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WO2025099742A1 - Matériau composite pour piles à combustible, son procédé de préparation et ses applications - Google Patents

Matériau composite pour piles à combustible, son procédé de préparation et ses applications Download PDF

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Publication number
WO2025099742A1
WO2025099742A1 PCT/IN2024/052180 IN2024052180W WO2025099742A1 WO 2025099742 A1 WO2025099742 A1 WO 2025099742A1 IN 2024052180 W IN2024052180 W IN 2024052180W WO 2025099742 A1 WO2025099742 A1 WO 2025099742A1
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composite material
electrode
carbon
metal
range
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Ajmal PANDIKASSALA
Mayank Udaypratap SINGH
Varsha NADUMATTUVAYIL
Athira YOYAKKI
Sreekumar Kurungot
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Council of Scientific and Industrial Research CSIR
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    • H—ELECTRICITY
    • H01—ELECTRIC ELEMENTS
    • H01M—PROCESSES OR MEANS, e.g. BATTERIES, FOR THE DIRECT CONVERSION OF CHEMICAL ENERGY INTO ELECTRICAL ENERGY
    • H01M8/00—Fuel cells; Manufacture thereof
    • H01M8/10—Fuel cells with solid electrolytes
    • H01M8/1016—Fuel cells with solid electrolytes characterised by the electrolyte material
    • H01M8/1018—Polymeric electrolyte materials
    • C—CHEMISTRY; METALLURGY
    • C23—COATING METALLIC MATERIAL; COATING MATERIAL WITH METALLIC MATERIAL; CHEMICAL SURFACE TREATMENT; DIFFUSION TREATMENT OF METALLIC MATERIAL; COATING BY VACUUM EVAPORATION, BY SPUTTERING, BY ION IMPLANTATION OR BY CHEMICAL VAPOUR DEPOSITION, IN GENERAL; INHIBITING CORROSION OF METALLIC MATERIAL OR INCRUSTATION IN GENERAL
    • C23C—COATING METALLIC MATERIAL; COATING MATERIAL WITH METALLIC MATERIAL; SURFACE TREATMENT OF METALLIC MATERIAL BY DIFFUSION INTO THE SURFACE, BY CHEMICAL CONVERSION OR SUBSTITUTION; COATING BY VACUUM EVAPORATION, BY SPUTTERING, BY ION IMPLANTATION OR BY CHEMICAL VAPOUR DEPOSITION, IN GENERAL
    • C23C18/00—Chemical coating by decomposition of either liquid compounds or solutions of the coating forming compounds, without leaving reaction products of surface material in the coating; Contact plating
    • C23C18/02—Chemical coating by decomposition of either liquid compounds or solutions of the coating forming compounds, without leaving reaction products of surface material in the coating; Contact plating by thermal decomposition
    • C23C18/08—Chemical coating by decomposition of either liquid compounds or solutions of the coating forming compounds, without leaving reaction products of surface material in the coating; Contact plating by thermal decomposition characterised by the deposition of metallic material
    • C—CHEMISTRY; METALLURGY
    • C23—COATING METALLIC MATERIAL; COATING MATERIAL WITH METALLIC MATERIAL; CHEMICAL SURFACE TREATMENT; DIFFUSION TREATMENT OF METALLIC MATERIAL; COATING BY VACUUM EVAPORATION, BY SPUTTERING, BY ION IMPLANTATION OR BY CHEMICAL VAPOUR DEPOSITION, IN GENERAL; INHIBITING CORROSION OF METALLIC MATERIAL OR INCRUSTATION IN GENERAL
    • C23C—COATING METALLIC MATERIAL; COATING MATERIAL WITH METALLIC MATERIAL; SURFACE TREATMENT OF METALLIC MATERIAL BY DIFFUSION INTO THE SURFACE, BY CHEMICAL CONVERSION OR SUBSTITUTION; COATING BY VACUUM EVAPORATION, BY SPUTTERING, BY ION IMPLANTATION OR BY CHEMICAL VAPOUR DEPOSITION, IN GENERAL
    • C23C18/00—Chemical coating by decomposition of either liquid compounds or solutions of the coating forming compounds, without leaving reaction products of surface material in the coating; Contact plating
    • C23C18/16—Chemical coating by decomposition of either liquid compounds or solutions of the coating forming compounds, without leaving reaction products of surface material in the coating; Contact plating by reduction or substitution, e.g. electroless plating
    • C23C18/1601—Process or apparatus
    • C23C18/1633—Process of electroless plating
    • C23C18/1635—Composition of the substrate
    • C—CHEMISTRY; METALLURGY
    • C23—COATING METALLIC MATERIAL; COATING MATERIAL WITH METALLIC MATERIAL; CHEMICAL SURFACE TREATMENT; DIFFUSION TREATMENT OF METALLIC MATERIAL; COATING BY VACUUM EVAPORATION, BY SPUTTERING, BY ION IMPLANTATION OR BY CHEMICAL VAPOUR DEPOSITION, IN GENERAL; INHIBITING CORROSION OF METALLIC MATERIAL OR INCRUSTATION IN GENERAL
    • C23C—COATING METALLIC MATERIAL; COATING MATERIAL WITH METALLIC MATERIAL; SURFACE TREATMENT OF METALLIC MATERIAL BY DIFFUSION INTO THE SURFACE, BY CHEMICAL CONVERSION OR SUBSTITUTION; COATING BY VACUUM EVAPORATION, BY SPUTTERING, BY ION IMPLANTATION OR BY CHEMICAL VAPOUR DEPOSITION, IN GENERAL
    • C23C18/00—Chemical coating by decomposition of either liquid compounds or solutions of the coating forming compounds, without leaving reaction products of surface material in the coating; Contact plating
    • C23C18/16—Chemical coating by decomposition of either liquid compounds or solutions of the coating forming compounds, without leaving reaction products of surface material in the coating; Contact plating by reduction or substitution, e.g. electroless plating
    • C23C18/1601—Process or apparatus
    • C23C18/1633—Process of electroless plating
    • C23C18/1646—Characteristics of the product obtained
    • C23C18/1648—Porous product
    • C—CHEMISTRY; METALLURGY
    • C23—COATING METALLIC MATERIAL; COATING MATERIAL WITH METALLIC MATERIAL; CHEMICAL SURFACE TREATMENT; DIFFUSION TREATMENT OF METALLIC MATERIAL; COATING BY VACUUM EVAPORATION, BY SPUTTERING, BY ION IMPLANTATION OR BY CHEMICAL VAPOUR DEPOSITION, IN GENERAL; INHIBITING CORROSION OF METALLIC MATERIAL OR INCRUSTATION IN GENERAL
