Redox copolymers and their use in preparing mixed conduction materials

• US 5,883,220 A
• Filed: 08/21/1997
• Issued: 03/16/1999
• Est. Priority Date: 12/01/1992
• Status: Expired due to Fees

• Current Assignee: Centre National De La Recherche Scientifique, Hydro-Quebec (Province of Québec)
• Original Assignee: Centre National De La Recherche Scientifique, Hydro-Quebec (Province of Québec)
• Inventors: Baril, Daniel, Michot, Christophe, Armand, Michel, Choquette, Yves, Sanchez, Jean-Yves
• Primary Examiner(s): MOORE, MARGARET G
• Application Number:
  US08/915,790
• Time in Patent Office: 572 Days
• Field of Search: 528/322, 528/331, 528/342, 528/374, 528/361, 359/321, 359/322, 430/58, 430/59, 430/80, 430/900
• US Class Current: 528/322
• CPC Class Codes: C08G 65/33317 heterocyclic
• CPC Class Codes: C08G 73/10 Polyimides; Polyester-imides; Polyamide-imides; Polyamide acids or similar polyimide precursors
• CPC Class Codes: G02F 1/15165 Polymers
• CPC Class Codes: H01B 1/122 Ionic conductors
• CPC Class Codes: H01G 9/022 Electrolytes; Absorbents
• CPC Class Codes: H01M 4/36 Selection of substances as active materials, active masses, active liquids
• CPC Class Codes: H01M 4/364 as mixtures
• CPC Class Codes: H01M 4/60 of organic compounds
• CPC Class Codes: H01M 6/181 with polymeric electrolytes
• CPC Class Codes: Y10S 430/10 Donor-acceptor complex photoconductor

Abstract

The copolymer described is a segmented copolymer consisting essentially of organic segments A which have a number i of reactive ends such that i is from 1 to 6 inclusive, and segments B which have a number j of reactive ends such that j is from 1 to 6 inclusive. The segments B have redox properties and each segment A is connected to at least one segment B by a group Y and vice versa, the group Y being an ether, thioether, secondary amine, tertiary amine, secondary amide, tertiary amide, imide, quarternary ammonium group, or a group having a carbon--carbon bond. The respective weighted molar mean of i and j is 2 or more. Application to electrochemical generators and electrochromic systems.

Claims

1. A segmented copolymer consisting essentially of identical or different organic segments A which have a functionality i such that 1≦

i≦

6 and by identical or different segments B which have a functionality j such that 1≦

j≦

6, wherein the segments B present redox properties and contain at least one unit derived from an aromatic molecule which can form stable anionic or cationic radical species and said segments B are one or more members selected from the group consisting of aromatic tetracarboxylic diimide groups, the segments A are selected from the group consisting of solvating segments having a number of solvating ether units of at least 5, and wherein segments A optionally include nonsolvating segments or are optionally replaced in part by segments A'"'"' containing a group that permits the formation of a network, each segment A is linked to at least one segment B by a group Y and each segment B is linked to at least one segment A by a group Y, with the group Y being selected from the group consisting of ether groups, thioether groups, secondary amine groups, tertiary amine groups, secondary amide groups, tertiary amide groups, imide groups, quaternary ammonium groups, and groups containing a --CH₂ --CH₂ -- bond, and wherein the weighted molar average of i and the weighted molar average of j are each greater than or equal to 2.

2. A copolymer according to claim 1, wherein said solvating segments are selected from the group consisting of homopolymers of ethylene oxide or propylene oxide, the copolymers of ethylene oxide and propylene oxide, and the copolymers of ethylene oxide or propylene oxide with a comonomer polymerizable by the formation of ether bonds.

3. A copolymer according to claim 2, wherein the comonomer polymerizable by formation of ether bonds is a member selected from the group consisting of oxymethylene, oxetane, tetrahydrofuran, methyl glycidyl ether and dioxolane.

4. A copolymer according to claim 1, wherein at least one part of the segments A are nonsolvating segments selected from the group consisting of arylene radicals and arylalkylene radicals.

