Electroactive polymers, manufacturing process thereof, electrode and use thereof

Abstract

Disclosed is an oligomeric or polymeric compound comprising at least two structural units of formula (I) wherein Ar is a carbocyclic aromatic radical or a heterocyclic aromatic radical with the two carbonyl carbon atoms being attached to two ring carbon atoms of the Ar group forming together with the imide-nitrogen atom a five-membered or a six-membered ring X is a divalent group selected from CR.sup.1R.sup.2, CO, SiR.sup.3R.sup.4, P(O)R.sup.5, P(O)(OR.sup.6), PR.sup.7, P(OR.sup.8), S(O) or S(O).sub.2. R.sup.1 to R.sup.8 independently of one another are hydrogen, alkyl, cycloalkyl, aryl or heteroaryl groups, R.sup.9 is a divalent hydrocarbon group or a covalent bond, and R.sup.10, R.sup.11 and R.sup.12 independently of one another are hydrogen or C.sub.1-C.sub.6 alkyl or R.sup.10 and R.sup.11 or R.sup.10 and R.sup.12 together with the carbon atoms to which they are attached form a cycloaliphatic ring or a bicyclic aliphatic system The oligomeric or polymeric compound comprising units of formula (I) of the invention can be used as redox-active material in storage means for electric energy, for example in batteries, redox-flow cells, fuel cells or capacitors. ##STR00001##

Claims

1. An electrode, comprising an oligomeric or polymeric compound as a redox-active material in combination with an electrically conductive material and optionally in combination with a binder agent, wherein: the oligomeric or polymeric compound comprises at least two structural units of formula (I): ##STR00008## Ar is a carbocyclic aromatic radical or a heterocyclic aromatic radical with the two carbonyl carbon atoms being attached to two ring carbon atoms of the Ar group forming together with the imide-nitrogen atom a five-membered or a six-membered ring; X is a divalent group selected from the group consisting of CR.sup.1R.sup.2, CO, SiR.sup.3R.sup.4, P(O)R.sup.5, P(O)(OR.sup.6), PR.sup.7, P(OR.sup.8), S(O) and S(O).sub.2; R.sup.1 to R.sup.8 independently of one another are hydrogen, alkyl, cycloalkyl, aryl or heteroaryl groups; R.sup.9 is a divalent hydrocarbon group or a covalent bond; and R.sup.10, R.sup.11 and R.sup.12 independently of one another are hydrogen or C.sub.1-C.sub.6 alkyl or R.sup.10 and R.sup.11 or R.sup.10 and R.sup.12 together with the carbon atoms to which they are attached form a cycloaliphatic ring or a bicyclic aliphatic system.

2. The electrode according to claim 1, wherein the oligomeric or polymeric compound is combined with a metal, a semiconducting inorganic material, an electrically conducting manic material, or a semiconducting organic material.

3. A battery, a redox-flow cell, or a fuel cell, comprising an oligomeric or polymeric compound comprising at least two structural units of formula (I): ##STR00009## wherein: Ar is a carbocyclic aromatic radical or a heterocyclic aromatic radical with the two carbonyl carbon atoms being attached to two ring carbon atoms of the Ar group forming together with the imide-nitrogen atom a five-membered or a six-membered ring, X is a divalent group selected from the group consisting of CR.sup.1R.sup.2, CO, SiR.sup.3R.sup.4, P(O)R.sup.5, P(O)(OR.sup.6), PR.sup.7, P(OR.sup.8), S(O) and S(O).sub.2; R.sup.1 to R.sup.8 independently of one another are hydrogen, alkyl, cycloalkyl, aryl or heteroaryl groups; R.sup.9 is a divalent hydrocarbon group or a covalent bond; and R.sup.10, R.sup.11 and R.sup.12 independently of one another are hydrogen or C.sub.1-C.sub.6 alkyl or R.sup.10 and R.sup.11 or R.sup.10 and R.sup.12 together with the carbon atoms to which they are attached form a cycloaliphatic ring or a bicyclic aliphatic system.

