Materials useful as electrolytic solutes

• US 6,365,301 B1
• Filed: 09/07/1999
• Issued: 04/02/2002
• Est. Priority Date: 02/03/1998
• Status: Expired due to Term

• Current Assignee: ACEP Inc.
• Original Assignee: ACEP Inc., Centre National De La Recherche Scientifique, Universite De Montreal, L'
• Inventors: Michot, Christophe, Ravet, Nathalie, Gauthier, Michel, Armand, Michel
• Primary Examiner(s): KALAFUT, STEPHEN J
• Application Number:
  US09/390,642
• Time in Patent Office: 938 Days
• Field of Search: 359/270, 568/9, 568/11, 568/13, 568/16, 568/17, 568/36, 568/557, 570/141, 570/142, 423/301, 423/302, 423/386, 423/387, 429/307, 429/315, 429/324, 361/505, 361/525
• US Class Current: 429/307
• CPC Class Codes: C07C 211/63 having quaternised nitrogen atoms bound to acyclic carbon atoms
• CPC Class Codes: C07C 211/64 having quaternised nitrogen atoms bound to carbon atoms of six-membered aromatic rings
• CPC Class Codes: C07C 317/04 of an acyclic saturated carbon skeleton
• CPC Class Codes: C07C 317/12 having sulfone or sulfoxide groups bound to carbon atoms of rings other than six-membered aromatic rings
• CPC Class Codes: C07C 381/00 Compounds containing carbon and sulfur and having functional groups not covered by groups C07C301/00 - C07C337/00
• CPC Class Codes: C07C 45/46 Friedel-Crafts reactions
• CPC Class Codes: C07C 45/72 by reaction of compounds containing >C = O groups with the same or other compounds containing >C = O groups
• CPC Class Codes: C07D 213/20 Quaternary compounds thereof
• CPC Class Codes: C07D 213/74 Amino or imino radicals substituted by hydrocarbon or substituted hydrocarbon radicals
• CPC Class Codes: C07D 231/12 with only hydrogen atoms, hydrocarbon or substituted hydrocarbon radicals, directly attached to ring carbon atoms
• CPC Class Codes: C07D 233/56 with only hydrogen atoms or radicals containing only hydrogen and carbon atoms, attached to ring carbon atoms
• CPC Class Codes: C07D 249/08 1,2,4-Triazoles; Hydrogenated 1,2,4-triazoles
• CPC Class Codes: C07D 311/82 Xanthenes
• CPC Class Codes: C07D 339/06 having the hetero atoms in positions 1 and 3, e.g. cyclic dithiocarbonates
• CPC Class Codes: C07F 9/54 Quaternary phosphonium compounds
• CPC Class Codes: H01G 11/56 Solid electrolytes, e.g. gels; Additives therein
• CPC Class Codes: H01G 11/60 characterised by the solvent
• CPC Class Codes: H01G 11/62 characterised by the solute, e.g. salts, anions or cations therein
• CPC Class Codes: H01G 9/20 Light-sensitive devices
• CPC Class Codes: H01G 9/2004 characterised by the electrolyte, e.g. comprising an organic electrolyte
• CPC Class Codes: H01M 10/052 : Li-accumulators
• CPC Class Codes: H01M 10/0525 : Rocking-chair batteries, i.e. batteries with lithium insertion or intercalation in both electrodes; Lithium-ion batteries
• CPC Class Codes: H01M 10/0565 : Polymeric materials, e.g. gel-type or solid-type
• CPC Class Codes: H01M 10/0566 : Liquid materials
• CPC Class Codes: H01M 10/0568 : characterised by the solutes
• CPC Class Codes: H01M 10/0569 : characterised by the solvents
• CPC Class Codes: H01M 10/36 : Accumulators not provided for in groups H01M10/05-H01M10/34
• CPC Class Codes: H01M 2300/0022 : Room temperature molten salts
• CPC Class Codes: H01M 2300/0082 : Organic polymers
• CPC Class Codes: H01M 4/13 : Electrodes for accumulators with non-aqueous electrolyte, e.g. for lithium-accumulators; Processes of manufacture thereof
• CPC Class Codes: H01M 4/505 : of mixed oxides or hydroxides containing manganese for inserting or intercalating light metals, e.g. LiMn2O4 or LiMn2OxFy
• CPC Class Codes: H01M 4/525 : of mixed oxides or hydroxides containing iron, cobalt or nickel for inserting or intercalating light metals, e.g. LiNiO2, LiCoO2 or LiCoOxFy
• CPC Class Codes: H01M 4/58 : of inorganic compounds other than oxides or hydroxides, e.g. sulfides, selenides, tellurides, halogenides or LiCoFy; of polyanionic structures, e.g. phosphates, silicates or borates
• CPC Class Codes: H01M 4/5825 : Oxygenated metallic salts or polyanionic structures, e.g. borates, phosphates, silicates, olivines
• CPC Class Codes: H01M 4/587 : for inserting or intercalating light metals
• CPC Class Codes: H01M 4/60 : of organic compounds
• CPC Class Codes: H01M 4/602 : Polymers
• CPC Class Codes: H01M 4/624 : Electric conductive fillers
• CPC Class Codes: H01M 6/164 : by the solvent
• CPC Class Codes: H01M 6/166 : by the solute
• CPC Class Codes: H01M 6/168 : by additives
• CPC Class Codes: H01M 6/181 : with polymeric electrolytes
• CPC Class Codes: H01M 8/1048 : Ion-conducting additives, e.g. ion-conducting particles, heteropolyacids, metal phosphate or polybenzimidazole with phosphoric acid
• CPC Class Codes: Y02E 10/542 : Dye sensitized solar cells
• CPC Class Codes: Y02E 60/10 : Energy storage using batteries
• CPC Class Codes: Y02E 60/13 : Energy storage using capacitors
• CPC Class Codes: Y02E 60/50 : Fuel cells

