Solar Energy Rseaerch and Innovation Prospects for the Sultanate of Oman, Presentation to the Research Council Oman Muscat 1.2.2012 - michael.graetzel
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Solar Energy Rseaerch and Innovation Prospects for the
Sultanate of Oman, Presentation to the Research Council Oman
Muscat 1.2.2012
michael.graetzel
Increasing world energyGlobal
pollution demandwarming
(quadrilliion Btu)
Exaustion of petroleum Nuclear risk
International Energy Outlook, 2010
Silicon solar cell farm
Solar cooker
Dye sensitized solar cells Dye sensitzed solar cells
(3G Solar) Fujikura (Tokyo)
Electricity, Fuels and Heat from Sunlight
H2O
H2O
CH3
O2
N
e-
O2
CO2
CO2
N HN
N N
sugar
H
H2, CH4
CH3OH
h+
O
NC
natural
H
p-n junction 50 - 200 °C 500 - 3000 °C
solar cell photosynthesis space, water heat engines
heating electricity generation
artificial process heat
photosynthesis
Solar Thermal
dye sensitized cell and
photoelectrochemical solar cells
photoelectrolysis/H2O splitting
Solar Electric
Solar Fuels
~ 14 TW additional C-free energy by 2050 from Arthur Nozik
Global Solar Light Capture by Spectral Splitting with Dieelectric Mirror
$
TE : thermoelectric converter SMSC : Sensitized Mesoscopic Solar Cell
Solar Energy Rseaerch and Innovation Prospects for the Sultanate of
Oman
Artificial photosynthesis Hydrogen generation from sunlight
Dye sensitized solar cells Photo‐induced water splitting on nano
mimic the green leaf structured Fe2O3
PV presently contributes currently only 0.04 % of the world’s energy supply. Disruptive breakthroughs needed for PV to become an unsubsidized market ! • Cost reduction, simple processing and up scaling • Higher efficiency & high stability • Low energy fabrication, readily available resources and low environmental impact. • Short energy pay back time
A new paradigme: mesoscopic solar cells
dye sensitized solar cells are the first to
employ a 3‐dimensional mesoscopic
junction to convert sunlight to electricity
SEM picture of a mesoscopic TiO2 film
B.O’Regan and M.Grätzel
“A Low Cost, High Efficiency Solar Cell based
Low ‐medium purity materials
on the Sensitization of Colloidal Titanium
Low cost processing
Dioxide ”
High Efficiency and Stability
Nature, 1991, 353, 7377‐7380.
Dye sensitized solar cells separate the generation and transport of
electric charges mimicking the light reaction in photosynthesis
e–
9
Electron transfer dynamics are key to achieve high performance and
stability with dye sensitized mesoscopic solar cells
electron electron interfacial
injection Dye regeneration transport recombination
time [s]
electron transport
coll = 1/(1+ trans/rec)
loss mechanism:
= 1/(1+ Rtrans/Rrec) interfacial
recombination
electron transport must be at least 100 x faster than recombination to
collect > 99 % of the photo‐generated charge carriersThe typical dye sensitized solar cell consists of 3 components
Sensitizing Dye Titania Nanoparticles Electrolyte
Iodide/Tri-iodide
Chemical Structure of N3 Dye 20 nm Titania nanoparticles Redox Coupleother DSC embodiments use solid state hole conductors
redox electrolyte Organic or inorganic hole transporter
dye
Redox electrolyte Hole transporter
dyeQuantum dot sensitized heterojunctions do not need a hole transport material
PbS
PCE = 5.1 %
ACS Nano, 2010, 4 (6), pp 3374–3380The present status of dye sensiitzed mesoscopic solar cells
• Power conversion efficiency (PCE) measured under AM 1.5 sunlight (STC):
laboratory cells: 12.3 % [1], modules: 9.9 % [2].
