WO2011073723A1 - Electrolytic apparatus including an active layer using fullerenes combined with a metal as a catalytic system - Google Patents

Electrolytic apparatus including an active layer using fullerenes combined with a metal as a catalytic system Download PDF

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Publication number
WO2011073723A1
WO2011073723A1 PCT/IB2009/055735 IB2009055735W WO2011073723A1 WO 2011073723 A1 WO2011073723 A1 WO 2011073723A1 IB 2009055735 W IB2009055735 W IB 2009055735W WO 2011073723 A1 WO2011073723 A1 WO 2011073723A1
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Prior art keywords
active layer
carbon
fullerene
carbon black
metal
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PCT/IB2009/055735
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French (fr)
Inventor
Guillaume Krosnicki
Alejandro Franco
Nicolas Guillet
Olivier Lemaire
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Commissariat A L'energie Atomique Et Aux Energies Alternatives
King Saud University
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Priority to PCT/IB2009/055735 priority Critical patent/WO2011073723A1/en
Priority to KR1020127018079A priority patent/KR101791103B1/en
Priority to BR112012014200-3A priority patent/BR112012014200B1/en
Priority to US13/515,424 priority patent/US9299992B2/en
Priority to CA2783404A priority patent/CA2783404A1/en
Priority to EP10809187.7A priority patent/EP2514012B1/en
Priority to JP2012543969A priority patent/JP5676639B2/en
Priority to PCT/IB2010/055797 priority patent/WO2011073897A1/en
Priority to CN201080056630.0A priority patent/CN102656730B/en
Publication of WO2011073723A1 publication Critical patent/WO2011073723A1/en

