1

Newly-developed Technique for

Real-time Observation of the Behavior of
Platinum Fuel Cell Catalyst

May 18, 2015

Toyota Motor Corporation

Introduction: Overview of new technique

1. Development of microscopic electrochemical cells for
fuel cells (FCs) to be embedded into a transmission
electron microscope
2. Application of voltage to microscopic electrochemical
cells in a transmission electron microscope, and
recreation of platinum nanoparticle behavior on a
nanometer level in the same chemical reaction state as
when electricity is generated
Successful real-time observation of the process
leading to platinum nanoparticle coarsening, which
is considered to cause decreased catalyst reactivity
(deterioration)

Topics covered in these materials

1. Role of platinum catalyst in fuel cells

2. Platinum nanoparticle observation
techniques using conventional technology
3. New technique for observing platinum
nanoparticle behavior

1. Role of platinum catalyst in fuel cells

2. Platinum nanoparticle observation
techniques using conventional technology
3. New technique for observing platinum
nanoparticle behavior

(1) Development of fuel cell vehicles (FCVs)

Development of eco-cars to solve environmental and
energy problems
Fuel diversification measures
Use of hydrogen

Developing FCVs that can be mass-produced

Further popularization of FCVs

Increasing performance, lowering costs of FCs
Encouraging the growth of hydrogen supply
infrastructure

Mirai
(launched December 15, 2014)

To popularize FCVs, Toyota needs to improve performance and

decrease costs of FCs

(2) Fuel cell stack installed in the Mirai

Fuel cell cross-section

370 cells

Series of 370 fuel cells for generating capacity of 114 kW

(3) Fuel cell schematic diagram

Power generation
Hydrogen

Air

Electron Electron

H2

Anode

Proton
H+

eO2

Polymer Cathode Water

membrane
H 2O

Separator

Separator

e-

Reaction in fuel cell

2H2 + O2 2H2O + electricity

Extracts electrons by reacting hydrogen and oxygen to generate

electricity (opposite of water electrolysis)

(4) Composition of anodes and cathodes

Catalyst layer
Thickness: tens of m*

Platinum
nanoparticle

Power generation
Hydrogen

Size: several nm*2

Air

Electron Electron

H2

Anode

proton
H+

eO2

Polymer Cathode Water

membrane

H 2O

Separator

Separator

e-

Mixed layer of platinum,

carbon and
ion-conducting polymers

Carbon
Diameter: tens of nm
*2: 1 nm (nanometer) is 1 billionth of 1 meter

*1: 1m (micrometer) is one millionth of 1 meter

Anodes and cathodes are primarily composed of platinum

nanoparticles and carbon

(5) Composition of platinum nanoparticles

Platinum
nanoparticle

Platinum nanoparticle
Size: several nm

Platinum
atoms
Diameter:
0.28 nm

Carbon
tens of nm

Carbon

Platinum nanoparticles are complex bodies of platinum atoms

(hundreds of thousands to millions of atoms)

(6) Catalytic role of platinum nanoparticles

Cathode

Anode
Hydrogen
H2

10

Oxygen
O2
Ion-conducting polymer

Proton
H+

Platinum
nanoparticle

Electron
eCarbon

Ion-conducting polymer

Water
H2O

Proton
H+
Electron
eCarbon

Platinum
nanoparticle

Chemical reaction: H2 2H+ + 2e-

Chemical reaction: 4H+ + O2 + 4e- + 2H2O

Hydrogen broken down into

protons and electrons

Water generated from protons, oxygen

and electrons

Platinum nanoparticles catalyze fuel cell chemical reactions

(7) Changes in fuel cell performance during driving

Decreased fuel cell voltage

11

Causes of decreased voltage

Decreased platinum nanoparticle catalyst reactivity
Change in polymer membrane qualities
Decreased anode/cathode gas diffusibility etc.

