Classifications

• • C—CHEMISTRY; METALLURGY
  • C09—DYES; PAINTS; POLISHES; NATURAL RESINS; ADHESIVES; COMPOSITIONS NOT OTHERWISE PROVIDED FOR; APPLICATIONS OF MATERIALS NOT OTHERWISE PROVIDED FOR
  • C09D—COATING COMPOSITIONS, e.g. PAINTS, VARNISHES OR LACQUERS; FILLING PASTES; CHEMICAL PAINT OR INK REMOVERS; INKS; CORRECTING FLUIDS; WOODSTAINS; PASTES OR SOLIDS FOR COLOURING OR PRINTING; USE OF MATERIALS THEREFOR
  • C09D11/00—Inks
  • C09D11/02—Printing inks
  • C09D11/03—Printing inks characterised by features other than the chemical nature of the binder
  • C09D11/033—Printing inks characterised by features other than the chemical nature of the binder characterised by the solvent
• • 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
  • H01M4/88—Processes of manufacture
• • B—PERFORMING OPERATIONS; TRANSPORTING
  • B41—PRINTING; LINING MACHINES; TYPEWRITERS; STAMPS
  • B41J—TYPEWRITERS; SELECTIVE PRINTING MECHANISMS, i.e. MECHANISMS PRINTING OTHERWISE THAN FROM A FORME; CORRECTION OF TYPOGRAPHICAL ERRORS
  • B41J2/00—Typewriters or selective printing mechanisms characterised by the printing or marking process for which they are designed
  • B41J2/005—Typewriters or selective printing mechanisms characterised by the printing or marking process for which they are designed characterised by bringing liquid or particles selectively into contact with a printing material
  • B41J2/01—Ink jet
  • B41J2/17—Ink jet characterised by ink handling
  • B41J2/175—Ink supply systems ; Circuit parts therefor
• • B—PERFORMING OPERATIONS; TRANSPORTING
  • B41—PRINTING; LINING MACHINES; TYPEWRITERS; STAMPS
  • B41J—TYPEWRITERS; SELECTIVE PRINTING MECHANISMS, i.e. MECHANISMS PRINTING OTHERWISE THAN FROM A FORME; CORRECTION OF TYPOGRAPHICAL ERRORS
  • B41J29/00—Details of, or accessories for, typewriters or selective printing mechanisms not otherwise provided for
• • B—PERFORMING OPERATIONS; TRANSPORTING
  • B41—PRINTING; LINING MACHINES; TYPEWRITERS; STAMPS
  • B41J—TYPEWRITERS; SELECTIVE PRINTING MECHANISMS, i.e. MECHANISMS PRINTING OTHERWISE THAN FROM A FORME; CORRECTION OF TYPOGRAPHICAL ERRORS
  • B41J29/00—Details of, or accessories for, typewriters or selective printing mechanisms not otherwise provided for
  • B41J29/377—Cooling or ventilating arrangements
• • B—PERFORMING OPERATIONS; TRANSPORTING
  • B41—PRINTING; LINING MACHINES; TYPEWRITERS; STAMPS
  • B41M—PRINTING, DUPLICATING, MARKING, OR COPYING PROCESSES; COLOUR PRINTING
  • B41M5/00—Duplicating or marking methods; Sheet materials for use therein
• • B—PERFORMING OPERATIONS; TRANSPORTING
  • B41—PRINTING; LINING MACHINES; TYPEWRITERS; STAMPS
  • B41M—PRINTING, DUPLICATING, MARKING, OR COPYING PROCESSES; COLOUR PRINTING
  • B41M5/00—Duplicating or marking methods; Sheet materials for use therein
  • B41M5/0023—Digital printing methods characterised by the inks used
• • C—CHEMISTRY; METALLURGY
  • C09—DYES; PAINTS; POLISHES; NATURAL RESINS; ADHESIVES; COMPOSITIONS NOT OTHERWISE PROVIDED FOR; APPLICATIONS OF MATERIALS NOT OTHERWISE PROVIDED FOR
  • C09D—COATING COMPOSITIONS, e.g. PAINTS, VARNISHES OR LACQUERS; FILLING PASTES; CHEMICAL PAINT OR INK REMOVERS; INKS; CORRECTING FLUIDS; WOODSTAINS; PASTES OR SOLIDS FOR COLOURING OR PRINTING; USE OF MATERIALS THEREFOR
  • C09D11/00—Inks
• • C—CHEMISTRY; METALLURGY
  • C09—DYES; PAINTS; POLISHES; NATURAL RESINS; ADHESIVES; COMPOSITIONS NOT OTHERWISE PROVIDED FOR; APPLICATIONS OF MATERIALS NOT OTHERWISE PROVIDED FOR
  • C09D—COATING COMPOSITIONS, e.g. PAINTS, VARNISHES OR LACQUERS; FILLING PASTES; CHEMICAL PAINT OR INK REMOVERS; INKS; CORRECTING FLUIDS; WOODSTAINS; PASTES OR SOLIDS FOR COLOURING OR PRINTING; USE OF MATERIALS THEREFOR
  • C09D11/00—Inks
  • C09D11/30—Inkjet printing inks
• • C—CHEMISTRY; METALLURGY
  • C09—DYES; PAINTS; POLISHES; NATURAL RESINS; ADHESIVES; COMPOSITIONS NOT OTHERWISE PROVIDED FOR; APPLICATIONS OF MATERIALS NOT OTHERWISE PROVIDED FOR
  • C09D—COATING COMPOSITIONS, e.g. PAINTS, VARNISHES OR LACQUERS; FILLING PASTES; CHEMICAL PAINT OR INK REMOVERS; INKS; CORRECTING FLUIDS; WOODSTAINS; PASTES OR SOLIDS FOR COLOURING OR PRINTING; USE OF MATERIALS THEREFOR
  • C09D11/00—Inks
  • C09D11/52—Electrically conductive inks
• • 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
  • H01M4/88—Processes of manufacture
  • H01M4/8825—Methods for deposition of the catalytic active composition
  • H01M4/8828—Coating with slurry or ink
  • H01M4/8832—Ink jet printing
• • 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 provides a method and apparatus for performing inkjet printing without clogging of the nozzles, including using an ink free of humectants. More specifically, the invention proposes to eject an ink at a temperature below room temperature.
