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

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.

1 . A method of forming a membrane, comprising sequentially depositing, under pH controlled conditions, a plurality of polymer layers on a surface; wherein each polymer layer is independently selected from the group consisting of pH dependent cationic polyelectrolytes, pH independent cationic polyelectrolytes, neutral polymers, pH dependent anionic polyelectrolytes, and pH independent anionic polyelectrolytes; wherein a polymer layer optionally comprises at least one additional chemical entity selected from the group consisting of hydrogels, polyions, colloids, latexes, zeolites, platelets, proton sponges, organic molecules, organic salts, inorganic salts, organic acids, inorganic acids, cationic dendrimers, anionic dendrimers, metals and carbon; and wherein said plurality of polymer layers comprises a first polymer layer and a second polymer layer; thereby forming a membrane.  
     
     
         2 . The method of  claim 1 , wherein said membrane further comprises at least one additional chemical entity selected from the group consisting of hydrogels, polyions, colloids, latexes, zeolites, platelets, proton sponges, organic molecules, organic salts, inorganic salts, organic acids, inorganic acids, cationic dendrimers, anionic dendrimers, metals and carbon.  
     
     
         3 . The method of  claim 1 , wherein said first polymer layer is a pH dependent cationic polyelectrolyte, a pH independent cationic polyelectrolyte or a neutral polymer; and wherein said second polymer layer is a pH dependent anionic polyelectrolyte or pH independent anionic polyelectrolyte; and wherein said membrane is removed from said surface; thereby forming an ion-exchange membrane or a LBL polyelectrolyte-carbon electrode.  
     
     
         4 . The method of  claim 1 , wherein said first polymer layer is a pH dependent cationic polyelectrolyte, a pH independent cationic polyelectrolyte or a neutral polymer; and wherein said second polymer layer is a pH dependent anionic polyelectrolyte or pH independent anionic polyelectrolyte; and wherein said surface is selected from the group consisting of organic hydrophilic porous filter membranes and inorganic hydrophilic porous filter membranes; thereby forming an ion-exchange membrane.  
     
     
         5 . The method of  claim 2 , wherein said first polymer layer is a pH dependent cationic polyelectrolyte, a pH independent cationic polyelectrolyte or a neutral polymer; and wherein said second polymer layer is a pH dependent anionic polyelectrolyte or pH independent anionic polyelectrolyte; and wherein said membrane is removed from said surface; thereby forming an ion-exchange membrane or a LBL polyelectrolyte-carbon electrode.  
     
     
         6 . The method of  claim 2 , wherein said first polymer layer is a pH dependent cationic polyelectrolyte, a pH independent cationic polyelectrolyte or a neutral polymer; and wherein said second polymer layer is a pH dependent anionic polyelectrolyte or pH independent anionic polyelectrolyte; and wherein said surface is selected from the group consisting of organic hydrophilic porous filter membranes and inorganic hydrophilic porous filter membranes; thereby forming an ion-exchange membrane.  
     
     
         7 . The method of  claim 2 , wherein said first polymer layer is a pH dependent cationic polyelectrolyte, a pH independent cationic polyelectrolyte or a neutral polymer; and wherein said second polymer layer is a pH dependent anionic polyelectrolyte or pH independent anionic polyelectrolyte; and wherein said surface is organic, semi-metallic or metallic; and wherein said at least one additional entity is carbon; thereby forming a LBL polyelectrolyte-carbon electrode.  
     
     
         8 . The method of  claim 2 , wherein said first polymer layer is a pH dependent cationic polyelectrolyte, a pH independent cationic polyelectrolyte or a neutral polymer; and wherein said second polymer layer is a pH dependent anionic polyelectrolyte or pH independent anionic polyelectrolyte; and wherein said at least one chemical entity is selected from the group consisting of metals and inorganic salts; and wherein said at least on additional entity is carbon; thereby forming a LBL polyelectrolyte-carbon electrode.  
     
     
         9 . The method of  claim 1 , wherein said first polymer layer is selected from the group consisting of PAH, PDAC, PDME, PAAm, LPEI, PEO, PVP, PVA, PEG and PANI.  
     
     
         10 . The method of  claim 1 , wherein said first polymer layer is selected from the group consisting of PDAC, PDME, PAAm, LPEI and PEO.  
     
     
         11 . The method of  claim 1 , wherein said second polymer layer is selected from the group consisting of PAA, PMA, SPS, PAMPS, OEGDA, PSSM3:1, and PAA-co-PAA.  
     