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    • C—CHEMISTRY; METALLURGY
    • C25—ELECTROLYTIC OR ELECTROPHORETIC PROCESSES; APPARATUS THEREFOR
    • C25B—ELECTROLYTIC OR ELECTROPHORETIC PROCESSES FOR THE PRODUCTION OF COMPOUNDS OR NON-METALS; APPARATUS THEREFOR
    • C25B11/00—Electrodes; Manufacture thereof not otherwise provided for
    • C25B11/04—Electrodes; Manufacture thereof not otherwise provided for characterised by the material
    • C—CHEMISTRY; METALLURGY
    • C25—ELECTROLYTIC OR ELECTROPHORETIC PROCESSES; APPARATUS THEREFOR
    • C25B—ELECTROLYTIC OR ELECTROPHORETIC PROCESSES FOR THE PRODUCTION OF COMPOUNDS OR NON-METALS; APPARATUS THEREFOR
    • C25B9/00—Cells or assemblies of cells; Constructional parts of cells; Assemblies of constructional parts, e.g. electrode-diaphragm assemblies; Process-related cell features
    • C25B9/17—Cells comprising dimensionally-stable non-movable electrodes; Assemblies of constructional parts thereof
    • C25B9/19—Cells comprising dimensionally-stable non-movable electrodes; Assemblies of constructional parts thereof with diaphragms
    • C25B9/23—Cells comprising dimensionally-stable non-movable electrodes; Assemblies of constructional parts thereof with diaphragms comprising ion-exchange membranes in or on which electrode material is embedded
    • 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
    • H01M4/8663—Selection of inactive substances as ingredients for catalytic active masses, e.g. binders, fillers
    • H01M4/8673—Electrically conductive fillers
    • 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
    • H01M4/921—Alloys or mixtures with metallic elements
    • 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
    • H01M4/923—Compounds thereof with non-metallic elements
    • 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 lies within the field of fuel cells, notably the "Proton Exchange Membrane Fuel Cell” (PEMFC), and proton exchange membrane electrolysers (PEM electrolysers). It proposes a solution for improving the electrochemical performances of doped fullerene- based catalysts.
  • PEMFC Proton Exchange Membrane Fuel Cell
  • PEM electrolysers proton exchange membrane electrolysers
  • PRIOR ART PEMFCs are current generators whose operating principle, illustrated in figure 1, is based on converting chemical energy into electric energy through a catalytic reaction between hydrogen and oxygen.
  • MEAs 1 Membrane-electrode assemblies, or MEAs 1, commonly called cell cores, comprise the basic components of PEMFCs. They are made up of a polymer membrane 2 and catalytic layers 3, 4 found on either side of the membrane and respectively comprising the anode and the cathode.
  • the membrane 2 is used to separate the anode 5 and cathode 6 compartments.
  • the catalytic layers 3, 4 are generally made up of platinum nanoparticles supported by carbon aggregates, usually carbon black.
  • Gas diffusion layers 7, 8 (carbon tissue, felt, etc.) are placed on either side of the MEA 1 to ensure electrical conduction, homogenous distribution of the reactive gases and elimination of the water produced.
  • oxidation of the hydrogen on the catalyst produces H + protons and e " electrons.
  • the protons then cross the polymer membrane 2 before reacting with the oxygen at the cathode 4.
  • the protons' reaction with the oxygen at the cathode leads to the formation of water and the production of heat.
  • PEM electrolysers whose operating principle is illustrated in figure 2, are systems that are very similar to reverse PEMFCs. They are used to produce hydrogen and oxygen through a chemical transformation of water, using electric energy. As is the case for PEMFCs, MEAs 1 are used. The components (membrane 2 and catalytic layers 3, 4) are usually of the same kind as for PEMFCs. The anode compartment is supplied with pure water. An electrical current is applied to break down the water. Oxygen is produced at anode 3, while the protons cross the membrane 2 to be recombined at cathode 4, thus producing hydrogen.
  • the catalyst used in electrochemical reactors is made up of carbon black-supported platinum, in other words carbon black doped with platinum.
  • This type of catalyst has its weaknesses, however, notably in terms of stability. That is why attempts have been made to develop other catalyst systems.
  • FuUerenes are molecules in the form of a closed cage made up of an even number of carbon atoms grouped in a structure comprised of pentagons and hexagons. They are the third allotrope of carbon after graphite and diamond. FuUerenes can have different chemical species or groups on their surface. These structures may also enclose other chemical species, such as alkali, as in a cage.
  • the present invention is part of the research for new technical solutions for catalysts designed for electrochemical apparatuses, notably PEMFC cells and PEM electrolysers.
  • the present invention concerns an active layer for an electrochemical apparatus including a catalyst system mixed with a carbon electronic conductor, said catalyst system including a metal or several metals combined with at least one fullerene.
  • the present invention proposes using fuUerenes in a fullerene-based catalytic system mixed with a carbon electronic conductor other than a fullerene.
