MgHMgH22nanonano--structured structured

powderspowdersfor hydrogen for hydrogen

storagestorage

serbien

MCPMCP MgMg--SerbienSerbien SASSASProduction unit Production unit atat Romans (Drôme), Romans (Drôme),

90 km 90 km southsouth LyonsLyons. France. France

Plant Plant atat Romans Romans -- DrômeDrôme

CompanyCompany developeddeveloped by M. Jehan 1995by M. Jehan 1995

MCP MCP MgMg--SerbienSerbien producesproduces granules, granules, powderspowders andand chips chips ofof pure Mg pure Mg andand itsitsalloysalloys, , aluminumaluminum andand otherother alcalinealcaline--

earthsearthsSpecificSpecific sievingsieving ofof reactingreacting powderspowders

((e.g.e.g. nuclearnuclear application application powderspowders))

ContinuousContinuous productionproduction24 24 hourshours a a dayday / 6 / 6 daysdays a a weekweek..

Production team : 22 personnes on a Production team : 22 personnes on a certifiedcertified site (DRIRE). site (DRIRE).

Mg Mg presentpresent capacitycapacity : 6 000 M tons: 6 000 M tons

Certification ISO 9001: 2000 Membre IMACertification ISO 9001: 2000 Membre IMA

EquipementsEquipements and processesand processesat MCP Mgat MCP Mg--SerbienSerbien -- RomansRomans

- Production up to 500 tons a year- of granules and powders- Morphologies suited for steel

production and chimistry (metal-organics, vitamines )

- Granules of Mg-alloys for “Thixomoulding”

- One of the two large facilities in Western-Europe for transformation of Mg into fines particles

- Automatised equipements- Laboratory complet for

caracterisation by laser granulometer

Production Production ofof Mg hydridesMg hydrides

• Cooperation with Centre National de la Recherche Scientifique –Grenoble to synthesise and produce activated Mg-hydride for reversible hydrogen storage

• Goal : industrial scale production

• European ProjectsHYSTORY « 6th PCRD : Energy, Environment and Sustainable Development » High Energy ball-milling of nanostructured MgH2

• NESSHY « 7th PCRD Novel Efficient Solid Storage of Hydrogen » Production of MgH2 powders with catalysts

• International patent MCP-CNRS

• Other Projects• Requests : More than 1000 MTons a year of MgH2

• French Label ENERDIS

HighHigh EnergyEnergy IndustrialIndustrial BallBall--MillingMilling

MecanosynthesisMecanosynthesis of MgHof MgH22with transition metal under with transition metal under controlled atmospherecontrolled atmosphere

IndustrielIndustriel scale production scale production (on request)(on request)

Other Other equipementsequipements

Controlled atmosphere glove boxes

Isostatic cold pressing up to 4000 bars

Pilot ball miller in liquid or gas

MgHMgH22 nanonano--structured powdersstructured powdersfor hydrogen storagefor hydrogen storage

D. D. FruchartFruchart, M. Jehan, M. JehanM. Artigas, A. Chaise, J. Charbonnier, P. de M. Artigas, A. Chaise, J. Charbonnier, P. de RangoRango, G. Girard,, G. Girard,

P. Marty, S. P. Marty, S. Miraglia, S. Rivoirard, M. Shelyapina, N.Miraglia, S. Rivoirard, M. Shelyapina, N. SkryabinaSkryabina

Institut Néel, CNRS, Grenoble, FranceInstitut Néel, CNRS, Grenoble, France

MCPMCP--MgMg--SerbienSerbien, Romans sur Isère, France, Romans sur Isère, FranceCRETA, CNRS, Grenoble, CRETA, CNRS, Grenoble, FranceFrance

LEGI, LEGI, CNRS, Grenoble, CNRS, Grenoble, FranceFrance

UniversidadeUniversidade de Zaragoza, Espagnede Zaragoza, Espagne

InstituteInstitute FoctFoct, St , St PetersbourgPetersbourg State State UniversityUniversity, , RussiaRussia

