reneweble energy

1. B. Fillon
CEA LITEN Grenoble
December 2010, Boston
Challenges for the future sustainable energy
generation, distribution and use.

2. Content
Introduce CEA/LITEN
Critical Material substitutes for energy transport applications
Energy storage
Energy conversion
Critical Material substitutes for solar energy
Bulk silicon
Thin film PV cells
Conclusion

3. R & D
for nuclear
energy
Fundamental
Research
Defense
programs
Technological
Research
for industry
One BU of Technological Research Division
15.000 researchers
3 Billions Euros annual
AREVA industrial group
Getting ready for the
New Economy

4. LITEN : New energy technologies
Electric
Transports
Electric Power
Batteries
Fuel Cells
Hybridation
Recycling
µ-power
sources
Nanomaterials
Organic Electronic
Energy recovery
Nano Surfaces
Solar Energy
& Buildings
Solar Energy
Solar PV, CSP,CPV
Electrical systems
Energetic efficiency
Biomass
& Hydrogen
Solid Storage
H2 Production
H2 Storage
Usages
30%
30%
20%
20%

5. Grenoble
Transport électrique &
nanomatériaux
550 P.
Chambéry
Solaire & Bâtiments à faible
consommation d’énergie
200 p.
Effectif 2010
750 Ingénieurs &
Techniciens
Brevets
350 actifs
135 dépôts en 2009
Budget 2010
120 M€
90 M€ de recettes externes
30 M€ de subvention CEA
LITEN: Key numbers

6. Building/Solar Energy
Transport
Nomad
Large companies SME
• Photovoltaic devices
• Thermal devices
• Fuel cell
• Energy storage
• Hydrogen
• Micro power sources
• Energy scavenging
M E T I S
Industrial partnerships
• Positive energy building
• Organic Electronic

7. Critical materials substitution in alignment with LITEN strategy
Harvesting Storage
Conversion

8. Content
Introduce CEA/LITEN
Critical Material substitutes for energy transport applications
Energy storage
Energy conversion
Critical Material substitutes for solar energy
Bulk silicon
Thin film PV cells
Conclusion

9. -Synthetic fuel – gen 2,
-Exhaust system,
-Air treatment,
-Thermal exchange system.
-Hydrogen storage and
production,
-Coupling with Renewable
energy,
2010 2010-15 2020-2030
Road-Map of motorization technologies
Thermal
Motorisation
Hybride
Motorisation
Fuel Cell
Motorisation
Hybride
Motorisation
2015-20
-High energy
batteries
-Energy storage,
-Energy management.

10. Nanotextured surfaces for catalysis
Less catalyst and well disperse:
Nanosized (dia.= 20 nm)
Nanoscattered (Pt =20 nm)

11. Cost of Li2CO3

12. Cost per kg
1°/Cobalt,
2°/Nickel
3°/Lithium
4°/Manganèse
5°/Aluminium
6°/Fer
Material and cost for the cathode component
25% of cobalt is used
for phone market in 2010

13. Cathode Anode
Li +
Cobalt (LiCoO2)
Manganese (LiMn2O4)
Phosphate (LiFePO4)
NCA (LiNiCoAlO2)
NMC (LiNiMnCoO2)
…
Graphite
Hard Carbone
Titanate
Lithium Oxydes :
Li-ion picture: courtesy of Prof. M. Winter
 Cathode : Avoid cobalt for cost/security
 Anode : Replace graphite by Ti oxydes for cost/security
Lithium-ion battery family : multiple contents
+ New material
development !!
Think recycling

14. Content
Introduce CEA/LITEN
Critical Material substitutes for energy transport applications
Energy storage
Energy conversion
Critical Material substitutes for solar energy
Bulk silicon
Thin film PV cells
Conclusion

15. Membrane-Electrodes Assemblies for PEMFC
Electrodes (carbon support +
catalyst + protonic polymer
conductor)
Monopolar plate
Oxygen Reduction
Reaction (cathode):
O2 + 4e- + 4H+ 2H2O
Hydrogen Oxidation
Reaction (anode)
H2 2H+ + 2e-
Heat
Heat
Electricity production
Excess Air/O2
output
H2
input
Excess H2
output
Air / O2
input
Polymer membrane
Strength of the CEA: it masters the whole
chain, from components to systems, through
assemblies and stacks

