Method for the manufacture of fluorinated cyclic carbonates and their use for lithium ion batteries
The present invention concerns methods for the manufacture of ethylene carbonate substituted with a fluorinated alkoxy group, certain ethylene carbonates substituted with a fluorinated alkoxy group as well as their use as solvent or solvent additive for lithium ion batteries and supercapacitors.
1. A method for the manufacture of a compound of general formula (I),
wherein R is fluorosubstituted alkyl or fluorosubstituted alkyloxyalkylene and R′ is hydrogen, fluorine, alkyl, fluorosubstituted alkyl or fluorosubstituted alkyloxyalkylene;
the method comprising a step of reacting a compound of general formula (II),
wherein R′ has the meaning as given above; with a compound of general formula R—OH or a compound of general formula R—O − M + , wherein R has the meaning as given above and M + is an alkali metal cation, an ammonium ion or a guanidinium ion, or a compound of general formula (R—O − ) 2 M + , wherein R has the meaning as given above and M + is an alkaline earth metal cation.
2. The method according to claim 1 wherein R′ is hydrogen.
3. The method according to claim 1 wherein R is fluorosubstituted alkyl.
4. The method according to claim 1 wherein the step of reacting the compound of general formula (II) is carried out in the presence of a base.
5. The method according to claim 4 wherein the base is present in an amount of equal to or less than 25 mol %, based on the amount of the compound of general formula (II).
6. The method according to claim 1 wherein the step of reacting the compound of general formula (II) is carried out in the absence of a solvent.
7. A method for the manufacture of a compound of general formula (I),
wherein R is fluorosubstituted alkyl or fluorosubstituted alkyloxyalkylene and R′ is hydrogen, fluorine, alkyl, fluorosubstituted alkyl or fluorosubstituted alkyloxyalkylene;
the method comprising a step of reacting a compound of general formula (III),
wherein R′ has the meaning as given above and LG is a leaving group;
with a compound of general formula R—OH or a compound of general formula R—O − M + , wherein R has the meaning as given above and M + is an alkali metal cation, an ammonium ion or a guanidinium ion, or a compound of general formula (R—O − ) 2 M + , wherein R has the meaning as given above and M + is an alkaline earth metal cation.
8. The method according to claim 7 wherein R′ is hydrogen.
9. The method according to claim 7 wherein R is fluorosubstituted alkyl.
10. The method according to claim 7 wherein LG is a halogen atom.
11. A compound of general formula (IV),
wherein R′ is hydrogen, fluorine, alkyl, fluorosubstituted alkyl or fluorosubstituted alkyloxyalkylene; R″ is fluorosubstituted alkyl or fluorosubstituted alkyloxyalkylene and R′″ is hydrogen, fluorine, alkyl, fluorosubstituted alkyl or fluorosubstituted alkyloxyalkylene.
12. The compound of claim 11 wherein R′ is hydrogen.
13. The compound of claim 11 wherein R″ is trifluoromethyl, R′″ is hydrogen and the compound is 4-(2,2,2-trifluoroethoxy)-1,3-dioxolan-2-one.
14. An electrolyte composition for lithium ion batteries, lithium air batteries, lithium sulfur batteries, supercapacitors or hybrid supercapacitors, the composition comprising at least one compound according to claim 11 , at least one solvent useful for lithium ion batteries or supercapacitors and at least one electrolyte salt.
15. The electrolyte composition according to claim 14 , further comprising at least one SEI-forming chemical compound and at least one swelling inhibiting compound.
16. The electrolyte composition according to claim 14 ,
wherein the at least one solvent comprises 70 to 90 vol % of at least one linear carbonate and 10 to 30 vol % of at least one cyclic carbonate, relative to the total volume of the solvent,
and wherein at least a part of the cyclic carbonate is the compound of general formula (IV).
17. A lithium ion battery, a lithium air battery, a lithium sulfur battery, a supercapacitor or a hybrid supercapacitor comprising at least one compound according to claim 11 .
18. The method according to claim 3 wherein R is trifluoromethyl, 2,2,2-trifluoroethyl, 2,2,3,3-tetrafluoropropoxy or 1,1,1,3,3,3-hexafluoropropan-2-yl.
19. The method according to claim 18 wherein R is 2,2,2-trifluoroethyl.
20. A lithium ion battery, a lithium air battery, a lithium sulfur battery, a supercapacitor or a hybrid supercapacitor comprising the electrolyte composition of claim 14 .