Dept. of Physics, Perm State University, RussiaDept. of Physics, Perm State University, Russia

serbien

NessHyNessHy

NCSR Demokritos GRUniversity of Salford UKAir Liquide FEC-Joint Research Centre NLStockholms Universitet SInstitut For Energiteknikk NUniversity of Fribourg CHUniversity of Birmingham UKVrije Universiteit Amsterdam NLCNRS Grenoble FDaimler Chrysler AG DGKSS Geesthacht GmbH DUniversity of Iceland ISJohnson Matthey PLC UKForschungZentrum Karlsruhe DMax-Planck MPI-MF DTechnical University Denmark DKMETU Ankara TINETI PTIFW Leibniz Gemeinschaft DDelft University of Technology NLSouthwest Research Institute USA

HYSTORYHYSTORY

ACI ACI –– HymetHymet

Cluster Cluster EnergyEnergy

CNRS GrenobleLMI - UCBL

ECFP6

N

S

F

GR

AUS

F

N

S

D

Patents 2006Patents 2006FR0651478FR0601615

Why store hydrogen ?Why store hydrogen ?

• Oil : cost increases, resources decrease, greenhouse effect…• Renewable energies (solar, wind,…) : irregular availability

HydrogenHydrogen : : EnergyEnergy--carriercarrier for the futur ?for the futur ?• Electric energy storage• Fuel Cell• ICE

Hydrogen storage in safe conditionsHydrogen storage in safe conditionsHigh gravimetric density of energy High gravimetric density of energy (142 MJ/kg)(142 MJ/kg)

141,9

55,55

3050,39 47,27 47,21

020406080

100120140160

Hydrogen Methane Ethanol Propane Gasoil Natural Gas

FuelsFuels

Ener

gyEn

ergy

dens

ityde

nsity

MJ/

kgM

J/kg

Reversible Metal HydridesReversible Metal Hydrides

+ High volume density of hydrogen+ Safe solution (low pressure, endothermic release)+ Large-scale production+ Purity of Hydrogen (Fuel Cells)– Low weight density !

kg H2 / m3 Weight %

H2 gas 700 b 62 100 *

H2 liquid 70 100 *LaNi5H6 123 1.4

Ti-V-Cr 205 3.5AlNaH4 96 7.5

MgH2 106 7.6

• Compressed gas (350-700 bars)

• Cryogenic liquid (20 K)

• Chemical hydrides

* not comprising mass of tank

WhyWhy metalmetal hydrides ? hydrides ? WhyWhy MgHMgH2 2 ??

AdvantagesAdvantages withwith MgMgMg is the 7th most abundantelement on earthMg is cheaper than… AlMg metallurgy is easyMg is non-toxicMg is re-cyclableMgH2 is mono-metalelement system:no demixtionMgH2 uptake is 7.6 w%

DifficultiesDifficulties withwith MgMgH-reaction kinetic are said low, but…Temperatures of reaction are high, but…

MgHMgH22 towards towards nanonano--structured powdersstructured powders

+ High weight storage capacity (7.6 wt. % H2 )- High thermodynamic stability

T > 300°C, but heat flow control…- Slow diffusion kinetics, but…

Ball-milling (BM) with catalysts (transition metals or oxides)

Mg + HMg + H22 ↔ MgH↔ MgH22

Co-milling process vs BM time

0

1

2

3

4

5

6

0 2 4 6 8 10

1h5h10h20h

H %

wt.

time (mn)

Absorption 240°C - 1 MPa

Large impact of the milling time, especially at desorption

Optimum ≈ 20 hours milling time with catalysts

MgH2 MCP + 5 % at. V (40 µm)

0

1

2

3

4

5

6

0 10 20 30 40 50 60 70 80

Desorption 240°C - 15 kPa

1h10h20h

H %

wt.

time (mn)

MgH2 and M transformation on BM

• High density of defects• Reduction to nanosize MgH2 crystallites• Progressive MHx formation from MgH2

V → V2H → VH0.81

Nb → NbH0.89 → NbH2

Ti → TiH1.7 → TiH1.7 + TiH1.92

Interfaces between MgH2 grains and M particles

▼ β-MgH2

● Mg● MgO▼V2H

* VH0.81

15’30’1h5h10h

Inte

nsity

(u.a

.)

