WO2023135218A1 - Procédé et dispositif pour fournir des revêtements d'encre catalytique contenant du carbone uniforme pour des électrodes et procédé associé - Google Patents

Procédé et dispositif pour fournir des revêtements d'encre catalytique contenant du carbone uniforme pour des électrodes et procédé associé Download PDF

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Publication number
WO2023135218A1
WO2023135218A1 PCT/EP2023/050654 EP2023050654W WO2023135218A1 WO 2023135218 A1 WO2023135218 A1 WO 2023135218A1 EP 2023050654 W EP2023050654 W EP 2023050654W WO 2023135218 A1 WO2023135218 A1 WO 2023135218A1
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WO
WIPO (PCT)
Prior art keywords
ink
slot
coating head
die
pressure
Prior art date
Application number
PCT/EP2023/050654
Other languages
English (en)
Inventor
Søren Juhl ANDREASEN
Original Assignee
Advent Technologies Gmbh
Priority date (The priority date is an assumption and is not a legal conclusion. Google has not performed a legal analysis and makes no representation as to the accuracy of the date listed.)
Filing date
Publication date
Application filed by Advent Technologies Gmbh filed Critical Advent Technologies Gmbh
Publication of WO2023135218A1 publication Critical patent/WO2023135218A1/fr

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Classifications

    • 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
    • H01M4/8803—Supports for the deposition of the catalytic active composition
    • H01M4/8807—Gas diffusion layers
    • B—PERFORMING OPERATIONS; TRANSPORTING
    • B05—SPRAYING OR ATOMISING IN GENERAL; APPLYING FLUENT MATERIALS TO SURFACES, IN GENERAL
    • B05C—APPARATUS FOR APPLYING FLUENT MATERIALS TO SURFACES, IN GENERAL
    • B05C11/00—Component parts, details or accessories not specifically provided for in groups B05C1/00 - B05C9/00
    • B05C11/10—Storage, supply or control of liquid or other fluent material; Recovery of excess liquid or other fluent material
    • B05C11/1002—Means for controlling supply, i.e. flow or pressure, of liquid or other fluent material to the applying apparatus, e.g. valves
    • B05C11/1007—Means for controlling supply, i.e. flow or pressure, of liquid or other fluent material to the applying apparatus, e.g. valves responsive to condition of liquid or other fluent material
    • B05C11/1013—Means for controlling supply, i.e. flow or pressure, of liquid or other fluent material to the applying apparatus, e.g. valves responsive to condition of liquid or other fluent material responsive to flow or pressure of liquid or other fluent material
    • B—PERFORMING OPERATIONS; TRANSPORTING
    • B05—SPRAYING OR ATOMISING IN GENERAL; APPLYING FLUENT MATERIALS TO SURFACES, IN GENERAL
    • B05C—APPARATUS FOR APPLYING FLUENT MATERIALS TO SURFACES, IN GENERAL
    • B05C5/00—Apparatus in which liquid or other fluent material is projected, poured or allowed to flow on to the surface of the work
    • B05C5/02—Apparatus in which liquid or other fluent material is projected, poured or allowed to flow on to the surface of the work the liquid or other fluent material being discharged through an outlet orifice by pressure, e.g. from an outlet device in contact or almost in contact, with the work
    • B05C5/0254—Coating heads with slot-shaped outlet
    • 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
    • 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 relates to the improving fuel cell electrode coating quality by ink pressure monitoring and control.
  • Printing the entire electrode layer-by-layer on the gas diffusion substrate requires improvement in the quality of the printed layers, in order to make electrode production by printing competitive compared to traditional manufacturing methods.
  • the objective of this invention is a system for producing electrode layers for electrolytic cells, such as fuel cells, of superior quality, and a related method.
  • An electrode that needs to function in an electrochemical cell is, in the case of a polymer electrolyte membrane (PEM) fuel cell assembled in a membrane electrode assembly (MEA) and consists of two electrodes (a cathode and an anode) and a polymer electrolyte membrane, as shown in Figure 1.
  • PEM polymer electrolyte membrane
  • MEA membrane electrode assembly
  • the electrodes need to contain an electrocatalyst, such as platinum, or an alloyed catalyst such as Pt-Rh, Pt-Pd, Pt-Ni, Pt-Co, have electrically conductive abilities, typically inflicted by comprising either a metal oxide or carbon, or a combination of both.
  • the electrodes need accessibility to an electrolyte, which is typically a liquid or a solid, and to the anode or cathode gas species, which are typically fluids, gaseous or liquid.
  • An electrode needs the presence of sites where catalyst material, the fuel species and electrolyte are present, these are the so-called triple phase boundaries, where the different electrochemical reactions can occur.
  • Other species can also be added to both the anode (for example, CO2, CO, H2O, N2, CH4 or CH3OH) or to the cathode (such as N2, CO2 or H2O).
  • the correct properties and distribution of the different layers comprising the electrodes is what creates a functional fuel cell that can deliver an electrical voltage continuously for as long as sufficient fuel and operating conditions are present.
  • a porous structure of an electrode is needed in order to fulfil these requirements.
  • the bulk substrate has the main function of distribution of gas to the triple phase boundaries, the active catalyst sites, but also acts as electron transportation layer for electrons freed in the reactions on either anode or cathode.