4. The electrode of claim 1, wherein Ar is a carbocyclic aromatic radical having one to six aromatic rings which are connected via covalent bonds or via divalent bridging groups or which are fused with one another and which aromatic radicals are unsubstituted or are substituted with one or more of alkyl, alkenyl, alkinyl, alkoxy, cycloalkyl, aryl, aralkyl, heteroaryl, hydrocarboncarbonyl, carboxyl, carboxylic acid ester, carboxylic acid amide, amino, nitro, cyano, hydroxyl, halogen, or wherein two adjacent alkyl substituents form a ring system or wherein two adjacent carbonyl groups together with a nitrogen atom form a five-membered or six-membered imide ring.

5. The electrode of claim 1, wherein the five-membered imide group is a group of formula (IIa) and the six-membered imide group is a group of formula (IIb), the CAr-atoms being C-atoms forming part of a carbocyclic aromatic ring or part of a heterocyclic aromatic ring: ##STR00010##

6. The electrode of claim 1, wherein Ar is phenylene, naphthylene, anthracenylene or a condensed aromatic system comprising at least four carbocyclic aromatic rings which Ar group being unsubstituted or substituted by one to four groups selected from the group consisting of alkyl, alkoxy, hydrocarbon, carboxyl, carboxylic ester, nitro and halogen, or wherein two adjacent carbonyl groups together with a nitrogen atom form one or more imide rings in addition to the imide ring of formula (I).

7. The electrode of claim 6, wherein Ar is a group of formula (IIIa), (IIIb), (IIIc), (IIId) or (IIIe): ##STR00011## wherein: the covalent bond in group (IIIc) is in 2, 3 or 4 position relative to the other covalent bond, the covalent bonds in group (IIIb) are in 1, 2- or in 2, 3- or in 1, 8-position, the covalent bonds in group (IIIc) are in 1, 2- or in 2, 3-position, the covalent bonds in group (IIId) are in 1, 2- or in 3, 4-position, the imide groups together with two ring carbon atoms in Ar.sub.1 each form a five-membered or a six-membered ring, R.sup.13, R.sup.14, R.sup.15 and R.sup.16 independently of one another are hydrogen, alkyl, alkoxy, cycloalkyl, aralkyl, aryl, heteroaryl, hydrocarboncarbonyl, carboxyl, carboxylic acid ester, carboxylic acid amide, nitro, hydroxyl, halogen, or wherein two adjacent alkyl substituents can form a ring system or wherein two adjacent carbonyl groups together with a nitrogen atom form a five-membered or six-membered imide ring, a, b, c and d independently of one another are integers between 0 and 3, n is an integer between 1 and 10, Ar.sub.1 is a tetravalent carbocyclic aromatic radical or a tetravalent heterocyclic aromatic radical with two carbonyl carbon atoms of an imide group being attached to two ring carbon atoms of the Ar.sub.1 group forming together with the imide-nitrogen atom a five-membered or a six-membered ring, Ar.sub.2 is a twovalent carbocyclic aromatic radical or a twovalent heterocyclic aromatic radical, and wherein Ar.sub.1 and Ar.sub.2 groups independently of one another are unsubstituted or are substituted with one or more of alkyl, alkoxy, cycloalkyl, aralkyl, aryl, heteroaryl, hydrocarboncarbonyl, carboxyl, carboxylic acid ester, carboxylic acid amide, nitro, hydroxyl and/or halogen.

8. The electrode of claim 1, wherein: X is a divalent CR.sup.1R.sup.2 or CO group; and R.sup.1 to R.sup.2 independently of one another are hydrogen or alkyl.

9. The electrode of claim 1, wherein: R.sup.9 is a covalent bond, a methylene group or a phenylene group, and R.sup.10, R.sup.11 and R.sup.12 independently of one another are hydrogen or C.sub.1-C.sub.6 alkyl.

10. The electrode of claim 9, wherein: R.sup.9 is a covalent bond or phenylene, R.sup.10, R.sup.11 and R.sup.12 are hydrogen or one of R.sup.10, R.sup.11 and R.sup.12 is methyl and the other two are hydrogen, and X is methylene or carbonyl.