• the present invention finds application in the field of electronics, for example for the preparation of catalytic layers in PEMFC type batteries (acronym for "Polymer Electrolyte Membrane Fuel Cells”).
• PEMFC type batteries acronym for "Polymer Electrolyte Membrane Fuel Cells”
• the general principle of the inkjet technique is to project and direct small drops of ink using a computer.
• the ink jet can, reproducibly, dispense spherical drops of 25 to 125 micrometers in diameter (8 pico liters to 1 nanolitre), at a frequency ranging from 25 kHz (drop on demand or DOD: English acronym for "Drop on Demand”) at 1MHz (continuous inkjet).
• inkjet technology has many advantages over conventional technologies such as screen printing, flexography and offset. Without a mask or screen, the media is printed using CAD software that stores the data.
• the inks used in an inkjet process are composed of at least one humectant, the effect of which is to avoid the drying of the ink at the outlet of the nozzle and thus to prevent clogging thereof. Because of their high boiling point and their good affinity for water, ethylene glycol, glycerol and propylene glycol are generally used as humectants in ink formulations.
• the inkjet process also has applications in the field of fuel cells and Solid Polymer Membrane (PEM) electrolysis.
• the ink used comprises catalysts such as platinum, particularly sensitive to physisorption pollution.
• catalysts such as platinum
• the introduction into such ink of a product having a high boiling point, as is the case of humectants, is also detrimental to the performance of the battery by a mechanism other than the pollution by physisorption. Indeed, during drying and during the formation of the active layer, such products do not evaporate completely and remain in the porosity of the active layer. The reduction of this porosity thus reduces the capacity of the gases to be diffused towards the catalytic sites.
• Y.-G. Yoon et al. (Y. Y. Y., G.-G. Park, T.H. Yang, J.-N. Han, WY., Lee, C.S.K., Effect of Pore Structure of Rent Catalyst in PEMFC on its performance, J. Hydrogen Energy 28 (2003) pp 657-662) illustrate the decrease in the performance of a fuel cell, following the introduction of 27 and 60% ethylene glycol into the fuel cell. formulation of a catalytic ink. As already stated, it appears necessary, for the production of fuel cell electrodes from the ink jet process, to minimize the humectant rate, or even to eliminate it. To date, the only technical solution proposed is however to retain the presence of a humectant in the ink, and then eliminate it after printing the layer.
• the present invention is based on the implementation of a temperature control system for ejecting the ink at a temperature below room temperature, and thus to avoid the evaporation of solvents and the clogging of the nozzles of the inkjet device.
• the present invention relates to an ink jet printing method in which the ejected ink is at a temperature of less than or equal to 20 ° C, advantageously between -20 ° C and 20 ° C. C, more preferably between -20 ° C and 10 ° C. More specifically, the lower bound relating to the temperature of the ink ejected is advantageously greater than or equal to -20 ° C.
• the temperature of the ink ejected is:
• the present invention provides an operating temperature below room temperature.
• the temperature in question is indeed the temperature of the ink ejected, not the possible temperature at which is maintained a device in which the ink transits or is stored (eg tank).
• the operating temperature is considered as that at which the ink is when it is ejected.
• the temperature of the ink can be adjusted to the claimed values, in particular by controlling the temperature at the ink tank and / or the ejection nozzles.
• a humectant is defined as a compound that avoids ink drying at the outlet of the nozzles and prevents clogging. of these.
• Such compounds are characterized in particular by their high affinity for water, and preferably a high boiling point.
• a class of preferred compounds according to the invention is the group of polyols (or glycols), and more particularly ethylene glycol, glycerol and / or propylene glycol.
• the invention is therefore characterized by the combination of the removal of humectants and the operation of the nozzles in a temperature range between -20 ° C and 20 ° C, preferably ⁇ 15 ° C, even ⁇ 10 ° C or even ⁇ 10 ° C.
• This operating mode results from the need to use an ink containing only solvents capable of evaporating at standard operating temperatures of a fuel cell (50 - 80 ° C), this to avoid any residual pollution of the fuel cell. catalyst or clogging of the porosity of the electrodes.