  • GDLs are, carbon paper, woven carbon felt, non-woven carbon material or hybrid/composite editions of these. Different treatments of the GDL are possible to achieve the properties needed, for example treatment with PTFE for adding hydrophobic characteristics.
  • MPL microporous layer
  • MPL can have the functionality of blocking unwanted access of liquids from the gasses to the electrolyte or from the electrolyte to the gas stream, depending on the type of fuel cell in question.
  • the catalyst layer (CL) is an electrically conductive porous layer that contains nano-particles of for example platinum or platinum alloys that support the desired fuel cell electrochemical reactions, typically in combination with for example carbon black particles.
  • Different coating techniques of distributing the microporous layer and the catalyst layer onto a GDL substrate or a membrane exist.
  • the system described could be used for, but is not limited to, slot-die coating of an ink for the catalyst layer of a fuel cell onto a gas diffusion layer substrate or onto another substrate.
  • the method presented in this application is usable for improving the coating process by controlling the ink/paste delivery pressure, either by using a sensor mounted on or near a slot-die coating head or by designing a special coating head that supports stabilization of the ink delivery.
  • Ink can be a complex medium, composed of solvents, pigments, dyes, resins, lubricants, solubilizers, surfactants, particulate matter, fluorescents, and other materials.
  • inks serve many purposes; the ink's carrier, colorants, and other additives affect the flow and thickness of the ink and its dry appearance.
  • Ink here for the purpose of printing layers of electrodes for an electrochemical cell is a gel, sol, or solution that comprises at least one electro-conducting component and catalyst for printing electrode designs. Ink can be in a thicker paste form.
  • Fig. 5 The Ink or paste pressure as a function of time
  • a membrane electrode assembly (MEA) is presented in top, comprising two electrodes (an anode and a cathode) with a polymer electrolyte membrane in between the electrodes.
  • a fuel cell electrode structure is shown in the lower part of Figure 1, comprising a catalyst layer (CL) positioned closest to the polymer electrolyte membrane, a microporous layer (MPL) and a gas diffusion layer (GDL) facing the gas or liquid stream, depending on the electrode type.
  • CL catalyst layer
  • MPL microporous layer
  • GDL gas diffusion layer
  • FIG 3 the principle of electrode coating is shown, where a roll delivery system (12) continuously moves a substrate (10) past a slot-die ink coating head (2) (stationary or moving) with an opening (4), where an ink (6) or paste is continuously pumped through, leaving an ink or paste layer on top of the substrate with the desired properties.
  • a roll delivery system (12) continuously moves a substrate (10) past a slot-die ink coating head (2) (stationary or moving) with an opening (4), where an ink (6) or paste is continuously pumped through, leaving an ink or paste layer on top of the substrate with the desired properties.
  • Several layers can be deposited on top of each other, the properties of the ink or paste can be different for each layer, if different properties are required. It shall be noted that of cause also only one layer containing one or the other material may be deposited.
  • the ink coating layer (6) could be deposited on a substrate (10) using a slot die coating head (2), as in the illustration, or by any other coating method.
  • the ink (6) is supplied from a reservoir (14) to the slot-die ink coating head (2).
  • a sensor (P) is integrated in the slot-die ink coating head (2)
  • the sensor (P) is connected to an ink pump (not illustrated) via a control unit (20) such that the pressure and/or flow of ink to the slot-die ink coating head (2) is kept constant, whereby the deposited ink (6) on the substrate (10) has a uniform thickness.
  • the control unit (20) may also receive data from the substrate delivery system (12) such that also the velocity of the substrate (10) passing by the opening (4)
  • FIG. 4 the possible positions of a pressure sensor, indicated with P, are shown.
  • the sensor In fig. 4a) the sensor is positioned in the supply line adjacent the inlet 18 of the coating slot die head (2).
  • the sensor (P) In fig. 4b) the sensor (P) is arranged at a special pressure sensor conduit (20), provided inside the slot die head (2).
  • the sensor (P) is arranged in the ink conduit (22) leading the ink towards the opening (4) in the slot die head (2).
  • the actual position of the sensor (P) may be decided according to the design options and possibilities in each specific case.
  • the important aspect of the invention is that the sensor detects the pressure and/or flow of ink at the sensors location and transmits this data to a control unit (20) - see fig 3.
  • This input data is used to adjust the ink pressure or flowrate such that a substantially constant amount of ink may be transferred to the substrate (10), as described above. It is also foreseen that the input data from the sensor P may be used to control the velocity of the substrate (10) past the opening (4), as constant ink flow and higher velocity will deposit a thinner ink layer (6) on the substrate (10), whereas the same constant ink flow at lower velocity will deposit a thicker layer (6) on the substrate (10).
