dsc roadmap1

7/31/2019 DSC Roadmap1

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Dye sensitized solar cells:from research to industrialization

Aldo Di CarloCenter for Hybrid and Organic Solar Energy (CHOSE)

Department of Electronics Engineering

University of Rome Tor [email protected]


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EU Renewable Energy Road Map

By 20 20 EU have to reduce by 20 % the CO 2 emissionsincrease by 20 % renewable energy and increase by

20 % the energy efficiency

Benefits:

443 billion euro investment 2001-2020 115.8 billion euro gained from fuel reduction 130 - 320 billion euro gained from additional costs 2 milioni additional jobs

http://ec.europa.eu/energy/index_it.html

20+20-20=2020 The European Community has defined (10 Jan 2007) the following equation


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Energy from the sun

To satisfy the electricity needs of a typicalfamily one needs 3kWp PV system, i.e.~20m 2 of photovoltaic surface (assumingsystem efficiencies of 13%).

20.000 euro

Cost reduction of PV systems per Wp/m 2 becomes paramount in order to

make PV technology an important instrument for energy production.

COST


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Could we reduce cell cost ?

Silicon is quite expansive (2 euro/ Wp, one doping level)Production plant are expansive (100 Meuro for 40 MWp/year amorphous silicon, 15Meuro for 30 MWp/year bulk silicon)

Energy payback is around 4 years for silicon cells

Is it possible to produce photovoltaic cell by

reducting production and material costs ?

This is possible but we have to re-invent the cells

Organic photovoltaics


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Organic photovoltaics

Transparent substrate

Light

Transparent substrate

DyeDye --SensitizedSensitized

(DSSC,(DSSC, GraetzelGraetzel ))

Small moleculeSmall molecule

PolymersPolymers

Type Max lab efficiency Stability R&D

Hybrid Dye Sensitized(Graetzel) 11-12% 15 years University and industry

Full organic solar cells 5% 3 years University and industry

HybridFull

organic


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Structure of Dye Sensitized Solar Cells

Dye Molecules on TiO 2

Glass Substrate

Electrolyte I - /I-3

Catalyst (Platinum, graphite)

Glass Substrate

Transparent Conducting Oxide (ITO or SnO2:F)

Transparent Conducting Oxide (ITO or SnO2:F)

nanocristalline TiO 2


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TiO 2 Electrolyte CathodeTCO

Injection

V Max

O x

S o /S + (HOMO)

S* (LUMO)

Dye

h

Principle of Dye Sensitized Solar Cells

Load

-0.5

0.0

0.5

E ( V )

3I - I - 3

Fermi Level in TiO 2

No permanent chemical transformation in the materials composing the cell


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Fabrication


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Optimizarion of TiO2 layer Ottimizzazione Spessori

WithScattieringParticles


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Available printing technologies for DSC


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Dyes

Natural Dyes

Industrial Dyes

Organic Dyes

Rutenium-Based Dyes

E f f i c i e n c

y

1%

11%

CHOSE UniFerrara

patent


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Dyes color


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Chemically stable;

Buffer to stabilise pH and thus voltage;

Additives to reduce recombination and maintain dye integrity; Secondary cations to screen electronic charge of electronsinjected into TiO2 nanoparticles to enable higher photocurrents;

Good transparency, particularly for inverse designs Processability;

Low volatility, even at 70oC or 80oC;

Low toxicity and cost.

Electrolyte requirements


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Electrolyte form : Liquid, quasi-solid (gel), and solid electrolyte;

Liquid Electroyte : organic solvent electrolyte and ionic liquid electrolyte;

Liquid Electrolyte Composition :

- organic solvent : ACN, MPN, EC, PE, ecc....

- redox couple : I- /I3-, Br - /Br2, Co II /Co III, SCN - /(SCN) 2, SeCN - /(SeCN) 2;

- additive : 4-tert-butylpiridine, N-Methylbenzimidazole, guanidine thiocyanate

Electrolyte Development @ CHOSE

El l Ki i


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(1) The photoexcited dye must inject an e - faster than it reacts with the mediator;

(2) The oxidized dye must be reduced by themediator more rapidly than it recombineswith the photoinjected electron;

(3) The oxidized mediator must, itself, reactslowly with electrons in both the TiO 2 andthe fluorine-doped tin oxide (SnO2:F)contact;

(4) Finally, the reduction of the oxidizedmediator at the cathode (CE) must be rapid.

