EPFL VALAIS/WALLIS

ISIC number

one in

continental

Europe

HYDROGEN CO2-REDUCTION

CO2-CAPTURE

PRODUCTIONSTORAGE

ISIC (Institut des sciences de ingénierie chimiques)

LABORATORY OF MATERIALS FOR RENEWABLE ENERGY

(LMER)

CONTACT

Director of the Lab

Prof. Andreas ZÜTTEL

EPFL-SB-ISIC

Energypolis

Rue de l’Industrie 17

CH-1950 Sion

mobil: +41 79 484 2553

E-mail: andreas.zuttel@epfl.ch

Administration

Annick EVEQUOZ

Tel.: +41 21 695 82

e-mail: annick.evequoz@epfl.chAndreas Züttel, Full Prof.

Physical Chemistry at EPFL

joint Lab of and

TOPICSEnergy storage materialsHydrogenHydridesCO2 ReductionHydrocarbonsCatalysisThermodynamics

URL: lmer.epfl.ch

PEOPLE

Dr. Z. Özlem KOCABAS

Post. Doc. EMPAPhD Sabancı University, TurkeyB. Mat. Sci. Sabancı UniversityThermodynamics Complex Hydrides

Dr. Elsa CALLINI

Post Doc EMPA

Visiting Sc. CALTECH

PhD University of BolognaM. (Physics) University of BolognaB. (Physics) University of MilanoReaction Mechanism Hydrides

Dr. Shunsuke KATO

Post. Doc. EMPA

Post Doc. PSI, SLS

PhD Uni. Fribourg, Switzerland

M. Eng. (Physics), Tokai University

Surfaces, catalysis

Dr. Philippe MAURON

Sci. Col. EMPA

Post Doc. VU, Amsterdam

PhD Uni. Fribourg, Switzerland

M. Sc. (Physics) Uni Fribourg

Hydrogen in Nanomaterials

Mr. Marco HOLZER

PhD Student at EPFLM. Chem. Eng. ETHZB. Chem. Eng. ETHZCO2 & H2 Sorption

Ms. Jianmei HUANG

Visiting Sc. EMPA

PhD Student South China Uni. of Tech.M. (Chem Eng.) South China Uni. of Tech.B. (Chem. Eng.) Guangxi Uni. of Nationall.Borohydrides

MISSION

H2 O2

H2O

OH-

e-

e-

Anode Cathode

Electrolyte

KOH/H2O

H OH-

H2

H2OH2O

O2

O2

U 2OH- H2O + ½ O2 + 2e-2 H2O + 2e- 2OH- + H2

H2O H2 + ½ O2

H2O

Laboratory of Materials for Renewable Energy (LMER): A. Züttel

RESEARCH TOPICS

Surface science, NAP-XPSClusters, Reactions

Thermodynamics, TDSLattice gas, Adsorption

Structure, electron density distribution

In-situRaman, TERS, and IR spectroscopy

Synthesis of intermetallic compounds, complex hydridesnano materials

ElectrochemistryDoS, Electrolysis

8

HYDROGEN ABSORPTION IN METALS

Ph. Mauron, M. Bielmann, EMPA, Switzerland

Andreas Züttel, Switzerland, 7/1/2015

HYDROGEN STORAGE IN METALS

FC canal boat, MH storage 2.5 kg H2, 1.0 mass%IC snowmobil, MH storage 5 kg H2, 1.0 mass%

FC vehicle MH storage 0.5 kg H2, 1.2 mass% H2 cat. heater

SELF

FC HyMove

METAL HYDRIDES AND COMPLEX HYDRIDES

DH0

Elements

Alloy

Hydride Complex

DHf

DHdec

Li[BH4]

LiH+B

Li7B6

Li + B + H2

-195

[kJ]

-90

-75 kJ/molH2

H2

Na10C60 + (18+y/2) H2 Na(10-y)C60H36 + y NaH Na10C60 + (18+y/2)

H2

Reversible H2 absorption of up to 3.5 mass% in Na10C60 and 5 mass% in Li12C60

HYDROGEN SORPTION IN METAL INTERCALATED

FULLERIDES

C, Na, H2

C60

Na6C60

6 NaH

C60H36 + 6 NaH

6 NaH + C60

C60H36

-2320 [C60]

-338 [6 NaH]

-670 [C60]

-1334 [C60]=-74 [H2]

Tdec=314 °C

ΔfH

0[k

J/m

olX

]

-1002 [C60H36]=-56 [H2]

Tdec=171 °C

-332 [6 NaH]

Na6-xC60H36

Na6C60H36

250

200

150

100

50

0

Activation E

nerg

y [kJ/m

ol]

1.00.80.60.40.20.0Alpha

1.0

0.8

0.6

0.4

0.2

0.0

(E

) -12

mean = 161 kJ/mol

H2 Abs H2 Des

Mauron et al. Int J Hydrogen Energ 37 (2012) 14307 / Phys Chem C 117 (2013) 22598 / Phys Chem C 119 (2015) 1714

Sir Théodore Turquet de

Mayerne (1573 – 1654)

"inflammable air"

was a Swiss-born physician who

treated kings of France and

England and advanced the

theories of Paracelsus.