tandem cells: 15‐16% [3]
• stability > 20 years outdoors [4]. pass standard accelerated test for outdoor PV [5]
• energy pay back time: < 1 year (3GSolar [5] and ECN [6] life cycle analysis)
• Industrial development: has been launched by several industrial companies , mass
production of light weight flexible modules started in 2009 by G24Innovation (
www.g24i.com )
1. Yella A, Lee H.‐W, Tsao H.N, Yi C. Chandiran A.K, Nazeeruddin Md.K,Diau E.W.‐G, Yeh C.‐Y,
Zakeeruddin S.M, Grätzel M (2011) Science 629‐634
2. Green M.A, Emery K, Hishikawa Y and Warta W (2011) Prog. Photovolt: Res. Appl. 19:84–92.
3. Liska P, Thampi R, Grätzel M, Brémaud D, Rudmann D, Upadhyaya H.M,Tiwari, A.N (2006). Appl.
Phys. Lett. 88: 203103.
4. Harikisun R. Desilvestro H (2011) Solar Energy 85: 1179–1188
5. Arakawa H, Yamaguchi T, Okada K, Matsui K, Kitamura T, Tanabe N, Highly Durable Dye‐
sensitized Solar Cells. Fujikura Tech. Rev. 2009:55‐59
6. http://3gsolar.com/NewsItem.aspx?ID=40
7. De Wild‐Scholten M.J, Veltkamp A.C (2007) Environmental Life Cycle Analysis of Dye Sensitized
Solar Devices. www.ecn.nl/publicaties/PdfFetch.aspx?nr=ECN‐M‐‐07‐081.Time Evolution of the Conversion Efficiency for Dye sensitized Solar Cells
Proposed research to meet the near term 15% efficiency goal • Enhanced light harvesting by new mesoporous structures. Light containment and plasmonic effects • New sensitizers • Redox mediators to replace the triidodide/iodide couple • Alternatives to Pt as electrocatalyst for the counterelectrode • Solid state sensitzed heterojunctions • Quantum dot injection cells • Tandem devices • New solid nanocomposite electrolytes
TiO2 anatase nanoparticles
40
30
Number
20
Well facetted surface,
preferred (101) orientation
of surface planes visible 10
0
17 0 10 20 30 40 50
Diameter of particles, nmZnO nanostructures
July, 2010
500 nm
D. Chen, F. Huang, Y.‐B. Cheng and R.A.
Caruso Adv.Mat2009, 21, 2206–2210Proposed research to meet the near term 15% efficiency goal • Enhanced light harvesting by new mesoporous structures. Light containment and plasmonic effects • New sensitizers • Redox mediators to replace the triidodide/iodide couple • Alternatives to Pt as electrocatalyst for the counterelectrode • Solid state sensitzed heterojunctions • Quantum dot injection cells • Tandem devices • New solid nanocomposite electrolytes
Photon capture by dye loaded mesoporous film is key to reach high photo currents
4 3.0
3 2.5 2.0 1.8 1.6 1.4
18
5x10 energy [eV]
photon flux [phtons/m /s/nm]
4
2
3 Fraction of photons
producing current in
a DSC sensitized
with C106
2
1
0
300 400 500 600 700 800 900
wavelength [nm] JSC -2.0
-20
ff VOC I SC
photo-current density [m A/cm ]
Jm
2
-1.5
-15 Maximum power point
power [m W /cm ]
Pin -1.0
-10
2
-5 -0.5
More light harvested = higher
Vm VOC
current 0 0.0
0.0 0.2 0.4 0.6V
bias voltage [V]
More surface area = lower voltagePanchromatic DX1 sensitizer matches spectral response of silicon PV cell
Voc (V) Jsc
(mA/cm2
)
a-Si:H 0.860 12.5
GaAs 0.994 23.2
nc-Si 0.539 24.4
CdTe 0.845 26.1
Dye X 0.55 26.6
Si module 0.492 29.7
N719 “Black dye” BD
DX 1 data presented by Prof. S Uchida,Tokyo University; at NTU Singapore Symposium July 26 2011The Incident photon to current conversion efficiency IPCE
(external quantum efficiency EQE) reaches over 90 percent
IPCE (EQE) = abs cg coll
ab: light harvesting efficiency
cg: quantum yield of charge carrier generation
cg = injection dye regeneration
coll = efficiency of charge carrier collection
coll = 1/(1+ trans/rec)Science 2011, 334, 629 – 634.
