PEM FUEL CELL ELECTROCATALYSTS AND CATALYST LAYERS

Ali Hashemi Sharif University of Technology

Catalyst Synthesis Techniques Particle Size and Shape Control Physical Characterization of Electrocatalysts Catalyst Contamination in PEM Fuel Cells

Fuel cell

is an electrochemical device that continuously and directly converts the chemical energy of externally supplied fuel and oxidant to electrical energy

Five most common technologies are:

Polymer electrolyte membrane fuel cells (PEM fuel cells or PEMFCs) Alkaline fuel cells (AFCs) Phosphoric acid fuel cells (PAFCs) Molten carbonate fuel cells (MCFCs) and Solid oxide fuel cells (SOFCs)

Basic Reactions

Anode Reaction
H22H++2e

Cathode Reaction
1/2O2+2H++2eH2O

Catalysis Synthesis Methods

Low-temperature Chemical Precipitation

Supported and unsupported catalysts

can

be made via addition of a reducing agent to a platinum-salt solution can be made by the co-precipitation of a solution of two metal precursor salts

Bimetallic catalysts

To avoid chloride contamination

One

route is to use carbonyl precursors that decompose at low temperatures

Colloidal

Same as chemical precipitation except

It

involves the added benefit of a capping agent that allows for size control of the catalysts and prevents agglomeration of the catalyst particles

The experimental procedure is as simple as

combining

the metal source, a reducing agent, and a capping agent together and mixing

Sol-gel(Chemical Solution Deposition)

Fabrication of materials (typically a metal oxide) starting from a chemical solution (or sol) that acts as the precursor for an integrated network (or gel) of either discrete particles or network polymers which undergo various forms of hydrolysis and polycondensation reactions. The precursor sol can be either deposited on a substrate to form a film (e.g., by dip coating or spin coating), cast into a suitable container with the desired shape (e.g., to obtain monolithic ceramics, glasses, fibers, membranes, aerogels), or used to synthesize powders (e.g., microspheres, nanospheres)

Sol-Gel Technologies and Their Products

In acid-catalyzed sols, the interparticle forces have sufficient strength to cause considerable aggregation and/or flocculation prior to their growth. In base-catalyzed sols, the particles may grow to sufficient size to become colloids, which are affected both by sedimentation and forces of gravity

Incorporation of metallic nanocatalysts:

Adding prefabricated particles into the sol-gel mixture Addition of metal salts during gel formation or after the mesoporous structure has formed A significant drawback!

catalytic nanoparticles may be buried within the structure rather than near the pores

Sol-Gel Process:
1.

2.

Formation of a liquid solution of suspended particles (a sol) Aging

to allow fine-tuning of the gel properties

3.

Drying

to remove the solvent from the gel

4.

Calcification

to permanently change the physical and chemical properties of the solid

Impregnation

High-surface-area carbon black can be impregnated with catalyst precursors by mixing the two in an aqueous solution Following the impregnation step, a reduction step is required to reduce the catalyst precursor to its metallic state

The most common platinum precursors used for impregnation are chloride salts To avoid chlorine poisoning
Metal sulfite salts, metal carbonyl complexes, and metal nitrate salts have been used instead Metal carbonyl complexes :

can

easily be made by direct oxidation of the metal chloride salt with carbon monoxide An external reducing agent is not required, as nanoparticles can then be formed by thermal decomposition of the metal carbonyl complexes

 Microemulsions
Schematic of a reversed micelle formed using Na+-AOT as surfactant ion

Microemulsions are clear, stable, isotropic liquid mixtures of oil, water and surfactant, frequently in combination with a cosurfactant. The aqueous phase may contain salt(s) and/or other ingredients, and the "oil" may actually be a complex mixture of different hydrocarbons and olefins.

In order to obtain the catalyst nanoparticles,

Metal salt is reduced by adding a reducing agent into the microemulsion system Mix the microemulsion system that contains a reducing agent with a microemulsion system that contains the metal salt

Another approach is to

Once the nanocatalysts are formed

They can be deposited onto a support

By adding a solvent like tetrahydrofuran (THF) in conjunction with the support powder to the microemulsion The solvent destabilizes the microemulsion by competing with the surfactant to adsorb onto the particles, and in the destabilized system the particles will adsorb onto the support.

It is likely that

Formation of catalysts via the microemulsion process proceeds in two steps:

1. 2.

Nucleation of the metal catalyst inside the droplet Aggregation of multiple nuclei via collision and coalescence of droplets to form the final nanocatalysts

Electrochemical Deposition

Occurs at the interface of an electronically conductive substrate and an electrolyte solution containing the salt of the metal to be deposited

Five stages to electrochemical deposition of metals

1.

2. 3.

4.

5.

Transport of metal ions in solution to the electrode surface Electron transfer Formation of metal ad-atoms via adsorption Nucleation and growth, two- or three-dimensional, of metal particles Growth of the three dimensional bulk metal phase

2D or 3D Nuclei Growth?