     
         12 . The method of  claim 1 , wherein said second polymer layer is selected from the group consisting of PAA, PAMPS, SPS, PSSM3:1, PAA-co-PAAm.  
     
     
         13 . The method of  claim 1 , wherein said at least one chemical entity is selected from the group consisting of sulfonated latex, sodium chloride, potassium chloride, lithium chloride, sulfonic acid, nitric acid, hydrochloric acid, hydrobromic acid, phosphonic acid, PEG, OEGDA, PAAm, PVA, PVP, polyphosphates, Nafions®, ethylene glycol and glycerol.  
     
     
         14 . The method of  claim 1 , wherein said at least on chemical entity is selected from the group consisting of sodium chloride, sulfonated latex, and Nafion 117.  
     
     
         15 . The method of  claim 1 , wherein said first polymer layer is selected from the group consisting of PAH, PDAC, PDME, PAAm, LPEI, PEO, PVP, PVA, PEG and PANI; and wherein said at least one chemical entity is selected from the group consisting of sulfonated latex, sodium chloride, potassium chloride, lithium chloride, sulfonic acid, nitric acid, hydrochloric acid, hydrobromic acid, phosphonic acid, PEG, OEGDA, PAAm, PVA, PVP, polyphosphates, Nafions®, ethylene glycol and glycerol.  
     
     
         16 . The method of  claim 1 , wherein said second polymer layer is selected from the group consisting of PAA, PMA, SPS, PAMPS, OEGDA, PSSM3:1, and PAA-co-PAA; and wherein said at least one chemical entity is selected from the group consisting of sulfonated latex, sodium chloride, potassium chloride, lithium chloride, sulfonic acid, nitric acid, hydrochloric acid, hydrobromic acid, phosphonic acid, PEG, OEGDA, PAAm, PVA, PVP, polyphosphates, Nafions®, ethylene glycol and glycerol.  
     
     
         17 . The method of  claim 1 , wherein said first polymer layer is selected from the group consisting of PAH, PDAC, PDME, PAAm, LPEI, PEO, PVP, PVA, PEG and PANI; and wherein said second polymer layer is selected from the group consisting of PAA, PMA, SPS, PAMPS, OEGDA, PSSM3:1, and PAA-co-PAA; and wherein said at least one chemical entity is selected from the group consisting of sulfonated latex, sodium chloride, potassium chloride, lithium chloride, sulfonic acid, nitric acid, hydrochloric acid, hydrobromic acid, phosphonic acid, PEG, OEGDA, PAAm, PVA, PVP, polyphosphates, Nafions®, ethylene glycol and glycerol.  
     
     
         18 . The method of  claim 1 , wherein said first polymer layer is selected from the group consisting of PDAC, PDME, PAAm, LPEI and PEO; and wherein said at least on chemical entity is selected from the group consisting of sodium chloride, sulfonated latex, and Nafion 117.  
     
     
         19 . The method of  claim 1 , wherein said second polymer layer is selected from the group consisting of PAA, PAMPS, SPS, PSSM3:1, PAA-co-PAAm; and wherein said at least on chemical entity is selected from the group consisting of sodium chloride, sulfonated latex, and Nafion 117.  
     
     
         20 . The method of  claim 1 , wherein said first polymer layer is selected from the group consisting of PDAC, PDME, PAAm, LPEI and PEO; and wherein said second polymer layer is selected from the group consisting of PAA, PAMPS, SPS, PSSM3:1, PAA-co-PAAm; and wherein said at least on chemical entity is selected from the group consisting of sodium chloride, sulfonated latex, and Nafion 117.  
     
     
         21 . The method of  claim 1 , wherein said first polymer layer is LPEI.  
     
     
         22 . The method of  claim 21 , wherein said second polymer layer is a pH independent anionic polyelectrolyte.  
     
     
         23 . The method of  claim 1 , wherein said first polymer layer is PEO.  
     
     
         24 . The method of  claim 23 , wherein said second polymer layer is a pH dependent polyelectrolyte.  
     
     
         25 . The method of  claim 1 , wherein said first polymer layer is PAAm.  
     
     
         26 . The method of  claim 25 , wherein said second polymer layer is a pH dependent polyelectrolyte.  
     
     
         27 . The method of  claim 1 , wherein said first polymer layer is PDAC.  
     
     
         28 . The method of  claim 27 , wherein said second polymer layer is a PH dependent polyelectrolyte.  
     
