WO2004098773A2 - Catalyst layer containing an acidic ion exchanger and specific base polymers, suitable catalyst paste, and method for the production thereof - Google Patents

Catalyst layer containing an acidic ion exchanger and specific base polymers, suitable catalyst paste, and method for the production thereof

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Publication number
WO2004098773A2
WO2004098773A2 PCT/DE2004/000896 DE2004000896W WO2004098773A2 WO 2004098773 A2 WO2004098773 A2 WO 2004098773A2 DE 2004000896 W DE2004000896 W DE 2004000896W WO 2004098773 A2 WO2004098773 A2 WO 2004098773A2
Authority
WO
Grant status
Application
Patent type
Prior art keywords
catalyst
paste
basic
layer
additive
Prior art date
Application number
PCT/DE2004/000896
Other languages
German (de)
French (fr)
Other versions
WO2004098773A3 (en )
Inventor
Kai Jakoby
Morten Schonert
Andreas GLÜSEN
Carola Schlumbohm
Detlef Stolten
Original Assignee
Forschungszentrum Jülich 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

Links

Classifications

    • HELECTRICITY
    • H01BASIC ELECTRIC ELEMENTS
    • H01MPROCESSES OR MEANS, e.g. BATTERIES, FOR THE DIRECT CONVERSION OF CHEMICAL INTO ELECTRICAL ENERGY
    • H01M4/00Electrodes
    • H01M4/86Inert electrodes with catalytic activity, e.g. for fuel cells
    • H01M4/8663Selection of inactive substances as ingredients for catalytic active masses, e.g. binders, fillers
    • H01M4/8668Binders
    • BPERFORMING OPERATIONS; TRANSPORTING
    • B01PHYSICAL OR CHEMICAL PROCESSES OR APPARATUS IN GENERAL
    • B01JCHEMICAL OR PHYSICAL PROCESSES, e.g. CATALYSIS OR COLLOID CHEMISTRY; THEIR RELEVANT APPARATUS
    • B01J23/00Catalysts comprising metals or metal oxides or hydroxides, not provided for in group B01J21/00
    • B01J23/38Catalysts comprising metals or metal oxides or hydroxides, not provided for in group B01J21/00 of noble metals
    • B01J23/40Catalysts comprising metals or metal oxides or hydroxides, not provided for in group B01J21/00 of noble metals of the platinum group metals
    • BPERFORMING OPERATIONS; TRANSPORTING
    • B01PHYSICAL OR CHEMICAL PROCESSES OR APPARATUS IN GENERAL
    • B01JCHEMICAL OR PHYSICAL PROCESSES, e.g. CATALYSIS OR COLLOID CHEMISTRY; THEIR RELEVANT APPARATUS
    • B01J31/00Catalysts comprising hydrides, coordination complexes or organic compounds
    • B01J31/02Catalysts comprising hydrides, coordination complexes or organic compounds containing organic compounds or metal hydrides
    • B01J31/06Catalysts comprising hydrides, coordination complexes or organic compounds containing organic compounds or metal hydrides containing polymers
    • B01J31/08Ion-exchange resins
    • BPERFORMING OPERATIONS; TRANSPORTING
    • B01PHYSICAL OR CHEMICAL PROCESSES OR APPARATUS IN GENERAL
    • B01JCHEMICAL OR PHYSICAL PROCESSES, e.g. CATALYSIS OR COLLOID CHEMISTRY; THEIR RELEVANT APPARATUS
    • B01J37/00Processes, in general, for preparing catalysts; Processes, in general, for activation of catalysts
    • B01J37/02Impregnation, coating or precipitation
    • B01J37/0215Coating
    • B01J37/0219Coating the coating containing organic compounds
    • HELECTRICITY
    • H01BASIC ELECTRIC ELEMENTS
    • H01MPROCESSES OR MEANS, e.g. BATTERIES, FOR THE DIRECT CONVERSION OF CHEMICAL INTO ELECTRICAL ENERGY
    • H01M4/00Electrodes
    • H01M4/86Inert electrodes with catalytic activity, e.g. for fuel cells
    • H01M4/8605Porous electrodes
    • HELECTRICITY
    • H01BASIC ELECTRIC ELEMENTS
    • H01MPROCESSES OR MEANS, e.g. BATTERIES, FOR THE DIRECT CONVERSION OF CHEMICAL INTO ELECTRICAL ENERGY
    • H01M4/00Electrodes
    • H01M4/86Inert electrodes with catalytic activity, e.g. for fuel cells
    • H01M4/88Processes of manufacture
    • H01M4/8825Methods for deposition of the catalytic active composition
    • H01M4/8828Coating with slurry or ink

