Session # GHT44b, Session Tittle # 147 November 19, 05.

00 pm

New Generation of Full Composite Vessels

for 70MPa Gaseous Hydrogen Storage.
Philippe MAZABRAUD
Eng., PhD, Senior Fellow,
Head of Laboratory

CEA,
The Atomic Energy Commission,
Monts France.
Monts,
France
PSA, Peugeot Citron, France

Fabien NONY, Dominique LEMOINE,

Pierre SERRE-COMBE, Stphane VILLALONGA,
CEA, (Monts, Grenoble), France.
CEA, France

November 16-19, 2009

Palm Springs Convention Center
Palm Springs, CA, USA

Philippe MAZABRAUD,
CEA France.

Presentation Outline

Brief Overview of CEA

H2 and Fuel Cells

Cells Program at CEA
H2

H2 Context and Technical Targets for Storage

CEA ongoing research activities for HP Storage

Achievements and Partnerships

Conclusions

November 16-19, 2009

Palm Springs Convention Center
Palm Springs, CA, USA

Philippe MAZABRAUD,
CEA France.

CEA - 3 Main Areas of Activity

Defense
D
f
and Global
Security

Fundamental
Research
Energy

Information and
H lth
Health
Technologies

(non-greenhouse gas emitting)

including

H2 and Fuel Cells

National and
Worldwide
Fundamental
Research
(with Universities, and
other research
g
)
organizations)

November 16-19, 2009

Palm Springs Convention Center
Palm Springs, CA, USA

Philippe MAZABRAUD,
CEA France.

CEA - Key Figures and Research Centres

14 910 employees

Fontenay aux Roses

CEA, France

9 main R&D Centres

Bruyeres le Chatel

Saclay

3 210 million euros of budget

Valduc

Le Ripault
9 8 PhD students
958
d

Grenoble

3.293 scientific publications (ISI base)

305 priority patents filed
1250 d
delivered
li
d priority
i it patents
t t iin portfolio
tf li

Cesta
Marcoule

667 active partnership agreements with industries

Cadarache

364 current license agreements

CEA, France

97 spin
spin-off
off start-ups
start ups since 1984 in the high
high-technology
technology sector
62 joint research units (UMR) with research partners
64 associated research laboratories (LRC)

November 16-19, 2009

Palm Springs Convention Center
Palm Springs, CA, USA

Philippe MAZABRAUD,
CEA France.

 Hydrogen and Fuel Cells Program at CEA

30 M total Budget
(12 M external contracts)
250 Manpower
p
CEA, France

3 major Fields of Application

Transportation,
Stationaryy applications,
pp
Portable and back up power systems

CEA, France

JTI

November 16-19, 2009

Palm Springs Convention Center
Palm Springs, CA, USA

Philippe MAZABRAUD,
CEA France.

Hydrogen Storage : a Key Issue

Honda, Japan

Public Funding for H2 & Fuel Cells,

USA, 2009

H2-storage systems are still expected to facilitate

deployment and market growth of fuel cell power systems
(especially on-board storage tanks for FC Vehicles)
(especially,
November 16-19, 2009
Palm Springs Convention Center
Palm Springs, CA, USA

Philippe MAZABRAUD,
CEA France.

CEA : Engineering Centre of Excellence in Europe

Materials and Processes
Research & Development
CEA has been involved for more
than 10 years in all scientific
and technical projects
focusing in CGH2 storage
systems in France and Europe

Characterization
under H2

Safety Tests
System Integration ;
Codes and Standards

CEA is not a business company

(no competition with tank makers or end users)
b CEA h
but
has an iindustrial
d
i l policy
li
(patents pending and license agreements)
Academic and Industrial international partnerships are welcome
November 16-19, 2009
Palm Springs Convention Center
Palm Springs, CA, USA

Philippe MAZABRAUD,
CEA France.

Increased Focus on Early Market Applications

different
CGH2* storage
systems
y
have
to be developed
for early market
applications
before
automotive
application
(long term).

* Compressed Gas H2

November 16-19, 2009

Palm Springs Convention Center
Palm Springs, CA, USA

Philippe MAZABRAUD,
CEA France.

DOE Revised Performance and Cost Targets

November 16-19, 2009

Palm Springs Convention Center
Palm Springs, CA, USA

Philippe MAZABRAUD,
CEA France.

Current Compressed Technologies

4 Types of CGH2* Storage Vessels
Type 1

Type 1: Full metal vessel

Type 2

Type 2: Metallic vessel with composite reinforcement

Type 3: Metallic liner
Type 3

Type 4: Polymeric liner

Type 4

with full composite wrapping

suitable for on-board H2 storage

at high pressure

Competitive advantages
of type IV vessels

Metallic boss
Polymer liner

no hydrogen embrittlement
no fatigue issue (70 MPa - 10.000 Psi)
low weight
low costs (materials & process)
manufacturing

Composite shell

CEA,
CEA F
France

November 16-19, 2009

Palm Springs Convention Center
Palm Springs, CA, USA

* Compressed Gas H2
Philippe MAZABRAUD,
CEA France.