     
         29 . The method of  claim 27 , wherein said second polymer layer is a pH independent polyelectrolyte.  
     
     
         30 . The method of  claim 1 , wherein said first polymer layer is PDME.  
     
     
         31 . The method of  claim 30 , wherein said second polymer is a pH independent polyelectrolyte.  
     
     
         32 . The method of  claim 1 , wherein said second polymer layer is PAMPS.  
     
     
         33 . The method of  claim 32 , wherein said first polymer layer is a neutral polymer.  
     
     
         34 . The method of  claim 32 , wherein said first polymer layer is a pH independent cationic polyelectrolyte.  
     
     
         35 . The method of  claim 1 , wherein said second polymer layer is SPS.  
     
     
         36 . The method of  claim 35 , wherein said first polymer layer is a neutral polymer.  
     
     
         37 . The method of  claim 1 , wherein said second polymer layer is PSSM3:1.  
     
     
         38 . The method of  claim 37 , wherein said first polymer layer is a neutral polymer.  
     
     
         39 . The method of  claim 1 , wherein said second polymer layer is PAA.  
     
     
         40 . The method of  claim 39 , wherein said first polymer layer is a neutral polymer.  
     
     
         41 . The method of  claim 1 , wherein said second polymer layer is PAA-co-PAAm.  
     
     
         42 . The method of  claim 41 , wherein said first polymer layer is a neutral polymer.  
     
     
         43 . The method of  claim 41 , wherein said first polymer is a pH independent cationic polymer.  
     
     
         44 . The method of  claim 1 , wherein the first polymer layer is LPEI; and wherein the second polymer layer is PAMPS.  
     
     
         45 . The method of  claim 1 , wherein the first polymer layer is LPEI; and the wherein the second polymer layer is SPS.  
     
     
         46 . The method of  claim 1 , wherein the first polymer layer is LPEI; and wherein the second polymer layer is PSSM.  
     
     
         47 . The method of  claim 1 , wherein the first polymer layer is LPEI; and wherein the second polymer layer is PAA.  
     
     
         48 . The method of  claim 1 , wherein the first polymer layer is PEO; and wherein the second polymer layer is PAA.  
     
     
         49 . The method of  claim 1 , wherein the first polymer layer is PAAm; and wherein the second polymer layer is PAA.  
     
     
         50 . The method of  claim 1 , wherein the first polymer layer is PAAm; and wherein the second polymer layer is PAA-coPAAm.  
     
     
         51 . The method of  claim 1 , wherein the first polymer layer is PDAC; and wherein the second polymer layer is PAA-co-PAAm.  
     
     
         52 . The method of  claim 1 , wherein the first polymer layer is PDAC; and wherein the second polymer layer is PAMPS.  
     
     
         53 . The method of  claim 1 , wherein the first polymer layer is PDME; and wherein the second polymer layer is PAMPS.  
     
     
         54 . The method of  claim 47 , wherein the PAA is deposited at a pH of about 4.0.  
     
     
         55 . The method of  claim 47 , wherein the PAA is deposited at a pH between about 3.5 and about 4.5.  
     
     
         56 . The method of  claim 48 , wherein the PAA is deposited at a pH of about 2.0.  
     
     
         57 . The method of  claim 48 , wherein the PAA is deposited at a pH of about 2.5.  
     
     
         58 . The method of  claim 48 , wherein the PAA is deposited at a pH between about 1.5 and about 3.0.  
     
     
         59 . The method of  claim 50 , wherein the PAA-co-PAAm is deposited at a pH of about 2.0.  
     
     
         60 . The method of  claim 50 , wherein the PAA-co-PAAm is deposited at a pH between about 1.5 and about 2.5.  
     
     
         61 . The method of  claim 51 , wherein the PAA-co-PAAm is deposited at a pH of about 5.  
     
     
         62 . The method of  claim 51 , wherein the PAA-co-PAAm is deposited at a pH between about 4.5 and about 5.5.  
     
     
         63 . The method of  claim 51 , wherein the PAA-co-PAAm is deposited at a pH between about 5.5 and about 6.5.  
     
     
         64 . The method of  claim 51 , wherein the PAA-co-PAAm is deposited at a pH between about 6.5 and about 7.5.  
     
     
         65 . The method of  claim 7 , wherein said surface is selected from the group consisting of carbon cloth, porous stainless steel, porous silicon, porous titanium alloys and gold.  
     
