Synthesis of hetero compounds using dialkylcarbonate quaternation

• US 9,793,586 B2
• Filed: 06/18/2012
• Issued: 10/17/2017
• Est. Priority Date: 06/17/2011
• Status: Active Grant

• Current Assignee: Form Energy, Inc.
• Original Assignee: Fluidic, Inc.
• Inventors: Friesen, Cody A., Wolfe, Derek, Johnson, Paul Bryan
• Primary Examiner(s): DOVE, TRACY MAE
• Application Number:
  US13/526,432
• Publication Number:
  US 20120321969A1
• Time in Patent Office: 1,947 Days
• Field of Search: None
• CPC Class Codes: C07D 471/04 Ortho-condensed systems
• CPC Class Codes: C07D 471/08 Bridged systems
• CPC Class Codes: C07D 487/08 Bridged systems
• CPC Class Codes: C25B 9/17 Cells comprising dimensionally-stable non-movable electrodes; Assemblies of constructional parts thereof
• CPC Class Codes: H01M 10/26 Selection of materials as electrolytes
• CPC Class Codes: H01M 12/06 with one metallic and one gaseous electrode
• CPC Class Codes: H01M 2004/021 Physical characteristics, e.g. porosity, surface area
• CPC Class Codes: H01M 2004/023 Gel electrode
• CPC Class Codes: H01M 2300/0014 Alkaline electrolytes
• CPC Class Codes: H01M 2300/0045 Room temperature molten salts comprising at least one organic ion
• CPC Class Codes: H01M 4/244 Zinc electrodes
• CPC Class Codes: H01M 4/38 of elements or alloys
• CPC Class Codes: H01M 50/44 Fibrous material
• CPC Class Codes: H01M 6/045 characterised by aqueous electrolyte
• CPC Class Codes: Y02E 60/10 Energy storage using batteries

Abstract

Methods of preparing hetero ionic complexes, and ionic liquids from bisulfate salts of heteroatomic compounds using dialkylcarbonates as a primary quaternizing reactant are disclosed. Also disclosed are methods of making electrochemical cells comprising the ionic liquids, and an electrochemical cell comprising an alkaline electrolyte and a hetero ionic complex additive.

Claims

1. An electrochemical cell comprising:

a first electrode;

a second electrode, wherein the second electrode is positioned apart from the first electrode thereby defining a gap therebetween; and

a low temperature ionic liquid electrolyte in the gap whereby the low temperature ionic liquid electrolyte contacts both the first and second electrodes, and wherein the low temperature ionic liquid electrolyte comprises an ionic liquid comprised of a 1,4, diazabicyclo[2,2,2]octane cation and an anion.

2. The electrochemical cell of claim 1, wherein the first electrode is an air cathode, and the second electrode is a metal anode.

40. The electrochemical cell of claim 1, wherein the 1,4, diazabicyclo[2,2,2]octane cation is 1-methyl-4-aza-1-azoniabicyclo[2,2,2]octane (methyl DABCO).

3. An electrochemical cell comprising a cell housing, an anode, a cathode, and an ionically conductive medium comprising an aqueous alkaline electrolyte and a hetero ionic complex additive comprising a heteroatomic compound cation and an anion dissolved in the aqueous alkaline electrolyte,

wherein the cell is a secondary cell and the anode comprises a solid metal fuel for oxidation during discharging and electrodeposition thereon by reduction during charging.

4. The electrochemical cell of claim 3, wherein the alkaline electrolyte is potassium hydroxide.

5. The electrochemical cell of claim 3, wherein the hetero ionic complex additive is prepared by:

(1) reacting a heteroatomic compound with dialkylcarbonate to produce an alkylcarbonate salt of the heteroatomic compound;

(2) acidifying the alkylcarbonate salt with a sulfate-containing acid to produce a bisulfate salt of the heteroatomic compound; and

(3) converting the bisulfate salt of the heteroatomic compound to a hetero ionic complex comprising an alkyl-heteroatomic cation and an anion.

6. The electrochemical cell of claim 3, wherein the heteroatomic compound has the formula hetero-R—

X, wherein R is selected from the group consisting of hydrogen, substituted and unsubstituted C1-C20 alkyl, and substituted and unsubstituted aralkyl, X is a heteroatom selected from the group consisting of N, O, P, S, and mixtures thereof, which can be linear or can form a hetero or heteroaromatic ring, or bicyclic ring.

7. The electrochemical cell of claim 6, wherein the heteroatomic compound is selected from the group consisting of pyrrolidines, morpholines, piperidines, piperazines, quinuclidines, bicyclic amines, amidines, guanidines, alkanolamines, monoalkylamines, dialkylamines, pyrroles, pyrazoles, triazoles, thiazoles, oxazoles, pyridines, imidazopyridines, imidazopyrimidines, monoalkylphosphines, dialkylphosphines, trialkylphosphines, monoalkylphosphites, dialkylphosphites, trialkylphosphites, phosphorus monoamines, phosphorus diamines, phosphorus triamines, mercaptans, thiophenes, dihydrothiophenes, tetrahydrothiophenes, thioethers, dialkylsulfoxides, and combinations thereof.