16. LITEN PEMFC for transport
EPICEA 2 kW
Composite
stack
GENEPAC 20 kW
Metallic stack
SPACT 80
30 kW
Composite stack
GENEPAC 80 kW
Metallic stack
Marathon Shell
200 W
Graphite stack
RobotPAC
200 W
Graphite stack
• Development of new materials and
substitution of critical material
• Optimization of materials and
membrane electrode assembly
• Design, manufacture and tests of
stacks
• Membrane degradation
mechanisms analysis
• Development of electrochemical
constitutive equations coupled with
thermohydraulic analysis
Bipolar plates

17. Active layer ?
• Catalyst = Pt
(1720 US$/oz = 45€/g ; 100kW  30g  1347€ )
PEMFC: Increase the contact surface

18. Catalysts Synthesis
Substitute noble metal by a
transition metal
Nano-achitectures
of catalyst layers
MEA engineering
Deposition of catalyst at the most
interesting place
Three potential approaches to substitute Pt

19. Same performances with a third of platinum quantity
Genepac 80KW
PEMFC : development on MEA with less Pt
1) Minimize Pt quantity

20. 1) Minimize Pt quantity
MEA engineering
Deposition of catalyst at the most
interesting place
Optimized dispersion of catalyst in the MEA :
• inlet / outlet
• channel / Ribs
• composition of ink (hydrophilic/ hydrophobic)
 Optimize the distribution of catalysts on MEA
for each design of bipolar plate and application

21. Nano-achitectures
of catalyst layers
Figure : Pt dendritic structures, K. Yamada et
al. J. Power Sources 180 (2008)181-184
Figure : tetrahexahedrals Pt nanoparticules
,N.Tian, Science Vol.316 may (2007) 732-735
Dr. Michael Brett / GLancing Angle Deposition
iCORE, NRC (Can)
Pt nanowire, nanotubes and
nanoflowers on carbon support,
CEA, (F)
Pt nanowire, on carbon support,
Dodelet and Sun (Can)
2) Improve the active layer structure

22. Catalysts synthesis
Substitute noble metal by a
transition metal
J-P. Dodelet INRS (Can)
P. Zelenay, LANL (USA)
V. Artero, CEA/IRTSV (F)
P. Gouérec, Sté GPMaterials (F)
B. Popov, Univ. South carolina (USA)
P. Zelenay, LANL (USA)
M.K Debe, 3M (USA)
Multimetallics
Core-Shell /
hollow spheres
R. Adzick, BNL (USA)
M.K Debe, 3M (USA)
P. Strasser, ORNL (USA)
Non noble and /
bio-mimetic
catalysts
3) Propose new materials

23. Content
Introduce CEA/LITEN
Critical Material substitutes for energy transport applications
Energy storage
Energy conversion
Critical Material substitutes for solar energy
Bulk silicon
Thin film PV cells
Conclusion

24. Silicon
Lingot
Wafer
Cell
Module
System
2,4 €/Wp
2 €/Wp
0,6 €/Wp
2008
5 €/Wp
0,8 €/Wp
0,2 €/Wp
1 €/Wp
2015/20
2 €/Wp
Photovoltaic cell : road map

25. New concepts
3rdgénération cells
Crystalline Si cells
Thin film technologies a-
Si/mc-Si, CIGS (CuInSe,
CdTe)
Three main categories for solar cells

26. PV Recycling : volume and value recycling
PV
Tech.
Silicon
Semi-conductor
compounds
Dye –
cells
Organic…
New concepts…
Crystal
Thin Film
Multi-junction
III-V / concen.
Thin Film
polycrystal.
Solid
Electrolyte
Liquid
Electrolyte
…
…
…
m-Si
p-Si
a-Si / µ-cryst.
Crystal.
CIS / CIGS
CdTe
• Material PV wastes
upcoming (<> tech.)
• Potential material
sourcing risks (rare
materials)
Ag
In
In, Ga
In, Pt, Ru
Ga, Ge, In, Au
Te, Cd toxicity