    • C23C—COATING METALLIC MATERIAL; COATING MATERIAL WITH METALLIC MATERIAL; SURFACE TREATMENT OF METALLIC MATERIAL BY DIFFUSION INTO THE SURFACE, BY CHEMICAL CONVERSION OR SUBSTITUTION; COATING BY VACUUM EVAPORATION, BY SPUTTERING, BY ION IMPLANTATION OR BY CHEMICAL VAPOUR DEPOSITION, IN GENERAL
    • C23C18/00—Chemical coating by decomposition of either liquid compounds or solutions of the coating forming compounds, without leaving reaction products of surface material in the coating; Contact plating
    • C23C18/16—Chemical coating by decomposition of either liquid compounds or solutions of the coating forming compounds, without leaving reaction products of surface material in the coating; Contact plating by reduction or substitution, e.g. electroless plating
    • C23C18/31—Coating with metals
    • C23C18/42—Coating with noble metals
    • C—CHEMISTRY; METALLURGY
    • C23—COATING METALLIC MATERIAL; COATING MATERIAL WITH METALLIC MATERIAL; CHEMICAL SURFACE TREATMENT; DIFFUSION TREATMENT OF METALLIC MATERIAL; COATING BY VACUUM EVAPORATION, BY SPUTTERING, BY ION IMPLANTATION OR BY CHEMICAL VAPOUR DEPOSITION, IN GENERAL; INHIBITING CORROSION OF METALLIC MATERIAL OR INCRUSTATION IN GENERAL
    • C23C—COATING METALLIC MATERIAL; COATING MATERIAL WITH METALLIC MATERIAL; SURFACE TREATMENT OF METALLIC MATERIAL BY DIFFUSION INTO THE SURFACE, BY CHEMICAL CONVERSION OR SUBSTITUTION; COATING BY VACUUM EVAPORATION, BY SPUTTERING, BY ION IMPLANTATION OR BY CHEMICAL VAPOUR DEPOSITION, IN GENERAL
    • C23C18/00—Chemical coating by decomposition of either liquid compounds or solutions of the coating forming compounds, without leaving reaction products of surface material in the coating; Contact plating
    • C23C18/16—Chemical coating by decomposition of either liquid compounds or solutions of the coating forming compounds, without leaving reaction products of surface material in the coating; Contact plating by reduction or substitution, e.g. electroless plating
    • C23C18/48—Coating with alloys
    • C—CHEMISTRY; METALLURGY
    • C23—COATING METALLIC MATERIAL; COATING MATERIAL WITH METALLIC MATERIAL; CHEMICAL SURFACE TREATMENT; DIFFUSION TREATMENT OF METALLIC MATERIAL; COATING BY VACUUM EVAPORATION, BY SPUTTERING, BY ION IMPLANTATION OR BY CHEMICAL VAPOUR DEPOSITION, IN GENERAL; INHIBITING CORROSION OF METALLIC MATERIAL OR INCRUSTATION IN GENERAL
    • C23C—COATING METALLIC MATERIAL; COATING MATERIAL WITH METALLIC MATERIAL; SURFACE TREATMENT OF METALLIC MATERIAL BY DIFFUSION INTO THE SURFACE, BY CHEMICAL CONVERSION OR SUBSTITUTION; COATING BY VACUUM EVAPORATION, BY SPUTTERING, BY ION IMPLANTATION OR BY CHEMICAL VAPOUR DEPOSITION, IN GENERAL
    • C23C18/00—Chemical coating by decomposition of either liquid compounds or solutions of the coating forming compounds, without leaving reaction products of surface material in the coating; Contact plating
    • C23C18/16—Chemical coating by decomposition of either liquid compounds or solutions of the coating forming compounds, without leaving reaction products of surface material in the coating; Contact plating by reduction or substitution, e.g. electroless plating
    • C23C18/48—Coating with alloys
    • C23C18/50—Coating with alloys with alloys based on iron, cobalt or nickel
    • H—ELECTRICITY
    • H01—ELECTRIC ELEMENTS
    • H01M—PROCESSES OR MEANS, e.g. BATTERIES, FOR THE DIRECT CONVERSION OF CHEMICAL ENERGY INTO ELECTRICAL ENERGY
    • H01M4/00—Electrodes
    • H01M4/86—Inert electrodes with catalytic activity, e.g. for fuel cells
    • H01M4/90—Selection of catalytic material
    • H01M4/9075—Catalytic material supported on carriers, e.g. powder carriers
    • H01M4/9083—Catalytic material supported on carriers, e.g. powder carriers on carbon or graphite
    • H—ELECTRICITY
    • H01—ELECTRIC ELEMENTS
    • H01M—PROCESSES OR MEANS, e.g. BATTERIES, FOR THE DIRECT CONVERSION OF CHEMICAL ENERGY INTO ELECTRICAL ENERGY
    • H01M4/00—Electrodes
    • H01M4/86—Inert electrodes with catalytic activity, e.g. for fuel cells
    • H01M4/90—Selection of catalytic material
    • H01M4/92—Metals of platinum group
    • H01M4/925—Metals of platinum group supported on carriers, e.g. powder carriers
    • H01M4/926—Metals of platinum group supported on carriers, e.g. powder carriers on carbon or graphite
    • H—ELECTRICITY
    • H01—ELECTRIC ELEMENTS
    • H01M—PROCESSES OR MEANS, e.g. BATTERIES, FOR THE DIRECT CONVERSION OF CHEMICAL ENERGY INTO ELECTRICAL ENERGY
    • H01M8/00—Fuel cells; Manufacture thereof
    • H01M8/10—Fuel cells with solid electrolytes
    • H01M8/1004—Fuel cells with solid electrolytes characterised by membrane-electrode assemblies [MEA]
    • B—PERFORMING OPERATIONS; TRANSPORTING
    • B82—NANOTECHNOLOGY
    • B82Y—SPECIFIC USES OR APPLICATIONS OF NANOSTRUCTURES; MEASUREMENT OR ANALYSIS OF NANOSTRUCTURES; MANUFACTURE OR TREATMENT OF NANOSTRUCTURES
    • B82Y30/00—Nanotechnology for materials or surface science, e.g. nanocomposites
    • H—ELECTRICITY
    • H01—ELECTRIC ELEMENTS
    • H01M—PROCESSES OR MEANS, e.g. BATTERIES, FOR THE DIRECT CONVERSION OF CHEMICAL ENERGY INTO ELECTRICAL ENERGY
    • H01M8/00—Fuel cells; Manufacture thereof
    • H01M8/10—Fuel cells with solid electrolytes
    • H01M2008/1095—Fuel cells with polymeric electrolytes
    • Y—GENERAL TAGGING OF NEW TECHNOLOGICAL DEVELOPMENTS; GENERAL TAGGING OF CROSS-SECTIONAL TECHNOLOGIES SPANNING OVER SEVERAL SECTIONS OF THE IPC; TECHNICAL SUBJECTS COVERED BY FORMER USPC CROSS-REFERENCE ART COLLECTIONS [XRACs] AND DIGESTS
    • Y02—TECHNOLOGIES OR APPLICATIONS FOR MITIGATION OR ADAPTATION AGAINST CLIMATE CHANGE
    • Y02E—REDUCTION OF GREENHOUSE GAS [GHG] EMISSIONS, RELATED TO ENERGY GENERATION, TRANSMISSION OR DISTRIBUTION
    • Y02E60/00—Enabling technologies; Technologies with a potential or indirect contribution to GHG emissions mitigation
    • Y02E60/30—Hydrogen technology
    • Y02E60/50—Fuel cells