  • FIG. 5 a diagram is showing the ink/paste pressure as a function of time. Initially in the first period after having started the system - for example as shown in fig. 3, the pressure will fluctuate until a near constant pressure is attained. If the printing system does not comprise the inventive pressure sensor and control unit according to the present invention the ink pressure will slowly drop as indicated by the average pressure line (30). Initially, the ink pressure is constant, but at a certain ink flow, the pressure continuously drops over the course of time the coating lasts. This could be due to changes in viscosity or in other related parameters and processes during the coating.
  • the average pressure will remain constant as indicated by the dashed line (32). From this it is clear that if the substrate is moving at the same speed in both instances, the deposited ink layer deposited according to the average line (30) will be thinner and thinner as time goes, due to the falling ink pressure, whereas if the inventive system is implemented and the pressure remains constant throughout the printing process the deposited ink layer will have an even thickness throughout the entire printing process. In this manner, by implementing sensor(s) and a control unit the quality of the finished product - for example an electrode, will be substantially improved over the electrode not having had its ink layer deposited by the inventive concept.
  • a system with a control over ink pressure is shown using for example feedback control. Compensation of the pressure changes of the delivered ink is possible.
  • the adjustment could be performed using a feedback control, based on a controller such as a P, PI or PID controller, or using any other type of control algorithm, depending on the size of the system, its components such as a pump, and parameters such as a coating width, a substrate speed, etc.
  • a system for manufacturing an electrochemical cell with printed electrode layers comprising a stationary slot-die ink coating head with a pressure sensor and a feedback control for compensating for the changing pressure of the delivered ink, and means for advancing a substrate to be printed on past the slot-die ink coating head.
  • the feedback control is configured to monitor the pressure of ink delivery measured by the pressure sensor and to compensate for the measured pressure changes by adjusting one or both of: a speed at which a substrate to be printed on is advancing past the slot-die ink coating head, a volume rate of the ink delivery, and, hence, the pressure of the delivered ink.
  • the feedback control for compensating for the changing pressure is performed using a controller that is selected from P, PI or PID controllers, or controllers using an algorithm depending on factors selected from one or more of: a type of an ink pump used; a width of the coating stripe to be applied;
  • the pressure sensor is located exterior to the slot-die ink coating head in direct connection with an ink inlet line of the slot-die ink coating head.
  • the pressure sensor is located exterior to the slot-die ink coating head, in a direct connection with the slot-die ink coating head, but without a direct connection with the ink inlet line of the slot-die ink coating head.
  • the pressure sensor is integrated into the slotdie ink coating head.
  • Another aspect of the invention is an electrochemical cell comprising a membrane electrode assembly wherein a polymer electrolyte membrane is placed in between a first electrode (a cathode) and a second electrode (an anode), characterized in that said first and second electrodes comprise layers printed with ink comprising an electrically conductive material and an electro catalyst, the printing is performed by the system disclosed in any of previous embodiments, resulting in homogeneous quality electrode layers in the electrochemical cell.
  • said first and second electrodes each comprises a catalyst layer (CL) facing towards the polymer electrolyte membrane, a microporous layer (MPL) and a gas diffusion layer (GDL), the catalyst layers being in contact with an electrolyte, and the gas diffusion layers being in contact with a gas stream during the operation of the electrochemical cell
  • the catalyst layer (CL) is an electrically conductive porous layer comprising nanoparticles of for example platinum or platinum alloys, optionally, in combination with carbon black particles
  • the gas diffusion layer (GDL) is selected as one single material or a hybrid or a composite of several materials selected from a group comprising carbon paper, woven carbon felt and non-woven carbon material
  • the gas diffusion layer (GDL) is treated to achieve a specific quality.
  • a treatment with PTFE is performed in order to render GDL layer hydro- phobic.
  • the MPL is a hygro-diode, biasing liquid transport in one direction, selected from the MPL being the hygro-diode blocking unwanted access of liquids from the gasses to the electrolyte, or the MPL being the hygro-diode blocking unwanted access of liquids from the electrolyte to the gas stream.
  • the electro catalyst is selected from a group comprising platinum and alloyed catalysts such as Pt-Rh, Pt- Pd, Pt-Ni or Pt-Co, and the electrically conductive material is a metal oxide or a carbon.
  • the anode is configured to receive additional compounds selected from one or more of CO2, CO, H2O, N2, CH4 and CH3OH
  • the cathode is configured to receive additional compounds selected from one or more of N2, CO2 and H2O.
  • the electrochemical cell is a fuel cell.