11. The electrode of claim 9, wherein: R.sup.9 is a covalent bond or methylene, R.sup.10, R.sup.11 and R.sup.12 are hydrogen or one of R.sup.10, R.sup.11 and R.sup.12 is methyl and the other two are hydrogen, and X is Si(CH.sub.3).sub.2, P(O)(CH.sub.3), P(O)(OCH.sub.3), P(CH.sub.3), P(OCH.sub.3), S(O) or S(O).sub.2.

12. The battery, the redox-flow cell, or the fuel cell of claim 3, wherein Ar is a carbocyclic aromatic radical having one to six aromatic rings which are connected via covalent bonds or via divalent bridging groups or which are fused with one another and which aromatic radicals are unsubstituted or are substituted with one or more of alkyl, alkenyl, alkenyl, alkoxy, cycloalkyl, aryl, aralkyl, heteroaryl, hydrocarboncarbonyl, carboxyl, carboxylic acid ester, carboxylic acid amide, amino, nitro, cyano, hydroxyl, halogen, or wherein two adjacent alkyl substituents form a ring system or wherein two adjacent carbonyl groups together with a nitrogen atom form a five-membered or six-membered imide ring.

13. The battery, the redox-flow cell, or the fuel cell of claim 3, wherein the five-membered imide group is a group of formula (IIa) and the six-membered imide group is a group of formula (IIb), the CAr-atoms being C-atoms forming part of a carbocyclic aromatic ring or part of a heterocyclic aromatic ring: ##STR00012##

14. The battery, the redox-flow cell, or the fuel cell of claim 3, wherein Ar is phenylene, naphthylene, anthracenylene or a condensed aromatic system comprising at least four carbocyclic aromatic rings which Ar group being unsubstituted or substituted by one to four groups selected from the group consisting of alkyl, alkoxy, hydrocarbon, carboxyl, carboxylic ester, nitro and halogen, or wherein two adjacent carbonyl groups together with a nitrogen atom form one or more imide rings in addition to the imide ring of formula (I).

15. The battery, the redox-flow cell, or the fuel cell of claim 14, wherein Ar is a group of formula (IIIa), (IIIb), (IIIc), (IIId) or (IIIe): ##STR00013## wherein: the covalent bond in group (IIIc) is in 2, 3 or 4 position relative to the other covalent bond, the covalent bonds in group (IIIb) are in 1, 2- or in 2, 3- or in 1, 8-position, the covalent bonds in group (IIIc) are in 1, 2- or in 2, 3-position, the covalent bonds in group (IIId) are in 1, 2- or in 3, 4-position, the imide groups together with two ring carbon atoms in Ar.sub.1 each form a five-membered or a six-membered ring, R.sup.13, R.sup.14, R.sup.15 and R.sup.16 independently of one another are hydrogen, alkyl, alkoxy, cycloalkyl, aralkyl, aryl, heteroaryl, hydrocarboncarbonyl, carboxyl, carboxylic acid ester, carboxylic acid amide, nitro, hydroxyl, halogen, or wherein two adjacent alkyl substituents can form a ring system or wherein two adjacent carbonyl groups together with a nitrogen atom form a five-membered or six-membered imide ring, a, b, c and d independently of one another are integers between 0 and 3, n is an integer between 1 and 10, Ar.sub.1 is a tetravalent carbocyclic aromatic radical or a tetravalent heterocyclic aromatic radical with two carbonyl carbon atoms of an imide group being attached to two ring carbon atoms of the Ar.sub.1 group forming together with the imide-nitrogen atom a five-membered or a six-membered ring, Ar.sub.2 is a twovalent carbocyclic aromatic radical or a twovalent heterocyclic aromatic radical, and wherein Ar.sub.1 and Ar.sub.2 groups independently of one another are unsubstituted or are substituted with one or more of alkyl, alkoxy, cycloalkyl, aralkyl, aryl, heteroaryl, hydrocarboncarbonyl, carboxyl, carboxylic acid ester, carboxylic acid amide, nitro, hydroxyl and/or halogen.