Definitions

  • the present invention generally relates to fuel cells, specifically the Proton Exchange Membrane Fuel Cell (PEMFC).
  • PEMFC Proton Exchange Membrane Fuel Cell
  • the present invention relates to a composite material for coating electrode(s) or membrane placed between electrodes in fuel cells, comprising Ml metal nanoparticles dispersed or anchored over nitrogen doped 3D graphitic carbon; and a process of preparation thereof.
  • the present invention relates to a composition for fuel cells comprising an effective amount or ratio of polymer based solid electrolyte (also can be termed as ionomer) and the composite material.
  • the invention also relates to half PEM fuel cell and/or full PEM fuel cell comprising said composite material.
  • PEMFCs Polymer electrolyte membrane fuel cells
  • ORR oxygen reduction reaction
  • mass transport restrictions at high current densities caused by the liquid water. Efficient removal of water from the cathode side of the fuel cell is often problematic, resulting in compromised oxygen transfer to the cathode electrode's reaction sites.
  • catalyst support materials play a crucial role in regulating various properties, including providing a large specific surface area, facilitating rapid electron transfer during reactions through superior electrical conductivity, ensuring excellent electrochemical stability in challenging operating conditions, and effectively immobilizing the catalyst to enhance the triple phase boundaries in the fuel cell electrodes.
  • Pt nanoparticle supported on carbon black (Pt/C) is considered as the state-of-the-art electrocatalyst for ORR occurring at the cathode (refer, Ashkan Koushanpour et al., ACS Appl. Mater. Interfaces 2022, 14, 17, pages 19285-19294).
  • the PEMFC’s efficiency declines as a consequence of the electrochemical oxidation of the supporting material, leading to catalyst detachment and simultaneous agglomeration, which restricts its real-world usage.
  • said Pt/C suffers from other disadvantages or limitations like low surface area, not efficient gas/H 2 /O 2 flow, and flooding which causes lower electrochemical reaction and analysis along with longer activation time required, and lesser stability of material towards electrochemical condition.
  • An objective of the present invention is to provide a composite material for coating electrode(s) or membrane of fuel cells, the composite material comprising Ml metal nanoparticles dispersed or anchored over nitrogen doped 3D graphitic carbon.
  • Another objective of the present invention is to provide a process of preparation of said composite material comprising Ml metal nanoparticles dispersed or anchored over nitrogen doped 3D graphitic carbon.
  • Another objective of the present invention is to provide a composition for fuel cells comprising an effective amount or ratio of polymer based solid electrolyte and the composite material, wherein said polymer based solid electrolytes act as proton exchange material.
  • Yet another objective of the present invention is to provide a half PEM fuel cell comprising said composite material as a coating layer onto electrode(s) or membrane placed over/in between electrode(s).
  • Another objective of the present invention is to provide a full PEM fuel cell comprising said composite material as a coating layer onto electrode(s) or membrane placed over/in between electrode(s).
  • the present invention provides a composite material for coating electrode(s) or membrane of fuel cells, the composite material comprising: i. Ml metal nanoparticles, and ii. nitrogen doped 3D graphitic carbon; wherein the Ml metal nanoparticles are dispersed or anchored over said nitrogen doped 3D graphitic carbon; and wherein the metal of said Ml metal nanoparticles is selected from a noble metal, alloy of noble metals, and alloy of noble metal and transition metal.
  • the noble metal is selected from platinum, palladium, silver, ruthenium, rhodium, and iridium.
  • the transition metal is selected from cobalt, nickel, tin, manganese, copper, and tungsten.
  • the surface area of the composite material is in the range of around 950 to 1000 m 2 /g.
  • the composite material is microporous in nature with microporosity below 2 nm or in the range of 0.2 to 2 nm.
  • the particle size of the Ml metal nanoparticles is in the range of 0.5 to 10 nm.
  • the pore volume of the composite material is in the range of 0.5 to 0.9 cc/g.
  • the present invention provides a process of preparation of composite material, the process comprising steps of: i) preparing oxidative polymerized intermediate by reacting melamine sponge or polyurethane sponge with polydopamine or catechol containing polymer in the presence of buffer at temperature in the range of 20-40 °C for a time period of 20 to 28 h to form the oxidative polymerized intermediate; ii) annealing the intermediate of i) at a temperature in the range of 800 to 1000 °C for a time period in the range of 2 to 4 h under an inert atmosphere to obtain an annealed product of nitrogen doped 3D carbon; and iii) decorating or anchoring Ml metal nanoparticles onto said annealed product of nitrogen doped 3D carbon of ii) by reacting Ml metal precursor with said annealed product of ii) in the presence of polyol or mixture of polyol and water at a temperature in the range of 110 to 150 °C for a time period in the
  • the metal in said Ml metal precursor is selected from noble metal, alloy of noble metals, and alloy of noble metal and transition metal.
  • the noble metal is selected from platinum, palladium, silver, ruthenium, rhodium, and iridium.
  • the transition metal is selected from cobalt, nickel, tin, manganese, copper and tungsten.
  • the Ml metal precursor is selected from chloroplatinic acid, potassium hexachloroplatinate, platinum(II) acetylacetonate, palladium(II) nitrate, palladium(II) chloride, tetraamminepalladium(II) chloride monohydrate, nickel(II) chloride, nickel(II) nitrate, nickel(II) acetylacetonate, cobalt(II) acetylacetonate, cobalt(II) nitrate hexahydrate, cobalt(II) chloride and combinations thereof.
  • the polyol is selected from ethylene glycol, propylene glycol (PG), glycerol, diethylene glycol (DEG), triethylene glycol (TEG), 1,2 -butanediol and combinations thereof.
  • the buffer used in step i) is selected from bicarbonate buffer, tris-HCl Buffer (Tris(hydroxymethyl)aminomethane), Bicine (N,N-Bis(2-hydroxyethyl)glycine), Glycine-NaOH Buffer and combinations thereof.
  • the process comprises acid-washing of an annealed product of nitrogen doped 3D carbon of ii) with 0.5 M of acid H 2 SO 4 at a temperature in the range of 60 to 100 °C for a time period in the range of 3 to 5 h, followed by at least three times washing with deionized (DI) water and subsequent drying.
  • DI deionized
  • the present invention provides a composition for fuel cells, comprising: an effective amount or ratio of polymer based solid electrolyte and the composite material, wherein said polymer based solid electrolyte act as proton exchange material; and wherein the ratio of polymer based solid electrolyte and the graphitic carbon of the composite material is in range of 0.4 to 0.8.
  • the polymer based solid electrolyte is in aqueous solution form and is selected from nafion, polybenzimidazole (PBI), sulfonated polyether ether ketone (SPEEK), poly(arylene ether sulfone) (PAES), poly(phenylene oxide) (PPG), and polyimide (PI).
  • PBI polybenzimidazole
  • SPEEK sulfonated polyether ether ketone
  • PAES poly(arylene ether sulfone)
  • PPG poly(phenylene oxide)
  • PI polyimide
  • the aqueous solution of polymer based solid electrolyte is in concentration ranging between 5 to 20% w/v.