27. New concepts
3rdgénération cells
Crystalline Si cells
Thin film technologies a-
Si/mc-Si, CIGS (CuInSe,
CdTe)
Three main categories for solar cells

28. Radial junction silicon nanowire technology
 High efficiency (>15%)
 Enhanced optical absorption of silicon nanowire arrays
 Effective extraction of photogenerated charges in the radial junction
configuration
 Low cost
 Low silicon material usage
 Metal substrate

29. Advantage of Si nanowires: enhanced optical absorption
5000 nm
 Si nanowire arrays with optimized periodicity offer an enhanced optical absorption
compared to Si thin films with same thickness
 Si nanowire arrays would allow to reach a higher ultimate efficiency, while reducing Si
material usage
J. Li et al., Appl. Phys. Lett. 95, 243113 (2009).
(diameter = periodicity / 2)

30. State of the art of radial junction Si nanowire technology
Group Substrate Nanowire (or
microwire)
Radial junction Front contact Energy conversion
efficiency
L. Tsakalakos, General Electric,
Appl. Phys. Lett. 91, 233117 (2007)
Metal CVD (gold) a-Si by PECVD ITO by PVD
Metal grid
0.1%
1.8 cm²
P. Yang, Univ. California, Berkeley,
J. Am. Chem. Soc. 130, 9224 (2008)
c-Si Wet etching (AgNO3
+ HF)
c-Si by CVD + RTA Metal grid 0.5%
0.1 cm²
H. A. Atwater, CalTech,
33rd IEEE Photovoltaic Specialist Conf. (2008)
c-Si RIE Diffusion Point contact 6%
0.04 cm²
O. Gunawan and S. Guha, IBM,
Sol. Energy Mater. Sol. Cell. 93, 1388 (2009)
c-Si CVD (gold) c-Si by CVD
Al2O3 by ALD
Metal grid 2%
0.5 cm²
P. Yang, Univ. California, Berkeley,
Nano. Lett. 10, 1082 (2010)
c-Si RIE Diffusion Metal grid 5%
0.25 cm²
T. S. Mayer, Pennsylvania State Univ.,
Appl. Phys. Lett. 96, 213503 (2010)
c-Si RIE Diffusion Point contact 9%
0.07 cm²
H. A. Atwater, CalTech,
Energy Environ. Sci. 3, 1037 (2010)
c-Si CVD (copper) Diffusion ITO by PVD 7.9%
0.0021 cm²
S. Guha, IBM Yorktown
Prog. Photovolt. Res. Appl. (2010)
c-Si RIE Diffusion Metal grid 5%
1 cm²
 The advantage of CVD over etching is the ability to directly prepare silicon nanowire arrays
on large-area, low-cost substrates (as demonstrated by General Electric)
 Promising results have been obtained experimentally by CVD (CalTech has demonstrated
very recently efficiencies up to 7.9% with an active volume of Si equivalent to a 4 µm thick Si
wafer).

31. New concepts
3rdgénération cells
Crystalline Si cells
Thin film technologies a-
Si/mc-Si, CIGS (CuInSe,
CdTe)
Three main categories for solar cells

32. 2nd generation
(thin films)
1st generation
(bulk silicon)
Largest potential for improvement among thin film technologies
Potential of CIGS technology
Veeco, Photon’s PV Production Equipment Conf. (2009)

33. DEPOSITION METHOD
FOR CIGS LAYER
EFFICIENCY
Best laboratory cell
(~ 1 cm²)
Best pilot line module
(30x30 cm²)
Commercial module
(~ 1 m²)
Co-evaporation
19% - 20%
ZSW, HZB (DE)
NREL (US)
14%
ZSW (DE)
8% - 12%
Würth Solar, Q-Cells, Solarion (DE)
Global Solar, Ascent Solar (US)
Sputtering of precursors
+ selenization/sulfurization
-
15% - 16%
Solar Frontier (JP)
Avancis (DE)
7% - 12%
Solar Frontier, Honda Soltec (JP)
Avancis, Sulfurcell, Bosch Solar (DE)
Sunshine PV (TW)
Printing of precursors
+ selenization/sulfurization
10% - 12%
IBM (US)
-
8% - 11% (?)
Nanosolar (US)
25th European Photovoltaic Solar Energy Conference (2010)
Cu(In,Ga)Se2 (1-2 µm)
Absorber layer (p type)
Buffer layer (n type)
Back contact
Substrate
Mo (0.2 µm) by sputtering
CdS or ZnS or In2S3 (0.05 µm) in chemical bath
ZnO:Al (0.5 µm) by sputtering
Glass, metal, polymer
Intrinsic ZnO (0.05 µm) by sputtering
Transparent conductive oxide
State of the art of CIGS technology

