fuel cells

DENERG: activities on Fuel Cells and Hydrogen SL 1 POLITECNICO DI TORINO - Dipartimento Energia

FUEL CELLS AND HYDROGEN

Massimo Santarelli

Dipartimento Energia

Politecnico di Torino

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Politecnico di Torino Hydrogen and

Fuel Cell Research Network

Laboratories for

Basic Research

• IN.TE.S.E

•Department laboratories

Applied Research

• HySy-Lab

•…

Prototypes

• Celco YACHT

• PEMFC, mCHP

• …

Demonstrations

• Fuel Cell Bus

• Solid Oxide Fuel Cell Large

Stack (with Siemens)

• Hydrogen Village

• …

Sistema Idrogeno Piemonte



Laboratorio Alta Qualita’ (LAQ) IN.TE.S.E.

(Politecnico di Torino)

“ IN.TE.S.E ” stands for “ Innovazione Energetica per la Sostenibilit à Energetica ” . It is a High Quality Laboratory joining together the multidisciplinary expertise avai lable in the different Departments.

Its mission is fundamental research aimed at the development of innovative matierials , technolo - gies and systems for a sustainable energy supply, with special focus on the Hydrogen field.



Hydrogen technologies and energy

systems

• LAQ (High Quality Lab.) IN.TE.S.E.

• SOFCOM Project (EU), Coordinators

• ENEFIELD Project (EU), Partners

• Stockage d’hydrogène et production d’éléctricité (avec CNRS

Grénoble)

• PRIN 2008 and 209: SOFC fed with biogas and coal syngas

• PFHC, MULTISS, NanoSOFC Projects, OZ-BOX, RES-COGEN

• Multi – Scale modelling of fuel cells

• EOS and EBE Projects (Energy from Solid Oxides)

• Direct High Pressure Electrolysis Project

• Environmentally Friendly Aircraft Powered by FC (VI

Framework Program)



Hydrogen technologies and energy

systems E

lectr

ic e

ffic

ien

cy, %

Power



LAQ IN.TE.S.E.

• Equipment for the

experimental characterization

of planar SOFC. • Polarisation curve detection

• Dynamic behaviour

• Fuel Utilisation factor effect

• Thermal characterization

• Analysis of materials and

technologies



LAQ IN.TE.S.E.

• Comparison between single planar

cells and multilayer stacks

• Effect of microscopic topology of

porous materials on their

performance



Cell Development Scheme

Anode

Substrate ~600mm

Anode Functional Layer

~2-5 mm

Electrolyte

~2-5 mm

Cathode Functional Layer

~10-15 mm

Cathode

~20-60 mm

Cell Assembly

Tape Casting, Warm Pressing

Screen printing, EB-PVD

Dense sintered electrolyte

Sintering

1400 °C

Sintering

1400°C

Sintering

1100°C

Screen printing, EB-PVD



Engineering of SOFC’s layers

Current collector

Cathode

Electrolyte

Anode

Substrate

Pure perovskite

Perovskite/stabilized zirconia

stabilized zirconia

Ni/stabilized zirconia


30-40%

10-20%

0%

10-20%

30-50%

Open

PorosityCurrent collector

Cathode

Electrolyte

Anode

Substrate

Pure perovskite


stabilized zirconia



30-40%

10-20%

0%

10-20%

30-50%

Open

PorosityCurrent collector

Cathode

Electrolyte

Anode

Substrate

Pure perovskite


stabilized zirconia



2-5 mm

~1 mm

~1 mm

~1 mm

~2-3 mm

Grain

Size

Current collector

Cathode

Electrolyte

Anode

Substrate

Pure perovskite


stabilized zirconia



2-5 mm

~1 mm

~1 mm

~1 mm

~2-3 mm

Current collector

Cathode

Electrolyte

Anode

Substrate

Pure perovskite


stabilized zirconia



2-5 mm

~1 mm

~1 mm

~1 mm

~2-3 mm

Grain

SizeState-of-art of the pore volume State-of-art of grain’s sizes

•High TPB Density, high electrical conductivity, cell robustness are

features to be pursued in SOFC engineering



Engineering of SOFC’s layers Materials&Processes: from nano-powders…

…to nano-structures



Cell Development II: Anode substrates

Spark-Plasma-Sintering (anode substrate)

I

Graphite

Die

Graphite

Block

Mechanical

Load

Pulsed

Current

GeneratorGraphite

Plunger

Powders

I

Graphite

Die

Graphite

Block

Mechanical

Load

Pulsed

Current

GeneratorGraphite

Plunger

Powders

Innovative technique to

produce in short-time

anodes through a

pulsated current-power

sintering. Nanostrcture

of the starting powder is

preserved during the

process.