Abstract

Known prior art catalyst pastes are, as a rule, to liquid for coating by means of silk-screen printing or colour ductors. The invention relates to a method for the production of a catalyst paste, containing an acidic ion exchanger and specific base polymers, which is especially suitable for coating methods such as silk-screen printing and colour ductors due to the viscosity thereof. A catalyst layer produced with said inventive catalyst paste does not regularly display any loss in performance compared to catalyst layers produced by prior art standard catalyst pastes. Even improved performance properties are partially obtained.

Description

Catalyst layer suitable catalyst paste, and the production method thereof

The invention relates to a process for producing a catalyst layer, in particular a catalyst layer which is suitable for use in a fuel cell.

State of the art

From the prior art standard commercially available catalyst powder are known which are usually applied by spraying or pouring. Further, other application method for applying a catalyst paste are known which are particularly suitable for large-scale applications. Difficulties arise regularly when a technically relevant application methods such as silk screening or screen printing, a certain minimum viscosity of the paste to be applied is required. The standard catalyst powder and commercially available conventional methods for producing a corresponding catalyst paste does not meet these requirements for viscosity regularly. The catalyst pastes prepared in the traditional way are usually very liquid, meaning they have a viscosity below 50 mPas and therefore are not suitable for some technically relevant application method (eg. As knife coating, screen printing). So far, suitable catalyst pastes were first produced, which lead to a powerful catalyst layer. Only after a procedure was sought, this paste was processed exactly with that. This meant that the application process has been adapted to the characteristics of the selected paste paste. The disadvantage only such application method could be selected frequently that are not suitable for large-scale implementation.

Trying to adapt by conventional thickeners, the catalyst pastes in a more advantageous application methods have regularly led to catalyst layers that no longer met the required performance requirements. To act to designate the required viscosity increase, the thickeners previously used the paste is supplied in an amount such that deteriorate the properties of the catalyst layer produced in generally disadvantageous.

Polymer networks known to lead even at low polymer content to an increase in viscosity of pastes. but the addition of cross-linked polymer to catalyst paste is not effective on a regular basis, as cross-linked polymers are only sparingly soluble, and homogeneous incorporation of all components of the paste is very difficult in the network. but a homogeneous distribution of the catalyst is often absolutely necessary for the performance of the final catalyst layer. In addition, the required in the dispersion manufacturing process steps leading high shear regularly to the destruction of the polymer network. For the transmission of the art in the doctor blade works a coating machine for example it is necessary to adjust the viscosity of the catalyst paste in a range of at least 200 mPas. In contrast, the conventional pastes for the production, for example, an anodic PtRu catalyst layer paste show other properties. When carbon supported PtRu catalysts C an increase in the solid-solvent ratio of 0.2 to 0.6, the paste viscosity can increase significantly from 15 to 150 mPas. However, such a significant increase in the solid solvent ratio usually leads to instability of the paste, since often the limit of solubility is reached. Therefore, these aforementioned Vorgehenswei- se is unsuitable for adjusting the paste viscosity. Further, has been found to be disadvantageous that very thick layers having poor mechanical properties and high PtRu assignments ben erge- when doctoring by the high solids content of the paste.

Problem and Solution

The object of the invention is to provide a catalyst layer which can be applied by a simple coating method, such as the doctor blade coating or screen printing, and as a finished layer has no significant performance degradation over those layers, which are applied with other application methods. The object of the invention is also to provide a suitable for such a catalyst layer and the application method above catalyst paste available.

A first object of the invention is achieved by a viscous catalyst paste according to the main claim. A WEI tere object is achieved by a process for preparing this catalyst paste according to independent claim 6 and by a method for producing a catalyst layer according to independent claim 14. Advantageous embodiments can be found in each case it rückbe- coated claims again.