  • the present invention provides a half PEM fuel cell comprising: a) working electrode, b) the counter electrode, c) reference electrode, d) proton exchange membrane, e) electrolyte, and f) the composite material, wherein the composite material is present in the fuel cell as coating layer onto said working electrode or as a membrane placed over/in between electrodes of a), b) or c).
  • the working electrode is selected from a carbon electrode, glassy carbon electrode, gas diffusion layer, carbon cloth, nickel foam/mesh coated with carbon.
  • the counter electrode is selected from graphite rod, platinum rod, and platinum mesh.
  • the reference electrode is selected from Ag/AgCl electrode, Hg/Hg 2 SO 4 , standard hydrogen electrode, Hg/HgO, standard calomel electrode.
  • the electrolyte is selected from perchloric acid, sulphuric acid, hydrocholric acid, potassium hydroxide, sodium hydroxide.
  • the present invention provides a full PEM fuel cell comprising: a) a cathode, b) an anode, c) gas diffusion layer, d) proton exchange membrane, e) electrolyte and f) said composite material, wherein the composite material is present in the fuel cell as coating layer onto said cathode,
  • the full PEM fuel cell comprises a membrane electrode assembly (ME A) made by sandwiching anode, proton exchange membrane, and cathode.
  • ME A membrane electrode assembly
  • Fig. 1 shows a schematic representation of the synthesis of Pt/3D-PDC.
  • Fig. 2 shows A) FESEM image of bare melamine sponge; B) and C) FESEM images of polydopamine coated and annealed melamine sponge; D) FEESEM image Pt/3DPDPC; and E) and F) TEM images of Pt/3DPDC, and G) the particle size distribution.
  • Fig. 3 shows A) the XRD profile of Pt/3DPDC, B) the comparative Raman spectra of Pt/C (JM) and Pt/3DPPDC, and C) the deconvoluted Pt4f XPS profile of Pt/3DPDC.
  • Fig. 4 shows a) The CV profiles of Pt/C (JM) and Pt/3DPDC recorded in 0.1 m HCIO 4 recorded at a scan rate of 50 mV s -1 ; and shows b) LSV comparison of Pt/C (JM) and Pt/3DPDC in 0.1 M HCIO 4 at an electrode rotation speed of 1600 rpm.
  • Fig. 6 shows comparative I-V polarization curves recorded in a single-cell mode on the membrane electrode assemblies (MEAs) based on Pt/3DPDPC and Pt/C (JM).
  • Fig. 7 shows a representative illustration of a full PEM fuel cell.
  • Fig. 8 shows a representative illustration of a half-cell setup.
  • Fig. 9 shows comparative I-V polarization curves recorded in single-cell mode on membrane electrode assemblies (MEAs) based on Pt/3DPDPC with lower & higher n/c ratios.
  • n/c ratio means ratio of polymer based solid electrolyte and the graphitic carbon of the composite material.
  • composite material comprises Ml metal nanoparticles, and nitrogen doped 3D graphitic carbon; wherein the Ml metal nanoparticles are dispersed or anchored over said nitrogen doped 3D graphitic carbon.
  • catalyst NPs metal nanoparticles acting as metal catalyst.
  • support material used herein means nitrogen doped 3D graphitic carbon.
  • membrane polymer membrane
  • material placed between electrodes used herein having the same meaning and are used interchangeably throughout the specification with meaning a component or material used in fuel cells, on which the composite material is coated, and here the triple phase boundary (TPB) of gas, liquid and solid is forming where the membrane is solid part of TPB.
  • TPB triple phase boundary
  • the examples of membranes are selected from but not limited to nafion, PBI, SPEEK, PAES, PPO and PI, all are in solid membrane form.
  • ionomers and “polymer based solid electrolyte” used herein having the same meaning and used interchangeably throughout the specification, with the meaning of forming TPB of gas, liquid, and solid is forming where the ionomer is the liquid part of TPB.
  • membranes are selected from but not limited to Nafion, PBI, SPEEK, PAES, PPO, and PI, all are in liquid or aqueous solution form.
  • the present invention provides an incorporation of heteroatoms, like nitrogen, into the graphene structure and offers several benefits. Firstly, it accelerates the catalyst's nucleation and growth, leading to a smaller size and even distribution. Secondly, it strengthens the chemical bonding between the catalyst and support, resulting in improved stability. Lastly, it enhances electronic conductivity by modifying the electronic structure. Nitrogen has been considered an excellent dopant for graphene due to its high electronegativity and similar atomic size to carbon, making it the preferred choice among other dopants. Typically, the Pt nanoparticles are not fully exposed at the edges of the carbon support, leading to reduced activity as only a limited number of active centres are utilized. To address this issue, arranging the Pt nanoparticles within a three- dimensional (3D) carbon support structure can significantly boost the catalyst's overall activity by providing more accessible active centers.
  • 3D three- dimensional
  • the inventors have developed a simple strategy to overcome issues related to water management, mass transfer, charge transfer, and catalyst utilization.
  • the size, shape, and distribution of the catalyst nanoparticles on the support materials significantly impact the device's performance. Additionally, support materials are crucial in regulating the properties of the catalyst, including high specific surface area, superior electrical conductivity for rapid electron transfer during the reactions, good electrochemical stability under harsh operating conditions, and strong immobilization of the catalyst to improve the triple phase boundaries in the PEMFC electrodes.
  • the present invention provides a composite material for coating electrode(s) or membrane of fuel cells, the composite material comprising: a) Ml metal nanoparticles, and b) nitrogen doped 3D graphitic carbon; wherein the Ml metal nanoparticles are dispersed or anchored over said nitrogen doped 3D graphitic carbon.
  • the Ml metal is selected from noble metal elements or alloys forms or combinations thereof.
  • the Ml metal is selected from noble metals such as platinum, palladium, silver, ruthenium, rhodium, iridium, or platinum alloys combined with other noble metals.
  • the surface area of the composite material is in the range of around 950 to 1000 m 2 /g; the composite material is microporous in nature with microporosity below 2 nm; and the pore volume of the composite material is in range of 0.5 to 0.9 cc/g.
  • the Ml metal is selected from but not limited to Group X element, a mixture thereof, or alloy form thereof.
  • the dispersion or anchoring comprises the presence of Ml NPs with an average particle size of more than or equal to 2.5 nm and less than or equal to 10 nm.
  • the dispersion or anchoring comprises the presence of Ml NPs with an average particle size of less than or equal to 2.5 nm and more than or equal to 0.5 nm.
  • the dispersion or anchoring comprises the presence of Ml NPs with an average particle size of approximately 2.5 nm.
  • Said smaller or nanometer sized particles possess a larger surface area relative to their volume, which allows for an increased number of active sites, thereby enhancing catalytic activity. For instance, as particle size decreases, the electrochemical active surface area (ECSA) increases, leading to higher mass activity and specific activity in catalysis in fuel cells.
  • ECSA electrochemical active surface area
  • the dispersion or anchoring comprises the presence of Ml NPs throughout or onto the surface of the nitrogen doped 3D graphitic carbon.
  • the surface area of the composite material is around 993.7 m 2 /g