PCE = 12.3 %
Frontier molecular
DFTorbital structure
calculations of highest
reveal occupiedexcitation
charge transfer & lowest
unoccupied molecular orbitals for YD2 donor‐ acceptor porphyrine
HOMO LUMO
Courtesy Filippo De Angelis0.86 V
0.96 V
Y123
Co(bpy‐pz)2Dye sensitized solar cells can meet future customer demands and needs
Emerging and new applications call for:
• ease of building integration
• transparency and multicolor option (for power window application) *
• flexibility
• Light weight
• low production cost
• feedstock availability to reach terawatt scale
• short energy pay back time (< 1 year)
• enhanced performance under real outdoor conditions
• bifacial cells capture light from all angles
• tandem cell configurations boost efficiency over 15 %
• outperforms competitors for indoor applications
* Unique selling proposition !
30Aesthetic Advantages of Dye Sensitized Solar Cells versus Conventional PV Devices • Dyes determine the color of the device. • Can be transparent • Can be flexible • Easy to make
Dye ooated TiO2 pigment nano-particles are printed to yield beautiful PV panel designs or transparent glass windows converting light to electric power Dye sensitized solar cells enable multicolor Colored tansparent glass panel panels, featuring beautiful artistic designs. producing electric power from sunlight Courtesy Sony Corporation Courtesy: Aisin Seiki/Toyota Inc.
34
Solar Powered Solar Panel Sun Glasses
The SIG, or “Self‐Energy Converting Sunglasses” are quite simple. The lenses of the glasses have
dye solar cells, collecting energy and making it able to power your small devices through the power jack
at the back of the frame. “Infinite Energy: SIG”
35Large dye sensized solar cell module produced by the Fraunhofer Institute for Solar Energy in Freiburg Germany, Courtesy Dr, Andreas Hinsch http://www.ise.fraunhofer.de/presse‐und‐ medien/presseinformationen/presseinformationen‐2011/auf‐dem‐weg‐in‐die‐fassade‐ fraunhofer‐ise‐praesentiert‐weltweit‐groesstes‐farbstoffsolarmodul‐in‐siebdruck
The worlds largest DSC module produced at Tata Steels Shotton site in Noth Wales UK Breakthrough announced in press release of June 10.2011
Ultra Low Cost PV DSC roofing and cladding,
Dyesol‐Tata joint venture manufacturing in Wales
DSC on Coil Coated Steel
Continuous high throughput
Standard Roofing Products
No vacuum processes
Low Temperature processes
25 Year Life
< 15 year Payback
Safe and durableUltra Low Cost DSC-PV
Tata/Dyesol production chain
Ultra Low Cost DSC‐PV
Tata/Dyesol production chain
80% of cost is materials – volume manufacture has
dramatic effect on product cost !Photographer - Thomas Bloch
Courtesy of
www.dyesol.comUnique Advantages of Dye Sensitized Solar Cells
• Architectural appeal
• Coloration
• Transparency
Photographer Thomas Bloch
Nina Buthke: Architectural School Aarhus
41Fujikuras DSC modules pass all stability tests for outdoor applications
3GSolar Photovoltaics – Durable Printed Dye Solar Cells
N719 sensitzer
Stable performance of first prototype cells
Printed solar cells in 2009 were 4% efficient
3GSolar printed solar technology achieves 10% efficiency in 2011G24i Flexible Dye sensitized Solar Cell Manufacturing plant in Cardiff, Wales (UK)
17,400 m2 manufacturing
plant on a 23 acres in
Cardiff, Wales (UK)
Wind turbine to provide all
energy needs to produce
G24i PV. Truly green from
green
Net contributor of energy
back to the national grid and
the local community
2.3 MW Wind Turbine Powers Solar Cells Plant Operation by Wind Energy.46
German President Christian Wulff, on a State visit to Switzerland and Swiss President Doris Leuthard inspecting G24 Innovation’s dye sensitized plastic solar cell powered keyboards Rolex Learning Center, Swiss Federal Institute of Technology (EPFL) Lausanne Switzerland September 9, 2010. 11 a.m.