A. Initial phase

e-

H+

O2

cathode

polymer
membrane

H2O

H2

anode

O2

Separator

cathode

polymer
membrane

e-

eH+

H2
anode

Driving time

Separator

e-

Decreased
power
generation

Air

Hydrogen

B. Decreased voltage

B. Decreased voltage

Water

Cell voltage

A. Initial phase

Decreased platinum nanoparticle reactivity may negatively

affect fuel cell voltage

(8) Decreased platinum nanoparticle reactivity

B. Voltage decrease

A. Initial phase

Platinum
nanoparticle state
(1000 platinum atoms)
:platinum atoms

Size
Reaction surface
(surface area)

Small

Large

Large

Small

High reactivity

Low reactivity

Decreased platinum nanoparticle reactivity is caused by

coarsening (increase in size, decrease in surface area)

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1. Role of platinum catalyst in fuel cells

2. Platinum nanoparticle observation
techniques using conventional technology
3. New technique for observing platinum
nanoparticle behavior

(1) Method for confirming platinum nanoparticle coarsening 14

A. Initial phase

B. Voltage decrease

Platinum
nanoparticle state
(1000 platinum atoms)
:platinum atoms

Observation
Size
Reaction surface
(surface area)

Small

Large

Large

Small

High reactivity

Low reactivity

Observation of platinum nanoparticle size

(2) Technique for observing platinum nanoparticles

Virus

Lactic acid
bacterium

Hair

Water flea

15

Bee

Diameter

(1 billionth (100 millionth

of 1 m)
of 1 m)

(10 millionths (1 millionth

of 1 m)
of 1 m)

(100,000th
of 1 m)

(10,000th of 1
m)

(1000th of
1 m)

(100th of 1 m)

(tenth of 1 m)

Naked eye

Platinum
atom
0.28 nm

Platinum
nanoparticle
Several nm

Optical microscope

Carbon
tens of nm

Electron microscope
Source: Japan Analytical Instruments Manufacturers Association website

Platinum nanoparticles can be observed using an

transmission electron microscope

(3) Observation with a transmission electron microscope

Transmission electron
microscope

Optical
microscope
Light source: light rays

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Transmission electron microscope

image

vs. electron beam

Platinum
nanoparticle

Electron source

light source
(lamp)
Condenser lens

Illumination lens
(electron lens)
Specimen
Objective lens

Projective lens

Platinum atom
Image
Source: Hitachi High-Technologies Corporation, Become a friend of TEM

Enlarging and observing specimens with electron beams

1 nm

Transmission electron microscopes enable observation of

platinum nanoparticles on a nanometer/atomic level

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(4) Conventional fixed point observation of coarsening

Decreased fuel cell voltage
Cell voltage
A. Initial phase

A. Initial phase

Distribution
of platinum nanoparticles
by number and size
Number
Coarsening
A. Initial
phase

10

B. Decreased
voltage

nm

B.
decreased
voltage
B.During
Decreased
voltage

Small

B. Decreased voltage
Driving time

Large

Size
10 nm

Conventional technology compares platinum nanoparticle

size during the initial phase and after voltage is decreased

(5) Problems with conventional observation techniques

10

A. Initial phase

nm

B. Decreased voltage

Platinum
nanoparticle

Process
is unclear
Carbon

10 nm

The process of platinum nanoparticle coarsening cannot be

fully understood using conventional techniques

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(6) Goal of developing new observation technique

10

A. Initial phase

Platinum
nanoparticle

nm

B. Decreased voltage

Real-time observation
of behavior during a
chemical reaction
Carbon

Aim: identify behavior, conditions and materials that make

platinum nanoparticles prone to coarsening

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1. Role of platinum catalyst in fuel cells

2. Platinum nanoparticle observation
techniques using conventional technology
3. New technique for observing platinum
nanoparticle behavior

