Granted Patent B2

US 12,416,088 · App. 18/300,380 · Granted Sep 16, 2025

Inventors: Ziyang Huo (Moraga, CA); Lihui Wang (Alameda, CA); Kenneth X. Hua (San Jose, CA); Sichao Ma (Dublin, CA); Edward Izett (Berkeley, CA); Sara Hunegnaw (Oakland, CA); Ajay R. Kashi (Berkeley, CA); Etosha R. Cave (Berkeley, CA); Kendra P. Kuhl (Oakland, CA); Maxwell Goldman (Berkeley, CA); Angelica L. Reyes (Berkeley, CA); Kathryn L. Corp (Berkeley, CA)

Assignee: Twelve Benefit Corporation

C25B9/23C08F293/00C25B1/23C25B13/02C25B13/08

Abstract

Claims (51)

1. A membrane electrode assembly comprising:

a cathode catalyst layer;

an anode catalyst layer; and

a bipolar membrane disposed between the cathode catalyst layer and the anode catalyst layer, wherein the bipolar membrane comprises an anion-conducting polymer layer, a cation-conducting polymer layer, and a bipolar interface between the anion-conducting polymer layer and the cation-conducting polymer layer, wherein the cation-conducting polymer layer is disposed between the anode catalyst layer and the anion-conducting polymer layer, wherein the bipolar interface comprises covalent crosslinking of the cation-conducting polymer layer and anion-conducting polymer layer and wherein the covalent crosslinking comprises a material comprising a structure of one of formulas (I)-(V):

or a salt thereof,

wherein:

each of R 7 , R 8 , R 9 , and R 10 is, independently, an electron-withdrawing moiety, H, optionally substituted aliphatic, alkyl, heteroaliphatic, heteroalkylene, aromatic, aryl, or arylalkylene, wherein at least one of R 7 or R 8 can include the electron-withdrawing moiety or wherein a combination of R 7 and R 8 or R 9 and R 10 can be taken together to form an optionally substituted cyclic group;

Ar comprises or is an optionally substituted aromatic or arylene;

each of n is, independently, an integer of 1 or more;

each of rings a-c can be optionally substituted; and

rings a-c, R 7 , R 8 , R 9 , and R 10 can optionally comprise an ionizable or ionic moiety, and

wherein R 7 or R 8 comprises the electron-withdrawing moiety selected from the group consisting of an optionally substituted haloalkyl, cyano, phosphate, sulfate, sulfonic acid, sulfonyl, difluoroboranyl, borono, thiocyanato, and piperidinium.

2. The membrane electrode assembly of claim 1 , wherein the covalent crosslinking comprises a material comprising one or more ionizable or ionic moieties selected from the group consisting of -L A -X A , -L A -(L A′ -X A ) L2 , -L A -(X A -L A′ -X A′ ) L2 , and -L A -X A -L A′ -X A′ -L A″ -X A″ ; wherein:

each L A , L A′ , and L A″ is, independently, a linking moiety;

each X A , X A′ , and X A″ comprises, independently, an acidic moiety, a basic moiety, a multi-ionic moiety, a cationic moiety, or an anionic moiety; and

L2 is an integer of 1 or more.

3. The membrane electrode assembly of claim 2 , wherein each X A , X A′ , and X A″ comprises, independently, carboxy, carboxylate anion, guanidinium cation, sulfo, sulfonate anion, sulfonium cation, sulfate, sulfate anion, phosphono, phosphonate anion, phosphate, phosphate anion, phosphonium cation, phosphazenium cation, amino, ammonium cation, heterocyclic cation, or a salt form thereof.

4. The membrane electrode assembly of claim 1 , wherein the covalent crosslinking comprises a material comprising a structure of one of the following formulas:

or a salt thereof, wherein:

Ar is or comprises an optionally substituted arylene or aromatic;

Ak is or comprises an optionally substituted alkylene, haloalkylene, aliphatic, heteroalkylene, or heteroaliphatic; and

L is a linking moiety, and

wherein one or Ar, Ak, and/or L is optionally substituted with one or more ionizable or ionic moieties.

5. The membrane electrode assembly of claim 4 , wherein the linking moiety comprises a covalent bond, spirocyclic bond, —O—, —NR N1 —, —C(O)—, —C(O)O—, —OC(O)—, —SO 2 —, optionally substituted aliphatic, alkylene, alkyleneoxy, haloalkylene, hydroxyalkylene, heteroaliphatic, heteroalkylene, aromatic, arylene, aryleneoxy, heteroaromatic, heterocycle, or heterocyclyldiyl.

6. The membrane electrode assembly of claim 1 , wherein the cathode catalyst layer comprises a catalyst configured to reduce CO 2 .

7. The membrane electrode assembly of claim 1 , wherein the cathode catalyst layer comprises a combination of metal catalyst materials.

8. The membrane electrode assembly of claim 7 , wherein the metal catalyst materials comprise a transition metal.

9. The membrane electrode assembly of claim 1 , wherein the cathode catalyst layer comprises metal catalyst particles supported on a conductive substrate.