June 2011: LOGITECH declares G24I preferred supplier of flexible dye sensitized solar cells for electric powering of its computer accessories
Commercial sales of the first mass‐produced flexible and light
weight dye sensitized solar cells has started 9/2009
www.G24i.com
Flexible dye‐sensitized solar panels attached to bags for recharging electronic equipment,
courtesy: Mascotte Industrial AssociatesG24i powered energy efficient window blinds being presently installed at MG Grand Hotel in Las Vegas, Dye sensitized thin film technology is the only PV cell type selected
Mass produced solar bags in rural India use G24I flexible solar cells to power batteries
:
f Abran Abeyta
G24 Innovations
Product Development Manager
info@g24i.com
aaabeyta@mac.com
+44 (0) 2920 837 340
+91 99-10-896701Dye sensitized solar cell powered lamps bring light into the dark
for Tsunami victims in Japan
Dye Sensitized Solar Cell powering LEDs providing light in the dark for numerous
Tsunami victims in Japan, left without electricity since the terrible earthquake +
tsunami + nuclear disaster hit the Sendai region this March
Courtesy Professor S. Uchida, DSC modules by Toyota Aisin SeikiThe first dye sensitized solar cell powered car racing in Japan
The DSC powered car finished within the first ten of 35 contenders in
the race
Courtesy Professor Satoshi Uchida: http://kuroppe.tagen.tohoku.ac.jp/~dscDaimler Benz new model of Smart car uses transparent solid state dye‐
sensitized solar cell on roof for electricity productiion from the sun
Courtesy Dr. Peter Erk BASF
YD 176Solar water splitting for Hydrogen Production
PECHouse: A Swiss center of excellence
Members LPI: Michael Grätzel, Kevin Sivula, Scott Warren, Florian Le Formal,
Adriana Paracchino, Jeremie Brillet, Maurin Cornuz, Elijah Thimsen (NanoPEC),
Celine Leroy (NanoPEC), Takashi Hisatomi, David Tilley. Energy center: Hans-Björn
Püttgen, Massimiliano Capezzali
• 4.5 % solar to hydrogen efficiency (STH) by 2009, 7.5 % STH by 2011
• 1000h with 5% degradation by 2011
• Hydrogen production cost by 2015: < 4 €/kg H2
• New material development Corporate sponsor:
NanoPEC Roel van de Krol, TU Delft:
Thin films, electrochemical and physical characterization
Consortium of European groups Jan Augustynski, U. Warsaw:
WO3, surface chemistry, electrochemistry
Avner Rothschild, Technion:
Pulsed laser deposition, nanofiber synthesis, physical characterization
Artur Braun & Anke Weidenkaff, EMPA:
Synchrotron characterization techniques, spray flame synthesis, complex oxide synthesis
Andrej Kutzenov, U. Oslo:
ZnO, nanowires
Adelio Mendes, U. Porto:
Device engineering and modeling, long-term testing
Laura Meda, Eni S.p.A.:
Theory, semiconductor synthesis, large-scale testingPhoto‐electrolectrocemical water splitting using an n‐type
semiconductor as photoanode
e‐
hν
+ + + + + +‐ + 4 H+ + 4 e ̶ → 2H2
+ + + + + +e + H2
+ + + + + + +
Electron energy
+ + + + + + + H+/H2
*
+ + + + + + +
+ + + + + + + 1.23 V
EORP
+ + + + + + + O2
+ + + + + + +
+ + + + + + + H2O/O2
+ + + + + + + *
+ + + + + + + 2 H2O + 4 h+ → 4 H+ O2
+ + + + + + h++
n‐type Semiconductor Aqueous electrolyte Metal cathode
Net Reaction: 2 H2O + hν → 2H2 + O2
P.J.Boddy, J.Electrochem.Soc.1968,115,199‐203.