  • This catalytic system is mixed with a conventional carbon electronic conductor such as carbon black.
  • an active layer according to the invention includes, beyond the catalytic system, a carbon electronic conductor. To differentiate this further from the prior art, this carbon electronic conductor is not a fullerene.
  • carbon black means a colloidal carbon material in the form of carbon aggregates and agglomerates of these aggregates. This may include Vulcan ® or Shawinigan ® products, for example.
  • the carbon electronic conductor may comprise or include carbon nanowires or nanotubes or nano-onions, or polymers such as polyaniline or polypyrole.
  • FuUerenes are therefore combined in a known manner with metal or metals, forming the catalytic system made up of doped fuUerenes.
  • doped fuUerenes can mean: metallofullerenes, i.e. the case in which the metal is coupled with the fullerene through a chemical bond or when it is located in the carbon cage;
  • the metallic catalyst comprising one or more metals is advantageously deposited on the fullerene(s) up to 5 to 60% by mass, advantageously 20% by mass of the metal(s) compared with the mass of the fullerene(s).
  • the fullerenes used in the present invention may receive a varied load of metal, notably including one or more metal atoms per fullerene molecule. It may also be a mixture of different fullerenes.
  • the carbon electronic conductor accounts for 5 to 50% by mass of the mixture made up of the catalytic system and the carbon electronic conductor, advantageously 20 to 30%> and even more advantageously 25%.
  • this also concerns the method of producing an active layer as described above.
  • a first step consists in combining the metal(s) with the fullerene, then mixing the catalytic system thus obtained with the carbon electronic conductor. Two situations can then occur: the carbon electronic conductor, notably carbon black, is mixed with a metallo fullerene;
  • the carbon electronic conductor notably carbon black
  • the carbon electronic conductor is mixed with a fullerene, on which the catalyst had previously been deposited, advantageously by chemical reduction as described in the document by Pinheiro et al. (J. New. Mat. Electrochem. Systems 6 (2003) 1-8).
  • the second step consists in producing the active layer itself.
  • the mixture obtained in the previous step (doped fullerene + carbon electronic conductor, notably carbon black), for example 20 mg, is formulated with a hydroalcoholic mixture (for example 200 ⁇ deionised water and 600 ⁇ isopropyl alcohol) and a polymer such as Nafion ® (172 mg Nafion ® solution at a concentration of 5% by mass).
  • the ink thus obtained is deposited using methods that are known to persons skilled in the art (spraying, pipette deposits, etc.).
  • the invention also concerns any electrochemical reactor or apparatus including an active or catalytic layer as defined previously, such as fuel cells (acid or basic) and low-temperature electrolysers of the PEM type.
  • Figure 1 represents a diagram of the operating principle for a fuel cell of the PEMFC type.
  • Figure 2 represents a diagram of the operating principle for a PEM electrolyser.
  • Figure 3 illustrates the improvement in the electrochemical performances of Pt 4 C 6 o metallofullerenes in oxygen reduction on a rotating electrode.
  • Figure 4 illustrates the improvement in the electrochemical performances of PdioC 6 o metallofullerenes in oxygen reduction on a rotating electrode.
  • Figure 5 illustrates the improvement in the electrochemical performances of reduced platinum (20%) on fullerenes in oxygen reduction on a rotating electrode.
  • the present invention will be further illustrated in relation to acid PEFC fuel cells.
  • the mixture of doped fullerene and carbon black powders was dispersed in ink in the same way as the doped fullerenes alone or the metal supported by the carbon black.
  • the inks were produced by adding the following substances to 20 mg of mixture:
  • the inks were then dispersed for several hours in an ultrasound bath, then deposited using a micropipette, for example, or by spraying.
  • Example 1 using fullerenes doped with metallic platinum
  • a first embodiment consists in using Pt 4 C 6 o metallofullerenes (a compound made up of 4 Pt atoms bound to a C 6 o fullerene molecule) mixed with 25% carbon black.
  • Pt 4 C 6 o metallofullerenes a compound made up of 4 Pt atoms bound to a C 6 o fullerene molecule
  • the results of these experiments, illustrated in figure 3, were compared with those obtained at the laboratory with [platinum - fullerene] pure (Pt 4 C 6 o without carbon black).
  • Example 2 using fullerenes doped with metallic palladium
  • a second embodiment consists in using PdioC 6 o metallo fullerenes (a compound made up of 10 Pd atoms bound to a C 6 o fullerene molecule) mixed with 25% and 75% carbon black, respectively.
  • a third embodiment consists in using chemically reduced platinum on fullerenes following the protocol described by Pinheiro et al. (J. New. Mat. Electrochem. Systems 6 (2003) 1-8). In practice, nanoparticles of platinum are deposited on fullerene aggregates to 20% platinum by mass. This catalytic system is mixed with 25% carbon black. Once again, the two tests were performed in parallel on a rotating electrode. The corresponding results are given in figure 5.