• the minimum temperature of -20 ° C is partly fixed by the formulation of the ink and its melting point, increasing the ratio of certain solvents such as ethanol to reduce this melting point.
• the temperature drop of the ink can cause changes in its properties, such as increasing its viscosity or changing its surface tension, making its implementation in the process more delicate. It is then possible to overcome these difficulties by making certain modifications to the composition of the ink or the inkjet device itself:
• the solvent or solvents represent at least 90% by weight of the ink, and even 95% or even 99%.
• the dry extract advantageously represents less than 10% by weight of the composition, more advantageously less than 5%, or even less than 1%;
• modifying the solvent ratio for example by increasing the rate or introducing solvents with a lower melting point
• the ink has the following composition:
• a catalyst advantageously Pt / C
• a solvent system advantageously a water / ethanol mixture, still more advantageously in a 50/50 or 25/75 mass ratio.
• a solvent system advantageously a water / ethanol mixture, still more advantageously in a 50/50 or 25/75 mass ratio.
• all the solvents present in the solvent system evaporate at the operating temperature of a fuel cell, generally between 50 and 80 ° C.
• the present invention relates to a device adapted to the implementation of the method described above.
• An ink jet device typically consists of:
• the inkjet device is further characterized by the fact that it comprises a temperature control system enabling the ink to be ejected at a temperature of less than or equal to 20 ° C., advantageously ⁇ 15 ° C. ° C, or even 10 10 ° C, or even ⁇ 10 ° C, but preferably> -20 ° C.
• Such a temperature control system can take many forms. It can be:
• a nozzle cooling system preferably with a Peltier effect in situ; and or a climatic chamber, advantageously at controlled temperature and humidity, intended to receive the printing device, or only the nozzles.
• the claimed process is advantageously carried out in a climatic chamber with controlled temperature and humidity.
• the use of the ink jet nozzles at a temperature below the dew point of the surrounding air can cause condensation (in the form of water or ice) on the nozzle and modify the ejection of the nozzle. 'ink.
• condensation in the form of water or ice
• a very hydrophobic product such as polytetrafluoroethylene (Teflon ® )
• the ink jet nozzles of the claimed device are thus coated with a hydrophobic product avoiding condensation, such as for example polytetrafluoroethylene (PTFE) better known under the trademark Teflon ® .
• PTFE polytetrafluoroethylene
• the present invention is further illustrated in connection with the printing of a catalytic layer of a PEMFC fuel cell electrode.
• the active ingredients are therefore on the one hand a catalyst, advantageously platinum carbon (Pt / C) and on the other hand a ionomer type Nation ® .
• the ink is formulated in a 50/50 water / ethanol binary solvent system.
• the device implemented according to the invention is represented in FIG.
• the reservoir (1) supplies the ink to the nozzle (2) which produces its ejection drop by drop on the support (4).
• the reservoir (1) can be refrigerated for example by the circulation of a fluid, allowing the ink to be sufficiently cooled to be ejected at the correct temperature. It is also possible to use a Peltier effect directly attached to the nozzle (2) to cool the ink at the time of its ejection. More generally, the implementation of the system in a refrigerated enclosure (3) is also possible. Of course, these different cooling means can be combined.
• T 50 ° C.
• the inks A and B are then ejected using the device according to the invention, shown in FIG. 1. This has an operating temperature lower than the ambient temperature, of the order of 3 ° C.
• the inks A and B certainly generate ejection difficulties because of an increased viscosity by decreasing the temperature. A greater tension is therefore necessary for their ejection. However, the inks and in particular the ink B no longer tend to clog the nozzles.
• the device and the method according to the invention therefore make it possible to use so-called conventional inks and, in a remarkable manner, to eliminate the presence of humectant.
• the formulation of the ink C corresponds to that of the ink B, in which the amounts of solvent have been doubled. Therefore, the printable assets, in this case the catalyst and the ionomer (itself diluted to 22%), are diluted.
• composition C no longer exhibits the ejection defects encountered with compositions A and B, and moreover, does not present any problems with nozzle clogging.