5. A copolymer according to claim 1, wherein at least a portion of the segments A are replaced by segments A'"'"' containing a group that permits the formation of a network and/or part of the segments B are replaced with segments B'"'"' not containing any redox function, but containing a group permitting the formation of a network.

6. The copolymer of claim 1, wherein said segments A are polyethylene oxide segments and said segments B are derived from pyromellitic diimide and said copolymer has an ionic conductivity of at least 10^-8 S.cm^-1.

7. A material containing a salt and a polymeric solid solvent, wherein the polymeric solvent consists essentially of at least one segmented copolymer consisting of identical or different organic segments A which have a functionality i such that 1≦

i≦

6, and by identical or different segments B which have a functionality j such that 1≦

j≦

6, in which copolymer segments B present redox properties and contain at least one unit derived from an aromatic molecule which can form stable anionic or cationic radical species and said segments B are one or more members selected from the group consisting of aromatic tetracarboxylic diimide groups, the segments A are selected from the groups consisting of solvating segments having a number of solvating ether units of at least 5, each segment A is linked to at least one segment B by a group Y, and each segment B is linked to at least one segment A by a group Y, with the group Y being selected from the group consisting of ether groups, thioether groups, secondary amine groups, tertiary amine groups, secondary amide groups, quaternary ammonium groups, and groups containing a --CH₂ --CH₂ -- bond, and the weighted molar average of i and the weighted molar average of j are each greater than or equal to 2.

8. A material according to claim 7, wherein the copolymer is crosslinked.

9. A material according to claim 4, wherein the salt is selected from the group consisting of salts M^m m(X³), with M representing a proton, an ion of a metal with the valence m, selected from the group consisting of alkali metals, alkaline-earth metals, transition metals, rare earth weighted molar average of i and the weighted molar average of j are each greater than or equal to 2.

10. A material according to claim 9, wherein X³ is Br, ClO₄^-, AsF₆^-, R_F SO₃^-, (R_F SO₂)₃ C^- or (R_F SO₂)₂ CY^1-, with R_F representing a perfluoroalkyl or perfluoroaryl group and Y¹ representing an electron-attracting group.

11. An electrochemical generator including a polymeric solid electrolyte or a plasticized electrolyte, or an electrolyte in the form of a gel consisting of a polymer and liquid solvent, wherein at least one of its electrodes contains a segmented copolymer consisting of identical or different organic segments A which have a functionality i such that 1≦

i≦

6, and by identical or different segments B which have a functionality j such that 1≦

j≦

6, with the segments B presenting redox properties and containing at least one unit derived from an aromatic molecule that can form stable anionic and cationic radical species by the loss or gain of at least one electron and said segments B are one or more members selected from the group consisting of aromatic tetracarboxylic diimide groups, the segments A being selected from the group consisting of solvating segments having a member of solvating ether units of at least 5, each segment A being linked to at least one segment B by a group Y, and each segment B being linked to at least one segment A by a group Y, with the group Y being selected from the group consisting of ether groups, thioether gropes, secondary amine groups;

tertiary amine groups, secondary amide groups, quaternary ammonium groups, and groups containing a --CH₂ --CH₂ -- bond, and the weighted molar average of i and the weighted molar average of j are each greater than or equal to 2.

12. A light modulation device, having a negative electrode consisting essentially of a segment copolymer consisting essentially of identical and different organic segments A which have a functionality i such that 1≦

i≦

6, with the segments B presenting redox properties and containing at least one unit derived from an aromatic molecule that can form stable anionic and cationic radical species by the loss or gain of at least one electron and said segments B are one or more members selected from the group consisting of aromatic tetracarboxylic diimide groups, the segments A being selected from the group consisting of solvating segments having a number of solvating ether units of at least 5, each segment A being linked to at least one segment B by a group Y, and each segment B being linked to at least one segment A by a group Y, with the group Y being selected from the group consisting of ether groups, thioether groups, secondary amine groups;

tertiary amine groups, secondary amide groups, quaternary ammonium groups, and groups containing a --CH₂ --CH₂ -- bond, and the weighted molar average of i and the weighted molar average of j are each greater than or equal to 2.