A. Fujishima and K. Honda, Nature 1972, 238, 37‐38.‐Fe2O3 (hematite) as a promising material Advantages Cheap and abundant Stable Environmentally benign Great light absorber in spite of indirect Kidney ore hematite from Michigan band gap! Challenges Short hole diffusion distance Poor electronic conductivity Anisotropic, antiferromagnetic High overpotential for water oxidation Does not straddle water redox potentials
Overcoming challenges of hematite
Challenge: Poor electronic conductivity Nb‐doped Fe2O3 single
Resolution: Aggressive substitutional doping crystal photo‐anode
400 nm LD = 5 nm Longer wavelength light
W = 5‐10 nm penetrates deeper!
Electron energy
H+/H2
1.23 V
Ef EORP
H2O/O2
Hematite photo‐anode Aqueous electrolyte
63
Sanchez, C.; Sieber, K. D.; Somorjai, G. A. J. Electroanal. Chem. 1988, 252, (2), 269‐290.Photocurrents due to water oxidation evolution on hematite in AM 1.5 sunlight
have increased steeply over the last decade
Optimized APCVD with IrO2
nanoparticle catalyst
APCVD, new dep. system (CoII catalyst )
APCVD (Si doped) with CoII catalyst
USP (Si doped)
Input: solar light of air mass
1.5 global (1000 W/m2) Ultrasonic spray pyrolysis
Solar to chemical conversion Spray pyrolysis
efficiency: output/input
Colloidal
= Iph [mA/cm2] x (1.45 – Vbia)
= Iph [mA/cm2] x (1.23 ‐ Vbias)
*Under AM1.5 G illumination spectrally corrected (100 mW cm‐2)State‐of‐the‐art Fe2O3 film performance
minus FTO series resistance
with IrO2 NP catalyst
2010 conditions
JACS 2006
conditions
• Optimal film thickness is higher at
6 L min1
• Photoanodes performance is
significantly better
• General reproducibility increases
Nature 2010, 466, 669.
Tilley, S. D.; Cornuz, M.; Sivula, K.; Grätzel, M. Angew. Chem. Int. Ed. 2010, 49, 6405.Solar hydrogen generation on p‐type cuprous oxide
Cu2O as a photocathode material candidate
e‐ Intrinsic p-type SC (Cu
vacancies)
Direct band gap 2.0 – 2.2 eV
H2 e‐
CB edge is – 0.7 V vs. RHE
H+/H2 * Good charge transport properties
Electron energy
e‐
hν Known for H2 evolution
O2
1.23 V
hν
2.0 eV H2O/O2
*
h+
Hematite Semiconductor
Photo‐anode Cathode
(or PV cell)
Copper(I) OxideStability is limiting factor for Cu2O
Before illumination After Illumination
a
bProtection of Cu2O
•ZnO:Al provides conductive and pinhole‐free
surface
•TiO2 provides stability in aqueous conditions
•Pt acts as a good catalyst for water reduction
• Photocurrent goal met!
• Advancing towards the project
goal of 5000 hour stability (less
than 10% loss of initial activity).
Adriana Paracchino et al. Nature Materials 2011, 10, 456–461.Scale‐up of Cu2O (100 cm2)
• Cu2O photocathode with ZnO:Al and TiO2 overlayers
0
Light intensity: 0.9 sun
-50 Active area: 63 cm2
Current / mA
-100
-150
-200
-250
0.0 0.2 0.4 0.6
Potential / V vs. RHEThe solar source: photo‐induced H2 Evolution on Cu2O
Hydrogen produced by renewable energy will be a central
component of a future European energy infrastructure
H2 is a key future energy vector
Environmental security
Economic security
National security
Price target: 5 €/kg by 2015*
By 2050, H2 is expected to
comprise 50% of transportation
fuels.*
*European Hydrogen & Fuel Cell Technology Platform, Implementation Plan, 2006.
