# US 12,768,059 B2 · Hybrid ceramic membrane for water electrolysis application > Agents: this data is available as JSON from the patentgrep API and MCP server — see https://patentgrep.com/llms.txt - Number: US 12,768,059 B2 - Document ID: US12768059B2 - Status: Granted - Kind: B2 - Application number: 18/873,960 - Filed: 2023-06-19 - Published: 2025-12-11 - Granted: 2026-10-20 - Earliest claimed: 2022-06-22 - Assignees: Vito NV - Applicants: Vito NV - Inventors: Bart Molenberghs; Deepak Pant; Jan Vaes; Fady Nahra; Misgina Tilahun Tsehaye; Wim De Schepper - Web page: https://patentgrep.com/patent/US12768059B2 ## CPC - C25B 13/07: based on ceramics - C25B 1/04: by electrolysis of water - C25B 1/30: Peroxides - C25B: ELECTROLYTIC OR ELECTROPHORETIC PROCESSES FOR THE PRODUCTION OF COMPOUNDS OR NON-METALS; APPARATUS THEREFOR (anodic or cathodic protection C23F13/00; single-crystal growth C30B) ## Abstract The present invention relates to a method of manufacturing a dense composite polymeric-ceramic membrane, compromising the steps of casting a porous ceramic support layer comprising YSZ and TiO2 flakes, followed by thermal curing and sintering steps, coating the prepared porous ceramic support structure with a thin layer of TiO2 to vary the pore size distribution of the support structure and further densification by using ion selective polymers to reduce gas crossover while maintaining a high enough conductivity. ## Claims ### Claim 1 A dense composite polymeric-ceramic material consisting of: a sintered ceramic porous support layer composed of TiO2 nanoparticles, and at least another metal oxide nanoparticle, wherein the TiO2 nanoparticles, and the at least another metal oxide nanoparticle are bonded to each other, wherein the at least another metal oxide nanoparticle is selected from alumina (Al2O3), yttria stabilized zirconia (YSZ), yttria tetragonal zirconia polycrystal (Y-TZP), CeO2, CeO2 tetragonal ZrO2 polycrystal (Ce-TZP), ZrO2, SiO2, and SnO2, a porous coating layer of TiO2 nanoparticles coated onto the ceramic porous support layer, and a polymer filling the pores of both the ceramic porous support layer and the porous coating layer of TiO2 nanoparticles, wherein the polymer is selected from polysulfone (PSU), polypropylene oxide (PPO), an ion-exchange polymer, an ionomer, and combinations thereof. ### Claim 2 (depends on 1) The dense composite polymeric-ceramic material according to claim 1, wherein the ceramic porous support layer comprises an amount of the TiO2 nanoparticles in a range of about 1 wt % to about 20 wt % based on a total weight of the ceramic porous support layer. ### Claim 3 (depends on 2) The dense composite polymeric-ceramic material according to claim 2, wherein the ceramic porous support layer comprises TiO2 nanoparticles in a range of 5 wt % to 15 wt % of the ceramic porous support layer. ### Claim 4 (depends on 1) The dense composite polymeric-ceramic material according to claim 1, wherein the ceramic porous support layer comprises an amount of the at least another metal oxide nanoparticles in a range of about 50 wt % to about 80 wt % based on a total weight of the ceramic porous support layer. ### Claim 5 (depends on 4) The dense composite polymeric-ceramic material according to claim 4, wherein the ceramic porous support layer comprises the at least another metal oxide nanoparticles in a range of 60 wt % to 70 wt % of the ceramic porous support layer. ### Claim 6 (depends on 1) The dense composite polymeric-ceramic material according to claim 1, wherein the ceramic porous support layer has an average pore size in a range of about 80 nm to 200 nm. ### Claim 7 (depends on 1) The dense composite polymeric-ceramic material according to claim 1, wherein the dense composite polymeric-ceramic material is a membrane with a thickness between about 50 μm and 2000 μm. ### Claim 8 (depends on 7) The dense composite polymeric-ceramic material according to claim 7, wherein the dense composite polymeric-ceramic material is a membrane with a thickness between 50 μm and 200 μm. ### Claim 9 (depends on 1) The dense composite polymeric-ceramic