Solvents and novel electrolytic compositions having a large range of stability and high conductivity

• US 20030162096A1
• Filed: 12/12/2002
• Published: 08/28/2003
• Est. Priority Date: 09/11/1997
• Status: Abandoned Application

• Current Assignee: ACEP Inc.
• Original Assignee: ACEP Inc.
• Inventors: Michot, Christophe, Armand, Michel, Bergeron, Jean-Yves, Baril, Daniel, Brouillette, Dany
• Application Number:
  US10/317,222
• Publication Number:
  US 20030162096A1
• Time in Patent Office: Days
• US Class Current: 429/307
• CPC Class Codes: C07C 311/48 having nitrogen atoms of sulfonamide groups further bound to another hetero atom
• CPC Class Codes: C07C 381/10 Compounds containing sulfur atoms doubly-bound to nitrogen atoms
• CPC Class Codes: H01G 11/56 Solid electrolytes, e.g. gels; Additives therein
• CPC Class Codes: H01G 11/62 characterised by the solute, e.g. salts, anions or cations therein
• CPC Class Codes: H01M 10/052 Li-accumulators
• CPC Class Codes: H01M 10/0564 the electrolyte being constituted of organic materials only
• CPC Class Codes: H01M 10/0565 Polymeric materials, e.g. gel-type or solid-type
• CPC Class Codes: H01M 10/0568 characterised by the solutes
• CPC Class Codes: H01M 10/0569 characterised by the solvents
• CPC Class Codes: H01M 2300/0085 Immobilising or gelification of electrolyte
• CPC Class Codes: H01M 6/164 by the solvent
• CPC Class Codes: H01M 6/181 with polymeric electrolytes
• CPC Class Codes: Y02E 60/13 Energy storage using capacitors

Abstract

The present invention is concerned with novel polar solvents and novel electrolytic compositions comprising such solvents, and having a high range of stability, as required for applications in the field of electrochemistry. The present solvents have a highly polar amide function, and preferably combine with a salt soluble in the solvent and having an anion with a delocalized charge, and at least one polymer, to form an electrolytic composition.

Claims

1. An aprotic polar compound having solvent properties, and of the general formula:

R¹R²NX(Z)R⁷

wherein

X═

C or SO;

Z=O, NSO₂NR₃R₄ or NCN;

R¹ et R² are the same or different and are C_1-18alkyl, C_1-18 oxaalkyl, C_1-18 alkylene or C_1-18oxaalkylene;

R³ à

R⁶ are the same or different and are C_1-18alkyl or C_1-18 oxaalkyl;

R⁷ is R_F, R_FCH₂O—

, (R_F)₂CHO—

, (R_FCH₂)₂N—

or NR⁵R⁶;

R_F is a fluorine atom, C_1-4alkyl, C_1-4oxaalkyl C_1-4azaalkyl,

with the proviso that;

1) if Z=O, then R_F is not C_1-4alkyl; and

2) if Z=O and X═

SO, then R⁵ or R⁶ is not is not C_1-4alkyl or C_1-4oxaalkyl.

2. An aprotic polar compound according to claim 1 wherein the C_1-4alkyle, C_1-4oxaalkyle or C_1-4azaalkyle in the definition of R_F is essentially fluorinated.

3. An electrolytic composition comprising at least one polar compound according to claim 1 or 2, a salt soluble in said compound having an anion with a delocalized charge, and at least one polymer.

4. An electrolytic composition according to claim 3, wherein the salt comprises I⁻

, ClO₄⁻

, BF₄⁻

, PF₆⁻

, AsF₆⁻

, SbF₆⁻

, R_FSO₃⁻

, XSO₂NSO₂X′

⁻

, (XSO₂)(X′

SO₂)(Y)C⁻

, anionic derivatives of 4,5-dicyano-1,2,3-triazole, 3,5-bis(R_F)-1,2,4-triazole, tricyanomethane, pentacyanocyclopentadiene and pentakis(trifluoromethyl)cyclopentadiene, R_FSO₂NCN⁻

, C(CN)₃⁻

, R_FSO₂C(CN)₂⁻

, and mixtures thereof, wherein

X and X′

comprise R_F, R_FCH₂O—

, (R_F) ₂CHO—

, (R_FCH₂) ₂N—

, R⁸, R⁹R¹⁰N—

, with the proviso that at least one X or X′

is R_F, R_FCH₂O—

, (R_F) ₂CHO—

, or (R_FCH₂)₂N—

;

Y═

R_F, R_FSO₂ or CN;

R_F is as defined above and can be part of a macromolecular chain; and

R⁸ to R¹⁰ are the same or different, and are C_1-18alkyl or C_1-18oxaalkyl, and R⁸ —

R¹⁰ can be part of a macromolecular chain.

5. An electrolytic composition according to claim 4, wherein the cation includes derivatives of alkaline metals, alkaline earth metals, and organic cations of the “

onium”

type, comprising ammonium, imidazolium, sulfonium, phosphonium, oxomum or mixtures thereof.

6. An electrolytic composition according to claim 5, wherein the cation is at least party lithium.

7. An electrolytic composition according to claim 3 further comprising a co-solvent.

8. An electrolytic composition according to claim 7, wherein the co-solvent is aprotic and polar, and comprises dialkyl ethers of ethylene glycol, diethylene glycol, triethylene glycol, polyethylene glycols;

carbonic acid esters, γ

-butyrolactone, nitriles, tricyanohexane, dimethyl formnamide, N-methylpyrrolidinone, or mixtures thereof.

9. An electrolytic composition according to claim 8, wherein the polyethylene glycol mass is comprised between 400 and 2000.

10. An electrolytic composition according to claim 3, wherein the polymer comprises monomer units derived from ethylene oxide, propylene oxide, epichlorohydrine, epifluorohydrine, trifluoroepoxypropane, acrylonitrile, methylmetacrylate, vinylidene fluoride, and N-vinylpyrolidinone, hexafluoropropene, either as homo- or copolymers, or mixtures thereof.

11. An electrolytic composition according to claim 8, wherein the composition is plasticized or in the form of a gel.

12. An electrolytic composition according to claim 9, wherein at least one polymer is a polyclectrolyte comprising a macromolecular woof similar to that of anions having a delocalized charge.

13. An electrochemical generator comprising as an electrolyte an electrolytic composition according to claim 3.

14. An electrochemical generator according to claim 13, wherein the negative electrode contains lithium metal, a lithium alloy, an carbon intercalation compound, an oxide having a low potential of intercalation, a double nitride of a transition metal in lithium, or mixtures thereof.

15. An electrochemical generator according to claim 14, wherein the carbon intercalation compound is petroleum coke or graphite, and wherein the oxide having a low potential of intercalation is a titanium spinel.

16. An electrochemical generator according to claim 14, wherein the positive electrode contains vanadium oxide, a mixed oxide of lithium and vanadium, an oxide of cobalt and lithium, a manganese spinel, a double phosphate of the olivine or Nasicon structure, a salt of rhodizonic acid, a polysidulfide derived from the oxidation of 2,5-dimercapto-1,3,4-thiadiazole, 2,5-dimercapto-1,3,4-oxadiazole, 1,2-dimercaptocyclobutene-3,4-dione, or mixtures thereof.

17. An energy storage system of the supercapacitor type comprising as an electrolyte an electrolytic composition according to claim 3.