Small ballon with a diameter of 4m

At 13:45 on December 1, 1783, Jardin des Tuileries in Paris,

1st manned ballon

Jacques Alexandre Cesar

Charles (1746 - 1823)

CHEMICAL HYDRIDES

Fe + H2SO4 ➞ FeSO4 +H2

Ref.: Encyclopædia Britannica

CHEMICAL HYDRIDES

Ref: A. Züttel, “Materials for hydrogen storage”, materialstoday, Septemper (2003), pp. 18-27

http://www.youtube.com/watch?v=uixxJtJPVXk

Al + 3 H2O Al(OH)3 + 1½ H2 5.6 mass%

NaAlH4 + 4 H2O NaOH + Al(OH)3+ 4 H2 14.8 mass%

NaBH4 + 3 H2O NaOH + HBO2+ 4 H2 21.3 mass%

LiBH4 + 3 H2O LiOH + HBO2+ 4 H2 37.0 mass%

NaBH4 + 4 H2O NaOH + HBO3+ 5 H2 35.7 mass%

LiBH4 + 4 H2O LiOH + HBO3+ 5 H2 45.5 mass%

M + x H2O M(OH)x + x/2 H2

x/2 H2 + x/4 O2 x/2 H2O

0

50

100

150

200

0 10 20 30

Hyd

ro

ge

n d

en

sit

y [

kg

/m3]

Hydrogen density [kg H2/ 100kg storage material] Andreas Züttel, Switzerland, 7/1/2015

HYDROGEN DENSITY

carbon

hydrates liq. hydro-

carbons

metal

hydrides

comp.

H2 gas

liq. H2

liq. natural

gas

NH3

complex

hydrides

physi-

sorption

ENERGY DENSITY OF FUELS

10

20

5 10 15

Vo

l. E

ne

rgy d

en

sity [

kW

h/l]

Grav. Energy density [kWh/kg]

Coal

OilMetal

hydride

Complex

hydride

Butane

Alcohol

liq. H2

→

Wood

comp. H2

Battery

SYNTHETIC HYDROCARBONS

ELECTROLYSIS

CO2

O2

O2

SUN

ENERGY

ENERGY

n CO2 + (3n+1) H2 CH3-(CH2)n-2- CH3 + 2n H2O

H2O

-(CH2)n-

COMBUSTION

H2

CO2

H2O

H2O

H2O H2 + ½O2

SYNTHESIS

H2 O2

H2O

OH-

e-

e-

Electrolyte

KOH/H2O

H OH-

H2

H2OH2O

O2

O2

H2O

Andreas Züttel, Switzerland, 7/1/2015

SYNTHETIC HYDROCARBONS

Sunlight

H2O H2 + O2

2H + CO2 -CHOH-

-CHOH- -(CHOH)n-

-(CHOH)n- -(CH2)n-

Renewable energy

H2O H2 + O2

H2 + CO2 CO + H2O

nCO + (2n+1)H2 CnH2n+2 + nH2O

light cycle

dark cycle

Photoelectrolysis

dil. CO2 conc. CO2

4H2 + CO2 CH4 + H2O

Electricity

Watergas-shift-reaction Sabatier-Process

Fischer-Tropsch Synthesis

H2 CO2

Energy < 0.8% Energy < 18%

CO2 ADSORPTION CO2 REDUCTION

DG = R×T × lnp

p0

æ

èç

ö

ø÷

Ivo A.W. Filot, Emiel J.M.

Hensen, Rutger A. van

Santen, Institute for

Complex Molecular

Systems, NRSC-Catalysis,

Eindhoven University of

Technology

CO2 in air: 380 ppm

DG = 20 kJ/mol = 0.44 kWh/kgC

air convection: 40 kgC/m2 per

year = 50 W/m2

Andreas Züttel, Switzerland, 7/1/20152

7

ENERGY STORAGE

1

10

100

1000

10000

100000

0.001 0.01 0.1 1 10 100Energy density [kWh/kg]

En

erg

y d

en

sit

y [

kW

h/m

3]

Pb-acid

battery

Li-ion

battery

mag. coil

EDLC comp. air

hot

water

biomass

coal oil

fusion

fission

hydrides

hydrogen

storage

capacitor

hydro-

powerhydrogen

natural gas

flywheel

3

NH3

GRAVITATION

ELECTROSTATIC

NUCLEAR

CHEMICAL

ELECTROCHEMICAL

INERTIA

ultimate

battery

comp. H2

synthetic fuel

SMALL SCALE DEMONSTRATION PROJECTEXPERIMENTAL PLATFORM

H2

Electrolyzer

MH Storage

CO2

Battery

CO2 + 4H2 ➞ CH4 + 2H2O

CH40.8 kg/h

LHV 13.9 kWh/kgHHV 15.4 kWh/kg

48 kWh1.2 kg H2

48 kWh

10 kW

Flow battery

4 kW

Sicryst.