40 603020

▼

▼

▼ ▼ ▼

▼

▼▼●●●

● ●

●●

▼

50 70

V2H

▼

* *

VH0.81

MicrostructuralMicrostructural evolution evolution on BMon BM

Milling Time Crystallite sizes (nm)

15 min 29,(3)30 min 14,(2)

1 h 12,(2)5 h 10,(9)

Starting powder : 20 – 80 µmAfter 15 min. milling time : 1 – 10 µm

No further evolution

• Granulometry measurements

• Crystallites size of the β-MgH2After 15 min. milling time : 30 nm

Further crystallites size reduction with increasing milling time

0

2

4

6

8

10

0,1 1 10 100

g

sans broyage15min30min1h5h

Taille des particules (µm)

15 min30 min1 hour5 hours

Hydrogen sorption properties not correlated toHydrogen sorption properties not correlated topowder grain size, but to the crystallites sizepowder grain size, but to the crystallites size

No milling

0,1 1 10 100Particle size (µm)

Vol

. (%

)

▼ β-MgH2

● Mg

● MgO

* VH0.81

The high density of defects disappears after D/H cyclesRecristallisation of hexagonal single cristallites of Mg

Fast hydrogen diffusion results from the very large amountFast hydrogen diffusion results from the very large amountof boundaries developed between of boundaries developed between nanometricnanometric crystallitescrystallites

Microstructure evolution Microstructure evolution on cyclingon cycling

2θ2 0 30 40 50 60 70

20

Inte

nsity

(u.a

.)

▼

▼ ▼

▼

▼▼● ●● ● ●●* *

After milling (20h)After 5 D/H cycles at 240°C

▼ ▼

40 50 603020 70

100nm

InIn--situ neutron diffraction studysitu neutron diffraction study ((ILL ILL -- D20)D20)

Surface dissociation

Mg

Nb

Mg / MgH2Propagation interface

MgH2 sead

H2

Role of the TM additives ~ “gates” favoring H2 dissociation,

then H diffusion

In-situ hydrogenation (T ~ 280°C, P = 2 MPa)

ε - NbD0.75 rapid formation prior to the MgD2 formation

ε-NbDxε-NbDx

MgD2 MgD2

UpUp--scaling powder productionscaling powder production@ MCP@ MCP--SerbienSerbien

1. Synthesis the MgH2 precursors from Mg powder2. Co-milling MgH2 + M additives

Large scale energetic ball miller (25 l)Batches of 1 kg of activated powders

Very reactive powder in air (to handle under Ar gas)

Patent FR 06-51478

Kinetics characterisation Kinetics characterisation vsvs TT

0

1

2

3

4

5

0 5 10 15 20 25 30

Absorption 1 MPa

200°C150°C50°CH

% w

t.

time (mn)

Absorption can be initiated at 50°C, reasonably faster at 150°C4% 4% wtwt. in 1 minute . in 1 minute atat 200°C200°C

Highly reactive powdersHighly reactive powdersStability of the sorption properties on cyclingStability of the sorption properties on cycling

MgH2 MCP + 5 at.%V (40 µm) ZOZ Miller - 8 h

For 15 For 15 kPakPa ::only 20 min at 240°Conly 20 min at 240°C

(1 h at 220°C)

0

1

2

3

4

5

0 5 10 15 20 25 30

Desorption 15 kPa

300°C260°C240°C200°C220°C

H %

wt

time (mn)

MgHMgH22 pilot tank developmentpilot tank development

120 g of MgH120 g of MgH22(6 (6 grgr HH22 / 0.86 MJ)/ 0.86 MJ)

Main problem = control of the heat transfers

• Strong exothermic Mg hydrogenation• Low thermal conductivity of MgH2 powder

Copper ring

Heating coil

2

3 4

H21

Equilibrium conditions are immediately reached, thus stopping hydrogenation

Charging processCharging process (initial 280°C / 8 bars)(initial 280°C / 8 bars)

Without cooling fluid :Huge increase of temperature (+ 80°C)Total charging : 50 min. - 57 Nl (5 wt. %)

The central part of the tank follows the thermodynamic The central part of the tank follows the thermodynamic equilibrium up to the end of reaction, equilibrium up to the end of reaction, slowing Hslowing H22 absorptionabsorption

H22

3 41

Charging processCharging process ((starting 280°C / 8 b.)starting 280°C / 8 b.)

With forced air as cooling fluidCharge in 30 min. - 42 Nl (3.6 % wt.)