10

Challenges
Performance

Cost
Focus on
cost reduction :

CEA, France

Safety
70 MPa CEA
Type IV vessel,
after
ft burst
b t test
t t
at 170 MPa
(test performed by
Wroclaw University,
Poland)

advanced materials
optimized processes
innovative designs
sensors integration
g

lower burst pressure

safety factor ( << 2.35 )

CEA,
CEA France

November 16-19, 2009

Palm Springs Convention Center
Palm Springs, CA, USA

Philippe MAZABRAUD,
CEA France.

11

Current Technologies for Polymer Liners

ROTATIONAL MOLDING
(thermoplastics
and thermosets)

EXTRUSION
(thermoplastics)

e.g., LINCOLN COMPOSITES

(DOE Project ID# STP_15, May 20, 2009)

e.g., CEA TECHNOLOGIES

(European Integrated Project STORHY,
STORHY 2008)

B OW MO
BLOW
MOLDING
DING
(thermoplastics)

e.g., QUANTUM TECHNOLOGIES

(DOE Project ID# STP_04, May 20, 2009)

November 16-19, 2009

Palm Springs Convention Center
Palm Springs, CA, USA

- 1-step process (chemical bonding)

- no welding
g and no mechanical stress
- part volume from 1L to 50.000 L
- thickness from 1 mm to 10 mm
- boss integration (no post
post--sealing)
- inexpensive process (machine & mold)

Philippe MAZABRAUD,
CEA France.

12

CEA Technology for Polymer Liners

Reactive
Rotational Molding
Final part

Mixing
machine

Mould

a) Loading phase

b) Rotating phase

An advanced technology
(one--step chemical process)
(one
suitable for thermoplastic
or thermosetting polymers
polymers.

c) Unmoulding

PERSICO, Italia

enhanced H2-barrier properties

suitable mechanical behavior
high operating temperature (fast filling)
short time p
process (no
( melting)
g)
quick and low cost process

Worldwide patented for polyamide 6 and polyurethane liners

November 16-19, 2009
Palm Springs Convention Center
Palm Springs, CA, USA

Philippe MAZABRAUD,
CEA France.

13

H2--Barrier Performance of Polymers

H2
-13,8

PE

-14,0

-10
Pe = 3,6,10
exp (-31400/RT)

Polyethylene

Ep = 31,4 KJ/mol

-14,2

Log ( Pe ) (mol/m.Pa.s)

-14,4
-14,6
-14,8

-9

Pe = 3,2 10 exp (-40180/RT)

PU

Ep = 40,2 KJ/mol

-15,0

Polyurethane
PA-6

-15,2
-10

Pe = 1,6,10 exp (-32920/RT)

-15,4

Ep
p = 32,9 KJ/mol

-15,6
15 6

Polyamide 6 (Nylon 6)

-15,8
-16,0
0,0025

0,0026

0,0027

0,0028

0,0029

0,0030

0,0031

0,0032

-1

1/T( K )

Pe : permeation coef.
T : temperature
Ep : Activ.0,0034
Energy 0,0035
0,0033
R:8
8,314
314 JJ.K
K-11.moll-11

Polyamide-6 and Polyurethane have enhanced H2-barrier properties

compared to Polyethylene (not suitable for hydrogen application)
November 16-19, 2009
Palm Springs Convention Center
Palm Springs, CA, USA

Philippe MAZABRAUD,
CEA France.

14

Type IV Tanks meet the Standards for H2 Leakage

P
Polyurethane

H2 permeation (Pe) decreases

when pressure (P) increases
Effect of temperature (T) is
lower for high pressures (P)

H2-barrier is not an issue

for Type IV vessels,
when technical polymers
are used for liners.

CEA Polymer Liners using engineered materials (PA6 or PU)

are fully suitable for CGH2 storage applications.
(tank leakage rate ~ 0.05cm
0 05cm3/h/L at 70 MPa compared to 1 cm3/h/L required by most severe standards)
November 16-19, 2009
Palm Springs Convention Center
Palm Springs, CA, USA

Philippe MAZABRAUD,
CEA France.

15

Reactive Process : Chemorheology Approach

R-N=C=O

Catalyst & Additive

R-O-H
polyols

isocyanates

100

100 Pa.s
50 Pa.s

Temperature (C
C)

polyurethane

30C

10C/min

5C/min

3D-crosslinked
networks
2C/min
1C/min

10 Pa.s

80

Infusible liner
(interesting for
fast filling of tank)

R-NH-CO-O-R

3 Pa.s

60

=0,8
=0
8
=0,6

Viscosit minimale

gel

=0,4

40

=0,2
20

0
1

10

100

Time (min)
November 16-19, 2009
Palm Springs Convention Center
Palm Springs, CA, USA

Philippe MAZABRAUD,
CEA France.