The invention

In the present invention it was found that the addition of a basic additive, results in a catalyst paste comprehensively supported and / or unsupported catalyst particles and at least one acidic ion-exchange to an advantageous increase in the viscosity of the paste. The advantage of the method is the small amount of additive, on the one hand leads to a significant increase in viscosity, on the other hand does not cause deterioration of the catalyst properties regularly.

The advantageous action of basic additives, in particular basic polymers and / or copolymerizable ren as an additive to a catalyst paste is based on an acid-base reaction that occurs regularly between a default, present in the paste acidic ion-exchange with a basic additive as an additive , As suitable basic additives in the context of the invention polymers and copolymers are in particular polymers to be understood with basic monomer units. Further, mixtures of different polymers and / or copolymers having basic units have been found to be Monomerei- basic additives suitable.

In the inventive pastes polymer networks are built up during the paste production by the basic additives by the existing ionenleitfähi- ge polymer (an acid) is crosslinked, for example with a basic polymer. The formation of a network of basic and acidic polymers is known in principle, but can not be applied in a simple and nahelie- restrictive manner because of the complexity of the system catalyst paste here.

The requirements of the inventive method for the production of a catalyst paste comprising this

- the selection of special basic additives, in particular polymers and / or copolymers fertil for the application are useful in a catalyst paste,

- the selection of the appropriate amount of basic additives, which at the same time causes an optimal viscosity of the paste and an optimal performance of the layer,

- the selection and adaptation of a Dispergierver- proceedings for the preparation of the catalyst layers, to achieve the formation of a network.

Polyethyleneimine is known for example as a basic polymer in the literature, which tends to form a gel with acidic polymers. For use in a catalyst paste is polyethyleneimine, however, has proved to be unusable.

In the context of this invention, basic polymers have been found comprising a ring system, a nitrogen atom to be particularly effective for an increase in viscosity in egg ner catalyst paste. These advantageous basic additives include, for example, polymers and / or copolymers containing monomeric units comprising pyridine, such as 4-vinylpyridine or 2-vinylpyridine. Also particularly suitable are polymers and / or copolymers of pyrrole

Monomer units. With included within the scope of this invention are also basic additives which are present as basic polymer blends, copolymer blends of basic or as a polymer-copolymer blend.

It has surprisingly been found that these

Network formation at very small quantities (> 0.1 wt .-%) of suitable basic additive is the desired effect. An advantageous additions have been found to be a conventional catalyst paste of only 0.1 to 3 wt .-%, in particular from 0.4 to 2 wt .-%, and particularly advantageously from 0.6 to 1.5 wt .-%. These additions cause such beneficial increase in viscosity (> 100 mPas, in particular> 200 mPas) of the catalyst paste that they proceed in APPLICATION: such as screen printing or blade coating can be applied. The wt .-% details relate to the solids content of basic additive based on the mass of dried catalyst layer. The viscosity is measured sen at a shear rate of 100 per second. the basic additive is advantageously added in the form of a solution. The use of such small amounts of basic additive does not regularly leads to an adverse effect on performance of the catalyst layer produced. Where appropriate, particularly at higher additions, a slight impairment of the performance can be reversed or even over-compensated by a post-treatment of the finished catalyst layer in a dilute acid. Be advantageous, in particular, sulfuric acid has been found as a dilute acid. The aforementioned effect can be even further improved by heating up to 90 ° C.

In the aforementioned basic additives in contact with the acidic ion-exchange gel formation occurs in the rule. The formation of the gel, and thus the desired increase in viscosity is regularly depending on the type of metering of the basic additive to the rest of the catalyst paste. An expert in rheology is known that gelation may not occur too slowly or too fast metering of the components, or an initially formed gel by high shear forces can be destroyed. Therefore, the mixing process is shut according to the components.

Ideally, the dispersion of the supported and / or unsupported catalyst and acidic ion-exchange polymer is prepared as is usual according to the prior art to ensure an even distribution of the catalyst particles for the preparation of the catalyst layer first. Only after that the basic additive, for example in the form of a basic polymer and / or copolymer is advanta- way as solution.