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• Chemical & Material Sciences (AREA)
• Engineering & Computer Science (AREA)
• Life Sciences & Earth Sciences (AREA)
• Materials Engineering (AREA)
• Wood Science & Technology (AREA)
• Organic Chemistry (AREA)
• General Chemical & Material Sciences (AREA)
• Chemical Kinetics & Catalysis (AREA)
• Electrochemistry (AREA)
• Manufacturing & Machinery (AREA)
• Inks, Pencil-Leads, Or Crayons (AREA)
• Ink Jet (AREA)
• Inert Electrodes (AREA)
• Ink Jet Recording Methods And Recording Media Thereof (AREA)
• Application Of Or Painting With Fluid Materials (AREA)
• Coating Apparatus (AREA)

Priority Applications (7)

Applications Claiming Priority (2)

Related Child Applications (1)

Publications (1)

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Family Applications (1)

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Families Citing this family (6)

Citations (12)

Family Cites Families (14)

• 2010
  • 2010-09-29 FR FR1057846A patent/FR2965214B1/fr not_active Expired - Fee Related
• 2011
  • 2011-07-19 WO PCT/FR2011/051719 patent/WO2012042133A1/fr not_active Ceased
  • 2011-07-19 BR BR112012033250A patent/BR112012033250A2/pt not_active IP Right Cessation
  • 2011-07-19 EP EP11752587.3A patent/EP2622671A1/fr not_active Withdrawn
  • 2011-07-19 KR KR1020127033783A patent/KR20130119334A/ko not_active Withdrawn
  • 2011-07-19 CA CA2803538A patent/CA2803538A1/fr not_active Abandoned
  • 2011-07-19 CN CN2011800314709A patent/CN102986068A/zh active Pending
  • 2011-07-19 JP JP2013530776A patent/JP2014501633A/ja active Pending
• 2012
  • 2012-12-19 US US13/719,628 patent/US20130127945A1/en not_active Abandoned

Patent Citations (12)

Non-Patent Citations (6)

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