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MATERIALS FOR GREEN ENERGY J.R.

Morante
IREC, Catalonia Institute for Energy Research, Plaa de les Dones de Negre,1. Sant Adri del Bess, 08930. Spain. Department of Electronics, University of Barcelona, C/Mart i Franqus,1. Barcelona,08028. Spain.

Catalonia Institute for Energy Research

toe= ton equivalent of oil

0-1.5 toe 1.5-3 toe 3-4.5 toe 4.5-6 toe >6 toe

c.a. c.a. c.a. c.a. c.a.

0- 5liters 5-10liters 10-15liters 15-20 liters. >20 liters.

Sources: BP + IREC

Renewables

831.1 237.4 560.4 3730.1

7% 2% 4% 30%

One million tonnes of oil or oil equivalent produces about 4400 gigawatt-hours (= 4.4 terawatt-hours) of electricity in a modern power station (42 GigaJoules)

Hydroelectricity Nuclear Coal

Natural Gas
Oil total

2987.1
4130.5 12476.6

24%
33% 100%

Equivalent to 6,3 TW (8760hours/year)


Sources: BP + IREC

STRUCTURE OF TOTAL NET GENERATION OF EUROPEAN UNION COUNTRIES MEMBERS OF THE CONTINENTAL EUROPE (ENTSO-E) (%)

Sources ENTSO-E (european network of transmission system operators for electricity)

Source: EPIA

Europe entire electricity consumption could be met if just 0.34% of the European land mass was covered with photovoltaic modules (an area equivalent to the Netherlands). International Energy Agency (IEA) calculations show that if 4% of the worlds very dry desert areas were used for PV installations, the worlds total primary energy demand could be met.

Scenarios: Electrical + gas & liquid power

SUN

Green electricity
Indirect way: electricity from renewal energies. 1.-PV energy 2.-Wind energy 3.-Ocean energy Etc. Direct way : energy from the photons ( sun light) 1.- Solar hydrogen 2.- Solar fuels 3.- Artificial photosynthesis Ect.

Energy

Feedstock
CO2, H2O

Intermediates: H& reduced CO2

Fuel Synthesis

Scenarios: Electrical + gas & liquid power + ENERGY STORAGE

ELECTRICITY AND GAS NETWORKS INTERACTION


Source: GNF

Chem Phys Phys Chem 2009

FUNCTIONAL NANOMATERIALS APPLICATIONS

FOR

ENERGY

1.-Photons to electrical energy conversion: photovoltaic and thermionic mechanisms and devices 2.-Phonons to electrical energy conversion: thermoelectricity mechanisms and devices. 3.- Chemicals in the energy conversion: sun power to fuel and chemical detection mechanisms and their devices Photon/Electron to chemical energy: SUN FUELS Chemical energy to electricity and vice versa: ENERGY STORAGE

Efficiency

Photon harvesting using one dimensional nanostructures

Sun Fuels: STH >12%

5%
Source: MRS Bulletin+IREC

What can bring the use of nanowires?

Advanced Materials, 19(10), 1347-1351 (2007)


Applied Physics Letters, 91(12) (2007)

I. Tsakalakos et al.) General Electric. Appl. Phys. Lett. (2007

Effective charge separation Large surface volume ratio

Light absorption is a complex phenomenon with strong dependence on the nanowire dimensions and the wavelength of the photons.

Improved strain relaxation using one dimensional nanostructures.

geometry of nanowire crystals is expected to favour elastic strain relaxation, providing great freedom in the design of new compositional multijunction solar cells grown on mismatched materials

Nanowire diameters are smaller than or comparable to the radiation wavelength. In this case, optical interference and guiding effects play a dominant role in relation to reflectivity and absorption spectra. For low-absorbing materials (for example, indirect band gap materials such as silicon), wave guiding effects plays a key role whereas highly absorbing semiconductors (such as direct-band gap GaAs or ZnO) exhibit resonances that increase the total absorption several times.

Rational design of optoelectronic devices in which the manipulation of light at the nanoscale is a key feature.
Nanoscale, 2012, 4, 16201626,

Nanowires lying on a substrate

The influence of wire size, incident wavelength, degree of polarization and the presence of a substrate on the optical near fields generated by cavity modes of individual hexagonal ZnO nanowires can be analyzed combining scanning near-field optical microscopy (SNOM) with electrodynamics calculations within the discrete dipole approximation (DDA).