  • the composite material is microporous in nature.
  • the composite material comprises particles with microporosity in the range of 1.6-2 nm.
  • the Ml nanoparticles uniformly dispersed over the network-structured carbon in said composite material.
  • Fig. 2e and 2f which confirms the uniform distribution of Ml nanoparticles over the network structured carbon.
  • Fig. 2g depicts the Ml nanoparticle size distribution over the network structured carbon
  • the composite material comprises a mesh like structure formed for nitrogen doped 3D graphitic carbon having microporous nature.
  • the composite material comprises higher active sites for Ml metal NPs in said nitrogen doped 3D graphitic carbon as interconnected network like structure.
  • Said Mesh like structure/specific orientation present in said nitrogen doped 3D structured graphitic carbon allows the smooth flow of gases/liquids/electrolyte in fuel cells.
  • the commercial Pt/C has a lesser surface area of around 250-300 and 450-500 m 2 /g; and in contrast, the surface area of said composite material is higher i.e., in the range of 993.7 m 2 /g.
  • the present invention relates to a process of preparation of said composite material comprising Ml metal nanoparticles dispersed or anchored over nitrogen doped 3D graphitic carbon, the process comprising steps of: i) preparing oxidative polymerized intermediate by reacting melamine sponge or polyurethane sponge with polydopamine or catechol containing polymer in the presence of buffer at temperature in the range of 20-40 °C for a time period of 20 to 28 h to form oxidative polymerized intermediate product; ii) annealing the intermediate product of step i) at a temperature in the range of 800 to 1000 °C for time period in the range of 2 to 4 h under an inert atmosphere to obtain an annealed product of nitrogen doped 3D carbon; and iii) decorating or anchoring Ml metal onto said annealed product of nitrogen doped 3D carbon of step ii) by reacting Ml metal precursor with said annealed product of nitrogen doped 3D carbon of step ii) in the presence
  • the Ml metal precursor is selected from chloroplatinic acid, potassium hexachloroplatinate, platinum(II) acetylacetonate, palladiumc(II) nitrate, plladium(II) chloride, tetraamminepalladium(II) chloride monohydrate, nickel(II) chloride, nickel(II) nitrate, nickel(II) acetylacetonate, cobalt(II) acetylacetonate, cobalt(II) nitrate hexahydrate, cobalt(II) chloride and combinations thereof;
  • the polyol is selected from ethylene glycol, propylene glycol (PG), glycerol, diethylene glycol (DEG), triethylene glycol (TEG), 1,2-butanediol, and combinations thereof; and the buffer used in step i) is selected from bicarbonate buffer, tris-HCl Buffer (Tris(hydroxymethyl)aminomethanethan
  • the Ml metal precursor is selected from but not limited to acetate, chlorides, sulfates or phosphates of Ml metal; wherein Ml metal is selected from transition metal elements.
  • the Ml metal precursor is selected from but not limited to acetate, chlorides, sulfates or phosphates of Ml metal; wherein Ml metal is selected from Group X metal elements.
  • the Ml metal precursor is selected from but not limited to acetate, chlorides, sulfates or phosphates of Ml metal; wherein Ml metal is selected from platinum, palladium, nickel, darmstadtium and Pt 3 Co alloy.
  • the buffer used in step i) is bicarbonate buffer.
  • the pH of step i) reaction mixture is in the range of 8 to 9.
  • step i) reaction mixture is 8.5.
  • the process comprises drying of oxidative polymerized intermediate product under an infrared lamp for time period in the range of 9 to 14 h at a temperature in the range of 50-90 °C.
  • the inert atmosphere in step ii) is attained by passing inert gas of neon, helium, argon or xenon.
  • the annealing step ii) is done at a heating rate of 10 °C min -1 .
  • the process further comprises acid-washing of the annealed product of nitrogen doped 3D carbon of step ii) with 0.5 M of acid H 2 SO 4 at a temperature in the range of 60 to 100 °C for a time period in the range of 3 to 5 h, followed by at least three times washing with deionized (DI) water and subsequent drying.
  • DI deionized
  • the acid used for washing of step ii) product is selected from but not limited to HC1, H 2 SO 4 , HNO 3 , and so on.
  • the mixture of polyol and water is used in step iii) with a ratio of 3: 1.
  • step iii) further comprises preparing two solutions i.e., solution A of annealed product of nitrogen doped 3D carbon of step ii), and solution B of metal precursor with around 30 to 50 wt. % of Ml metal NPs.
  • the solution B is prepared by adding a specific amount of Ml metal precursor so as to attain 30 to 50 wt. % of Ml metal NPs and polyol or a mixture of polyol and water, followed by sonicating the solution for 5 to 15 minutes to obtain solution B.
  • the process further comprises slowly adding the solution B drop wise into the solution A under stirring for a time period in the range of 9 to 15 h at temperature in the range of 25 to 35 °C followed by heating, filtering, washing and drying to obtain the said composite material.
  • said heating is done at a temperature in the range of 120 to 150 °C for a time period in the range of 6 to 10 h.
  • the washing is done using deionized (DI) water at least two times.
  • the drying is done at a temperature in the range of 100 to 140 °C in a vacuum oven for a time period of 6 to 18 h.
  • the present invention relates to a composition for fuel cells comprising an effective amount or ratio of polymer based solid electrolyte and the composite material, wherein said polymer based solid electrolyte acts as proton exchange material; the ratio of polymer based solid electrolyte (n) and the graphitic carbon (c) of the composite material is in the range of 0.4 to 0.8.
  • said polymer based solid electrolyte is placed in contact with membrane material and/or electrode material wherein said membrane material and/or electrode material is coated with the composite material disclosed herein.
  • the polymer based solid electrolyte is in aqueous solution form and is selected from nafion, polybenzimidazole (PBI), sulfonated polyether ether ketone (SPEEK), Poly(arylene ether sulfone) (PAES), Poly(phenylene oxide) (PPO), and Polyimide (PI); wherein the aqueous solution of polymer based solid electrolyte is in a concentration ranging between 5 to 20% w/v.
  • PBI polybenzimidazole
  • SPEEK sulfonated polyether ether ketone
  • PAES Poly(arylene ether sulfone)
  • PPO Poly(phenylene oxide)
  • PI Polyimide
  • the membrane material is in solid form and is selected from but not limited to nafion, polybenzimidazole (PBI), sulfonated polyether ether ketone (SPEEK), poly(arylene ether sulfone) (PAES), poly(phenylene oxide) (PPO), and polyimide (PI).
  • PBI polybenzimidazole
  • SPEEK sulfonated polyether ether ketone
  • PAES poly(arylene ether sulfone)
  • PPO poly(phenylene oxide)
  • PI polyimide
  • the polymer based solid electrolyte or ionomer is in aqueous solution form and is selected from but not limited to nafion, polybenzimidazole (PBI), sulfonated polyether ether ketone (SPEEK), poly(arylene ether sulfone) (PAES), poly(phenylene oxide) (PPO), and polyimide (PI).
  • PBI polybenzimidazole
  • SPEEK sulfonated polyether ether ketone
  • PAES poly(arylene ether sulfone)
  • PPO poly(phenylene oxide)
  • PI polyimide
  • the nafion is a polytetrafluoroethylene (PTFE) backbone with perfluorinated-vinyl-polyether side chains containing sulphonic acid end groups.
  • PTFE polytetrafluoroethylene
  • the aqueous solution of polymer based solid electrolytes or ionomers is in a concentration ranging between 5 to 20% w/v.