Electrolyte - Kinetics

The I - /I3- couple works well in the DSSCs because of a fortunate confluence of the right kinetics for at least four different heterogeneouselectron-transfer reactions:

El l F


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Electrolyte Forms

Gel Electrolyte:

High ionic conducibility; High chemical and electrochemical stability; Easy to prepare; Low cost;

PEO(polyethyleneoxide)PEG(polyehtyleneglycole)

+ LiI / I 2

Liquid Electrolyte:

High volatility of the solvent; Maybe Ionic Liquid to replace the solvent;

Low viscosity; Additives; Easy to put into the cells;


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Ionic Liquid based Electrolytes

In collaboration with the Chemistry Group of Tor Vergata we can synthesize differentIonic liquid. Suitable ionic liquid are for examples:

PMII : 1-methyl 3 propylimidazolium iodide; HMII : 1-hexyl 3 methylimidazolium iodide;

BMIM : 1- butyl 3 methylimidazolium iodide;= High viscosity -> low conducibility

EMIm-I : 1 ethyl - 3 methylimidazolium iodide; EMIm-SCN : 1 ethyl - 3 methylimidazolium thiocyanate;

EMIm-DCA : 1 ethyl - 3 methylimidazolium dicyanamide; EMIm-BF4 : 1 ethyl - 3 methylimidazolium tetrafluoroborate;

= Low viscosity -> high conducibility

Ionic Liquid Electrolyte typical composition:

EMIm + I -, Dicyanamide, Trifluorometanesulfonilmide + I 2

cation anion mediator

Ref. Iolitec

l d b d


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Ionic liquid based DSC

= 7.19%

In collaboration with the Chemistry Group of TorVergata (Conte, Mirruzzo) we have synthesizedifferent Ionic liquid.

l d


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Electro-Impedance Spectroscopy

5

6

7

89

10

20

30

40

0

5

10

15

20

25

30

35

0,1 1 10 100 1000 10 4 10 5

Modulus Commercial IL ElectrolyteModulus C.H.O.S.E. IL Electrolyte

Phase Commercial IL ElectrolytePhase C.H.O.S.E IL Electrolyte

M o

d u

l u s

( O h m

)

P h

a s e ( D e g )

Frequency (Hz)

IL Electrolyte

G l a s s

Spacer

TCO/Pt

Symmetric cell

C dl /2

Zw

Rs

Equivalent circuit

Sample R ct (Ohm*cm 2)

Commercial IL 5.0

C.H.O.S.E. IL 1.5

2 Rct

C f t Effi i / D t Li idi I i i


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Confronto tra:

- Liquido Ionico prodotto in C.H.O.S.E

- Liquido Ionico Commerciale

Confronto Efficienza / Durata Liquidi Ionici

Counterelectrode development
http://www.dbu.de/533bild16137_734_25928_123.html


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Counterelectrode development

0,0 0,1 0,2 0,3 0,4 0,5 0,6 0,7

-10

-8

-6

-4

-2

0

Carbon black dispersion TIMCAL RE - 182Platisol Solution - Solaronix

J [

m A / c m

2 ]

V [V]

Catalizzatore

Vetroconduttivo Elettrolita

Pigmenti assorbitiTiO 2

Platinum

Carbon Black

Carbon Black:good alternative to Pt

Reduction of cost

Typical Photovoltaic performance


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Typical Photovoltaic performance

QE = 70-80%

J sc = 15-20 mA cm -2 Voc = 0.8 V

= 7 %

Challenges : Improving photocurrent : dyes, light management Improving photovoltage : minimise recombination

alternative materials

Example of DSC (sigle cells)


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Example of DSC (sigle cells)

Series resistance is very critical !!!

100cm 2 Module Fabrication with 3 cells series interconnected


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100cm 2 Module Fabrication with 3 cells series interconnected

Glass

TCO

Dye sensitized TiO2

Electrolyte

Pt catalyst

Define contacts Coat the different layers Leave in Dye Solution Seal

Series interconnect of a number of cells

DSC Modules with Ionic Liquids


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DSC Modules with Ionic Liquids

= 3.15 %on active area

0,0 0,5 1,0 1,5 2,0 2,5

-36-32-28-24

-20-16-12

-8-4

0

I [ m A ]

V [V]