16

Summary : CEA innovative Polymeric Liners

First Generation
INSA, France
PERSICO, Italia

CEA, France

Thermoplastic polymer
Specific Polyamide-6
Operating Temperature : 110C
Processing Temperature # 160C
160 C
Processing Time : 30 min (boss included)
Raw material cost : 3,5 /kg
Worldwide Patented

Second Generation

CEA, France

Thermosetting resin
Specific
S
ifi Polyurethane
P l
th
Operating Temperature : 130C
Processing Temperature : 30C
Processing Time : 10 min (boss included)
Raw
Ra material cost # 4
4,5
5 /kg
Worldwide Patented

License agreements can be delivered to tanks manufacturers

November 16-19, 2009
Palm Springs Convention Center
Palm Springs, CA, USA

Philippe MAZABRAUD,
CEA France.

ULLIT, France

17

Composite Developments at CEA

Testing of new fibers (carbon, )
Development of enhanced resins.
Development of innovative processes.
Sensors integration (embedded in
composite thickness).
Optimization
O ti i ti off Design
D i & Sh
Shape.
Modeling codes & Simulation tools
developments.
Current Ring Winding Machine at CEA
CEA, France

Composite usage is still

THE challenge
for CGH2 tank deployment
(cost and amount of raw
materials are too high)

November 16-19, 2009

Palm Springs Convention Center
Palm Springs, CA, USA

Durability Studies (thermomechanical)

Composite is core business
of industrial actors
in the domain.
Confidential work.
Philippe MAZABRAUD,
CEA France.

18

An iterative Approach for Composite Optimization

Netting analysis

Process
optimization

Mechanical
behavior studying

Process
simulation

Finite Elements
analysis
Process
and test
monitoring

CEA,
CEA France

November 16-19, 2009

Palm Springs Convention Center
Palm Springs, CA, USA

Philippe MAZABRAUD,
CEA France.

19

Testing of type IV prototype tank (CEA)

CEA, France

CEA
A, France

CEA
A, France

CEA,
CEA France

Burst Pressure # 1750 bar

Polyurthane liner

T700 carbon Fiber

(internal Volume : 2L)

2L@700 bar
(5%w)
CEA, France

CEA,
CEA F
France

November 16-19, 2009

Palm Springs Convention Center
Palm Springs, CA, USA

CEA, France

UltraFast
Cameras
(20.000 fps)

Hydraulic burst test

Philippe MAZABRAUD,
CEA France.

20

Some of CEA type IV prototype tanks

Working Pressure : 350 bar
Polyamide 6 Liner
Volumes : 22 L and 32 L
W capacity : 4,6 wt.%
TV approval
CEA, France

Working Pressure : 700 bar

Polyamide 6 Liner
Volume : 37 L
W capacity : 5
5,5
5 wt
wt.%
%
TV approval
CEA, France

Working Pressure : 700 bar

Polyurethane Liner
Volumes : 2 L and 37 L
W capacity
p
y : 5 wt.% ((2L)) and 5,5
, wt.% ((37L))
November 16-19, 2009
Palm Springs Convention Center
Palm Springs, CA, USA

Philippe MAZABRAUD,
CEA France.

21

French Partnerships for CGH2 Composite Vessels

CEA, France

November 16-19, 2009

Palm Springs Convention Center
Palm Springs, CA, USA

Philippe MAZABRAUD,
CEA France.

22

Conclusions
CEA is a European leader for advanced composite tank development
CEA proposes innovative and suitable polymeric liners (e.g., polyurethane)
CEA is looking for major industrial partners (license agreement, Joint-Venture)
in Europe, North America and Japan for manufacturing and commercialization

Future work at CEA aim to improve the cost and weight of Type IV CGH2
g raw material costs ((especially
p
y composite
p
ones)) through
g
vessels byy reducing
material development, process optimization and design modifications.

Advanced
Ad
d storage
t
systems
t
to
t facilitate
f ilit t d
deployment
l
t
and market growth of fuel cell power units for early market applications,
before long-term mass markets (e.g., automotive)

November 16-19, 2009

Palm Springs Convention Center
Palm Springs, CA, USA

Philippe MAZABRAUD,
CEA France.

23

Thank you for your attention !

philippe.mazabraud@cea.fr
fabien.nony@cea.fr

November 16-19, 2009

Palm Springs Convention Center
Palm Springs, CA, USA

Philippe MAZABRAUD,
CEA France.

24