  • ratio of polymer based solid electrolyte (n) and the graphitic carbon (c) of the composite material on which active sites are decorated is in the range of 0.4 to 0.8.
  • This ratio is known as n/c ratio, where the inventors got results of effective activity of half and full fuel cells when the ratio is in the range of 0.4 to 0.8.
  • the 3D interconnected structure of the electrocatalyst support membrane or composite membrane owing to its highly porous networked structure, enhances the triple phase boundary (TPB), which is the interface where the polymer based solid electrolyte, reactant gas, and electrically connected catalyst (i.e., composite membrane) come into contact with each other.
  • TPB triple phase boundary
  • the interconnected microporous carbon network of the composite membrane aids in withstanding high humidity while having no impact on the permeability of the reactant gases.
  • the present invention relates to a half PEM fuel cell comprising said composite material as a coating layer onto electrode(s) or membrane placed over/in between electrode(s), wherein the cell comprises a working electrode, counter electrode, reference electrode, proton exchange membrane, and electrolyte, wherein the working electrode is selected from a carbon electrode, glassy carbon electrode, gas diffusion layer, carbon cloth, nickel foam/mesh coated with carbon; wherein the counter electrode is selected from graphite rod, platinum rod, and platinum mesh; wherein the reference electrode is selected from Ag/AgCl electrode, Hg/Hg 2 SC 4 , standard hydrogen electrode, Hg/HgO, standard calomel electrode; wherein the electrolyte is selected from perchloric acid, sulphuric acid, hydrocholric acid, potassium hydroxide, sodium hydroxide.
  • the present invention relates to a full PEM fuel cell comprising said composite material as a coating layer onto electrode(s) or membrane placed between electrode(s).
  • half fuel cell further comprises continuous purging of oxygen gas.
  • the half fuel cell comprises 0.1 M HCIO 4 as the electrolyte, continuous purging of O 2 gas, composite membrane or electrocatalyst coated glassy carbon electrode as working electrode, graphite rod as counter electrode, and Ag/AgCl electrode employed as reference electrode.
  • the full fuel cell comprising a cathode, anode, composite membrane or electrocatalyst, gas diffusion layer, proton exchange membrane, and electrolyte; wherein the composite membrane or electrocatalyst is coated onto said proton exchange membrane.
  • the full fuel cell comprises a membrane electrode assembly (ME A) made by sandwiching an anode, proton exchange membrane, and a cathode.
  • ME A membrane electrode assembly
  • the 3D foam structure of the catalyst support material offers a perfect platform for several TPB sites throughout the porous network; however, the electrochemical reaction can only take place at TPBs when these zones are effectively connected to each other.
  • These highly interconnected porous networks are large enough for the diffusion of reactant gas and favorable for the ionomer chains to penetrate and interact with the active sites for the maximum utilization of CL.
  • 3D structural engineering on the carbon support morphology to spatially isolate the active site-bearing surfaces is an effective solution to eliminating mass transfer and water dissipation concerns.
  • the relative humidity of incoming gases is normally maintained at a high value to make sure that the membrane is fully hydrated in order to maintain good proton conductivity.
  • the pores of the catalyst layer (CL) and the gas diffusion layer (GDL) are frequently flooded by excessive liquid water, resulting in blockage of the catalyst surface and restricting reactant gas transport, which will lead to a mass transport resistance-related performance loss.
  • a delicate balance must be maintained between membrane drying and liquid water flooding to prevent fuel cell breakdown and ensure good performance, which is the fundamental water management problem.
  • increasing humidity is used to activate the CL quickly, but with time, the permeability of the CL to gas decreases.
  • the interconnected microporous carbon network aids in withstanding high humidity while having no impact on the permeability of the reactant gases.
  • a solution of dopamine hydrochloride with a concentration of approximately 3 mg/ml, was prepared in a bicarbonate buffer at pH 8.5.
  • Commercially available melamine foam slices were immersed in this solution at a concentration of 1 mg/ml and stirred for a duration of 24 h.
  • the melamine foam impregnated with polydopamine underwent a drying process under an infrared lamp for an entire night, followed by annealing in an argon (Ar) atmosphere at 900 °C for 3 h, utilizing a heating rate of 10 °C min -1 .
  • the resulting carbonized material was further subjected to acid-washing with 0.5 M H 2 SO 4 at 80 °C for 4 h, followed by triple washing with deionized (DI) water and subsequent drying.
  • DI deionized
  • H 2 PtCl 6 , salt over 3D Dopamine Carbon (3DPDC) was carried out using the polyol method in ethylene glycol.
  • 50 mg of 3DPDC was introduced and stirred for 1 hour, while the other portion, containing H 2 PtCl 6 , (corresponding to 40% Pt), was sonicated for 10 minutes and then slowly added drop wise into the solvent mixture containing 3DPDC using a burette. After completing the addition, the resulting solution was continuously stirred overnight.
  • the solution was then heated to 140 °C for 8 h.
  • the final catalyst was subsequently filtered, washed with deionized (DI) water, and subjected to drying at 120 °C in a vacuum oven, resulting in preparation of final catalyst, denoted as Pt/3DPDC.
  • DI deionized
  • the synthesis of the Pt-supported onto 3D nitrogen doped graphitic carbon is schematically illustrated in Fig. 1.
  • the synthesis involves three main steps. Firstly, polydopamine is coated onto the melamine foam. Then, the coated material is annealed at 900 °C for 3 h. Subsequently, acid washing is performed to remove the metal present in the material. Finally, Pt nanoparticles are decorated onto the 3D carbon using polyol synthesis. During the annealing process, the melamine foam undergoes conversion to carbon nitride, and the polydopamine that grew over it is transferred to the N-doped graphitic carbon.
  • the amine groups in both dopamine and melamine foam contribute nitrogen, which is uniformly distributed over the graphitic carbon, leading to the creation of sites involving iron coordination.
  • Melamine foam serves as a template for forming the 3D morphology and also acts as a nitrogen source for the doping process.
  • Fig. 2a displays the FESEM image of the bare melamine foam, showing a smooth surface. Even after the polydopamine coating and subsequent high-temperature annealing, the structure of the melamine foam remains unchanged, as seen in Fig. 2b and 2c. Further, morphological characterization of Pt/3DPPDC using FESEM reveals a network and porous structure, as depicted in Fig. 2d.
  • the TEM images show Pt nanoparticles uniformly dispersed over the network- structured carbon.
  • the histogram depicts the size distribution of Pt nanoparticles on the network- structured carbon, with an average particle size of 2.5 nm.
  • the powder X-ray diffraction (XRD) pattern of Pt/3DPDC exhibits identical peak positions corresponding to both the Pt nanoparticles and the carbon support materials.
  • the peaks at 2 ⁇ values of 39.6° (111), 45.4° (200), and 68.1° (220) are attributed to different planes of Pt (JCPDS: 87-0647), indicating the presence of a face-centred cubic crystal lattice of Pt nanoparticles in a crystalline state.