16. The battery, the redox-flow cell, or the fuel cell of claim 3, wherein: X is a divalent CR.sup.1R.sup.2 or CO group; and R.sup.1 to R.sup.2 independently of one another are hydrogen or alkyl.

17. The battery, the redox-flow cell, or the fuel cell of claim 3, wherein: R.sup.9 is a covalent bond, a methylene group or a phenylene group, and R.sup.10, R.sup.11 and R.sup.12 independently of one another are hydrogen or C.sub.1-C.sub.6 alkyl.

18. The battery, the redox-flow cell, or the fuel cell of claim 17, wherein: R.sup.9 is a covalent bond or phenylene, R.sup.10, R.sup.11 and R.sup.12 are hydrogen or one of R.sup.10, R.sup.11 and R.sup.12 is methyl and the other two are hydrogen, and X is methylene or carbonyl.

19. The battery, the redox-flow cell, or the fuel cell of claim 17, wherein: R.sup.9 is a covalent bond or methylene, R.sup.10, R.sup.11 and R.sup.12 are hydrogen or one of R.sup.10, R.sup.11 and R.sup.12 is methyl and the other two are hydrogen, and X is Si(CH.sub.3).sub.2, P(O)(CH.sub.3), P(O)(OCH.sub.3), P(CH.sub.3), P(OCH.sub.3), S(O) or S(O).sub.2.

Description

EXAMPLE 1

Synthesis of 5-methyl-2-(4-vinylbenzyl)isoindoline-1,3-dione

(1) 0.5 g 4-Methylphthallmide (3.10 mmol), 0.53 mL 4-vinylbenzylchloride (3.72 mmol, 1.2 eq), 100 mg tetra-n-buytlammoniumbromide (0.31 mmol) and 1.29 g potassium carbonate (9.30 mmol, 3 eq), were blended for 5 min with pestle in a montar. After standing for 1 h at room temperature water (50 mL) was added to the mixture and the suspension was filtered. The filtrate was washed with water (50 mL) and methanol (50 mL) dried under vacuum to yield 0.75 g 4-methyl-2-(4-vinylbenzyl)isoindoline-1,3-dione (87%) as pale yellow powder.

EXAMPLE 2

Synthesis of poly(5-methyl-2-(4-vinylbenzyl)isoindoline-1,3-dione)

(2) 711 mg of 5-methyl-2-(4-vinylbenzyl)isoindoline-1,3-dione (2.56 mmol) and 8.42 mg of AlBN (0.05 mmol, 0.02 eq) were dissolved in degassed THF. The reaction mixture was stirred for 18 h at 75 C. and was then poured into could ether. The precipitate was filtered and after reprecipitation from cold ether 680 mg polymer (86%) was obtained as white powder (SEC, DMAc: M.sub.n 9,500 g/mol PS standard).

EXAMPLE 3

Electrode Preparation

(3) The polymer/carbon nanocomposite electrode was prepared by coating about 0.6 mg of a slurry of the polymer (5.47 mg), wafer-grown carbon fibers (VGCF) (85 mg), and PVdF (10 mg) in NMP (1 mL) on an graphite foil (1 cm.sup.2) and allowing the NMP to evaporate at 40 C. under vacuum for 12 h to give the poolymer/carbon composite layer at 20-50 mm in thickness with a ratio of polymer/VGCF/PVdF (5/85/10)

EXAMPLE 4

Fabrication and Characterization of Test Cells

(4) A coin cell was manufactured by sandwiching the electrode layer of 0.1 M tetrabutylammonium perchlorate (TBAClO.sub.4) in acetonitrile with a polymer carbon nanofibre composite coated electrode and a PTMA carbon nanofibre composite coated on a graphite foil as cathode with a composition of PTMA/VGCF/PVdF=5/85/10 (w/w/w), using a separator film (cell guard #2400 from Holsten Co.) under argon atmosphere. The amount of the anode and cathode active material was adjusted to obtain equal capacities. Cycles performance of these cells were examined by repeated charge discharge glavanostatic cycles at different current densities. These experiments were typically performed at 10 C. After 250 cycles the capacity maintained at 90% of the original capacity.