     
         66 . The method of  claim 7  or  8 , wherein said carbon is selected from the group consisting of carbon powder, aqueous carbon paste, and Hispec3000 powder.  
     
     
         67 . The method of  claim 8 , wherein said metal is selected from the group consisting of Pd, Pt, Au, Ru, Zn, Cu, Ag and Al.  
     
     
         68 . The method of  claim 8 , wherein said first polymer layer is PDAC; and wherein said second polymer layer is PAMPS; and wherein said carbon is carbon powder; and wherein said metal is Pd.  
     
     
         69 . The method of  claim 8 , wherein said first polymer layer is PDAC; and wherein said second polymer layer is PAMPS; and wherein said carbon is Hispec 3000; and wherein said metal is Pt.  
     
     
         70 . The method of  claim 8 , wherein said first polymer layer is LPEI; and wherein said second polymer layer is PAA deposited at a pH of about 4.0; and wherein said carbon is aqueous carbon paste; and wherein said metal is Pt.  
     
     
         71 . A membrane, comprising a plurality of polymer layers held together by electrostatic or hydrogen bonding interactions deposited on a porous framework, wherein said membrane has a total uniform thickness of less than about 10 μm and a conductance of less than about 1.0×10 −3  S/cm and this conductance does not degrade over time.  
     
     
         72 . The membrane of  claim 71 , wherein said membrane has a total thickness of less than about 1 μm.  
     
     
         73 . The membrane of  claim 71 , wherein said membrane has a total thickness of less than about 0.75 μm.  
     
     
         74 . The membrane of  claim 71 , wherein said membrane has a total thickness of less than about 0.5 μm.  
     
     
         75 . The membrane of  claim 71 , wherein said membrane has a total thickness of less than about 0.25 μm.  
     
     
         76 . The membrane of  claim 71 , wherein said membrane has a total thickness of less than about 0.1 μm.  
     
     
         77 . The membrane of  claim 71 , wherein said membrane has a conductance of less than about 5.0×10 −4  S/cm.  
     
     
         78 . The membrane of  claim 71 , wherein said membrane has a conductance of less than about 2.0×10 −4  S/cm.  
     
     
         79 . The membrane of  claim 71 , wherein said membrane has a conductance of less than about 5.0×10 −5  S/cm.  
     
     
         80 . The membrane of  claim 71 , wherein said membrane has a conductance of less than about 2.0×10 −5  S/cm.  
     
     
         81 . The membrane of  claim 71 , wherein said membrane has a conductance of less than about 5.0×10 −6  S/cm.  
     
     
         82 . The membrane of  claim 71 , wherein said membrane has a conductance of less than about 1.0×10 −6  S/cm.  
     
     
         83 . The membrane of  claim 71 , wherein the first polymer layer is LPEI; and wherein the second polymer layer is PAMPS.  
     
     
         84 . The membrane of  claim 71 , wherein the first polymer layer is LPEI; and the wherein the second polymer layer is SPS.  
     
     
         85 . The membrane of  claim 71 , wherein the first polymer layer is LPEI; and wherein the second polymer layer is PSSM.  
     
     
         86 . The membrane of  claim 71 , wherein the first polymer layer is LPEI; and wherein the second polymer layer is PAA.  
     
     
         87 . The membrane of  claim 71 , wherein the first polymer layer is PEO; and wherein the second polymer layer is PAA.  
     
     
         88 . The membrane of  claim 71 , wherein the first polymer layer is PAAm; and wherein the second polymer layer is PAA.  
     
     
         89 . The membrane of  claim 71 , wherein the first polymer layer is PAAm; and wherein the second polymer layer is PAA-coPAAm.  
     
     
         90 . The membrane of  claim 71 , wherein the first polymer layer is PDAC; and wherein the second polymer layer is PAA-co-PAAm.  
     
     
         91 . The membrane of  claim 71 , wherein the first polymer layer is PDAC; and wherein the second polymer layer is PAMPS.  
     
     
         92 . The membrane of  claim 71 , wherein the first polymer layer is PDME; and wherein the second polymer layer is PAMPS.  
     
     
         93 . The membrane of  claim 71 , wherein said membrane can be used as an ion-exchange membrane, a gas diffusion membrane or an electrode.  
     
     
         94 . The membrane of  claim 71 , wherein the said membrane can be used in a membrane-electrode assembly, a battery, a galvanic cell, an electrochemical cell, a micro-electrochemical cell, a catalytic converter, a solid-state hydrogen pump, an electrolyzer, or an electrochromic device.