A National Centre of Excellence in

Electromaterials Science

Professor Doug MacFarlane FAA FTSEARC Federation FellowSchool of Chemistry Monash University

ElectromaterialsScience

ArtificialPhotosynthesis

Energy Generation

Energy Storage

BionicsCorrosion and Interfacial Science

Wollongong

Deakin/Monash Universities

Prof Gordon Wallace FAA FTSEFederation Fellow

Director, ACES, UoW

Prof Leone SpiccaACES Monash

Prof Doug MacFalane FAA FTSEFederation Fellow

Energy Program Leader, ACES, Monash

Prof David OfficerMaterials Program Leader

ACES UoW

ACES People

Prof Maria ForsythAustralian Laureate Fellow

Associate DirectorACES Deakin

ACES People

Nobel Laureate Alan McDairmid (ACES Advisory Board Chairman until his death in 2009)with ACES students and postdocs (and Prof MacFarlane)

ACES Outcomes

• Publications in:Science, Nature Chemistry, Nature Nanotechnology, Advanced Materials

• Typically more than 150 papers published per year

• Typically approx 4 patent applications per year

• Aquahydrix spin out company

• Hosts 3 Centre workshops per year plus one national conference

• Hosts > 30 visiting students and researchers from all over the world, per year.

ACES Funding

• Funding from the Australian Research Council - core funding approx $2.5 M per year- Fellow salaries (Australian Postdoctoral Fellows, Future Fellows,

Federation Fellows, Laureate Fellows) approx $2.0M per year

• Funding from partner Universitiesapprox $1.0M per year

• State government fundingapprox $800k per year

Nanostructured

Electromaterials

Energy Medical Bionics

ACES Programs

A National Centre

With Global Collaborations

ACES

Drawing students, working with collaborators and

building commercial linkages in 18 countries

Energy

ProgramProgram Leader

Professor Doug MacFarlane FAA FTSE – Monash University

Goal: Advanced Sustainable Energy Generation and Storage

Program Themes

- Advanced Batteries (Li, Mg, Na)

- Dye sensitised solar cells

- Solar water splitting (Hydrogen Generation)

Aquahydrix spin-out

- CO2 reduction to fuels

- Electrochemical Hydrogen Peroxide Production

- Thermocells

Renewable Energy Issues

• Less than 10% of Australia’s energy comes form renewable sources

• Often generated in remote areas

• Energy storage a limiting factor

Clean Energy 2010 Report - http://www.cleanenergycouncil.org.au/

Energy Storage Technologies

Comparison of energy densities for various battery chemistries – [http://www.nexergy.com/battery-

density.htm]

Power/Energy characteristics of batteries

Ionic Liquid electrolytes for metal air batteries

Salts that are liquid at room temperature!

– Stabilise metal anode

– Low volatility – reduce evaporation

– Good solubility of discharge products

– Improved safety

Organic solvent electrolytes:

Ethylene carbonate

Diethyl carbonate

Problems: high vapor pressure, flammable，leakage

Armand, M. et. al. Nat Mater 2009, 8, 621

www.unicam.it/discichi/dottchi/nobili

Ionic liquids as stable electrolytes for

Iithium batteries

Ionic liquids and reactions at the electrochemical interface. D.R. MacFarlane, J.M. Pringle, P.C. Howlett, M. Forsyth, Phys.Chem. Chem. Phys. 2010, 12, 1659

100 µm100 µm100 µm 100 m100 m100 m

> 99% Li cycling efficiency

demonstrated

P. C. Howlett, D. R. MacFarlane and A. F. Hollenkamp, Electrochemical and Solid-State Letters, 2004, 7, A97-A101.

Li reactivity – a problem for the electrolyte => ILs provide a solution

Magnesium-Air Batteries

Battery System Energy Density

MJ/kg

Pb-acid 0.08

Li ion 0.4-0.80

Li metal 1.3

Mg-air 8

Petrol 47

Howlett PC et al The effect of potential bias on the formation of Ionic liquid generated surface films on Mg alloys. Electrochim. Acta 2010.

Cheaper than other high performance

batteries (Mg $2,700/ton, Li $65,000/ton)

Magnesium is non-toxic, biocompatible and

environmentally friendly

We have shown IL can passivate

Mg

Manganese oxide catalysts

Catalytic performance of the manganese oxide in 1 M NaOH and various catalystsBAS – 0.4M dibutyl ammonium sulfate pH10, BAS-IL - 2M dibutyl ammonium sulfate pH10

F. Zhou, A. Izgorodin, R.K. Hocking, L. Spiccia, D.R. MacFarlane, Electrodeposited MnOx Films from Ionic Liquid for Electro-Catalytic Water Oxidation, Adv. Energy Mater. (2012) In printM. W. Kanan, D. G. Nocera, Science 321, 1072 (2008).G. Lodi, E. Sivieri, A. de Battisti, S. Trasatti, J. App. Electrochem. 8, 135 (1978).S. Gottesfeld, S. Srinivasan, J. Electroanal. Chem. 86, 89 (1978).

MnCat – manganese dioxide deposited from aqueous elecrolyteDau et al Energy and Environ Sci in press 2012

Energy loss, %

IdealCatalyst

GoodCatalyst

BadCatalyst

0.0 0.1 0.2 0.3 0.4 0.50.0

0.5

1.0

1.5

2.0MnOx

BAS

MnOx

BAS-IL

MnCatCo-Pi

IrOx MnOx

Curr

ent density

(mA

·cm

-2)

Overpotential (V)

RuOx

252015105 0

Hydrogen peroxide production

Concentration of H2O2 detected over time in the BAS electrolyte with and without MnO2 disproportionation catalyst.

0 10 20 30 400.0

0.2

0.4

0.6

0.8A

mo

un

t o

f H

2O

2, m

ole

Time, hours

BAS

BAS with MnO2 powder

Izgorodin et al Patent Application March 2012

Thermoelectrochemical Cells

Utilise a redox couple dissolved in an

electrolyte.

The potential of the redox couple changes with

temperature. Magnitude of change again given

by the Seebeck coefficient Se

Se = Δ V/ ΔT = ∆S/ nF

Majority of prior research has focussed on aqueous

electrolytes: 0.4M Fe(CN)63-/4- gives Se 1.4 mV K-1.

Current improved using MWNT electrodes.*

Hu, Cola, Haram, Barisci, Lee,

Stoughton, Wallace, Too, Thomas,

Gestos, dela Cruz, Ferraris, Zakhidov,

Baughman. Nanoletters 2010, 10, 838

ILs in Thermoelectrochemical Cells

– Use of IL electrolytes as replacement for water:

– increases operational temperature up to ca. 200 oC:

heating/cooling water pipes in power stations.

geothermal activity

– Increased device lifetime through use of non-volatile electrolytes.

– Targeting large scale, low cost devices.

*Hu et al. Nanoletters 2010, 10, 838.

Further Information

www.electromaterials.edu.auwww.chem.monash.edu.au/ionicliquids