 Potassium or lithium salt Onium salt employed employed Ionic liquid [N(C.sub.2H.sub.5).sub.3(CH.sub.2C(O)OC.sub.2H.sub.5)] K or Li BOB [N(C.sub.2H.sub.5).sub.3(CH.sub.2C(O)OC.sub.2H.sub.5)] Br BOB [N(C.sub.2H.sub.5).sub.3(CH.sub.2C(O)OC.sub.2H.sub.5)] K or Li DFOB [N(C.sub.2H.sub.5).sub.3(CH.sub.2C(O)OC.sub.2H.sub.5)] Br DFOB [N(C.sub.2H.sub.5).sub.3(CH.sub.2C(O)OC.sub.2H.sub.5)] K or Li TOP [N(C.sub.2H.sub.5).sub.3(CH.sub.2C(O)OC.sub.2H.sub.5)] Br TOP [N(C.sub.2H.sub.5).sub.3(CH.sub.2C(O)OC.sub.2H.sub.5)] K or Li D(Ac)OAl [N(C.sub.2H.sub.5).sub.3(CH.sub.2C(O)OC.sub.2H.sub.5)] Br D(Ac)Oal [N(CH.sub.3).sub.2(C.sub.2H.sub.5) (CH.sub.2CH.sub.2C(O)OCH.sub.3)] K or Li BOB [N(CH.sub.3).sub.2(C.sub.2H.sub.5) (CH.sub.2CH.sub.2C(O)OCH.sub.3)] Br BOB [N(CH.sub.3).sub.2(C.sub.2H.sub.5) (CH.sub.2CH.sub.2C(O)OCH.sub.3)] K or Li DFOB [N(CH.sub.3).sub.2(C.sub.2H.sub.5) (CH.sub.2CH.sub.2C(O)OCH.sub.3)] Br DFOB [N(CH.sub.3).sub.2(C.sub.2H.sub.5) (CH.sub.2C(O)CH.sub.2C(O)OCH.sub.3)] K or Li BOB [N(CH.sub.3).sub.2(C.sub.2H.sub.5) (CH.sub.2C(O)CH.sub.2C(O)OCH.sub.3)] Br BOB [N(CH.sub.3).sub.2(C.sub.2H.sub.5) (CH.sub.2C(O)CH.sub.2C(O)OCH.sub.3)] K or Li DFOB [N(CH.sub.3).sub.2(C.sub.2H.sub.5) (CH.sub.2C(O)CH.sub.2C(O)OCH.sub.3)] Br BDFOB [N(CH.sub.3).sub.2(C.sub.2H.sub.5) (CH.sub.2OC(O)OCH.sub.3)] K or Li BOB [N(CH.sub.3).sub.2(C.sub.2H.sub.5) (CH.sub.2OC(O)OCH.sub.3)] Br BOB [N(CH.sub.3).sub.2(C.sub.2H.sub.5) (CH.sub.2OC(O)OCH.sub.3)] K or Li DFOB [N(CH.sub.3).sub.2(C.sub.2H.sub.5) (CH.sub.2OC(O)OCH.sub.3)] Br DFOB [P(C.sub.4H.sub.9).sub.3(CH.sub.2C(O)OC.sub.2H.sub.5)] K or Li BOB [P(C.sub.4H.sub.9).sub.3(CH.sub.2C(O)OC.sub.2H.sub.5)] Br BOB [P(C.sub.4H.sub.9).sub.3(CH.sub.2C(O)OC.sub.2H.sub.5)] K or Li DFOB [P(C.sub.4H.sub.9).sub.3(CH.sub.2C(O)OC.sub.2H.sub.5)] Br DFOB K or Li BOB K or Li DFOB K or Li TOP K or Li D(Ac)OAl 0 K or Li BOB K or Li DFOB K or Li BOB K or Li DFOB K or Li BOB 0 K or Li DFOB K or Li BOB K or Li DFOB K or Li BOB K or Li DFOB 0 K or Li BOB K or Li DFOB K or Li BOB K or Li DFOB K or Li BOB 0 K or Li DFOB K or Li BOB K or Li DFOB

(47) TABLE-US-00017 TABLE 14 Lithium or potassium salt or methyl triflate or anhydride Onium salt employed employed Ionic liquid N(C2H5)3(CH2CH2CN)] LiBOB or N(C2H5)3(CH2CH2CN)] Cl KBOB BON N(C2H5)3(CH2CH2CN)] K or Li N(C2H5)3(CH2CH2CN)] Cl DFOB DFOB K or Li DFOB LiBOB or KBOB 0 K or LiTOP K or Li D(Ac)OAl K or Li DFOB LiBOB or KBOB K or Li DFOB 0 K or Li DFOB LiBOB or KBOB K or Li DFOB K or Li DFOB LiBOB or KBOB 00 01 K or Li DFOB 02 03 LiBOB or KBOB 04

Example 8

Investigations on Graphite

(48) 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.sup.+ at a rate of 0.1 mV/s and then returned to the rest potential.

(49) The electrolyte used is 1 M LiPF.sub.6 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.sup.+ 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.

(50) TABLE-US-00018 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 05 75 95 98 99 99 06 76 98 99 99 99 07 72 96 98 98 99 08 70 95 98 99 99 09 77 97 99 99 100 0 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 0 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 0 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 = LiPF.sub.6 in EC:DEC (3:7)

Example 9

Investigations on Graphite

(51) 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.sup.+ at a rate of 0.1 mV/s and then returned to the rest potential.

(52) The electrolyte used is 1 M LiPF.sub.6 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.sup.+. 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.

(53) Co-intercalation of the reactive ionic liquid selected from Table 16 in the graphite cannot be observed.

(54) TABLE-US-00019 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 0 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 0 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 0 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 = LiPF.sub.6 in EC:DEC (3:7)

Example 10

Investigations of the Oxidation Stability

(55) 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.sup.+ at a rate of 10 mV/s and then returned to the rest potential.

(56) The electrolyte used is 1 M LiPF.sub.6 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.sup.+.

(57) A signal below the oxidation stability of the reference electrolyte is not found in any of the systems investigated.

(58) TABLE-US-00020 TABLE 17 Oxidation stability E.sub.ox Reference* no IL additive >5 V >5 V >5 V >5 V 0 >5 V >5 V >5 V >5 V >5 V >5 V >5 V >5 V >5 V >5 V 0 >5 V >5 V >5 V >5 V >5 V >5 V >5 V >5 V >5 V >5 V 0 >5 V >5 V >5 V >5 V >5 V >5 V >5 V >5 V *Reference = LiPF.sub.6 in EC:DEC (3:7)

Example 11

Investigations of the Oxidation Stability

(59) 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.sup.+ at a rate of 10 mV/s and then returned to the rest potential.

(60) The electrolyte used is 1 M LiPF.sub.6 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/Li.sup.+. A signal below the oxidation stability of the reference electrolyte is not found in any of the systems investigated.

(61) TABLE-US-00021 TABLE 18 Oxidation stability Ionic liquid E.sub.ox Reference* no IL additive >5 V >5 V >5 V 00 >5 V 01 >5 V 02 >5 V 03 >5 V 04 >5 V 05 >5 V 06 4.6-4.8 V 07 4.5-4.7 V 08 >5 V 09 4.6-4.8 V 0 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 0 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 = LiPF.sub.6 in EC:DEC (3:7)