An Overview of

Nanomaterials for
Energy Applications

Dr Peter Bishop
Technology Manager
Johnson Matthey Technology Centre
Reading U.K
bishopt@Matthey.com

HORIZON 2020
EUROPEAN UNION FUNDING
FOR RESEARCH & INNOVATION
Todays Presentation

• Introduction
• Low Emission Vehicles JM Activities
• Nanomaterials Opportunities
• Nanomaterial Synthesis
• Examples in Functional Coatings, Batteries, Fuel cells
Divisional Structure

Emission Control Process Precious Metal Fine New

Technologies Technologies Products Chemicals Businesses

• Light Duty Catalysts Chemicals Services • Active Pharmaceutical • New Business

Ingredient (API) Development
• Heavy Duty Catalysts • Chemical Technologies • Platinum Marketing
Manufacturing
(DPT) and Distribution • Water
• Stationary Emissions
• Catalysis and Chiral
Control • Syngas • Refining • Battery Technologies
Technologies
• Chemical Catalysts Manufacturing • Fuel Cells
• Research Chemicals
(inc. Formox)
• Noble Metals
Oil and Gas
• Colour Technologies
• Refineries
• Chemical Products
• Purification
• Tracerco

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 JM Activities in Low Emission Vehicles
JM has a broad set of products, technology and research linked to the automotive sector
Light duty gasoline and diesel Fuel Cells
Gasoline: Research and Development of fundamentals of Automotive and niche stationary power sectors
emission control by catalysts Research and development of catalysts and catalysed
Application engineering to customise solutions for most OEMs components
Diesel: Research, development and manufacture of a range of
• Fuel cell stack catalysts
catalyst and filter configurations
- Flow through catalysts • Membrane electrode assemblies
- Diesel particulate filters (CRT® technology) • Reforming and gas processing catalysts
- Selective catalytic reduction (SCR)

Heavy Duty and Non-Road applications Battery Technologies

Global Truck Industry
Battery Electric, Plug-in Hybrid, mild and micro
Research, development and manufacture of HDD
hybrid vehicles
emission control systems
• Developer and assembly of advanced automotive
DOC, DPF (CRT®), SCR, Combined (SCRT®)
battery systems
systems
• Lithium ion batteries
• Advanced battery materials

Glass Coatings Additional businesses / products in automotive

• Design & supply of glass obscuration enamels • Supply of piezo-electric actuators for seats
• Supply of conductive Inks (heated windscreens) • PGM tips for spark plugs

Development projects in automotive

• CO2 removal in cabin Additional Capabilities
• Partial reforming of fuel using exhaust heat
• Diesel / Gasoline reforming • On-board Syngas formation for aftertreatment
• Engine calibration
• Gas purification techniques
• Chemical process design
• Nitinol and other metals (MIM)
• Thermoelectrics

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Challenges Opportunities for Nanomaterials
Johnson Matthey is investigating the
challenges and opportunities arising from
the automotive sector’s need to reduce
carbon and increase efficiency in vehicles

2014
2011 2012 Low Carbon
Electrification Purification Vehicles

Aim to understand challenges from the market

Battery Technologies Cabin Air Smart Windows Sensors / OBD

• Battery Systems • Advanced air

• Battery Materials management Thermal Interface
Emissive Coatings
concept Materials

On-board H2
Thermoelectrics
Generation

Piezoelectric Friction

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Case study
JM has used its materials expertise to approach problems in new ways

On-board H2 Generation
Three year project funded by Technology Strategy
Board to reduce CO2 and improve fuel economy

Project aim: To improve and re-optimise the engine and

after-treatment as a complete system

Strategies to improve fuel economy and reduce CO2:

1.On-board H2 generation
2.Catalyst development
3.Total powertrain optimisation

What JM did: Used its materials competencies to study the

effects of temperature, Fuel addition, Type of fuel ,Monolith
length (GHSV), PGM loading and Washcoat loading and found
improved catalyst development could improve H2 yield.

Partners involved: Ford Motor Co., Land Rover, ITM Power,

Revolve Technologies, Cambustion Ltd, University of
Bradford, University of Liverpool, University of Birmingham

Next phase: Ongoing work with OEMs to address challenges

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 Nanoparticle Formation
Nanoparticles have different properties to atomic or bulk materials:

Optical Physical Electronic

Why are we interested?

