# US 8,465,857 B2 · Proton exchange membranes (PEM) based on hybrid inorganic-organic copolymers with grafted phosphoric acid groups and implanted metal cations > Agents: this data is available as JSON from the patentgrep API and MCP server — see https://patentgrep.com/llms.txt - Number: US 8,465,857 B2 - Document ID: US8465857B2 - Status: Granted - Kind: B2 - Application number: 12/885,926 - Filed: 2010-09-20 - Published: 2011-01-13 - Granted: 2013-06-18 - Earliest claimed: 2004-05-13 - Assignees: Toyota Motor Engineering & Manufacturing North America, Inc. - Applicants: Wen Li; Siwen Li; Meilin Liu - Inventors: Wen Li; Siwen Li; Meilin Liu - Web page: https://patentgrep.com/patent/US8465857B2 ## CPC - C08G 77/395: containing phosphorus - B01D 67/00091: {by evaporation} - B01D 67/0048: {by sol-gel transition} - B01D 67/00793: {Dispersing a component, e.g. as particles or powder, in another component} - B01D 67/00931: {by introduction of specific groups after membrane formation, e.g. by grafting} - B01D 69/148: {Organic/inorganic mixed matrix membranes} - B01D 71/00: Semi-permeable membranes for separation processes or apparatus characterised by the material; Manufacturing processes specially adapted therefor - B01D 71/70: Polymers having silicon in the main chain, with or without sulfur, nitrogen, oxygen or carbon only - C08G 77/58: Metal-containing linkages - C08J 5/2256: {based on macromolecular compounds obtained by reactions other than those involving carbon-to-carbon bonds, e.g. obtained by polycondensation} - H01M 8/1037: having silicon, e.g. sulfonated crosslinked polydimethylsiloxanes - H01M 8/1048: Ion-conducting additives, e.g. ion-conducting particles, heteropolyacids, metal phosphate or polybenzimidazole with phosphoric acid - H01M 8/1074: {Sol-gel processes} - B01D 2323/38: Graft polymerization - B01D 2325/26: Electrical properties - B01D 2325/42: Ion-exchange membranes - C08J 2383/14: in which at least two but not all the silicon atoms are connected by linkages other than oxygen atoms (C08J2383/10 takes precedence) - Y02E 60/50: Fuel cells - Y02P 70/50: Manufacturing or production processes characterised by the final manufactured product - C08G: MACROMOLECULAR COMPOUNDS OBTAINED OTHERWISE THAN BY REACTIONS ONLY INVOLVING UNSATURATED CARBON-TO-CARBON BONDS - B01D: SEPARATION (separating solids from solids by wet methods B03B, B03D; by pneumatic jigs or tables B03B; by other dry methods B07; magnetic or electrostatic separation of solid materials from solid materials or fluids, separation by high-voltage electric fields B03C; centrifuges, vortex apparatus B04; presses per se for squeezing-out liquid from liquid-containing material B30B9/02; treatment of water C02F, e.g. softening by ion-exchange C02F1/42; {arrangements of air intake cleaners in gas turbine plants F02C7/05} ; arrangements or mounting of filters in air-conditioning, air-humidification or ventilation F24F13/28) - C08J: WORKING-UP; GENERAL PROCESSES OF COMPOUNDING; AFTER-TREATMENT NOT COVERED BY SUBCLASSES C08B, C08C, C08F, C08G or C08H (working, e.g. shaping, of plastics B29) - H01M: PROCESSES OR MEANS, e.g. BATTERIES, FOR THE DIRECT CONVERSION OF CHEMICAL ENERGY INTO ELECTRICAL ENERGY - Y02E: REDUCTION OF GREENHOUSE GAS [GHG] EMISSIONS, RELATED TO ENERGY GENERATION, TRANSMISSION OR DISTRIBUTION - Y02P: CLIMATE CHANGE MITIGATION TECHNOLOGIES IN THE PRODUCTION OR PROCESSING OF GOODS ## Abstract A proton exchange membrane comprises a hybrid inorganic-organic polymer that includes implanted metal cations. Acid groups are bound to the hybrid inorganic-organic polymer through an interaction with the implanted metal cations. An example process for manufacturing a proton exchange membrane includes sol-gel polymerization of silane precursors in a medium containing the metal cations, followed