Electrochromic salts, solutions, and devices

• US 7,436,570 B2
• Filed: 11/24/2004
• Issued: 10/14/2008
• Est. Priority Date: 06/20/2002
• Status: Expired due to Fees

• Current Assignee: TRIAD National Security, LLC
• Original Assignee: Los Alamos National Security LLC (Government of the United States of America)
• Inventors: Burrell, Anthony K., Warner, Benjamin P., McClesky, T. Mark
• Primary Examiner(s): DENTZ, BERNARD I
• Application Number:
  US10/996,927
• Publication Number:
  US 20050116627A1
• Time in Patent Office: 1,420 Days
• Field of Search: 359/272
• US Class Current: 359/272
• CPC Class Codes: C09K 2211/1029 containing one nitrogen atom as the heteroatom
• CPC Class Codes: C09K 2211/1044 containing two nitrogen atoms as heteroatoms
• CPC Class Codes: C09K 2211/1059 containing three nitrogen atoms as heteroatoms
• CPC Class Codes: C09K 9/02 Organic tenebrescent materials
• CPC Class Codes: G02F 1/1503 caused by oxidation-reduction reactions in organic liquid solutions, e.g. viologen solutions
• CPC Class Codes: H01G 11/02 using combined reduction-oxidation reactions, e.g. redox arrangement or solion
• CPC Class Codes: H01G 11/62 characterised by the solute, e.g. salts, anions or cations therein
• CPC Class Codes: H01G 9/145 Liquid electrolytic capacitors H01G11/00 takes precedence
• CPC Class Codes: H01G 9/22 Devices using combined reduction and oxidation, e.g. redox arrangement or solion
• CPC Class Codes: Y02E 60/13 Energy storage using capacitors

Abstract

Electrochromic salts. Electrochromic salts of dicationic viologens such as methyl viologen and benzyl viologen associated with anions selected from bis(trifluoromethylsulfonyl)imide, bis(perfluoroethylsulfonyl)imide, and tris(trifluoromethylsulfonyl)methide are produced by metathesis with the corresponding viologen dihalide. They are highly soluble in molten quarternary ammonium salts and together with a suitable reductant provide electrolyte solutions that are used in electrochromic windows.

Claims

1. An electrochemical device comprising:

(a) a chamber for receiving an electrolyte solution;

(b) at least one anode in contact with said electrolyte solution in said chamber;

(c) at least one cathode in contact with said electrolyte solution in said chamber; and

(d) an electrolyte solution comprising a molten salt solvent comprising at least one anion selected from the group consisting of bis bis(perfluoroethylsulfonyl)imide and tris(trifluoromethylsulfonyl)methide;

at least one reductant soluble in said molten salt solvent, said reductant comprising at least one phenazine; and

at least one oxidant soluble in said molten salt solvent, said oxidant having the chemical formula [A][B]₂ wherein B is selected from the group consisting of bis(perfluoroethylsulfonyl)imide and tris(trifluoromethylsulfonyl)methide and wherein A is a dication having the structural formula

2. The electrochemical device of claim 1, wherein A is a dication having the structural formula

3. The electrochemical device of claim 1, wherein R₂=R₂′

=R₃=R₃′

=hydrogen and wherein R₁ and R_1′

are independently selected from alkyl having 1-9 carbons, aryl, and alkyl-substituted aryl having 7-20 carbons.

4. The electrochemical device of claim 1, wherein R₂=R₂′

=R₃=R₃′

=hydrogen and wherein R₁=R_1′

and are selected from the group consisting of alkyl having 1-9 carbons, aryl, and alkyl-substituted aryl having 7-20 carbons.

5. The electrochemical device of claim 1, wherein R₂=R₂′

=R₃=R₃′

=hydrogen and wherein R₁=R_1′

and are selected from methyl and benzyl.

6. The electrochemical device of claim 1, wherein said phenazine is selected from the group consisting of N,N,N,N′

-tetramethyl-p-phenylenediamine, 2,5,10-trimethyl-3-phenyl-5,10-dihydrophenazine, 5-ethyl-10-methyl-5,10-dihydrophenazine, 5,10-dimethyl-5,10-dihydrobenzo(A)phenazine, 2,7-diphenoxy-5,10-dimethyl-5,10dihydrophenazine, 2-phenoxy-5,10-dimethyl-5,10-dihydrophenazine, 2,7-bis(o-tolyl)-5,10-dimethyl-5,10-dihydrophenazine, 2,3-dimethyl-7-trifluoromethyl-5,10-diethyl-5,10-dihydrophenazine, 5,10-dimethyl-5,10-dihydrophenazine, 2,3-diphenyl-5,10-dimethyl-5,10-dihydrophenazine, 2,7-diphenyl-5,10-dimethyl-5,10-dihydrophenazine, 2-vinyl-5,10-dimethyl-5,10-dihydrophenazine, 2-phenyl-5,10-dimethyl-5,10-dihydrophenazine, 5,10-diisopropyl-5,10-dihydrophenazine, 5,10-dimethyl-5,10-dihydrodibenzo(A,C)phenazine, 1,5,10-trimethyl-2-phenyl-5,10-dihydrophenazin, 2,3,5,10-tetramethyl-7-trifluoromethyl-5,10-dihydrophenazine, and 2,3,5,10-tetramethyl-5,10-dihydrobenzo(B)phenazine.

7. The electrochemical device of claim 1, wherein said electrolyte solution does not include chloride anion, bromide anion, iodide anion, perchlorate anion, tetrafluoroborate anion, tetraphenylborate, carboxylate anion, carbonate anion, hexafluorophosphate anion, or hexafluoroantimonate anion.

8. The electrochemical device of claim 1, wherein said molten salt comprises cations selected from the group consisting of ammonium cations.

9. The electrochemical device of claim 8, wherein said quaternary ammonium cations comprise pyridinium, pyridazinium, pyrimidinium, pyrazinium, imidazolium, pyrazolium, thiazolium, oxazolium, triazolium, tetraalkylammonium cations, or N-methyl morpholinium cations, or mixtures thereof.

10. The electrochemical device of claim 9, wherein said quaternary ammonium cations have the formula (CH₃CH₂)₃N(R₂₄), wherein R₂₄ is alkyl having 2-10 carbons;

or having the formula (CH₃)₂(CH₃CHCH₃)N(R₂₅), wherein R₂₅ is alkyl having 2-10 carbons;

or having the structural formula