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  • Chemical & Material Sciences (AREA)
  • Chemical Kinetics & Catalysis (AREA)
  • Electrochemistry (AREA)
  • Engineering & Computer Science (AREA)
  • Materials Engineering (AREA)
  • General Chemical & Material Sciences (AREA)
  • Metallurgy (AREA)
  • Organic Chemistry (AREA)
  • Catalysts (AREA)
  • Inert Electrodes (AREA)

Abstract

The invention concerns an active layer for an electrochemical apparatus including a catalytic System comprising a métal or a mixture of metals combined with a fullerene, mixed with a carbon electronic conductor which is not a fullerene. It also concerns an electrochemical apparatus including such an active layer.

Description

ELECTROLYTIC APPARATUS INCLUDING AN ACTIVE LAYER USING FULLERENES COMBINED WITH A METAL AS A CATALYTIC SYSTEM
FIELD OF THE INVENTION
The present invention lies within the field of fuel cells, notably the "Proton Exchange Membrane Fuel Cell" (PEMFC), and proton exchange membrane electrolysers (PEM electrolysers). It proposes a solution for improving the electrochemical performances of doped fullerene- based catalysts.
PRIOR ART PEMFCs are current generators whose operating principle, illustrated in figure 1, is based on converting chemical energy into electric energy through a catalytic reaction between hydrogen and oxygen.
Membrane-electrode assemblies, or MEAs 1, commonly called cell cores, comprise the basic components of PEMFCs. They are made up of a polymer membrane 2 and catalytic layers 3, 4 found on either side of the membrane and respectively comprising the anode and the cathode.
The membrane 2 is used to separate the anode 5 and cathode 6 compartments. The catalytic layers 3, 4 are generally made up of platinum nanoparticles supported by carbon aggregates, usually carbon black. Gas diffusion layers 7, 8 (carbon tissue, felt, etc.) are placed on either side of the MEA 1 to ensure electrical conduction, homogenous distribution of the reactive gases and elimination of the water produced. On the anode 3, oxidation of the hydrogen on the catalyst produces H+ protons and e" electrons. The protons then cross the polymer membrane 2 before reacting with the oxygen at the cathode 4. The protons' reaction with the oxygen at the cathode leads to the formation of water and the production of heat. PEM electrolysers, whose operating principle is illustrated in figure 2, are systems that are very similar to reverse PEMFCs. They are used to produce hydrogen and oxygen through a chemical transformation of water, using electric energy. As is the case for PEMFCs, MEAs 1 are used. The components (membrane 2 and catalytic layers 3, 4) are usually of the same kind as for PEMFCs. The anode compartment is supplied with pure water. An electrical current is applied to break down the water. Oxygen is produced at anode 3, while the protons cross the membrane 2 to be recombined at cathode 4, thus producing hydrogen.
Conventionally, the catalyst used in electrochemical reactors (batteries and electrolysers) is made up of carbon black- supported platinum, in other words carbon black doped with platinum. This type of catalyst has its weaknesses, however, notably in terms of stability. That is why attempts have been made to develop other catalyst systems.
Amongst the solutions described, the use of doped fuUerenes has been proposed, notably doped with platinum, or the use of fuUerenes as a catalyst support in fuel cells instead of the carbon black that is commonly used.
FuUerenes are molecules in the form of a closed cage made up of an even number of carbon atoms grouped in a structure comprised of pentagons and hexagons. They are the third allotrope of carbon after graphite and diamond. FuUerenes can have different chemical species or groups on their surface. These structures may also enclose other chemical species, such as alkali, as in a cage.
Silva et al. (Electrochimica Acta 44 (1999) 3565-3574) demonstrated that doped fuUerenes can be effectively used as catalysts in PEMFCs, and that their use can both reduce the metal load (notably platinum) on the electrodes and improve carbon's stability against corrosion compared with a carbon black catalyst support. Unfortunately, the electrochemical performances of doped fuUerenes have proven to be inferior to those obtained with metal (platinum, for example) supported by carbon black. It should be pointed out that carbon black alone, like fuUerenes alone, has very weak electrocatalytic activity. Furthermore, Pinheiro et al. (J. New. Mat. Electrochem. Systems 6 (2003) 1-8) used chemical reduction to deposit platinum on fuUerenes and applied a similar method to deposit platinum on carbon black. With this system, the authors demonstrated that they obtained electrochemical performances with fuUerenes as the platinum support that were inferior to those obtained with carbon black.
Thus, it can be seen in the prior art that, while the use of fuUerenes had already been suggested in the context of research on new catalysts for electrochemical apparatuses, the results obtained were not very encouraging. DISCLOSURE OF THE INVENTION
The present invention is part of the research for new technical solutions for catalysts designed for electrochemical apparatuses, notably PEMFC cells and PEM electrolysers.
Thus, according to a first embodiment, the present invention concerns an active layer for an electrochemical apparatus including a catalyst system mixed with a carbon electronic conductor, said catalyst system including a metal or several metals combined with at least one fullerene.
While it was known in the prior art that a metal catalyst and carbon black or alternatively a metal catalyst and a fullerene, possibly in the form of a metallo fullerene, could be mixed together, the present invention proposes using fuUerenes in a fullerene-based catalytic system mixed with a carbon electronic conductor other than a fullerene. This catalytic system is mixed with a conventional carbon electronic conductor such as carbon black.
This is surprising in that fuUerenes alone and carbon black alone are inert in terms of electrochemical reactions. In the context of the invention, it is advantageous for the catalyst to be a metal or a mixture of metals conventionally used in the context of catalytic layers for electrochemical apparatuses. Such metals are advantageously chosen from the group including platinum (Pt) and palladium (Pd). Platinum has been advantageously selected. As indicated above, an active layer according to the invention includes, beyond the catalytic system, a carbon electronic conductor. To differentiate this further from the prior art, this carbon electronic conductor is not a fullerene.