500 nm dense ultra-thin electrolyte through

YSZ sputtered on NiO-YSZ anode substrate

Atmospheric plasma spraying with

thermal quenching of LSM/8YSZ or LSCF

cathode



Cell Development III: Anode substrates

R vs T

0.0001

0.001

0.01

0 100 200 300 400 500 600 700 800 900

T (°C)

rho

(O

hm

*cm

)

FN1G

FN2G

DISMIC

INDEC



Cell Development IV: Electrolyte layer

• Obtained thin, high purity/integrity,

dense YSZ films

•Thickness in the range of 1-3 mm

Experiments of deposition of thin YSZ electrolyte

films by EB-PVD: high vacuum (base pressure 10-5-

10-4 mbar); substrate heating to R.T.- 800 °C; 8 kW

electron beam evaporator; supersonic cleaning with

organic solvents

200°C

2.5mm

400°C

3mm

500°C

3.5mm



Stack schematic: the elemental unit

CROFER APU 22 bipolar plate

Nickel mesh

ASC SOFC

LSM mesh

Glass Ceramic sealing

Compressive mica insulation and sealing

CROFER APU 22 bipolar plate



Stack schematic: sealing

Heat treatment 900°C, 30 min, 5°C/min

Crofer 22

Glass-ceramic seal

Anode supported electrolyte

Crofer 22APU

Glass-ceramic sealant

anode

YSZ

50 mm

Glass-ceramic sealant

YSZ

anode

5 mm

sodium–calcium–aluminosilicate

glass-ceramic

Ca2Al2SiO7 + NaAlSiO4



Stack schematic: the elemental unit

Housing Stack Fuel Mica Insulation Air Plate Mica Insulation

Nickel Mesh Inconel Mesh Mica Insulation Fuel Cell

Fuel Plate Mica Insulation Housing Stack Fuel



Stack schematic: modeling



Cell Testing @ LAQ Laboratory

stack elements testing

fully automated station for planar SOFCs

multi-fuel capability station

durability testing



Biogenous fuel



Biogenous fuel

Quantitative results

We

igh

t%

0

20

40

60

80

100

C O Ni

Sulphur compounds analysis

GC (mg/m

3)

Hydrogen sulfide H2S 153

Carbonyl sulfide COS < 0.4

Methyl mercaptan CH3-SH 9,9

Ethyl mercaptan C2H5-SH 0,6

Methylthiomethane CH3-S-CH3 1,9

Carbon disulfide CS2 10

Tetrahydrothiophene THT < 0.6



Biogenous fuel

Biogas: Direct Dry Reforming, degradation by carbon

0,000

0,002

0,004

0,006

0,008

0,010

0,000 0,010 0,020 0,030 0,040 0,050

-Im

(Z

)/Ω

Re(Z)/Ω

CH4/CO2 (1:1 mol%) - 60%FU - 0h

CH4/CO2 (1:1 mol%) - 60% FU - 100h

CH4/CO2 (1:1 mol%) - 60% FU - 150h

CH4/CO2 (1:1 mol%) - 60% FU - 200h

CH4/CO2 (1:1 mol%) - 60% FU - 250h



Biogenous fuel



Mechanical test

Apparatus load to estimate the Young’s

modulus of anode-supported cells The axial displacement of the cell under

different weigth loads is measured at its

center and in correspondence of two

semi-radii.

Comparison of deformation curves

between unreduced and reduced

LSCF-type cell. The reduced cell

has an halved elastic modulus,

essentially due to the reduction of

NiO to Ni.



LABORATORIO IN.TE.S.E. DENER Politecnico Torino

3D Reconstruction of POROUS ELECTRODES 20x20x20 µm reconstruction of a porous cathode current collector layer



EOS and EBE Projects (Energy from Solid Oxides)

Politecnico di Torino – TurboCare spa (Siemens Power Generation)

Laboratory with a pilot plant composed by two solid oxide fuel cell (SOFC) plants (rated 100 kW and 5 kW) in CHP asset:

– Design of the laboratory, of the plants and of the control and data acquisition systems (on site and remote).

– Management: installation, monitoring, operation of the plants.

– Modeling: energetic, fluid-dynamic, chemical and electric of the primary generator and of the Balance of Plant.

– Experimental: design and operation of the experimental sessions. Data analysis.