A cooling system reduces the tank loadingA cooling system reduces the tank loading--timetime(managing the cooler is needed to complete the charge)(managing the cooler is needed to complete the charge)

H22

3 4

1With cooling fluid

Fluent®

software• hydrogenation reaction • H2 consumption• heat generation

0 %wt H

5 %wt H

Bottom Top

Hydrogenation rate without cooling systemAfter 600 s 2200 s 5200 s

Copper ring

Hydrogenation rate with forced air cooling systemAfter 400 s 800 s 1400 s

• thermal conductivity • gradient of pressure

Numerical modeling

Fuel CellFuel Cell -- PAXITECHPAXITECH

120 g MgH120 g MgH22 (6 (6 grgr HH2 2 / 0.86 MJ) : lightening for ~ 72 h./ 0.86 MJ) : lightening for ~ 72 h.

New metallurgy routes (Severe Plastic Deformation : ECAP)New metallurgy routes (Severe Plastic Deformation : ECAP)Pilot tank development 5 kg MgHPilot tank development 5 kg MgH22 (250 (250 grgr HH2 2 / 36 MJ)/ 36 MJ)

Recycling waste heat (SOFC, thermal engines, factories)Recycling waste heat (SOFC, thermal engines, factories)

ConclusionConclusion

• Systematic investigation of the ball-milling process

- Activation role of the transition metal hydride directly evidenced

• Highly reactive powders available by kg batches

- Stability of the sorption properties on cycling

• Small scale tank tested with success ( 6 gr H2 / 0.86 MJ)- Loading process : P < 10 bars, starting at 150°C- Loading time strongly dependent of the cooling efficiency- Overall weight capacity to be optimized

Fuel = Fuel = HydrogenHydrogen

ICE PEMFC SOFCThermal engineThermal engine Low temperature Fuel Cell High temperature Fuel Cell

Hydrogen storageHydrogen storage

Gasoline Gasoil/gas High pressure Cryogenic liquid SolidSolidhydrideshydrides

Reforming

MgHMgH22

30 to 70 MPa 20 K

IntegratedIntegrated Project :Project :EnergyEnergy regeneratingregenerating ICE / MgHICE / MgH2 2 tanktank

~ 100 kg MgH~ 100 kg MgH22 for ~ 250 for ~ 250 –– 300 km 300 km withwith ICE carICE car

EstablishEstablish energyenergy balance !balance !

WhatWhat couldcould bebe promissingpromissingfor Mg technologies ?for Mg technologies ?

108 ICE cars being equipped with MgH2 tanks

250 kg MgH2 for 700 km autonomy

20 years shift from gazoline to hydrogen civilisation

NeedsNeeds for more for more thanthan 101066 tons Mg a tons Mg a yearyear duringduringmore more thanthan 20 20 yearsyears !!

NB NB -- fuel fuel cellcell : 0.3kW/kg, large volume, : 0.3kW/kg, large volume, veryvery expensiveexpensive,,veryvery fragile, short fragile, short lifelife, ressources , ressources ofof Pt, Rh ???? Pt, Rh ????

ContactsContacts

Michel Jehan, Michel Jehan, D.Ing.D.Ing.HeadHeadM.C.P. M.C.P. -- SerbienSerbien SASAZ.I. rue Vaucanson, F Z.I. rue Vaucanson, F –– 26100 ROMANS, France26100 ROMANS, FranceTel (33) (0) 4 75 70 75 50 Tel (33) (0) 4 75 70 75 50 –– Fax (33) (0) 4 75 70 75 51Fax (33) (0) 4 75 70 75 51EE--mail mail corporatecorporate@@mcpmcp--technologies.comtechnologies.com

Daniel FRUCHART, Daniel FRUCHART, D.Hab.D.Hab.Directeur de Recherche au C.N.R.SDirecteur de Recherche au C.N.R.SInstitut Néel Institut Néel –– groupe IICEgroupe IICEBP 166,BP 166, 38042 Grenoble Cedex 9, France38042 Grenoble Cedex 9, FranceTel (33) (0) 4 76 88 11 43 Tel (33) (0) 4 76 88 11 43 –– Fax (33) (0) 4 76 88 10 38Fax (33) (0) 4 76 88 10 38EE--mail mail daniel.fruchartdaniel.fruchart@@grenoble.cnrs.frgrenoble.cnrs.fr

serbien