34. M. A. Green, Prog. Photovolt. Res. Appl. 17, 347 (2009).
G. Phipps et al., Renewable Energy Focus, July/August 2008, 56-59.
• Forecast: supply of « virgin » In can be increased up to 1000
tons/year at prices consistent with photovoltaic use (<1600 $/kg).
• Demand of In for CIGS module fabrication < 0.1 g/Wp
 In is abundant enough for 10 GWp/year of production
capacity
Cu(In,Ga)(S,Se)2 (CIGS)  Cu2(Zn,Sn)(S,Se)4 (CZTS)
Deposition method for CZTS layer Best laboratory cell ( 1 cm²)
Sputtering
+ selenization/sulfurization
6.7%
Nagaoka National College of Technology 1
Wet deposition
11.2%
IBM 2
1 H. Katagiri et al., Applied Physics Express 1, 041204 (2008)
2 T. K. Todorov et al., 25th European Photovoltaic Solar Energy Conference (2010)
Indium supply issue
State of the art of CZTS technology

35. Content
Introduce CEA/LITEN
Critical Material substitutes for energy transport applications
Energy storage
Energy conversion
Critical Material substitutes for solar energy
Bulk silicon
Thin film PV cells
Conclusion

36. High price volatility prior to current crisis

37. The Hype Cycle: Five stages
New product
“take off”
From revolution to evolution
Lithium
Hyper-
entusiasm
Market
saturation
Productivity
plateau
Rare earth
Gallium
Demand
and
price
Mass
production
R&D
Indium
Selenium

38. Conclusion
 Lithium for batteries
 Indium, Tellurium,.. for photovoltaics
 Pt for fuel cell
1) Three examples of potential crisis at short, medium
and long term for sustainable energy components.
2) Three potential approaches to avoid the crisis
 Decrease the amount of material in the component
 Develop new architectures
 Replacement with non noble or non rare earth materials
3) Think « Life Cycle »
 Integrate recycling considerations in R&D for new
technologies

39. Thank you
Thank you for your attention
A bientôt
Bertrand FILLON
Tel:0033685324833
bertrand.fillon@cea.fr

40. CxHy
CO
NOx
CO2
H2O
N2
O2
Pt ou Pd for CO et CxHy oxydation
Rh for NOx reduction
Transport : Exhaust gas
Today technology TWC
Washcoat Al2O3 (20-60 µm)
+ catalyst (Pt(Pd)/Rh) par
imprégnation (1-2% wt)
DECADE

41. LCA studies & evaluation
 Technical & economical evaluations
 Life cycle analysis (LCA)
Optimisation of energy process
Support to technology
development : targeting prioritary
R&D
Ecoinvent
Evaluation
Design /
Dimens.
Demonstration

42. Active layer ?
• Catalyst = Pt
(1720 US$/oz = 45€/g ; 100kW  30g  1347€ )
 Minimize the Pt quantity
 Improve the active layer structure
 Propose new materials
PEMFC: Increase the contact surface

43. • Bottlenecks :
Turn over frequency !
(more reactions)
f (s-1)= i / (eN)
i – current (A.cm-2),
e – electron charge(1.6 10-19 C)
N – Active site density (cm-2)
Non noble metal
Gasteiger et al. Science 324, 48 (2009)
 recent progress :
Iron based catalyst similar of Pt nanoparticules
3) Propose new materials

44. Lefèvre et al, Science, 324, 71 (2009)
Los Alamos Nat Lab. (2010)
 Durability?
• Specific properties obtain with some architecture of transition metal oxide.
3) Propose new materials