It may be carbon black, for example. In the context of the invention, "carbon black" means a colloidal carbon material in the form of carbon aggregates and agglomerates of these aggregates. This may include Vulcan® or Shawinigan® products, for example.
Alternatively, the carbon electronic conductor may comprise or include carbon nanowires or nanotubes or nano-onions, or polymers such as polyaniline or polypyrole.
FuUerenes are therefore combined in a known manner with metal or metals, forming the catalytic system made up of doped fuUerenes. In the context of the present invention, doped fuUerenes can mean: metallofullerenes, i.e. the case in which the metal is coupled with the fullerene through a chemical bond or when it is located in the carbon cage;
the metallic catalyst deposited on the fullerenes, as conventionally done with carbon black and as described, for example, in the document by Pinheiro et al. (J. New. Mat. Electrochem. Systems 6 (2003) 1-8).
In this last case, the metallic catalyst comprising one or more metals is advantageously deposited on the fullerene(s) up to 5 to 60% by mass, advantageously 20% by mass of the metal(s) compared with the mass of the fullerene(s).
It should be pointed out that the fullerenes used in the present invention may receive a varied load of metal, notably including one or more metal atoms per fullerene molecule. It may also be a mixture of different fullerenes. According to an advantageous embodiment, the carbon electronic conductor accounts for 5 to 50% by mass of the mixture made up of the catalytic system and the carbon electronic conductor, advantageously 20 to 30%> and even more advantageously 25%.
According to another embodiment of the invention, this also concerns the method of producing an active layer as described above.
A first step consists in combining the metal(s) with the fullerene, then mixing the catalytic system thus obtained with the carbon electronic conductor. Two situations can then occur: the carbon electronic conductor, notably carbon black, is mixed with a metallo fullerene;
the carbon electronic conductor, notably carbon black, is mixed with a fullerene, on which the catalyst had previously been deposited, advantageously by chemical reduction as described in the document by Pinheiro et al. (J. New. Mat. Electrochem. Systems 6 (2003) 1-8).
The second step consists in producing the active layer itself. For this, the mixture obtained in the previous step (doped fullerene + carbon electronic conductor, notably carbon black), for example 20 mg, is formulated with a hydroalcoholic mixture (for example 200 μΐ deionised water and 600 μΐ isopropyl alcohol) and a polymer such as Nafion® (172 mg Nafion® solution at a concentration of 5% by mass). The ink thus obtained is deposited using methods that are known to persons skilled in the art (spraying, pipette deposits, etc.). The invention also concerns any electrochemical reactor or apparatus including an active or catalytic layer as defined previously, such as fuel cells (acid or basic) and low-temperature electrolysers of the PEM type. BRIEF DESCRIPTION OF THE FIGURES
The way the invention is implemented and the resulting advantages can be better understood with the following examples of embodiments, which are given for informational purposes and are not limiting, as illustrated by the appended figures, including:
Figure 1 represents a diagram of the operating principle for a fuel cell of the PEMFC type. Figure 2 represents a diagram of the operating principle for a PEM electrolyser.
Figure 3 illustrates the improvement in the electrochemical performances of Pt4C6o metallofullerenes in oxygen reduction on a rotating electrode.
Figure 4 illustrates the improvement in the electrochemical performances of PdioC6o metallofullerenes in oxygen reduction on a rotating electrode.
Figure 5 illustrates the improvement in the electrochemical performances of reduced platinum (20%) on fullerenes in oxygen reduction on a rotating electrode. EMBODIMENTS OF THE INVENTION
The present invention will be further illustrated in relation to acid PEFC fuel cells.
The mixture of doped fullerene and carbon black powders was dispersed in ink in the same way as the doped fullerenes alone or the metal supported by the carbon black. The inks were produced by adding the following substances to 20 mg of mixture:
200 μΐ deionised water;
600 μΐ isopropyl alcohol;
172 mg Nation® solution at a concentration of 5% by mass.
The inks were then dispersed for several hours in an ultrasound bath, then deposited using a micropipette, for example, or by spraying.
Example 1 : using fullerenes doped with metallic platinum
A first embodiment consists in using Pt4C6o metallofullerenes (a compound made up of 4 Pt atoms bound to a C6o fullerene molecule) mixed with 25% carbon black. The results of these experiments, illustrated in figure 3, were compared with those obtained at the laboratory with [platinum - fullerene] pure (Pt4C6o without carbon black).
It can be observed, for example, that at 0.6 V/SHE, adding carbon black improves oxygen reduction: the current density goes from -0.12 mA/cm2 (without carbon black) to -3.22 mA/cm2 (with 25% carbon black).
Example 2: using fullerenes doped with metallic palladium A second embodiment consists in using PdioC6o metallo fullerenes (a compound made up of 10 Pd atoms bound to a C6o fullerene molecule) mixed with 25% and 75% carbon black, respectively. The results of these experiments, illustrated in figure 4, were compared with those obtained at the laboratory with [palladium - fullerene] pure (PdioC6o without carbon black).
It can be observed, for example, that at 0.6 V/SHE, adding carbon black improves oxygen reduction: the current density goes from -1.68 mA/cm2 (without carbon black) to -3.81 mA/cm2 (with 75% carbon black) and -4.05 mA/cm2 (with 25% carbon black). Example 3 : use of chemically reduced metallic platinum on the fullerenes
A third embodiment consists in using chemically reduced platinum on fullerenes following the protocol described by Pinheiro et al. (J. New. Mat. Electrochem. Systems 6 (2003) 1-8). In practice, nanoparticles of platinum are deposited on fullerene aggregates to 20% platinum by mass. This catalytic system is mixed with 25% carbon black. Once again, the two tests were performed in parallel on a rotating electrode. The corresponding results are given in figure 5.
It can be observed, for example, that at 0.6 V/SHE, adding carbon black improves oxygen reduction: the current density goes from -0.70 mA/cm2 (without carbon black) to -2.28 mA/cm2 (with 25% carbon black).
As these examples illustrate, a proportion of 5 to 50% carbon black on the total mass of the doped fullerene - carbon black mixture significantly improves electrochemical performances on the anode and on the cathode. In most cases, the optimum proportion is approximately 25% carbon black.