How do we produce, store, transport, and utilize H2?OMAN National Solar Energy Center (ONSEC)
The vision of the proposed Oman National Solar Energy Center
(ONSEC) is to develop new strategic research fronts, in particular
novel photonic and electronic materials, enhanced by
nanotechnology, in order to convert solar energy into electricity or
heat, and other applications such as water desalination and the
photo‐generation of fuels.
The Oman National Solar Energy Center aims at promoting
research and development to fully exploit this abundant
resource for the benefit of mankind, and specifically economic
and educational development of OMAN’s population.
In cooperation with the Research Council OmanThe research themes of the “OSEC” include
four work packages:
WP1. Solar Energy Conversion into
Electricity
WP2. Fuel Production by Photocatalysis and
Photoelectrochemistry
WP3. Thermoelectric Conversion of Heat to
Electric Power
WP4. Water DesalinationPlanned cooperation with ERI@N the NTU Singapore Energy Center
Acknowledgements
Fe2O3:
• S. David Tilley
• Scott Warren
• Maurin Cornuz
• Diane Zhong (UW)
• Florian Le Formal
• Jeremie Brillet
• Takashi Hisatomi
Cu2O:
• Elijah Thimsen
(ANL)
• Adriana Paracchino
External collaborators:
• nanoPEC FP7 consortium
• Anke Weidenkaff (EMPA)
• Radek Zboril (Palacký University)
• James Durrant (Imperial College)
• Daniel Gamelin (University of Washington)
• Hans‐Björn Püttgen (EPFL energy center)30 20 cm
W-type, transparent
Dye sensitized solar
cell module
Tsinghua University
Beijing 2010.Japanese school children thank the DSC
community for promoting education.
Easy-to-make solar power kits for kids
78High School Students make their own solar cell
anthocyanine dye from blackberries Labor
www.solideas.com, www.mansolar.com ,Cite des métiers Genève Novembre 2006
Getting infatuated: Young school children make their own cells
Thanks to the members of my group
• PhD Students : Soo‐Jin Moon, Hauke Harms, Philippe Labouchère
Adriana Paracchino, Magdalena Marszalek, Jérémie Brillet, Florian
Le Formal, Pootrakulchote Nuttapol, Maurin Cornuz, Julian
Burschka, Amalie Dualeh, Aravind Kumar Chandiran, Leo Phillip
Heininger
• Postdocs: Yella Aswani, Celine Leroy, Etienne Baranoff, Takeeru
Bessho, Takashi Hisatomi, Kevin Sivula, Jun‐Ho Yum, Nok Tsao,
Chenyi Yi, Peng Gao, Jared Heath Delcamp, Etienne Baranoff, Lioz
Etgar, Julien Edouard Frey, Florian Kessler, Il Jung, Masataka Katano
Thomas Moehl,
• Staff Scientists: Robin Humphrey Baker, François Rotzinger. Guido
Rothenberger, Jaques Moser (titled professor), Peter Pechy, Carole
Graetzel, Kuppuswamy Kalyanasundaram, Shaik M. Zakeeruddin,
Md. Khaja Nazeeruddin, Paul Liska, Ngoc‐Le Cevey, Anne Sophie
Chauvin.
• Technical and administrative staff: Pascal Comte, Francine Duriaux
Arendse, Jean David Décoppet, Manuel Tschumi, Ursula Gonthier,
Nelly Gourdou.
82We are grateful for funding from Swiss CTI , CCEM‐CH Swiss National Science Foundation, Swiss Energy Office US Air Force (European Office of Aerospace Research and Development) FP7 European Joule Projects: NANOPEC, INNOVASOL, ESCORT, SANS European Research Council: Adv. Research. Grant GRL Korea (with KRICT) KAUST Center for Advanced Molecular Photovoltaics (CAMP) at Stanford University Industrial Partners
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