Siamorph CIGS

Grätzelcell

Photovoltaics

MethanationH2

H2

CO2 Absorber

CH4

Jan VAN HERLE

François MARÉCHAL

Berend SMIT

Mohammad KhajaNAZEERUDDIN

Wendy QUEEN

Hubert GIRAULT

Andreas ZÜTTEL

Christoph ElLLERT

RENEWABLE ENERGY FOR BIOGAS UPGRADE

H2

H2

CH4

H2 fueling station

Methanation

alk. Electrolyzer 100 kW

Photovoltaics50’000 m2

PP = 2 MWPavg 200 kW

MH Storage 48 kg H2(2800 kg MH)

CO2

Flow-battery 4 MWh / 2 MW

Biogas (60% CH4, 40% CO2)

H2

CO2 + 4H2 ➞ CH4 + 2H2O

2 GWh CH4/y

32 kg/h

17 kg/h

2 kg/h

CH4

24 kg/h

LHV 13.9 kWh/kgHHV 15.4 kWh/kg

Grid

Gas grid CH4

4 kg H2

2 kg/h

CO2 absorption from air (40t/y) PEM Electrolyzer 100 kW

2 kg/h

CO2

4 kg/h

H2 Storage 48 kg H2(200 bar, 2.4 m3)

2 kg/h

H2 compressor 2 kg/h

8/12/2014 29

? kg/h

CO2

19 kg/h

BOARD

Prof. M. Höckel

Uni Appl. Science

Mr. U. Elber

Research Programs

Dr. U. Vogt

Nat. Research Lab.

N.N.

Secretary

Dr. S. Oberholzer

Gov. Energy Policy

Prof. Dr. A. Züttel

President

Prof. J.-F. Affolter

AuditorMr. F. Holdener

Vice-President

Mr. A. Hegglin

Auditor

Mr. H. Vock

Industry

Mrs. N. Seraidou

MobilityProf. Dr. P. Dyson

University

www.hydropole.ch

Andreas Züttel, Switzerland, 01.07.2015

SWISS HYDROGEN REPORT 15/16

HYDROGEN REPORT 15/16

Title: Energy Turnaround

konkrete Umsetztungsprojekte

Editorial (Berend Smit, Patrick

Aebischer, Philippe Gillet)

Summary (A. Züttel)

Beiträge:

Hydropole (A. Züttel)

STEP Martigny (H. Girault)

PSI (Felix Büchi, Oliver Kröcher)

Mobility Demonstrater (EMPA) (Ch. Bach)

Power to gas/Heat in Solothurn (Hansjörg Vock)

Postauto (Nikoletta SERAIDOU)

Energy autark building (Roger Balmer)

EPFL Valais/Wallis (P. Dyson)

SCCER (Thomas Schmidt, J. Roth)

H2Energy (R. Huber, A. Züttel)

Projekt liste: S. Oberholzerwww.hydropole.ch

FUEL LEAK SIMULATION

Before ignition t = 0 s

Ref.: Michael R. Swain, University of Miami, Coral Cables, FL 33124, USA

Hydrogen powered vehicle on the left.Gasoline powered vehicle on the right.

Ignition of both fuels occur.Hydrogen flow rate 2100 SCFM (0.18 m3/min.)

Gasoline flow rate 680 cm3/min.

Ignition t = 3 s

Andreas Züttel, University of Fribourg, 7/1/2015

t = 60 s

Ref.: Michael R. Swain, University of Miami, Coral Cables, FL 33124, USA

Hydrogen flow is subsiding, view of gasolinevehicle begins to enlarge

Hydrogen flow almost finished. View of gasoline powered vehicle has been expanded to nearly full screen.

t = 90 s

FUEL LEAK SIMULATION

New Jersey / Lakehurst, May 6th 1937, 6 pm

Accident:

While the airship was landing it has got on fire

about 80 meters above ground level and crashed.

Fatalities:

13 of 36 passengers,

22 of 60 crew members

1 member of 228 ground staff holding the ship.

LZ 129 “HINDENBURG”

Andreas Züttel, University of Fribourg, 15.12.200235

CAUSE OF FIRE

New investigation: The inflammable skin of the Hindenburg was

ignited by an electric discharge arc between the electrostatic

charged skin and the grounded metallic frame.

Ref.: Addison Bain, Wm. D. Van Vorst, "The Hindenburg tragedy revisited: the fatal flaw found", Int. Journal

of Hydrogen Energy 24 (1999), pp. 399-403

Paris / July 25th 2000, 4:44 pm

Accident:

While the jet was taking off flames were

noticed at the rear side of the left side wing.

All on board were killed:

9 crew, 100 passengers

4 people were killed on the ground.

5 injured on the ground, one seriously

AF 4590 CONCORDE

10th HYDROGEN & ENERGY SYMPOSIUM

www.hesymposium.ch

INTERNATIONAL SYMPOSIUM ON METAL-

HYDROGEN SYSTEMS (MH 2016)

MH2016 vom 7. – 12. August 2016 in Interlaken, Schweiz www.mh2016.ch

Merci beaucoup de votre attention!

Image: theark.ch