As a particularly effective method has been found, in which a basic polymer solution is coated on a dispersion of the supported and / or unsupported catalyst and acidic ion-exchange. By shaking a mixture of the two phases and the gelation occurs regularly. By a subsequent ultrasound treatment, the homogenization can be further increased advantageous.

In this invention, the new viscous catalyst paste is regarded as an intermediate product for further processing into a catalyst layer as a final product ..

SPECIFIC DESCRIPTION

The subject matter of the invention with reference to figures is explained in detail, without departing from the subject matter of the invention be limited thereby. Show it

1 shows the half-cell measurement at 80 ° C, wherein in each case the anode comprises a catalyst layer: bold curve: catalyst paste containing 0.9 wt .-% PVP, thin curve: catalyst paste without addition of PVP.

Figure 2: Half-cell measurement at 50 ° C, wherein in each case the anode comprises a catalyst layer:

Catalyst paste containing 1.5 wt .-% PVP treatment (bold curve), a catalyst paste containing 1.5 wt .-% PVP no post-treatment (thin curve) and catalyst paste without the addition of PVP (dashed curve).

In this invention, a catalyst paste for the production of a catalyst layer to Verfü- g ng is provided, wherein a catalyst paste, a basic additive, in particular a basic polymer, preferably poly (4-vinylpyridine) (PVP), is added in such an amount so that the now present catalyst paste has a viscosity of more than 100 mPas, in particular of more than 200 mPas, which is regularly required for application by doctor blade or screen printing.

In the case of the anodic PtRu catalysts that the viscosities of the pastes is raised abruptly by a gerin- ge amount of added polymeric additive has been found. Simultaneously, the electrochemical performance of the layers as little as possible in this way. The influence of the additive polyvinyl pyridine (PVP) on the viscosity and e- lektrochemische performance of pastes turned out to be particularly advantageous. The basic functional groups of the polyvinylpyridine perform interaction with sulfonic acid groups of the Nafion ® to form a crosslinked polymer gel on ion cluster in the catalyst paste.

The electrochemical performance of the catalyst layers produced by the novel process with PVP addition to the anode diffusion layer were evaluated. For this purpose the pastes were plotted with a table knife coater on diffusion layers gene and then to the membrane electrode assemblies (MEAs) with an area of 2 cm 2 processed. Then half-cell measurements were carried out in which carried out the survey for a hydrogen evolving cathode as a reference electrode, in order to rule cathode side effects on the performance curves. Between anode and cathode a voltage (anode positive) was applied and the current measured. 1 molar solution of methanol is oxidized at the anode, at the cathode hydrogen is evolved. The anode potential is based on an electroless hydrogen evolution electrode in the cathode chamber. The higher current densities to be achieved at very low anode potential, the better is the performance of the tested anode for the oxidation of methanol. A correction for ohmic see losses is made. Since different samples typically have slightly different precious metal assignments, is standardized to the noble occupation.

The results, which are shown in Figure 1, shows that the performance curves of the PVP-layers which an analog layer without PVP are comparable at a level of 0.9 wt .-%.

At higher PVP-contents (> 1.5 wt .-%) was a one-hour after-treatment of the gas diffusion electrodes kelten screened at 80 ° C carried out in dilute sulfuric acid in order to achieve comparable performance curves (see Figure 2). In PVP content of 0.9 wt .-% this after-treatment resulted in only minor improvements. The results show that the invention mixed with basic additives catalyst paste has similarly good performance as a finished catalyst layer, such as conventional, highly liquid catalyst pastes, al- lerdings has the great advantage of being able to be applied with technical application method.

Subsequently, the parameter for increasing the viscosity of a PtRu catalyst paste with polyvinylpyridine are listed as basic supplementary in one embodiment.

Approach to catalyst paste:

3.0 g Pt / Ru-C (40% noble metal) 6.0 ml of water 6.0 ml of 2-propanol 8.55 g Nation ® - solution (15 wt .-%)

Treatment of the catalyst paste: 10 min ultrasonic bath 3 min Ultraturrax

Approach to the basic additive: 342 mg PVP solution (PVP 210 mg in 2 ml of 2-propanol =

11.6 wt .-%) corresponds to 0.92 wt .-% PVP in solid

Addition of the additive:

the PVP solution is allowed to walk carefully to the vessel wall coming down, containing the catalyst paste. There is an overlay of the catalyst paste through which the additive-containing solution. 1 min shaking

10 min ultrasonic

By the aforementioned mode of mixing is particularly simple a polymer network is formed, which leads to a significant increase in viscosity.