• Advantages of nanoparticles over conventional materials and catalysts.
• Catalytic properties.
• Functional materials.
• Applications in the Automotive sector

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Key Competence
Controlling Materials on a Nanometre Scale

A typical heterogeneous Control of particle size Control of particle shape

catalyst Pd/C

2 nm Pd particles 2 nm

Small anchored particles,

highly dispersed, very 50 nm
active, best use of
expensive metals Control of particle size,
tunes activity and
selectivity
New shapes can take us
into new applications

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Core-Shells and Alloys
Aucore-Pdshell AuPd nanoalloy Pdcore-Aushell

2-chloronitrobenzene hydrogenation
Au@Pd
2:1Pd@Au
PdAu

Pd:Au 5:1

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Flame Spray Pyrolysis
Coagulation and agglomeration

Nucleation

Precursor dispersion,
evaporation, and
combustion
Precursor(s)

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FSP Nanomaterials

Pt on Alumina
Increase in
transmittance due to in
decrease in crystallite
size
CeO2

ZnO

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Materials Development Nanoparticle
– Materials Expertise
• Synthetic expertise – Manufacturing Capability
– Solid State, Solvo/Hydro-thermal, • R&D
Precipitation,
– Novel nanotechnology
– Microwave assisted technology,
etc

• Scale Up
• Particle Design
– Size, Shape, Composition (e.g.
multimetallic) structure (e.g. alloys,
core-shells) at nano-dimensions
– Fundamental relationship between
structure and activity
– Application to battery materials

• Manufacturing

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 Vacuum Deposition Metal to Metal Synthesis

• Using a mass filter allows precise size selected clusters to

be observed

University of Birmingham
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 From Clusters to Catalysts

• Precise clusters (e.g. Au923) can be deposited onto substrate and the
rich top layer diced to provide an active powder
• Scale currently limited

STEM images
of Au923
particles

University of Birmingham

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Challenges and Opportunities Nanomaterials
Johnson Matthey is investigating the challenges and opportunities arising from the automotive
sector’s need to reduce carbon and increase efficiency in vehicles

Early investigations Aim to understand

challenges from
the market
On-board
Sensors

Thermal
On-board H2 Materials
Generation

Thermoelectrics Emissive
Coatings

Smart
Windows

Piezoelectric Lightweighting

Commercial
products Time

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 Smart Windows: Existing technologies
Solar Control Glazing

Static Dynamic (Smart Glass)

Low Emissivity Passive Active

Commercially Spectrally-selective bulk glass, Responds to non- Responds to
coatings or films electrical stimuli (heat / electrical stimuli.
Available Absorbs NIR whilst maximising UV). Cannot be Controllable manually
transmission of visible light controlled manually or automatically

Non-Spectrally Selective

Electronically switchable, near-Infrared selective,

smart glass
Spectrally Selective,
- the ability to control the transmission of heat and light
Electronically
independently -
Switchable
has been described as the “Holy Grail” for the
advanced glazing industry

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NEAT Material to TEG Process

Nanocomposite Fast Sintering Cutting

Preparation

Environmental Testing Module Testing

Module Assembly

SiGe

Ag
Cu
AlN

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Nano Embedded Composite: (CoSi2)0.015:n-Si80Ge20
mix and mill 3bar Ar
• 2011-2014, eight-partner , EU project to develop
advanced nano-embedded alloy materials for
high-temperature thermoelectric applications.
FSP 6nm Co3O4 + n-Si80Ge20
• A host-guest approach was followed with two reduce H2 500ºC
principal host alloys: (i) SiGe and (ii) Mg2SiSn.
(CoSi2)0.015:n-Si80Ge20
• A range of nano-embedded guest materials
were investigated with a central theme of host-
guest lattice-matching
(CoSi2)0.015:n-Si80Ge20
• Synthetic methods based on controlled
atmosphere,
high-energy ball-milling.

CoSi2 Nanoparticle
• Selected area diffraction confirms CoSi2 along
[00-1] within less than 1%

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Johnson Matthey Battery Technologies

– Battery Technologies group formed in 2012

• Focus on advanced materials and applications engineering for high performance battery systems
– Building the business in batteries through internal R&D and acquisition
• Acquisition of the Axeon Group in Oct 2012
• Expanded internal R&D programme
• Second acquisition announced in June 2014, manufacturing assets of A123 materials business
• Acquisition of Clariant Energy Systems – battery materials business-completed March 2015
• Plans for expanded product development in 2015/16

► Johnson Matthey spans the battery value chain

► Applications knowledge helps drive basic technology materials R&D

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JMBM – A leading supplier of LiFePO4

Group of materials P2 & P2E P2S

• Powder • Spherical agglomerates

Physical
characteristics

• Life Power ® P2 • Life Power® P2S

very high rate capability, especially spherical agglomerates for easier
Grades at low temperature, due to small product handling and electrode coating
primary particles
• Life Power ® P2E • Pilot Scale
reduced BET surface area and
increased D50 versus P2 for easier
dispersion, coating, and
compression

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Going “Nano” for Lithium Ion Batteries
Advantages

1. The reduced dimensions increases significantly the rate of lithium insertion/removal,

because of the short distances for lithium-ion transport within the particles..