Although many basic studies have been performed using nanowires lying on a substrate which exhibit also such rich phenomena concerning absorption; nanowire vertical arrays currently seem to be the most reasonable device proposal. Recently, EPFL researchers. have published this analysis determining the influence of the diameter and probing experimentally that light absorption in single standing nanowires is more than one order of magnitude more efficient than is predicted from the LambertBeer law.

The periodic modulation with wavelength is a result of FabryPerot interference in the polymer layer and not an artefact of the simulation.

NATURE PHOTONICS | VOL 7 | 306 APRIL 2013 | www.nature.com/naturephotonics A. Fontcuberta et al.

An interesting point of view reported by A. Fontcuberta et al., (NanoPhotnic 2013) is the use of the absorption cross section probing that it is larger that the physical section area of the nanowire. It is equivalent to have an effective photon concentration. Here, the concentrator factor have been estimated to be more than a factor 10 for a diameter of 380nm and wavelength near the band gap. Two dominant branches for low and high diameters are observed, corresponding to resonances similar to those observed in wires lying on a substrate. Experimental electrical measurements have been performed on this individual nanowires corroborating these results and confirming the large differences concerning thin films.

How success in getting standing array of nanowires?

Nano Lett. 2011, 11, 38273832

Nanoscale, 2012, 4, 1486 Nano Lett. 2011, 11, 38273832

The Ga droplet first pins on the substrate and, after dissolution of the native oxide, it dissolves the silicon forming a nanoscale hole. Upon saturation of the Ga droplet, the GaAs nanowire growth starts.

SEM micrographs of a field of nanowires grown at 620 C under a V/III BEP ratio of 15, 30 and 60. The percentage of vertical nanowires increases.
Nanoscale, 2012, 4, 1486 Nano Lett. 2011, 11, 38273832

120s

20s

300s

Schematic drawing of the initial and advanced stages of self-catalyzed nanowire growth and the effect of the relative size of the Ga droplet with respect to the seed on the nanowire orientation, Schematic drawing showing the evolution of the vertical to angled wires as a function of the temperature and V/III ratio. The approximate incubation times are indicated.
Nanoscale, 2012, 4, 1486 Nano Lett. 2011, 11, 38273832

Nanoscale, 2012, 4, 1486

Representative cross-section SEM micrograph of a field of nanowires grown at 645 C under a V/III BEP ratio of 60.

New Photovoltaic Technologies of high efficiency based on nanowires

Small 4, 7, 899-903 (2008) Applied Physics Letters, 92(6) (2008)

Nanowires with coaxial shells

a)

b)

(42-2) (220) (20-2)

(242)

(022)

[1-11] GaAs
(110)

c)
(10-1)
B A

d)
(011)

Small 4, 7, 899-903 (2008)

AlAs/GaAs MQWs

GaAs Core [1-11]

GaAs S2 MQWs B GaAs S1

GaAs S1 GaAs S2
1 0 n m

MQWs A

GaAs Core [1-11]

J. Wallentin et al. Science (2013)

Challenge: New idea for harvesting the sun light, produce fuel and/or storage the energy at social and sustainable cost

Stanford group Nat. Mat.(2010)

31

ITO p-type substrate

Nanowires multijunction: possibilities to stack many junctions without restrictions due to the lattice matching

Silicon n-type substrate

For large ground-mounted systems, the generation costs in 2010 range from around 0.29/kWh in the north of Europe to 0.15/kWh in the south and as low as 0.12/kWh in the Middle East. According to EPIA estimations those rates will fall significantly over the next decade. Expected generation costs for large, ground-mounted PV systems in 2020 are in the range of 0.07 to 0.17/kWh across Europe. In the sunniest Sunbelt countries the rate could be as low as 0.04/kWh by 2030.
EPIA forecasts that prices for residential PV systems will also decrease strongly over the next 20 years. However, they will remain more expensive than large ground-mounted systems

Critic materials

Source: JRC ispra ( Italy)

Critic materials

1 GW ca. 63 Tm of Te

Source: Solar Energy Materials and Solar Cells journal (2013)

PV technologies: State of the art


Tandem cells

1st generation

2nd generation

Emerging technologies
Source: NRL+IREC

Energy Harvesting
CO2 feedstock preparation 4%

Could be CO2 captured from the air ?