Binding energy of the metal ad-atom to the substrate Vs Binding energy of the metal ad-atom to itself

Spray Pyrolysis

A process in which a thin film is deposited by spraying a solution on a heated surface, where the constituents react to form a chemical compound

Spray Pyrolysis Process:

An aqueous solution containing the metal precursor is atomized into a carrier gas that is passed through a furnace. Second, the atomized precursor solution deposits onto a substrate, where it reacts and forms the final product

Advantages compared to other metal-forming techniques

Very easy to dope films or form alloys in any proportion by manipulating the spray solution Neither high-purity targets and substrates nor vacuum set-ups are required Deposition rates and therefore film thickness can easily be controlled by controlling the spray parameters Moderate operation temperatures (100500 C) allow for deposition on temperature-sensitive substrates Low energy consumption Relatively limited environmental impact since aqueous precursor solutions can be used The process is scalable, with production rates as high as 1.1 kg/h

Vapor Deposition

Chemical Vapor Deposition (CVD)

In

a typical CVD process, the wafer (substrate) is exposed to one or more volatile precursors, which react and/or decompose on the substrate surface to produce the desired deposit.

Types of chemical vapor deposition Classified by operating pressure:

Atmospheric

pressure CVD Low-pressure CVD (LPCVD): Reduced pressures tend to reduce unwanted gas-phase reactions and improve film uniformity across the wafer Ultrahigh vacuum CVD (UHVCVD)

Metal alloys can be fabricated by CVD Using a single-source precursor (that remains coordinated in the vapor phase) allows for precise control of the ratio of the two metals

Physical Vapor Deposition (PVD)

A

variety of methods to deposit thin films by the condensation of a vaporized form of the material onto various surfaces Four essential components
Vacuum

source to supply the material, called a target A substrate on which the film is deposited An energy supply to transport the material from the source to the substrate.

High-energy Ball Milling

Is a mechanical alloying process and a method of

Grinding

and mixing materials in the absence or presence of a liquid.

Lead antimony grinding media with aluminum powder

Particle Size and Shape Control

Why?
Increase

in the ratio of surface atoms to bulk atoms Activity for many reactions shows a maximum at a particular particle size Importance of crystal phases for catalytic reactions

Mechanism for Size Control Using Colloidal Synthesis Methods

Size range of interest in practical fuel cell catalysis

1 to 5 nm range

In the case of the reduction of O2 (ORR), Pt particles in the 3.5 to 4 nm size range are believed to be the most active catalysts, while for bi-metallic Pt/Ru catalysts the optimal size range appears to be in the range of 2.5 nm

 Pt-sols Made Using Organic Stabilizers

The stabilizer adsorbs on the surface of the Pt nuclei and prevents them from agglomerating Control particle size via
Concentration

of the metal precursor salts Stabilizing agent, Synthesis temperature.

 Modified Polyol Methods

Polyol Method:
Synthesis of high surface area catalysts in ethylene glycol Ethylene glycol acts as solvent and reducing agent.

Modified Polyol Method: A straightforward, inexpensive catalyst synthesis method of low toxicity
Size of the Pt and Ru colloids can be controlled by the addition of H2O to the synthesis solution. A large amount of glycolic acid (D) is formed which acts as a stabilizer for the Pt/Ru colloids

 Size Control Using Electrochemical Methods

May not be as attractive for the preparation of large-scale catalysts as, for example, chemical methods. Advantages:
Stabilizers

and/or capping agents are not required Particle size can be controlled by varying the length and the amplitude of the potential pulse

Attention!
Progressive
Assuming

Vs Instantaneous Nucleation

that all the nuclei grow at the same rate, instantaneous nucleation results in mono-sized particles and is preferable in fabricating nanocatalysts of a specific size

shift from progressive to instantaneous nucleation by:

Increasing deposition overpotential

or Increasing the electrolyte conductivity (using chloride, sulfate, and perchlorate anions)

Shape Control

Final shape of the nanoparticles is affected by:

Reducing

agent Ratio of capping agent to platinum source Identity of the capping agent Extent of particle growth

Physical Characterization of Electrocatalysts

Analysis of Composition and Phase of Catalyst

X-ray

Diffraction (XRD) and Electron Diffraction (ED) X-ray Fluorescence (XRF), X-ray Emission (XRE), and Proton-induced X-ray Emission (PIXE)

 Measurement of Physical Surface Area and Electrochemical Active Surface Area

BET Method and Physical Surface Area

Basically uses the surface of adsorbed gas molecules as a ruler Is based on the formation of a hydrogen monolayer electrochemically adsorbed on the catalysts surface

Electrochemical Hydrogen Adsorption/Desorption

 Morphology of Catalysts and Their Active Components

Scanning Electron Microscopy (SEM)

Uses a beam of electrons to scan the surface of a sample and build a three-dimensional image of the specimen

Signals can include: Secondary electrons (electrons from the sample itself), Backscattered electrons (beam electrons from the filament that bounce off the nuclei of atoms in the sample), X-rays, Light, heat, and even transmitted electrons (beam electrons that pass through the sample)

Transmission Electron Microscopy(TEM)

