Organic thermoelectric material and thermoelectric generator including the same
Disclosed are an organic thermoelectric material and a thermoelectric generator including the same. More particularly, the thermoelectric generator includes an ionically conductive active layer containing a polyanion including an anionic group and a counter cation in a repeat unit thereof; a conductive polymer; and a polyvalent crosslinking agent as a single molecule including a plurality of acid functional groups. First and second electrodes are disposed to be connected to the ionically conductive active layer.
1. A thermoelectric generator; comprising:
an ionically conductive active layer containing a polyanion comprising an anionic group and a counter cation in a repeat unit thereof, a conductive polymer, wherein the conductive polymer is a conductive polymer having an amine group in a backbone thereof; and a polyvalent crosslinking agent as a single molecule comprising a plurality of acid functional groups or basic functional groups; and
first and second electrodes connected to the ionically conductive active layer.
2. The thermoelectric generator according to claim 1 , wherein the ionically conductive active layer is a gel containing a liquid.
3. The thermoelectric generator according to claim 1 , wherein a dissociation constant of the polyvalent crosslinking agent having acid functional groups is larger than a dissociation constant of the polyanion.
4. The thermoelectric generator according to claim 1 , wherein the polyanion, the conductive polymer, and the polyvalent crosslinking agent are crosslinked by a hydrogen bond and an electrostatic bond.
5. The thermoelectric generator according to claim 1 , wherein an anionic group of the polyanion is —O − , —SO 3− , —OSO 3 − , —COO − , —OPO 3 2− , or —PO 3 2− , and a counter cation thereof is H + , Li + , K + , or Na + .
6. The thermoelectric generator according to claim 1 , wherein a repeat unit of the polyanion is represented by Formula 1A below:
wherein R 1 and R 2 are each independently a hydrogen or a methyl group,
L is a functional group comprising a bond, —CONH—, —COO—, or phenylene,
X − is —O − , —SO 3 − , —OSO 3 − , —COO − , —OPO 3 2− , or —PO 3 2− , and
Y + is H + , Li + , K + , or Na + .
7. The thermoelectric generator according to claim 6 , wherein the repeat unit of the polyanion of Formula 1A is represented by Formula 1B below:
wherein L a is O or NH,
R 3 is a C1 to C6 substituted or unsubstituted alkylene group, and
R 1 , R 2 , X − , and Y + are each the same as those defined in Formula 1A.
8. The thermoelectric generator according to claim 1 , wherein the polyanion is poly(2-acrylamido-2-methyl-1-propanesulfoinc acid) (PAAMPSA).
9. The thermoelectric generator according to claim 1 , wherein the conductive polymer is a polymer having an amine group (—NH—) in the backbone represented by Formula 2A or a polyaniline-based polymer having a repeat unit represented by Formula 2B:
wherein Ar is 5- to 13-membered aromatic ring including N,
wherein n is 0 to 1, and R 3 to R 18 are each independently hydrogen, C1 to C6 alkyl, C1 to C6 alkoxy, C1 to C6 haloalkyl, C1 to C6 haloalkoxy, F, Cl, Br, I, or CN, or R 3 and R 4 , R 5 and R 6 , R 7 and R 8 , R 9 and R 10 , R 11 and R 12 , R 13 and R 14 , R 15 and R 16 , or R 17 and R 18 form an aromatic ring fused to a benzene ring to which R 3 to R 18 are attached.
10. The thermoelectric generator according to claim 1 , wherein the polyvalent crosslinking agent comprises 3 to 6 acid functional groups or basic functional groups, and
the functional group is carboxylic acid, sulfonic acid, phosphoric acid, or an amine group.
11. The thermoelectric generator according to claim 10 , wherein the polyvalent crosslinking agent is represented by Formula 3 below:
wherein ring C is a benzene ring, cyclohexane, or cyclohexene, and
R a , R b , R c , R d , R e , and R f are each independently, hydrogen, carboxylic acid, sulfonic acid, or a phosphate group, and at least three of R a , R b , R c , R d , R e , and R f are each independently carboxylic acid, sulfonic acid, or a phosphate group.
12. The thermoelectric generator according to claim 1 , wherein the polyvalent crosslinking agent is phytic acid (PA).
13. The thermoelectric generator according to claim 1 , wherein the ionically conductive active layer comprises 100 parts by weight of the polyanion, about 1 to 50 parts by weight of the conductive polymer, and about 1 to 80 parts by weight of the polyvalent crosslinking agent.
14. The thermoelectric generator according to claim 1 , wherein at least one of the electrodes is a metal oxide, a conductive polymer or porous carbon.
15. A thermoelectric material, comprising an ionically conductive active layer containing a polyanion comprising an anionic group and a counter cation in a repeat unit thereof, a conductive polymer comprising an amine group in a backbone thereof, and a polyvalent crosslinking agent as a single molecule having a plurality of acid functional groups,
wherein the polyanion, the conductive polymer, and the polyvalent crosslinking agent are crosslinked by a hydrogen bond and an electrostatic bond.