(1) Technique for observing platinum nanoparticle behavior 21

Sample holder

Cathode

Anode

3m

Hydrogen
H2

Oxygen
O2
Ionconducting polymer

Proton
H+

Platinum
nanoparticle

Electron
eCarbon
Chemical reaction: H2 2H+ + 2e-

Transmission electron
microscope

Observation on
nanometer/atomic level

Ionconducting polymer

Water
H2O

Proton
H+
Electron
eCarbon

Platinum
nanoparticle

Chemical reaction: 4H+ + O2 + 4e- + 2H2O

Incorporate electrochemical cells into equipment

Recreate catalyst behavior

Recreate a fuel cell catalyst chemical reaction in a

transmission electron microscope

(2) Recreating a reaction in a transmission electron microscope

Requirements for
observation by
transmission electron
microscope

Electron beam
Several mm

3m

Sample

Lens

Observation

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Several
100 nm

The electron beam

must pass through the
sample

Generally, samples
must have thickness
of several 100 nm or
smaller

The site of the fuel cell catalyst chemical reaction must

be extremely small

(3) Reproducing a fuel cell chemical reaction (conventional technique) 23

e-

General catalyst
evaluation method
Use two electrodes
and electrolyte to
produce a chemical
reaction

Counter
electrode

Cathode
Oxygen
O2
Ion-conducting polymer
Ionconducting
polymer

Water

Water
H2O

Proton
H+

Separator

O2
cathode

polymer
membrane

H2

Thickness:
of m
m
Thickness:tens
10s of

eH+

anode

Separator

Fuel cell

Catalyst layer
Catalyst
layer

Air

Hydrogen

Electron
eCarbon

H2O

Platinum
nanoparticle

Chemical reaction: 4H+ + O2 + 4e- + 2H2O

Working
electrode

Ion-conducting polymer

Oxygen
(dissolved in electrolytes)

Proton

Water

Catalyst sample
(electron)

Electrolyte (acid solution)

Beaker

Carbon
Platinum
nanoparticle

Chemical reaction: 4H+ O2 + 4e- + 2H2O

The conventional technique uses the general catalyst evaluation

method to reproduce the chemical reactions that occur in fuel cells

(4) Use of microscopic electrochemical cells as samples

Using micro-electromechanical systems
technology to create millimeter-sized
microscopic electrochemical cells (plane view)
counter
electrode

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Using silicon nitride (SiN) film to confine

electrolytes within a thickness of several
100 nm (cross-section)

working
electrode

Several
hundred nm

Electrode

50m

6 mm

200m

SiN
Platinum and carbon

Electrode

Platinum and carbon

SiN

Electrolyte
Several
hundred nm

4.5 mm

Using micro-electromechanical systems technology to create microscopic

electrochemical cells that can be observed via transmission electron microscope

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(5) Real-time observation results

0 sec.

337 sec.

620 sec.

50 nm

Successful real-time observation of platinum nanoparticle behavior at

nanometer levels during a chemical reaction leading to coarsening

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(6) Real-time observation results

0 sec.

337 sec.

620 sec.

Coarsening

50 nm

Phenomenon observed (schematic diagram)

Platinum nanoparticle

Carbon

Platinum nanoparticles migrate over carbon and coarsen

(7) Future uses of this new observation technique

Voltage changes during

driving

Voltage

Start
Acceleration
and
deceleration

Aim: Increase lifespan of fuel cells and reduce platinum used

Driving conditions
Voltage
Voltage changes
Materials
Carbon type
Platinum
nanoparticle size

Idling

High load

Platinum nanoparticle behavior

Analyze
relationship

Time

Analysis of relationship between voltage changes during driving and

platinum nanoparticle behavior changes

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(Reference) Exhibit at Automotive Engineering Exposition

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Exhibit at the Automotive Engineering

Exposition (held May 20 22 at Pacifico
Yokohama)
Lecture at 2015 JSAE Annual Congress
(Spring) held concurrently (May 20, from 9:30)

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