Modulo Chose 3 celle in serie

tipo connessione ZArea attiva singola cella=4.5 cm 2

Area modulo= 13.5 cm 2

Aperture Ratio=66%Isc = 35.4 mA V oc= 2.16V

P max = 42.5 mW@30mA & 1.42V

FF= 55.7%

With Ionic Liquid

DSC in the world


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DSC in the worldDSSC Faade Systemat the CSIRO Energy CentreNewcastle, Australia

USA (KONARKA)UK (G24i)

DYESOL - AUSTRALIA

AISIN - Japan

Fraunofer - Germany


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COST: IMEC vision


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COST: IMEC vision

For DSC cost of the cell is mainly related to the cost of glass (Pilkington)

Limpegno della Regione Lazio alla sfida delle Rinnovabili


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L impegno della Regione Lazio alla sfida delle Rinnovabili

POLO MOBI LI TA

CHOSE

CHOSE: fatti


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CHOSE: fatti Nasce il 19 dicembre 2006 Scopi

Sviluppare un processo tecnologico per le celle organiche/ibride Definire una processo di industrializzazione del fotovoltaico organico

Punto di riferimento sul fotovoltaico nel panorama regionale Trasferimento tecnologico verso le PMI

Attualmente coinvolge 6 gruppi di Tor Vergata (Ingegneria,

Chimica, Fisica), 5 gruppi esterni (UniFerrara, UniSapienza,PoliTorino, UniTorino e CNR) e diverse societ di ricerca

Punto di aggregazione per sviluppo di progetti correlati alfotovoltaico organico (FP7, MAP, FIRB, FIRS, PRIN etc.etc.)

Laboratorio CHOSE (21 July 2008)


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Laboratorio CHOSE (21 July 2008)

Il Polo svilupper la linea

pilota al TecnopoloTiburtino dove la vicinanzacon la realt industriale edimprenditoriale permetter iltrasferimento tecnologico.

600 m 2 di laborat orio dicui 400 m 2 di camerapuli ta

I l laborat orio principalm ent e dedicat oallo sviluppo di una lineapil ot a di pr oduzione DSSC

Tecnopolo Tiburt ino

Dettagli di CHOSElab


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g

Rientro dei cervelli e degli investimenti


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DallInghilterra (Dott. Thomas M. Brown) ora Professore a Tor Vergata

Dalla Francia (Dott. Adalberto Brunetti) Dalla Germania (Dott. Massimiliano Liberatore, Dott. Alessio Gagliardi)

La nascita di un centro di eccellenza sul fotovoltaico organico hapermesso il rientro in Italia di giovani Cervelli che operavano daanni allestero

La DYESOL australiana, industria leader neimateriali per celle organiche ha deciso diinvestire in Italia, a Roma, attraverso laDYESOL Italia.

Questa iniziativa stata motivata dalla nascitadel Polo Solare Organico con cui intendefortemente collaborare.

Sono previste diverse assunzioni nellambito diesperti chimici.

Il team di ricerca si compone di circa 30 ricercatori ( 7 dottorandi, 3 post doc, 6 contrattisti e

4 staff) e circa 10 studenti di laurea

Master in Ingegneria del Fotovoltaico


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Il Master ha lobiettivo di rispondere alle richieste del mondo industriale e dellaricerca preparando profili in grado di comprendere e di operare sullintera filiera

del fotovoltaico.400 ore frontali350 ore di lavoro in laboratorio750 ore di studio individuale

I corsi sono iniziati l11 febbraio2008

www.masterpv.org

Attivit di divulgazione presso lescuole

SPIN-OFF: DYERS.srl


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Si concluso a Giugno 2008 liter

accademico per la nascita di una spin-offuniversitario, Dyers, per lo sviluppo e lapromozione delle tecnologie fotovolaicheorganiche

DYEPOWER consortium


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September 2008:

ERG Renew, Permasteelisa, Dyesol Italia,CHOSE (Uni Tor Vergata),Uni. Torino, Uni Ferrara

Signed a Framework agreement for theindustrialization of DSC for BIPV

Conclusion


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Organic materials introduce a new way forsilicon free photovoltaics. Large tunability,

easy manufacture, low plant cost. However, we need chemical company toscale up materials

Sept. 2007 BASF and others announcedan investment for 400 million euro in this

field. December 2007 Dyesol Italia has beenestablished

Acknowledgments


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UniFerrara (Bignozzi team)

UniRoma 1 (Decker team) UniTorino (Viscardi team)

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Regione Lazio

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