  • the support materials used here is conducting carbon which displays the same peaks corresponding to carbon (2 ⁇ values of 26.3°).
  • Fig. 3b presents a comparison of the Raman spectra between state-of-the-art Pt/C (40% Pt on 60% C) (JM - Johnson Matthey), and Pt/3DPDC of the present invention.
  • both materials show similar Raman shift values for the G and D bands frequencies
  • the catalysts differ in terms of the intensity ratio between the D and G bands.
  • the G and D bands appear at 1590 and 1334 cm -1 , respectively.
  • the G band indicates the presence of graphitic content and originates from the zone-center Eig mode, while the D band corresponds to the peak caused by disorder in the graphite lattice and is associated with the A 1g zone-edge phonon.
  • the G band represents sp 2 carbons in the hexagonal framework of the carbon
  • the D band indicates defective sp 3 carbons formed within the sp 2 carbon lattice. Calculating the ratio of intensities between the defective and graphitic bands provides valuable information about the defects in the carbon morphologies.
  • the ID/IG ratio for Pt/3DPDC and Pt/C (JM) is 1.25 and 1.12, respectively, indicating that nitrogen doping creates defects in Pt/3DPDC.
  • X-ray photoelectron spectroscopy (XPS) analysis can provide valuable insights into the nature and condition of the catalytic systems.
  • Pt/3DPDC the Pt 4f XPS spectra display two characteristic peaks at different binding energy values, representing Pt 4f 5/2 and Pt 4f 7/2 , respectively (Fig. 3c).
  • These Pt 4f signals can be further broken down into three doublets, each corresponding to distinct states: Pt° state, Pt 2+ state, and Pt 4+ state.
  • the doublets with lower binding energies, such as 71.9 and 75.3 eV, are associated with the metallic Pt particles (Pt°), while the ones with higher binding energies indicate the presence of surface oxidized Pt species (Pt 4+ ).
  • XPS analysis reveals existence of electron deficient and atomically dispersed Pt particles, formed as Pt 2+ on graphitic carbon surface.
  • Example 3 Analysis and testing of said synthesized Pt/3DPDC in fuel cell:
  • Fig. 4a presents a comparison of the CVs for Pt/3DPDC and commercially available Pt/C (JM) in N2-saturated 0.1 m HCIO 4 at a scan rate of 50 mV s -1 .
  • the CV profiles exhibit typical Pt characteristics, showing regions associated with hydrogen adsorption-desorption, oxygen adsorption-desorption, and non-faradaic capacitance.
  • the electrochemically active surface area was determined from hydrogen desorption, resulting in ECSA values of 48.5 m 2 g -1 for Pt/3DPDC and 55.5 m 2 g -1 for Pt/C (JM).
  • Fig. 4b displays the Linear sweep voltammograms (LSVs) for oxygen reduction reaction (ORR) recorded at 1600 rpm in oxygen- saturated 0.1 M HCIO 4 .
  • the LSV of the state- of-the-art Pt/C JM catalyst is also included for comparison.
  • Pt/3DPDC exhibited the highest onset potential (0.982 V vs. RHE) followed by Pt/C JM (0.969 V vs. RHE).
  • Pt/3DPDC demonstrated a substantially higher E1/2 value (0.852 V vs. RHE) compared to Pt/C JM (0.822 V vs. RHE). This advantage is mainly attributed to Pt/3DNG's unique structural features, providing improved reactant distribution and active site accessibility. Consequently, Pt/3DPDC outperforms other systems in terms of E1/2 under current dragging condition due to its distinct structural characteristics.
  • LT-PEMFC low- temperature PEMFC
  • CCM catalyst-coated membrane
  • GDL gas diffusion layers
  • the performance evaluation primarily involved state-of-the-art Pt/C (JM) catalyst, employing the usual Nafion to carbon (n/c) ratio of 0.6.
  • JM state-of-the-art Pt/C
  • n/c Nafion to carbon
  • the attainment of the maximum output current of 55 A, at a rate of 5.77 Ah 1 required approximately 8 h.
  • Analysis of the conditioning data in Fig. 5a reveals signal irregularities during the process, suggestive of water molecule flooding.
  • the indigenous Pt/3DPDC catalyst Fig. 5b was subjected to the same procedure, taking around 8 h at a rate of 6.40 Ah 1 , yet no noisy peaks were observed, indicating superior water management.
  • n/c ratio was further reduced to 0.5 for Pt/3DPDC, resulting in a remarkable achievement of a maximum current of 70 A within 3.8 h, with a rate of 18.37 Ah 1 , and without any signs of flooding characteristics (Fig. 5c).
  • Fig. 6 depicts the comparative I-V polarization plots obtained during the evaluation of a single cell membrane electrode assembly (MEA).
  • the MEA is based on Pt/C (JM) with an n/c ratio of 0.6, and Pt/3DPPDC with two distinct n/c ratios, namely 0.5 and 0.6.
  • JM Pt/C
  • Pt/3DPPDC Pt/3DPPDC with two distinct n/c ratios
  • This performance increment is directly linked to the current density, leading to a remarkable disparity in the maximum power density displayed by all systems.
  • This significant difference can be attributed to the in-house system's enhanced ability to effectively address mass transfer requirements, particularly under high current conditions, owing to its favorable morphological characteristics.
  • the present invention provides better water management by using composite material in fuel cells, e.g. the humidity level of the incoming gases is typically maintained at a high value to ensure full hydration of the membrane in said fuel cells, thereby promoting optimal proton conductivity.
  • the humidity level of the incoming gases is typically maintained at a high value to ensure full hydration of the membrane in said fuel cells, thereby promoting optimal proton conductivity.
  • an issue arises when excessive liquid water floods the pores of the Catalyst Layer (CL) and the Gas Diffusion Layer (GDL), leading to the blockage of catalyst surfaces and hindering the transport of reactant gases. This, in turn, results in a decline in performance due to mass transport resistance. Therefore, achieving an appropriate balance between membrane drying and liquid water flooding is essential to prevent fuel cell breakdown and ensure optimal performance, which constitutes the fundamental challenge of water management.
  • the potential of enhancing triple phase boundaries and creating high-performance fuel cell electrodes lies in the three-dimensional hierarchical and porous structures of the composite membrane materials as disclosed herein. These possess a significant specific surface area, distinctive porous architecture, a substantial level of heteroatom doping, excellent mechanical stability, and multiple pathways for electrical conduction.
  • the present invention emphasizes the use of a 3D-structured carbon material with a high surface area, which facilitates the formation of a more efficient triple-phase boundary.
  • This improved boundary enhances the interaction between the liquid electrolyte, gas reactant, and solid electrocatalyst surface, leading to significantly higher performance.
  • the unique 3D carbon structure improves mass transport, enabling the fuel cell to activate within 1.5 hours, a notable improvement over the 6-hour activation time reported in other works.
  • This structure also provides process-friendly advantages for PEMFC electrode fabrication, minimizing flooding issues and allowing faster activation with lower energy requirements.
  • the high surface area and optimized 3D structure contribute to superior catalytic performance, faster activation, and improved efficiency, distinguishing the present invention from literature known materials.
  • the composite material provides better activation energy within lesser period of time during electrochemical testing (9 h vs 4 h).