Builds

an image by way of differential contrast

Those

electrons that pass through the sample go on to form the image, while those that are stopped or deflected by dense atoms in the specimen are subtracted from the image

TEM images of microwave-synthesized PtRu nanoparticles supported on different carbon samples: (a) Vulcan XC72 carbon; (b) carbon nanotubes

Electrochemical Methods for Catalyst Activity Evaluation

 Cyclic Voltammetry

Basic Principles
Refers to cycling the potential between chosen low and high points and recording the current in the potential cycling region The highest anodic (or cathodic) current is reached when the potential reaches a value at which all the reduced (or oxidized) form of the electrochemically active species at the electrode surface is consumed

Applications
Features of a Pt Electrode in Acidic Electrolyte Catalyst Activity Analysis

Catalyst Contamination in PEM Fuel Cells

Kinetic losses

Poisoning of both anode and cathode catalyst sites or a decrease in the catalyst activity
Increase in the resistance of membrane and ionomer, caused by alteration of the proton transportation path Changes in structure and in the ratio between the hydrophobicity and hydrophilicity of CLs, GDLs, and the PEM

Ohmic losses

Mass transfer losses

 Anode Catalyst Layer Contamination

Strategies for mitigating CO Poisoning

Using

CO-tolerant PtRu alloy catalyst Introducing a small amount of oxidant(for example, air or oxygen) into the fuel stream Operating the PEMFC at elevated temperatures (> 120 C)

 Impacts of Carbon Dioxide

In situ production of CO from CO2 on the platinum surface through either

Reverse

water-gas shift reaction or Electrochemical reduction of CO2

A common reformate gas that contains about 25% CO approximately 20100 ppm CO in equilibrium concentrations
2

Effect of CO2 concentration on PEM fuel cell performance

 Impacts of Hydrogen Sulfide (H2S)

H2S also strongly adsorbs on the Pt catalyst, competing for the active sites with hydrogen adsorption and hydrogen oxidation

Comparison of the effects of CO and H2S on PEMFC performance

Effect of current density on performance degradation during exposure to 20 ppm H2S in the H2 stream.

Effect of temperature on cell performance deterioration during exposure to (a) 10 ppm and (b) 20 ppm H2S/H2 at 0.5 A cm2

 Impacts of Ammonium (NH3)

Ammonium (NH3) is present in the hydrogen-rich fuel stream, either due to

Use

of NH3 as the hydrogen carrier Reforming process involves homogeneous precombustion with air Fuel itself contains nitrogen-containing species

NH in the fuel stream of a PEMFC, even at the level of a few ppm, can cause significant cell performance loss
3

Degradation of cell performance mainly

by

increasing membrane conductivity through NH3 reacting with protons in both the bulk membrane and the ionomer in the catalyst layer
NH3 (gas) NH3 (membrane) NH3 (membrane) + H+ NH4+

 Cathode Catalyst Layer Contamination

SOx Contamination In the presence of SOX pH inside the MEA is decreased

resulting

in free acids in the MEA and causing potential

shifts.

SOx can also adsorb on the Pt surface

competing

with oxygen adsorption and leading to performance degradation

Constant-current discharging curve of the PEMFC during running with 1 ppm SO2/air for 100 hours at 70 C. Current density: 0.5 A cm2

Recoverability of Fuel Cell Performance After SOx Contamination

After the contamination source is cut off

Setting cell voltage at open circuit voltage (OCV) Operating the fuel cell with pure air CV scanning

Pt Alloy and CO-tolerant Catalysts

CO

is adsorbed strongly and irreversibly at the active sites on a pure Pt surface, mostly through BridgeBonding

Poisoning Mechanism
Blocking

H2 adsorption CO lowers the reactivity of the remaining uncovered sites through dipole interactions and electron capture

Pt Alloy and CO-tolerant Catalysts

Alloying Pt with a second element can enhance the catalytic ability of the primary element Bifunctional effects

Second component provides one of the necessary reactants Promoter alters the electronic properties of the catalytically active metal to affect the adsorption /desorption of the reactants/intermediates/poisons; Dilution of the active component, Pt, with the catalytically inert metal changes the distribution of the active sites, thereby opening different reaction pathways

ligand (electronic) effects

Ensemble (morphological) effects

Figure 8: CO coverage on various surfaces of alloy electrodes, under steady H2 oxidation conditions

Supported Pt Catalysts

Carbon Black

Relatively higher stability than unsupported catalysts

In terms of agglomeration

Porosity of carbon black

assures gas diffusion to the active sites

Allows electron transfer from catalytic sites to the conductive carbon electrodes

Good electric conductivity of the carbon support

Small dimensions of catalyst particles

Maximize the contact area between catalyst and reagents.

Further Supporting Materials

Nanostructured carbon such as carbon nanotubes Ultra-thin nanostructured (NS) film system Carbon aerogels and carbon cryogel

 The Mere Reference!

Jiujun Zhang, PEM Fuel Cell Electrocatalysts and Catalyst Layers (Fundamentals and Applications)

Any Questions?

Thank You!