2. A high surface area permits a high contact area with the electrolyte and hence a high
lithium-ion flux across the interface.

3. The range of composition over which solid solutions exist is often more extensive for
nanoparticles, and the strain associated with intercalation is often better accommodated.

Disadvantages

1. High electrolyte/electrode surface area may lead to more significant side reactions with the
electrolyte, and more difficulty maintaining inter-particle contact.

2. The density of a nano-powder is generally less than the same material formed from micro-
meter-sized particles. The volume of the electrode increases for the same mass of material
thus reducing the volumetric energy density.

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Ordered Inorganic-Organic Hybrids using
Ionic Liquids for Emerging Applications

Ionic • Fundacion Cidetec

Liquids Generation 1 • Consiglio Nationalle Delle
Ricerche
• CEA-Liten
Inorganic New Ordered • WWU Muenster
Inorganic-Organic • IMEC VZW
Materials • Ustav Fyzikalni Chemie
Hybrid Materials JHIPC
• EPFL Lausanne
Light Universitat de Valencia
Sensitizers Generation 2 • CNRS
• Universitat Jaume I de
Castellon
• Universite de Mons-
Solar Hainaut
Batteries
cells Solvionic S.A.
• Centro Ricerche Fiat
SCPA
• Cegasa
• Solaronix S.A.

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http://www.cidetec.es/ORION/index.html
Ordered Inorganic-Organic Hybrids using Ionic
Liquids for Emerging Applications

Conversion Materials for Li-ion batteries:

20-30nm Li4Ti5O12 prepared by FSP
MOx + 2x Li+ + 2x e- ↔ M0 + x Li2O shows higher rate capability vs.
(M= transition metal, e.g. Co, Ni, Fe, Cu, …) micron sized particles from
conventional synthesis

Effect of Precursor concentration

in Flame Spray Pyrolysis

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Lithium Sulfur battery Exploiting
Nanotechnology
• nanostructured electrodes & electrolyte materials
• practical implementation of high energy Li-S battery
• lithium metal-free battery configuration
• lithiated silicon as anode and a nanostructured sulfur-carbon
• Cegasa
composite as the cathode • Volkswagen
• Chalmers Univerity
• Consorsio Sapienza
Ctheo = 1672 mAh g-1
S8 Innovazione
• Stena Recycling
Highest practical capacity International AB
reported so far ≈ 800 mAh g-1 • WWU Muenster
(but: high fading) • DLR
• Hanyang Univeristy
• Unichieti
• Uniroma 1
• ZSW

Dissolution in electrolyte, Li2S

followed by reduction on
Anode!

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http://www.lissen.eu
FC Cars for 2015

Hyundai ix35

Next-generation fuel-cell concept "FCV-R“ = Mirai

This concept model is a highly practical fuel-cell vehicle (FCV) that
was launched in 2015.
With the fuel-cell unit located beneath the specially designed body,
the vehicle can accommodate up to four passengers and boasts
impressive luggage space. The fuel cell stack, consisting of a
70MPa high-pressure hydrogen tank, has been improved to
provide a cruising distance of approximately 700 km (440 miles) or
more (under the JC08 test cycle; according to TMC).

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Automotive Research: New Materials for New Challenges

The main challenges for MEAs remain for Automotive:

– Low Pt loadings driven by metal cost.
– DOE target of 0.125 gPtkW-1
– 5000 hours durability.
New challenges arise as more real-life operational experience gained:
– Start-stop degradation mechanisms lead to damaging high
potentials on the cathode.
– Hydrogen may contain small amounts of CO (1-2 ppm).
– Anodes may be starved of hydrogen leading to damaging high
potentials on the anode (cell reversal).
New materials are under development to meet the needs of all these
situations.

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The Catalyst

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 Thank You
Dr Peter Bishop
Johnson Matthey Technology
Center
Reading U.K
bishopt@matthey.com

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