Agreement with Siemens Power Generation



EOS and EBE Projects (Energy from Solid Oxides)

Politecnico di Torino – TurboCare spa (Siemens Power Generation)

EBEΗΒΕEBEΗΒΕ

COHOHOHHC 24 2252

COHOHCH 224 3

0.4,2 eqH

0.6,2 eqH

The strategy was

• to keep the H2-equivalents

constant

• to run in safety condition

(avoid C deposition)

5 slpm EtOH/water

3 slpm NG



Future Plants: biogas-fed SOFC CCHP systems with CCS

Water Treatment

Unit

CO2 Separation

CO2

Storage and Management

Wel

Φheating

Φcooling

SMAT (IT) UNITO (IT)

•Biogas Production and

Characterization

VTT (FI) •Gas Cleaning

Unit Development •Maintenance

CNR (IT) •Fuel Processor Development •Maintenance

POLITO (IT) •SOFC CCHP

Management •Maintenance

O2 Production Anode exhaust

burning

MATGAS (SP) •Carbon storage,

management and disposal

Gas Cleaning

Fuel Processing

SOFC System 5 kWe

IEN (PL) •O2 separation •Exhaust oxy-combustion

TUM (DE) •CO2 Separation

Proof-of Concept 1 (Torino, Italy)



Energy Box Prototype

Concept:

(1) SOFC air inlet – (2) Hydrogen inlet – (3) Air inlet in the pre-heater – (4) Hot exhaust inlet in the pre-

heater – (5) System exhaust – (6) Water inlet (hot water loop) – (7) Water outlet (hot water loop)



Direct High Pressure Electrolysis Project

End Plate

Anode Out

H2O & O2 Out

Cathode Out

High Pressure H2

Electrical Connection

(Cathode)

Electrical Connection

(Anode)

Tie Bolts & Belleville

Washers to Seal

Bipolar Cells w/

Separators, MEAs,

Cell Internals

Anode In

H2O

Tie Down Holes

(For Installation)

PEM high pressure

electrolyzer (differential

pressure)

This systems present

unbalanced pressure: the anode

side is at ambient (or neat

ambient) pressure, while the

cathode side is maintained at the

delivering pressure of hydrogen.

At present, pressure up to 70 bar

and mass flow of 0.1 kg/h.

12 cells in series, active area of

160 cm2/cell; operating at around

50°C.

Current of 224 A (1.4 A/cm2), and

voltage of 25 V (at 35 bar): total

power 5.6 kW




Metal foams: passivated aluminium or stainless steel MEA Nafion 110 (anode IrRuOx, cathode Pt black)

Bipolar plate nickel Current collector ribbed expanded metal micromesh




0

1 0

2 0

3 0

4 0

5 0

6 0

7 0

0 .0 0 .2 0 .4 0 .6 0 .8 1 .0

D e fo rm a z io n e

Te

nsi

on

e (

MP

a)

T e s t 1

T e s t 2

Caduta di pressione trasversale

y = 0.007x2 + 0.1215x + 0.4645

R2 = 0.9997

y = 0.0343x2 + 1.1534x - 0.5909

R2 = 0.9929

y = -0.109x2 + 59.485x - 80.028

R2 = 0.9975

y = 0.015x2 - 0.0197x

R2 = 0.9765

0

50

100

150

200

250

300

350

400

450

500

550

600

0 5 10 15 20 25 30 35 40 45 50 55 60 65 70 75 80 85 90 95 100

Portata acqua [l/h]

?P

[m

bar]

Solo portacampioni

Spugna alluminio 1

Spugna alluminio 2

Spugna acciaio inox

Poli. (Solo portacampioni)

Poli. (Spugna alluminio 1)

Poli. (Spugna alluminio 2)

Poli. (Spugna acciaioinox)



Environmentally Friendly Aircraft Powered by FC (VI Framework Program)

AIMS

Develop and validate the use of

a fuel cell based power system

for propulsion of more/all

electric aircraft.

Feasibility analysis carried out

to define preliminarily transport

aircraft APU systems that can

be provided by fuel cell

technologies.

A two-seat electric-motor-

driven airplane powered by fuel

cells will be developed and

validate by flight-test, by

converting a high efficiency

existing aircraft.

Partners



Environmentally Friendly Aircraft Powered by FC (VI Framework Program)

Hybrid SOFC/µGT System



Other projects

FIAT RESEARCH CENTER:

MHYTO PROJECT

Development of the hydrogen fuelled MITO car

ELECTRO POWER SYSTEMS:

HYSYPOWER PROJECT

Development of a UPS system based on PEMFC



Thanks for your attention


fuel cells - course introduction

Documents

vi framework

politecnico

hot water

siemens power

electrical

stack schematic

biogenous