Claims

1. Active layer for an electrochemical apparatus including a catalytic system made up of a metal or a mixture of metals combined with a fullerene, mixed with a carbon electronic conductor which is not a fullerene.
2. Active layer as claimed in claim 1, characterised in that the metal or mixture of metals is chosen from the group including platinum (Pt) and palladium (Pd).
3. Active layer as claimed in claim 1 or 2, characterised in that the catalytic system is made up of a metallo fullerene.
4. Active layer as claimed in claim 1 or 2, characterised in that the metal or mixture of metals is deposited on the fullerene to constitute the catalytic system.
5. Active layer as claimed in any of claims 1 to 4, characterised in that the carbon electronic conductor is chosen among carbon black, carbon nanowires, carbon nanotubes and carbon nano-onions.
6. Active layer for an electrochemical apparatus as claimed in any of claims 1 to 4, characterised in that the carbon electronic conductor is chosen among the conductive polymers, advantageously polyaniline and polypyrole.
7. Active layer as claimed in any of the previous claims, characterised in that the carbon electronic conductor accounts for 5 to 50% of the mixture by mass, advantageously between 20 and 30%.
8. Electrochemical apparatus, notably a fuel cell or electrolyser, including an active layer as claimed in any of claims 1 to 7.
PCT/IB2009/055735 2009-12-14 2009-12-14 Electrolytic apparatus including an active layer using fullerenes combined with a metal as a catalytic system WO2011073723A1 (en)

Priority Applications (9)

Application Number Priority Date Filing Date Title
PCT/IB2009/055735 WO2011073723A1 (en) 2009-12-14 2009-12-14 Electrolytic apparatus including an active layer using fullerenes combined with a metal as a catalytic system
KR1020127018079A KR101791103B1 (en) 2009-12-14 2010-12-14 Electrochemical reactor and an active layer integrated into said reactor
BR112012014200-3A BR112012014200B1 (en) 2009-12-14 2010-12-14 electrochemical reactor
US13/515,424 US9299992B2 (en) 2009-12-14 2010-12-14 Electrochemical reactor and active layer integrated into said reactor
CA2783404A CA2783404A1 (en) 2009-12-14 2010-12-14 Electrochemical reactor and active layer integrated into said reactor
EP10809187.7A EP2514012B1 (en) 2009-12-14 2010-12-14 Electrochemical reactor and active layer integrated into said reactor
JP2012543969A JP5676639B2 (en) 2009-12-14 2010-12-14 Electrochemical reactor and active layer integrated in said reactor
PCT/IB2010/055797 WO2011073897A1 (en) 2009-12-14 2010-12-14 Electrochemical reactor and active layer integrated into said reactor
CN201080056630.0A CN102656730B (en) 2009-12-14 2010-12-14 Electrochemical reactor and the active layer be integrated in described reactor

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Cited By (2)

* Cited by examiner, † Cited by third party
Publication number Priority date Publication date Assignee Title
FR3081082A1 (en) * 2018-05-14 2019-11-15 Commissariat A L'energie Atomique Et Aux Energies Alternatives CATALYTIC LAYERS COMPRISING A FULLERENE
CN114512196A (en) * 2022-02-16 2022-05-17 哈尔滨工业大学 Method for accurately and rapidly predicting catalytic active site of heteroatom-doped amorphous carbon

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