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B. FillonCEA LITEN Grenoble
December 2010, Boston
Challenges for the future sustainable energy generation, distribution and use.
ContentIntroduce 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
R & Dfor
nuclear
energy
Fundamental
Research Defense
programs
Technological
Research
for industry
One BU of Technological Research Division
15.000 researchers3 Billions Euros annualAREVA industrial group
Getting ready for the New Economy
LITEN : New energy technologies
ElectricTransportsElectric Power
BatteriesFuel Cells
HybridationRecycling
µ-power sources
Nanomaterials
Organic ElectronicEnergy recoveryNano Surfaces
Solar Energy& Buildings
Solar Energy
Solar PV, CSP,CPVElectrical systems
Energetic efficiency
Biomass& Hydrogen
Solid Storage
H2 Production H2 Storage
Usages
30%
30%
20%
20%
Grenoble
Transport électrique & nanomatériaux
550 P.
Chambéry
Solaire & Bâtiments à faible consommation d’énergie
200 p.
Effectif 2010
750 Ingénieurs & Techniciens
Effectif 2010
750 Ingénieurs & Techniciens
Brevets
350 actifs
135 dépôts en 2009
Brevets
350 actifs
135 dépôts en 2009
Budget 2010
120 M€90 M€ de recettes externes
30 M€ de subvention CEA
Budget 2010
120 M€90 M€ de recettes externes
30 M€ de subvention CEA
LITEN: Key numbers
Building/Solar Energy
Transport
Nomad
Large companies SME
• Photovoltaic devices
• Thermal devices
• Fuel cell
• Energy storage
• Hydrogen
• Micro power sources
• Energy scavengingM E T I S
Industrial partnerships
• Positive energy building
• Organic Electronic
ContentIntroduce 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
-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.
Nanotextured surfaces for catalysis
Less catalyst and well disperse:
NanosizedNanosized (dia.= 20 nm)
NanoscatteredNanoscattered (Pt =20 nm)
Cost per kg
1°/Cobalt,2°/Nickel3°/Lithium4°/Manganèse5°/Aluminium6°/Fer
Material and cost for the cathode component
25% of cobalt is used for phone market in 2010
Cathode Anode
Li Li ++
Cobalt Cobalt (Li(LiCoCoOO22))
Manganese (LiMn2O4)
Phosphate (LiFePO4)
NCA (LiNiCoAlO2)
NMC (LiNiMnCoO2)
…
GraphiteGraphite
Hard CarboneHard Carbone
TitanateTitanate
Lithium Oxydes :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 materialdevelopment !!
Think recycling
ContentIntroduce 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
Membrane-Electrodes Assemblies for PEMFC
Electrodes (carbon support + catalyst + protonic polymer conductor)
Monopolar plate
Oxygen Reduction Reaction (cathode):O2 + 4e- + 4H+ 2H2O
Oxygen Reduction Reaction (cathode):O2 + 4e- + 4H+ 2H2O
Hydrogen Oxidation Reaction (anode)H2 2H+ + 2e-
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
LITEN PEMFC for transport
EPICEA 2 kWComposite
stack
GENEPAC 20 kW
Metallic stack
SPACT 80 30 kW
Composite stack
GENEPAC 80 kWMetallic stack
Marathon Shell200 W
Graphite stack
RobotPAC200 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
Active layer ?
• Catalyst = Pt (1720 US$/oz = 45€/g ; 100kW 30g 1347€ )
PEMFC: Increase the contact surface
Catalysts SynthesisSubstitute noble metal by a
transition metal
Nano-achitecturesof catalyst layers
MEA engineeringDeposition of catalyst at the
most interesting place
Three potential approaches to substitute Pt
Same performances with a third of platinum quantity
Genepac 80KW
PEMFC : development on MEA with less Pt
1) Minimize Pt quantity
1) Minimize Pt quantity
MEA engineeringDeposition 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
Nano-achitecturesof 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 DepositioniCORE, 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
Catalysts synthesisSubstitute 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
ContentIntroduce 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
SiliconLingot
Wafer
Cell
Module
System
2,4 €/Wp
2 €/Wp
0,6 €/Wp
20085 €/Wp
0,8 €/Wp0,2 €/Wp
1 €/Wp
2015/202 €/Wp
Photovoltaic cell : road map
New concepts
3rdgénération cells
Crystalline Si cellsThin film technologies a-Si/mc-Si, CIGS (CuInSe, CdTe)
Three main categories for solar cells
PV Recycling : volume and value recycling
PVTech.