material according to claim 1, wherein the porous coating layer of TiO2 nanoparticles has an average thickness between 0.5 mm and 5 mm, and pores with an average pore size distribution between 50 nm and 150 nm. ### Claim 10 (depends on 1) The dense composite polymeric-ceramic material according to claim 1, wherein the polymer filling the pores is carried out via polymer impregnation. ### Claim 11 (depends on 1) The dense composite polymeric-ceramic material according to claim 1, wherein the ionomer is selected from a halogen ionomer, an anion-containing ionomer, a hydrocarbon ionomer, and combinations thereof. ### Claim 12 (depends on 1) A fuel-cell comprising the dense composite polymeric-ceramic material according to claim 1. ### Claim 13 (depends on 1) A method of manufacturing the dense composite polymeric-ceramic material according to claim 1, comprising: combining TiO2 nanoparticles, at least another metal oxide nanoparticle, and a curable polymer resin to create a mixture, wherein the at least another metal oxide nanoparticle is selected from alumina (Al2O3), yttria stabilized zirconia (YSZ), yttria tetragonal zirconia polycrystal (Y-TZP), CeO2, CeO2 tetragonal ZrO2 polycrystal (Ce-TZP), ZrO2, SiO2, and SnO2; curing the mixture to obtain a first composite material; heating the first composite material to a first temperature for removing the polymer from said first composite material to obtain a second composite material; heating the second composite material to a second temperature for sintering the TiO2 nanoparticles, and the at least another metal oxide nanoparticle, thereby creating the ceramic porous support layer wherein the TiO2 nanoparticles, and the at least another metal oxide nanoparticle are bonded to each other; coating the ceramic porous support layer with a TiO2 suspension to obtain a TiO2-coated ceramic porous support layer; and filling the pores of the TiO2-coated ceramic porous support layer with a polymer selected from polysulfone (PSU), polypropylene oxide (PPO), an ion-exchange polymer, an ionomer, and combinations thereof. ### Claim 14 (depends on 13) The method of claim 13, wherein the curable polymer resin comprises is selected from an acrylate that is cross-linked using a thermal initiator or an ultraviolet (UV) light-activated initiator. ### Claim 15 (depends on 13) The method of claim 13, wherein the ceramic porous support layer comprises an amount of the TiO2 nanoparticles in a range of about 1 wt % to about 20 wt % based on a total weight of the ceramic porous support layer. ### Claim 16 (depends on 13) The method of claim 13, wherein the ceramic porous support layer comprises an amount of the at least another metal oxide nanoparticles in a range of about 50 wt % to about 80 wt % based on a total weight of the ceramic porous support layer. ### Claim 17 (depends on 13) The method of claim 13, wherein the TiO2 suspension comprises an amount of the TiO2 in a range of about 1 wt % to about 5 wt %. ### Claim 18 (depends on 13) The method of claim 13, wherein: the pores from a first side of the TiO2-coated ceramic porous support layer are filled with a first ionomer via diffusion of a solution of the first ionomer followed by precipitation of the first ionomer, and the pores from a second side of the TiO2-coated ceramic porous support layer are filled with a second ionomer via diffusion of a solution of the second ionomer followed by precipitation of the second ionomer. ### Claim 19 (depends on 13) The method of claim 13, wherein the at least another metal oxide nanoparticle comprises yttrium-doped zirconium oxide (Y2O3-doped ZrO2). ### Claim 20 (depends on 13) The method of claim 13, wherein the ceramic porous support layer comprises an amount of the TiO2 nanoparticles in a range of 5 wt % to 15 wt % based on a total weight of the ceramic porous support layer. ### Claim 21 (depends on 13) The method of claim 13, wherein the ceramic porous support layer comprises an amount of the at least another metal oxide nanoparticles in a range of 60 wt % to 70 wt % based on a total weight of the ceramic porous support layer.