by exposure of the metal-implanted hybrid inorganic-organic polymer to an acid compound. ## Claims ### Claim 1 A process for making a proton-exchange membrane, the process comprising: forming a metal-implanted hybrid inorganic-organic polymer through a sol-gel polymerization of one or more silane precursors in a medium containing metal cations, the metal-implanted hybrid inorganic-organic polymer having an inorganic portion comprising silicon, oxygen, and implanted metal cations; and exposing the metal-implanted hybrid inorganic-organic polymer to an acid compound, so as to form the proton-exchange membrane, the acid compound directly attaching to the metal-implanted hybrid inorganic-organic polymer through an interaction between the acid compound and the implanted metal cations, the acid compound being selected from a group of compounds consisting of free mineral acids and organic acids, the interaction between the implanted metal cations and the acid compound having an electron withdrawing effect on the acid compound, so as to increase proton mobility within the proton-exchange membrane. ### Claim 2 (depends on 1) The process of claim 1, the acid compound including a phosphoric acid group. ### Claim 3 (depends on 1) The process of claim 1, wherein the acid compound is represented by the formula A-L-B, wherein A is an acid group, L is a linking group or a chemical bond, and B is a group including a second acid group or an aromatic heterocycle including at least one heteroatom selected from the group consisting of N, O, and S. ### Claim 4 (depends on 3) The process of claim 3, wherein B is a group including an aromatic nitrogen-containing heterocycle. ### Claim 5 (depends on 3) The process of claim 3, wherein A is a phosphonic acid group. ### Claim 6 (depends on 1) The process of claim 1, wherein the one or more silane precursors include at least a first silane and a second silane. ### Claim 7 (depends on 1) The process of claim 1, wherein the medium containing the metal cations is a medium including a dissolved alkoxymetal compound. ### Claim 8 (depends on 1) The process of claim 1, wherein exposing the metal-implanted hybrid inorganic-organic polymer to an acid compound includes infusing a solution of the acid compound into the metal-implanted hybrid inorganic-organic polymer. ### Claim 9 (depends on 1) The process of claim 1, wherein the metal cations are cations of one or more metals selected from the group of metals consisting of Mg, Ca, Sr, Ba, Al, Fe, W, Zn, Mn, Zr, Mo, Nb, Ti, V, Co, Pb, Ga, In, Ge, and Sn. ### Claim 10 (depends on 1) The process of claim 1, wherein the metal cations are cations of one or more metals selected from the group consisting of alkaline-earth metals, transition metals, rare-earth metals, group 13 metals, and group 14 metals. ### Claim 11 (depends on 1) The process of claim 1, wherein forming the metal-implanted hybrid inorganic-organic polymer comprises: providing a medium including one or more silane precursors and a hydrolysable metal compound; and initiating a sol-gel process, the sol-gel process including hydrolysis of the of the one or more silane precursors and hydrolysis of the hydrolysable metal compound. ### Claim 12 (depends on 11) The process of claim 11, wherein the hydrolysable metal compound is an alkoxymetal compound. ### Claim 13 (depends on 1) The process of claim 1, wherein the metal cations are cations of one or more metals selected from the group consisting of titanium, zirconium, and aluminum. ### Claim 14 (depends on 1) The process of claim 1, wherein the metal cations are zirconium cations. ### Claim 15 (depends on 1) The process of claim 1, wherein the inorganic portion of the hybrid inorganic-organic polymer includes regions having a structure -A-O—Si—, wherein A represents the implanted metal cation.