Abstract

The invention concerns novel ionic compounds with low melting point whereof the onium type cation having at least a heteroatom such as N, O, S or P bearing the positive charge and whereof the anion includes, wholly or partially, at least an ion imidide such as (FX¹O)N⁻(OX²F) wherein X¹ and X² are identical or different and comprise SO or PF, and their use as solvent in electrochemical devices. Said composition comprises a salt wherein the anionic charge is delocalized, and can be used, inter alia, as electrolyte.

Claims

1. An ionic compound having a cation of the onium type with at least one heteroatom comprising N, O, S or P bearing the positive charge and the anion including, in whole or in part, at least one imide ion of the type (FX¹O)N⁻

(OX²F) wherein X¹ and X² are the same or different and comprise SO or PF,

wherein the onium type cation comprises a compound of formula;

a compound of formula

a compound of formula

a compound of formula

wherein

W is O, S or N, and wherein N isoptionally substituted with R¹ when the valence allows it;

R¹, R³, R⁴ are the same or different and represent H;

an alkyl, alkenyl, oxaalkyl, oxaalkenyl, azaalkyl, azaalkenyl, thiaalkyl, thiaalkenyl, dialkylazo, each of these can be either linear, branched or cyclic and comprising from 1 to 18 carbon atoms;

cyclic or heterocyclic aliphatic radicals of from 4 to 26 carbon atoms optionally comprising at least one lateral chain comprising one or more heteroatoms;

aryl, arylalkyl, alkylaryl and alkenyaryl of from 5 to 26 carbon atoms optionally comprising one or more heteroatoms in the aromatic nucleus;

groups comprising aromatic or heterocyclic nuclei, condensed or not, optionally comprising one or more atoms of nitrogen, oxygen, sulfur or phosphorous;

and wherein two groups R¹, R³ or R⁴ can form a cycle or a heterocycle of from 4 to 9 carbon atoms, and wherein one or more R¹, R³ or R⁴ groups on the same cation can be part of a polymeric chain;

R² and R⁵ to R⁹ are the same or different and represent R¹, R¹O—

, (R¹)₂N—

, R¹S—

, R¹ being as defined above, and

wherein R¹, R³ and R⁴ can comprise a polymerisation active group.

2. A compound according to claim 1 wherein the polymerisation active group comprises double bonds, epoxides, or functional groups reactive in polycondensations.

3. A compound according to claim 1 wherein the cation comprises an ammonium, imidazolium, or phosphonium ion unsubstituted or substituted with an alkyl group, or an oxaalkyl group comprising from 1 to 8 carbon atoms.

4. A electrolytic composition comprising at least one ionic compound according to claim 3 in combination with at least another component comprising a metallic salt, a polar polymer and/or an aprotic co-solvent.

5. An electrolytic composition according to claim 4 wherein the cation of the metallic salt is selected from the proton, an alkaline metal, an alkaline-earth metal, a transition metal or a rare earth.

6. An electrolytic composition according to claim 4 wherein at least one metallic salt is a lithium salt.

7. An electrolytic composition according to claim 4 wherein the polar polymer comprises monomer units of ethylene oxide, propylene oxide, epichlorohydrine, epifluorohydrine, trifluoroepoxypropane, acrylonitrile, methacrylonitrile, esters and amides of acrylic and methacrylic acids, vinylidene fluoride, N-methylpyrolidone and polyelectrolytes of the polycation or the polyanion type.