10. The membrane electrode assembly of claim 1 , wherein the bipolar interface is characterized by interpenetration of the anion-conducting polymer layer and the cation-conducting polymer layer and wherein the bipolar interface comprises: (a) protrusions having a dimension of between 10 μm-1 mm in a plane parallel to the anion-conducting polymer layer (the in-plane dimension); and/or (b) protrusions each having a thickness of between 10% to 75% of the total thickness of the anion-conducting polymer layer.

11. The membrane electrode assembly of claim 1 , wherein the bipolar interface is characterized by interpenetration of the anion-conducting polymer layer and the cation-conducting polymer layer and wherein the bipolar interface comprises: (a) a gradient of the anion-conducting polymer and/or the cation-conducting polymer; and/or (b) a mixture of the anion-conducting polymer and/or the cation-conducting polymer.

12. A membrane electrode assembly comprising:

a cathode catalyst layer;

an anode catalyst layer; and

a bipolar membrane disposed between the cathode catalyst layer and the anode catalyst layer, wherein the bipolar membrane comprises an anion-conducting polymer layer, a cation-conducting polymer layer, and a bipolar interface between the anion-conducting polymer layer and the cation-conducting polymer layer, wherein the cation-conducting polymer layer is disposed between the anode catalyst layer and the anion-conducting polymer layer, wherein the bipolar interface comprises covalent crosslinking of the cation-conducting polymer layer and anion-conducting polymer layer and wherein the covalent crosslinking comprises a crosslinker comprising a structure of one of the following formulas:

wherein:

Ak is an optionally substituted aliphatic or an optionally substituted alkylene;

Ar is an optionally substituted aromatic or an optionally substituted arylene;

L is a linking moiety;

L3 is an integer that is 2 or more; and

X′ is absent, —O—, —NR N1 —, —C(O)—, or -Ak-, in which R N1 is H or optionally substituted alkyl, and Ak is optionally substituted alkylene, optionally substituted heteroalkylene, optionally substituted aliphatic, or optionally substituted heteroaliphatic, wherein the covalent crosslinking comprises a material comprising one or more ionizable or ionic moieties selected from the group consisting of -L A -X A , -L A -(L A′ -X A ) L2 , -L A -(X A -L A′ -X A′ ) L2 , and -L A -X A -L A′ -X A′ -L A″ -X A″ ; wherein:

each L A , L A′ , and L A″ is, independently, a linking moiety;

each X A , X A′ , and X A″ comprises, independently, an acidic moiety, a basic moiety, a multi-ionic moiety, a cationic moiety, or an anionic moiety; and

L2 is an integer of 1 or more.

13. The membrane electrode assembly of claim 12 , wherein each X A , X A′ , and X A″ comprises, independently, carboxy, carboxylate anion, guanidinium cation, sulfo, sulfonate anion, sulfonium cation, sulfate, sulfate anion, phosphono, phosphonate anion, phosphate, phosphate anion, phosphonium cation, phosphazenium cation, amino, ammonium cation, heterocyclic cation, or a salt form thereof.

14. The membrane electrode assembly of claim 12 , wherein the linking moiety comprises a covalent bond, spirocyclic bond, —O—, —NR N1 —, —C(O)—, —C(O)O—, —OC(O)—, —SO 2 —, optionally substituted aliphatic, alkylene, alkyleneoxy, haloalkylene, hydroxyalkylene, heteroaliphatic, heteroalkylene, aromatic, arylene, aryleneoxy, heteroaromatic, heterocycle, or heterocyclyldiyl.

15. The membrane electrode assembly of claim 12 , wherein the cathode catalyst layer comprises a catalyst configured to reduce CO 2 .

16. The membrane electrode assembly of claim 12 , wherein the cathode catalyst layer comprises a combination of metal catalyst materials.

17. The membrane electrode assembly of claim 16 , wherein the metal catalyst materials comprise a transition metal.

18. The membrane electrode assembly of claim 12 , wherein the cathode catalyst layer comprises metal catalyst particles supported on a conductive substrate.

19. The membrane electrode assembly of claim 12 , wherein the bipolar interface is characterized by interpenetration of the anion-conducting polymer layer and the cation-conducting polymer layer and wherein the bipolar interface comprises: (a) protrusions having a dimension of between 10 μm-1 mm in a plane parallel to the anion-conducting polymer layer (the in-plane dimension); and/or (b) protrusions each having a thickness of between 10% to 75% of the total thickness of the anion-conducting polymer layer.

20. The membrane electrode assembly of claim 12 , wherein the bipolar interface is characterized by interpenetration of the anion-conducting polymer layer and the cation-conducting polymer layer and wherein the bipolar interface comprises: (a) a gradient of the anion-conducting polymer and/or the cation-conducting polymer; and/or (b) a mixture of the anion-conducting polymer and/or the cation-conducting polymer.

Assignments (1)

Continuity (3)

References Cited (400)