Silicon
Semi-conductorcompounds
Dye –cells
Organic…
New concepts…
Crystal
Thin Film
Multi-junctionIII-V / concen.
Thin Filmpolycrystal.
SolidElectrolyte
LiquidElectrolyte
…
…
…
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
New concepts
3rdgénération cells
Crystalline Si cellsThin film technologies a-Si/mc-Si, CIGS (CuInSe, CdTe)
Three main categories for solar cells
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
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)
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 YorktownProg. 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).
New concepts
3rdgénération cells
Crystalline Si cellsThin film technologies a-Si/mc-Si, CIGS (CuInSe, CdTe)
Three main categories for solar cells
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)
DEPOSITION METHOD FOR CIGS LAYER
EFFICIENCY
Best laboratory cell(~ 1 cm²)
Best pilot line module(30x30 cm²)
Commercial module(~ 1 m²)
Co-evaporation19% - 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 sputteringTransparent conductive oxide
State of the art of CIGS technology
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 $/kg).
• Demand of In for CIGS module fabrication < 0.1 g/Wp
In is abundant enough for 10 GWp/year of production capacity
Cu(In,Ga)(S,Se)2 (CIGS) Cu2(Zn,Sn)(S,Se)4 (CZTS)
Deposition method for CZTS layer Best laboratory cell ( 1 cm²)
Sputtering
+ selenization/sulfurization
6.7%
Nagaoka National College of Technology 1
Wet deposition11.2%
IBM 2
1 H. Katagiri et al., Applied Physics Express 1, 041204 (2008)2 T. K. Todorov et al., 25th European Photovoltaic Solar Energy Conference (2010)
Indium supply issue
State of the art of CZTS technology
ContentIntroduce CEA/LITEN
Critical Material substitutes for energy transport applications
Energy storage
Energy conversion
Critical Material substitutes for solar energy
Bulk silicon
Thin film PV cells
Conclusion
The Hype Cycle: Five stages
New product
“take off”
From revolution to evolution
Lithium
Hyper-entusiasm
Market saturation
Productivity
plateau
Rare earth
Gallium
De
ma
nd
an
d p
rice
Mass production
R&D
Indium
Selenium
Conclusion
Lithium for batteries Indium, Tellurium,.. for photovoltaics Pt for fuel cell
1) Three examples of potential crisis at short, medium and long term for sustainable energy components.
2) Three potential approaches to avoid the crisis Decrease the amount of material in the component Develop new architectures Replacement with non noble or non rare earth materials
3) Think « Life Cycle » Integrate recycling considerations in R&D for new
technologies
CxHy
CONOx
CO2
H2ON2
O2
Pt ou Pd for CO et CxHy oxydation
Rh for NOx reduction
Transport : Exhaust gas
Today technology TWC
Washcoat Al2O3 (20-60 µm)+ catalyst (Pt(Pd)/Rh) par imprégnation (1-2% wt)
DECADE
LCA studies & evaluation
Technical & economical evaluations
Life cycle analysis (LCA)
Optimisation of energy process
Support to technology development : targeting prioritary R&D
Ecoinvent
Evaluation
Design /Dimens.
Demonstration
Active layer ?
• Catalyst = Pt (1720 US$/oz = 45€/g ; 100kW 30g 1347€ )
Minimize the Pt quantity Improve the active layer structure Propose new materials
PEMFC: Increase the contact surface
• 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