8. An electrolytic composition according to claim 4 wherein the aprotic co-solvent is selected from dialkylated ethers of ethylene glycol, diethylene glycol, triethylene glycol, polyethylene glycols of weight comprised between 400 and 2000;

esters, comprising those of carbonic acid, either linear or cyclic, cylic carbonylic esters nitriles, 1,2,6-tricyanohexane, amides, sulfamides and sulfonamides and mixtures thereof.

9. An electrochemical generator having at least one positive electrode and at least one negative electrode, wherein the positive electrode comprises a mixed oxide of lithium and vanadium LiV₃O₈, a double oxide of cobalt and lithium optionally partially substituted of general formula Li₁₋

aCo<sub>1−

x+y</sub>Ni_xAl_y wherein 0<

x+y<

1;

0<

y<

0,3 ;

0<

a<

1, a double phosphate of the olivine or Nasicon structure comprising Li<sub>1−

a</sub>Fe<sub>1−

x</sub>Mn_xPO₄, Li<sub>1−

x+2a</sub>Fe₂P<sub>1−

x</sub>Si_xO₄ wherein 0<

x, a<

1, a rhodizonic acid salt, a polydisulfide obtained after the oxidation of dimercaptoethane, 2,5-dimercapto-1,3,4-thiadiazole, 2,5-dimercapto-1,3,4-oxadiazole, 1,2-dimercaptocyclobutene-3,4-dione, or mixtures thereof, and

wherein said electrochemical generator uses as the electrolyte an electrolytic composition which comprises a combination of;

an ionic compound having a cation of the onium type with at least one heteroatom comprising N, O, S or P bearing the positive charge and the anion including, in whole or in part, at least one imide ion of the type (FX¹O)N⁻

(OX²F) wherein X¹ and X² are the same or different and comprise SO or PF; and

at least another component comprising a metallic salt, a polar polymer and/or an aprotic co-solvent.

10. An electrochemical generator according to claim 9 characterized in that the negative electrode comprises lithium or an alloy thereof, a carbon insertion compound, an oxide comprising a titanium spinel Li_4x+3yTi₅₋

xO₁₂ wherein 0≦

x,y≦

1, a double nitride of a transition metal and lithium comprising Li<sub>3−

x</sub>Co₂N wherein 0≦

z≦

1 or having a structure of the antifluorite type comprising Li₃FeN₂ or Li₇MnN₄, or mixtures thereof.

11. An electrochemical generator according to claim 10, wherein the negative electrode comprises petroleum coke or graphite.

12. An electrochemical generator having at least one positive electrode and at least one negative electrode, wherein the positive electrode comprises a mixed oxide of lithium and vanadium LiV₃O₈, a double oxide of cobalt and lithium optionally partially substituted of general formula Li₁₋

aCo<sub>1−

x+y</sub>Ni_xAl_y wherein 0<

x+y<

1 ;

0<

y<

0,3 ;

0<

a<

1, a double phosphate of the olivine or Nasicon structure comprising Li<sub>1−

a</sub>Fe<sub>1−

x</sub>Mn_xPO₄, Li<sub>1−

x+2a</sub>Fe₂P<sub>1−

x</sub>Si_xO₄ wherein 0<

x, a<

1, a rhodizonic acid salt, a polydisulfide derived from the oxidation of dimercaptoethane, 2,5-dimercapto-1,3,4-thiadiazole, 2,5-dimercapto-1,3,4-oxadiazole, 1,2-dimercaptocyclobutene-3,4-dione, or mixtures thereof, and

wherein said electrochemical generator uses as the electrolyte an electrolytic composition which comprises a combination of;

an ionic compound having a cation of the onium type with at least one heteroatom comprising N, O, S or P bearing the positive charge and the anion including, in whole or in part, at least one imide ion of the type (FX¹O)N⁻

(OX²F) wherein X¹ and X² are the same or different and comprise SO or PF; and

at least another component comprising a metallic salt, a polar polymer and/or an aprotic co-solvent, and

wherein at least one of the electrodes is mixed with the electrolytic composition to form a composite electrode.

13. A modulation system of the electrochromic type comprising at least one electrochromic material wherein the electrolyte comprises a combination of:

an ionic compound having a cation of the onium type with at least one heteroatom comprising N, O, S or P bearing the positive charge and the anion including, in whole or in part, at least one imide ion of the type (FX¹O)N⁻

(OX²F) wherein X¹ and X² are the same or different and comprise SO or PF; and

at least another component comprising a metallic salt, a polar polymer and/or an aprotic co-solvent, wherein the electrochromic material is dissolved in the electrolyte.

14. A modulation system according to claim 13 characterized in that the electrochromic material is deposited on a semi-conductor layer transparent in the visible, derived from tin oxide or indium oxide on a glass or polymer substrate.

15. A modulation system according to claim 14 wherein the electrochromic material is an oxide of molybdenum, tungsten, titanium, vanadium, niobium, cerium, tin or mixtures thereof.