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  • Engineering & Computer Science (AREA)
  • Manufacturing & Machinery (AREA)
  • Chemical & Material Sciences (AREA)
  • Chemical Kinetics & Catalysis (AREA)
  • Electrochemistry (AREA)
  • General Chemical & Material Sciences (AREA)
  • Physics & Mathematics (AREA)
  • Fluid Mechanics (AREA)
  • Inert Electrodes (AREA)

Abstract

L'invention concerne un système pour des électrodes de revêtement d'encre pour des piles à combustible comprenant une commande de pression et permettant de compenser les changements de pression, ce qui permet d'obtenir des revêtements d'électrode de qualité homogènes.
PCT/EP2023/050654 2022-01-14 2023-01-12 Procédé et dispositif pour fournir des revêtements d'encre catalytique contenant du carbone uniforme pour des électrodes et procédé associé WO2023135218A1 (fr)

Applications Claiming Priority (2)

Application Number Priority Date Filing Date Title
DKPA202270018 2022-01-14
DKPA202270018 2022-01-14

Publications (1)

Publication Number Publication Date
WO2023135218A1 true WO2023135218A1 (fr) 2023-07-20

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Citations (5)

* Cited by examiner, † Cited by third party
Publication number Priority date Publication date Assignee Title
US20090169950A1 (en) * 2007-12-28 2009-07-02 E. I. Du Pont De Nemours And Company Production of catalyst coated membranes
JP4974580B2 (ja) * 2006-05-08 2012-07-11 日東電工株式会社 ダイ方式塗布装置及び塗布方法
JP6057539B2 (ja) * 2012-02-28 2017-01-11 三星エスディアイ株式会社Samsung SDI Co., Ltd. コーティング幅が調節可能なスロットダイ
JP2018069230A (ja) * 2016-10-20 2018-05-10 株式会社Sat 塗布ヘッド及び塗布装置
CN111804529A (zh) * 2019-04-10 2020-10-23 耿晋 一种电池极片涂布调节装置及其调节方法

Patent Citations (5)

* Cited by examiner, † Cited by third party
Publication number Priority date Publication date Assignee Title
JP4974580B2 (ja) * 2006-05-08 2012-07-11 日東電工株式会社 ダイ方式塗布装置及び塗布方法
US20090169950A1 (en) * 2007-12-28 2009-07-02 E. I. Du Pont De Nemours And Company Production of catalyst coated membranes
JP6057539B2 (ja) * 2012-02-28 2017-01-11 三星エスディアイ株式会社Samsung SDI Co., Ltd. コーティング幅が調節可能なスロットダイ
JP2018069230A (ja) * 2016-10-20 2018-05-10 株式会社Sat 塗布ヘッド及び塗布装置
CN111804529A (zh) * 2019-04-10 2020-10-23 耿晋 一种电池极片涂布调节装置及其调节方法

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