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Abstract

La présente invention concerne de manière générale des piles à combustible, en particulier une pile à combustible à membrane échangeuse de protons (PEMFC). La présente invention concerne un matériau composite pour revêtir une ou plusieurs électrodes ou une membrane dans des piles à combustible comprenant des nanoparticules métalliques M1 dispersées ou ancrées sur du carbone graphitique 3D dopé à l'azote ; et un procédé de préparation de celui-ci. En outre, la présente invention concerne une composition pour piles à combustible comprenant une quantité ou un rapport efficace d'électrolyte solide à base de polymère et du matériau composite. L'invention concerne en outre une pile à combustible semi-PEM et/ou une pile à combustible totalement PEM comprenant ledit matériau composite en tant que couche de revêtement sur une électrode ou une membrane placée sur/entre une ou plusieurs électrodes.
PCT/IN2024/052180 2023-11-06 2024-11-05 Matériau composite pour piles à combustible, son procédé de préparation et ses applications Pending WO2025099742A1 (fr)

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Cited By (1)

* Cited by examiner, † Cited by third party
Publication number Priority date Publication date Assignee Title
CN121035233A (zh) * 2025-10-29 2025-11-28 中国海洋大学 一种海洋沉积物微生物燃料电池用改性阳极及其制备方法和海洋沉积物微生物燃料电池

Citations (2)

* Cited by examiner, † Cited by third party
Publication number Priority date Publication date Assignee Title
CN108666591A (zh) * 2018-06-13 2018-10-16 广州大学 一种氮掺杂石墨烯-钯纳米颗粒复合材料及其制备方法与应用
WO2022015888A2 (fr) * 2020-07-14 2022-01-20 The Research Foundation For The State University Of New York Matériaux carbonés poreux, nanoparticules, leurs procédés de préparation et utilisations associées

Patent Citations (2)

* Cited by examiner, † Cited by third party
Publication number Priority date Publication date Assignee Title
CN108666591A (zh) * 2018-06-13 2018-10-16 广州大学 一种氮掺杂石墨烯-钯纳米颗粒复合材料及其制备方法与应用
WO2022015888A2 (fr) * 2020-07-14 2022-01-20 The Research Foundation For The State University Of New York Matériaux carbonés poreux, nanoparticules, leurs procédés de préparation et utilisations associées

Non-Patent Citations (3)

* Cited by examiner, † Cited by third party
Title
CHANDRAN PRIJI, GHOSH ARPITA, RAMAPRABHU SUNDARA: "High-performance Platinum-free oxygen reduction reaction and hydrogen oxidation reaction catalyst in polymer electrolyte membrane fuel cell", SCIENTIFIC REPORTS, NATURE PUBLISHING GROUP, US, vol. 8, no. 1, US , XP093315140, ISSN: 2045-2322, DOI: 10.1038/s41598-018-22001-9 *
CHEN TAIPU, LV BO, SUN SHUCHENG, HAO JINKAI, SHAO ZHIGANG: "Novel Nafion/Graphitic Carbon Nitride Nanosheets Composite Membrane for Steam Electrolysis at 110 °C", MEMBRANES, M D P I AG, CH, vol. 13, no. 3, CH , pages 308, XP093205305, ISSN: 2077-0375, DOI: 10.3390/membranes13030308 *
EUN-KI KIM ET AL.: "Solid electrolyte membranes based on polybenzimidazole containing graphitic carbon nitride moiety (PBICN) for high-temperature fuel cell applications", POLYMER, vol. 235, 19 November 2021 (2021-11-19), pages 124247, XP086851924, DOI: 10.1016/j.polymer.2021.124247 *

Cited By (1)

* Cited by examiner, † Cited by third party
Publication number Priority date Publication date Assignee Title
CN121035233A (zh) * 2025-10-29 2025-11-28 中国海洋大学 一种海洋沉积物微生物燃料电池用改性阳极及其制备方法和海洋沉积物微生物燃料电池

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