Carbon-polymer electrochemical systems and methods of fabricating them using layer-by-layer technology

• US 8,075,951 B2
• Filed: 04/30/2009
• Issued: 12/13/2011
• Est. Priority Date: 09/17/2004
• Status: Active Grant

• Current Assignee: Massachusetts Institute of Technology
• Original Assignee: Massachusetts Institute of Technology
• Inventors: Hammond-Cunningham, Paula T., Farhat, Tarek R.
• Primary Examiner(s): LIGHTFOOT, ELENA TSOY
• Application Number:
  US12/433,508
• Publication Number:
  US 20090269491A1
• Time in Patent Office: 957 Days
• Field of Search: 427/243, 427/245, 427/247, 427/402
• US Class Current: 427/243
• CPC Class Codes: B01D 69/02 characterised by their properties
• CPC Class Codes: B01D 69/12 Composite membranes; Ultra-thin membranes
• CPC Class Codes: B01D 69/122 Separate manufacturing of ultra-thin membranes
• CPC Class Codes: B01D 69/141 Heterogeneous membranes, e.g. containing dispersed material; Mixed matrix membranes
• CPC Class Codes: B01D 71/28 Polymers of vinyl aromatic compounds
• CPC Class Codes: B01D 71/281 Polystyrene
• CPC Class Codes: B01D 71/40 Polymers of unsaturated acids or derivatives thereof, e.g. salts, amides, imides, nitriles, anhydrides, esters
• CPC Class Codes: B01D 71/401 Polymers based on the polymerisation of acrylic acid, e.g. polyacrylate
• CPC Class Codes: B01D 71/44 Polymers obtained by reactions only involving carbon-to-carbon unsaturated bonds, not provided for in a single one of groups B01D71/26-B01D71/42
• CPC Class Codes: B01D 71/60 Polyamines
• CPC Class Codes: B01D 71/601 Polyethylenimine
• CPC Class Codes: B01D 71/82 characterised by the presence of specified groups, e.g. introduced by chemical after-treatment
• CPC Class Codes: C25B 13/04 characterised by the material
• CPC Class Codes: H01M 4/8605 Porous electrodes
• CPC Class Codes: H01M 4/92 Metals of platinum group H01M4/94 , H01M4/9058 take precedence
• CPC Class Codes: H01M 4/926 on carbon or graphite
• CPC Class Codes: H01M 50/414 Synthetic resins, e.g. thermoplastics or thermosetting resins
• CPC Class Codes: H01M 50/42 Acrylic resins
• CPC Class Codes: H01M 50/423 Polyamide resins
• CPC Class Codes: H01M 50/46 Separators, membranes or diaphragms characterised by their combination with electrodes
• CPC Class Codes: H01M 50/489 : Separators, membranes, diaphragms or spacing elements inside the cells, characterised by their physical properties, e.g. swelling degree, hydrophilicity or shut down properties
• CPC Class Codes: H01M 50/497 : Ionic conductivity
• CPC Class Codes: H01M 8/1004 : characterised by membrane-electrode assemblies [MEA] H01M8/12 takes precedence
• CPC Class Codes: H01M 8/1023 : having only carbon, e.g. polyarylenes, polystyrenes or polybutadiene-styrenes
• CPC Class Codes: H01M 8/103 : having nitrogen, e.g. sulfonated polybenzimidazoles [S-PBI], polybenzimidazoles with phosphoric acid, sulfonated polyamides [S-PA] or sulfonated polyphosphazenes [S-PPh]
• CPC Class Codes: H01M 8/1039 : halogenated, e.g. sulfonated polyvinylidene fluorides
• CPC Class Codes: H01M 8/1046 : Mixtures of at least one polymer and at least one additive
• CPC Class Codes: H01M 8/1048 : Ion-conducting additives, e.g. ion-conducting particles, heteropolyacids, metal phosphate or polybenzimidazole with phosphoric acid
• CPC Class Codes: H01M 8/1051 : Non-ion-conducting additives, e.g. stabilisers, SiO2 or ZrO2
• CPC Class Codes: H01M 8/1053 : consisting of layers of polymers with at least one layer being ionically conductive
• CPC Class Codes: Y02E 60/10 : Energy storage using batteries
• CPC Class Codes: Y02E 60/50 : Fuel cells
• CPC Class Codes: Y02P 70/50 : Manufacturing or production processes characterised by the final manufactured product
• CPC Class Codes: Y10T 428/31504 : Composite [nonstructural laminate]
• CPC Class Codes: Y10T 428/31855 : Of addition polymer from unsaturated monomers

Abstract

One aspect of the invention provides ion-exchange and gas-diffusion membranes, fabricated by a layer-by-layer approach, for use, e.g., in electrochemical cells; a process for making membrane electrode assemblies fabricated using porous frameworks, LBL composite membranes and LBL carbon-Polymer electrodes; and the application of the membrane and electrode assemblies to a variety of devices, both electrochemical and otherwise.

Claims

1. A method of forming an electrically conductive membrane comprising:

sequentially depositing, under pH controlled conditions, a mixture of a colloid and a charged polymer on a surface to form a plurality of layers comprising a first layer and a second layer;

wherein

the surface is a porous surface;

said first layer is deposited from a mixture of a first colloid and a first polymer selected from the group consisting of polyallylamine hydrochloride, polydiallyldimethylammonium chloride, poly(dimethylamine-co-epichlorohydrin), linear poly(ethyleneimine), and poly(aniline);

said second layer is deposited from a mixture of a second colloid and a second polymer selected from the group consisting of polyacrylic acid, polymethacrylic acid, polystyrene sulfonate, poly(2-acrylamido-2-methyl-1-propane sulfonic acid), oligoethylene glycol dicarboxylic acid, poly(styrene sulfonic acid-maleic acid), and poly(acryl-co-acrylamide acid);

said first colloid consists essentially of a carbon powder, a metal or a combination thereof; and

said second colloid consists essentially of a carbon powder, a metal or a combination thereof.

2. The method of claim 1, further comprising the step of removing said electrically conductive membrane from said porous surface.

3. The method of claim 1, wherein said porous surface is organic, semi-metallic or metallic.

4. The method of claim 1, wherein said first polymer is selected from the group consisting of polydiallyldimethylammonium chloride, linear poly(ethyleneimine), and poly(aniline).

5. The method of claim 1, wherein said second polymer is selected from the group consisting of polyacrylic acid, polystyrene sulfonate, poly(2-acrylamido-2-methyl-1-propane sulfonic acid), and poly(acryl-co-acrylamide acid).

6. The method of claim 1, wherein said second polymer is poly(2-acrylamido-2-methyl-1-propane sulfonic acid).

7. The method of claim 3, wherein said porous surface is selected from the group consisting of metal, carbon cloth, porous stainless steel, porous silicon, porous titanium alloys and gold.

8. The method of claim 1, wherein said first polymer is poly(aniline).

9. The method of claim 1, wherein said plurality of layers comprises a plurality of first layers and a plurality of second layers;

and said first layers are deposited in an alternating fashion with said second layers.

10. The method of claim 1, wherein said first colloid is made charged by said first polymer.

11. The method of claim 1, wherein said second colloid is made charged by said second polymer.

12. The method of claim 1, wherein the porous surface is conductive.