Photovoltaic farm = 15%

CO2
Fuel synthesis 8%

H2
Water electrolysis 85% Auxiliary system. 2%

Energy Storage
Water vapor

transportation

Water feedstock preparation 1%

Synthetic gasoline

photons

electrons 12-20%
<1/Wp <5c/kWh

chemicals

Solar fuels
>12% < 4c/Kwh

Electrolyzers/E.C. < 70%

Data source: DOE +IREC

Photo electrochemical process: photo anode, photo cathode, dark electrodes

TiO2, fotoconduction at 387,4 nm, CB i VB correct WO3, fotoconduction at 476,6 nm, it is necessary to apply a potential Fe2O3, fotoconduction at 590,47 nm, it is necessary to apply a potential

New concepts:

Schematic of the nano-emmiter concept photoelectrode working in the photoelectrocatalytic mode: p type semiconductor. The high electric field induced under the nanoscopic MOS junctions introduces finger-like drains that scavenge photo-generated minority charge carriers whiles the majority charge carriers are driven towards the back contact. Electrons reaching the semiconductor surface are rapidly transferred to the metal-electrolyte interface and consumed by the redox reaction

Photocathodes

STH >15%

SUN LIGTH to HEAT and from HEAT to ELECTRICITY improving the energy harvesting from the sun Sun radiates energy as a 6000K blackbody radiator with part of the energy in the ultraviolet (UV) spectrum and part in the infrared (IR) spectrum

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Cu2xS nanoparticles
Chem. Commun., 2011, 47, 1033210334

Cu2ZnGeSe4 Nanocrystals: Synthesis and Thermoelectric Properties JAC2012, 134, 40604063

Composition Control and Thermoelectric Properties of Quaternary Chalcogenide Nanocrystals: The Case of Stannite Cu2CdSnSe4 Chemistry of materials 2012 ; 24, 562570

(PbTe)0.28@(PbS)0.72 coreshell nanoparticles with crystalline PbS shells

CoreShell Nanoparticles As Building Blocks for the Bottom-Up Production of Functional Nanocomposites: PbTePbS Thermoelectric Properties . ACS nano 2013 VOL. 7 NO. 3 2573

Powders

inks

Layer depositions

Batteries
Battery definition
A battery is a device which directly convert the chemical energy (contained at the electodes) in electric energy through an electrochemical reaction of oxidation/reduction.

Anode: it loses electrons Chatode: it gains electrones Electrolyte: good ionic conductivity

Zn (s) + Cu2+(aq) Zn2+(aq) + Cu(s)

E = Echatode Eanode = 0.36 (-0.76) = 1.12 V

Primary battery: the chemical reaction between the two electrodes is not reversible; chemical energy turn into electric energy but not in the opposite way (no rechargeable) Secundary batteries: to recharge is allowed, through a reversible redox reaction Energy density Price Security Power density Ciclability

Potential (V)

Environment

Batteries
Ion- Li batteries
Negative electrode: Positive electrode:

Liz[H1]
+

Liz-x[H1] + xLi + xe-

3.7 V

Liy[H2] + xLi + xe

Lix+y[H2]

Li advantages Very high redox system Light element High energy density High power density Low thickness No memory effect No heavy metals Li disadvantages No watery electrolytes Difficult manipulation of Li Low abailability High cost Dendritic growth Poor ciclability Security

Structure of ntTiO2/Fe2O3 Nanowires

VANADIUM 35000 (>20 years) Energy density low

LITHUM 1000 (3 years) Energy density high

Prototype from Zigor (Spain).

24M (A123)

New Liquid Electrolyte or Semi Solid Continuous Flow Cells: Increase the energy density To change electrodes materials as sulfuric based electrolyte can be avoided. To wide the range of potential active ions

Dream or Reality?
Mass and Volume density can be increased more than a factor 12 Improving the performances of the standard solid state ion lithium batteries And changing all the strategy for infrastructures developments for EV?

Source: 24M

I R E

Conclusions and future research

New nanomaterials and processing to achieve new or improved devices for third solar generation is nowadays a challenge for achieving reliable high efficiency solar energy conversion . Next efforts will be crucial for corroborating the promising features arisen by the artificial photosynthesis based processes. Photo catalysis offer clean competitive alternatives for the photogeneration of hydrogen and photoreduction of CO2 New materials and devices are needed. The use of new concept combining materials and catalysts at the nano scale is outstanding and must allow future improvement Gas and liquid photo reactors become a system engineering challenge. The very big challenge concerns new materials, new ideas and novel systems able to effectively capture CO2 (from the air). New high efficiency thermoelectricity is also an outstanding challenge Finally, energy storage ( electrical and chemical ) is likely the more serious challenge

Mercs per la vostra atenci! Gracias por vuestra atencin! Thanks for your attention!

Patronos:

Prof. J.R.Morante jrmorante@irec.cat


Con financiacin de:

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