Claims

claims
1. A catalyst layer comprising supported or un- supported catalyst particles and at least one acidic ion-exchange polymer, characterized in that the catalyst-paste at least by weight, a polymer or copolymer comprising monomer units having a nitrogen-containing basic ring system as a basic additive in a proportion of 0.1 to 3 comprises .-%, based on a prepared therefrom dried catalyst layer.
2. Catalyst layer according to claim 1, the basic additive with a contents of 0.4 to 2 wt .-%, in particular in a proportion of 0.6 to
1.5 wt .-% comprising.
3. The catalyst layer according to any one of the preceding
Claims 1 to 2, comprising at least one polymer or copolymer comprising 4-vinyl pyridine and / or 2-vinylpyridine and / or pyrrole as a basic additive.
4. A process for producing a catalyst layer according to any one of claims 1 to 3 on a substrate, comprising the steps of
- to prepare a paste is satorteilchen to a mixture of supported or unsupported catalysis and at least one acidic ion-exchange at least a polymer or copolymer comprising monomer units having a nitrogen-containing basic ring system as a basic additive with a content between 0.1 and 3 wt .-% , based on a prepared therefrom dried catalyst layer is added and homogenized so that the vis- viscosity by increasing the total paste to more than 100 mPas, in particular more than 200 mPas, - the paste thus prepared is applied to the substrate.
5. The method of claim 4 wherein the basic additive in a proportion between 0.4 and 2 wt .-%, in particular between 0.6 and 1.5 wt .-% is added to prepare the paste.
6. The method according to any one of claims 4 to 5, in the preparation of the paste at least one polymer or copolymer comprising 4-vinyl pyridine or 2-
Vinyl pyridine or pyrrole is added as monomer units.
7. The method according to any one of claims 4 to 6 wherein the basic additive is added in the form of a solution for the preparation of the paste.
8. The method of claim 4 to 7, wherein the basic additive is layered-exchangeable as a solution over the mixture of supported or ungetragerte catalyst particles and at least one acidic Io for the preparation of the paste and is then homogenized by shaking.
9. The method of claim 4 to 8, wherein the catalyst paste is applied by doctor blading or screen printing to the substrate.
10. The method according to any one of claims 4 to 9, wherein the catalyst layer applied to post-treatment is subjected.
11. The method according to any one of claims 4 to 10, wherein the coated catalyst layer is treated at temperatures up to 90 ° C in a dilute acid.
12. The method according to any one of claims 4 to 11, wherein the anode diffusion layer of a fuel cell is selected as a substrate.
PCT/DE2004/000896 2003-05-06 2004-04-29 Catalyst layer containing an acidic ion exchanger and specific base polymers, suitable catalyst paste, and method for the production thereof WO2004098773A3 (en)

Priority Applications (2)

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DE10320320.6 2003-05-06
DE2003120320 DE10320320B4 (en) 2003-05-06 2003-05-06 Catalyst layer suitable catalyst paste, and the production method thereof

Applications Claiming Priority (1)

Application Number Priority Date Filing Date Title
EP20040730194 EP1624966A2 (en) 2003-05-06 2004-04-29 Catalyst layer, suitable catalyst paste, and method for the production thereof

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WO2007054570A1 (en) * 2005-11-14 2007-05-18 Basf Se Amine-containing catalyst ink for fuel cells

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DE102004024845A1 (en) * 2004-05-13 2005-12-08 Volkswagen Ag Catalyst layer`s manufacture for high-temperature fuel cells, involves applying electrode paste on substrate under blade pressure to form catalyst layers, drying layers above room temperature and soaking dried layers in acid

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WO2007054570A1 (en) * 2005-11-14 2007-05-18 Basf Se Amine-containing catalyst ink for fuel cells

Also Published As

Publication number Publication date Type
EP1624966A2 (en) 2006-02-15 application
DE10320320A1 (en) 2004-12-16 application
DE10320320B4 (en) 2007-08-16 grant
WO2004098773A3 (en) 2005-02-10 application

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