8. The electrochemical cell of claim 6, wherein the heteroatomic compound is 1,4, diazabicyclo[2,2,2]octane.

9. The electrochemical cell of claim 3, wherein the anion is selected from the group consisting of halophosphates, hexafluorophosphate, alkylphosphates, arylphosphates, nitrate, sulfate, bisulfate, carbonates, alkyl carbonates, alkylsulfates, arylsulfates, perfluorinated alkyl- and arylsulfates, sulfonate, alkylsulfonates, arylsulfonates, perfluorinated alkyl- and arylsulfonates, trifluoromethylsulfonate, tosylate, perchlorate, tetrachloroaluminate, heptachlorodialuminate, tetrafluoroborate, alkylborates, arylborates, amides, perfluorinated amides, dicyanamide, saccharinate, thiocyanate, carboxylates, acetates, trifluoroacetate, bis(perfluoroalkylsulfonyl)amide, chloride (Cl—

), hydroxide (OH—

), hexafluorophosphate (PF6Õ

), iodide, other halides, tetrafluoroborate, bis(trifluoromethylsulfonyl)imide (C2F6NO4S2-), trifluoromethanesulfonate (CF3SO3-;

TfO—

), dicyanamide (N(CN)2-;

dca), benzoate, acesulfame, saccharinate, methanesulfonate, and mixtures thereof.

10. The electrochemical cell of claim 9, wherein the anion is an alkyl carbonate anion.

11. The electrochemical cell of claim 3, wherein the heteroatomic compound cation is 1-methyl-4-aza-1-azoniabicyclo[2,2,2]octane, and the anion is hydroxide or methyl carbonate.

12. The electrochemical cell of claim 3, wherein the heteroatomic compound cation is methyl-3-quinuclidinolium, and the anion is hydroxide or methyl carbonate.

13. The electrochemical cell of claim 3, wherein the hetero ionic complex additive is present in an amount sufficient to reduce the formation of dendrites on the cathode or anode.

14. The electrochemical cell of claim 13, wherein the hetero ionic complex additive is present in an amount of less than about 200 mM.

15. The electrochemical cell of claim 13, wherein the hetero ionic complex additive is present in an amount of from about 10 to about 40 mM.

16. The electrochemical cell of claim 3, wherein the cathode is an air cathode exposed to air.

17. The electrochemical cell of claim 11, wherein the cathode is an air cathode exposed to air.

18. The electrochemical cell of claim 3, wherein the heteroatomic compound cation is 1-methyl-4-aza-azoniabicyclo[2,2,2]octane.

19. The electrochemical cell of claim 18, wherein the anion is hydroxide.

20. The electrochemical cell of claim 18, wherein the anion is an alkyl carbonate anion.

21. The electrochemical cell of claim 18, wherein the anion is methyl carbonate.

22. The electrochemical cell of claim 18, wherein the alkaline electrolyte is potassium hydroxide.

23. The electrochemical cell of claim 19, wherein the alkaline electrolyte is potassium hydroxide.

24. The electrochemical cell of claim 20, wherein the alkaline electrolyte is potassium hydroxide.

25. The electrochemical cell of claim 21, wherein the alkaline electrolyte is potassium hydroxide.

26. The electrochemical cell of claim 22, wherein the hetero ionic complex additive is present in an amount of less than about 200 mM.

27. The electrochemical cell of claim 26, wherein the hetero ionic complex additive is present in an amount of from about 10 to about 40 mM.

28. The electrochemical cell of claim 23, wherein the hetero ionic complex additive is present in an amount of less than about 200 mM.

29. The electrochemical cell of claim 28, wherein the hetero ionic complex additive is present in an amount of from about 10 to about 40 mM.

30. The electrochemical cell of claim 24, wherein the hetero ionic complex additive is present in an amount of less than about 200 mM.

31. The electrochemical cell of claim 30, wherein the hetero ionic complex additive is present in an amount of from about 10 to about 40 mM.

32. The electrochemical cell of claim 25, wherein the hetero ionic complex additive is present in an amount of less than about 200 mM.

33. The electrochemical cell of claim 32, wherein the hetero ionic complex additive is present in an amount of from about 10 to about 40 mM.

34. The electrochemical cell of claim 18, wherein the cathode is an air cathode exposed to air.

35. The electrochemical cell of claim 19, wherein the cathode is an air cathode exposed to air.

36. The electrochemical cell of claim 20, wherein the cathode is an air cathode exposed to air.

37. The electrochemical cell of claim 21, wherein the cathode is an air cathode exposed to air.

38. The electrochemical cell of claim 3, wherein the hetero ionic complex additive is present in an amount sufficient to reduce the formation of dendrites on the anode.

39. The electrochemical cell of any one of claims 18-21, wherein the hetero ionic complex additive is present in an amount sufficient to reduce the formation of dendrites on the anode.

41. The electrochemical cell of claim 3, wherein the heteroatomic compound cation is an alkyl heteroatomic compound.

42. An electrochemical cell comprising a cell housing, an anode, a cathode, and an ionically conductive medium comprising an aqueous alkaline electrolyte and an additive comprising a cation of 1,4, diazabicyclo[2,2,2]octane and an anion dissolved in the aqueous alkaline electrolyte.

43. The electrochemical cell of claim 42, wherein the cation is 1-methyl-4-aza-1-azoniabicyclo[2,2,2]octane, and the anion is hydroxide or methyl carbonate.