lolipem long-life pem-f h &hp systems at ... · tel: ++48 (12) 628 26 60; e-mails:...

Project acronym: LOLIPEM website address: www.lolipem.eu

title: Long-life PEM-FCH &CHP systems at temperatures ≥100°C

Funding Scheme: Fuel Cells and Hydrogen Joint Undertaking (FCH JU)

Funding board: EC (FP7) and FCH JU

Starting date: January 1st, 2010

Duration: 36 months

Date of latest version of Annex against which the assessment is made: February 2012

Deliverable number: D 4.9

Deliverable: “Final plan of use and dissemination of foreground knowledge”

Contractual deliver date: M36, December 2012

Responsible: PartnerP8 Krakow University of Technology

Tel: ++48 (12) 628 26 60; e-mails: mailto:[email protected]; [email protected];

[email protected]

Authors: Jarosław OSIADACZ, Bogna GROCHOLA and Dawid GACEK

DISSEMINATION LEVEL

PU Public X

PP Restricted to other project participants (including the Commission Services)

CO Confidential, only for members of the consortium (including the Commission Services)

mailto:

mailto:

mailto:[email protected]

mailto:[email protected]

GA N° 245339 Deliverable D4.9

TABLE OF CONTENTS:

ABBREVIATIONS ........................................................................................................ 3

1. INTRODUCTION .......................................................................................... 4

2. THE LoLIPEM PROJECT: ASSUMPTIONS, METHODOLOGY & RESULTS........ 6

2.1. Introduction / Assumptions .......................................................................................................... 6

2.2. Project objectives .......................................................................................................................... 8

2.3. Methodology and materials .......................................................................................................... 9

2.4. Experimental setup and measurement principles ..................................................................... 11

2.4.1. Test bench for long term durability measurements and advanced control strategies ............ 21

2.4.2. Durability measurements ........................................................................................................... 26

2.5. Results .......................................................................................................................................... 34

3. DISSEMINATION OF KNOWLEDGE ............................................................ 35

3.1. Introduction ................................................................................................................................. 35

3.2. Dissemination strategy ............................................................................................................... 35

3.3. Dissemination actions – activities undertaken .......................................................................... 36

3.3.1. Project Website ....................................................................................................................... 36

3.3.2. Events ...................................................................................................................................... 37

3.3.3. Researchers exchanges between partners ............................................................................ 38

3.3.4. Publications related to the project results............................................................................. 39

3.3.5. Summary ................................................................................................................................. 49

3.4. Dissemination actions – plans for the future ............................................................................. 50

4. STRATEGY OF EXPLOITATION ................................................................... 51

4.1. Introduction ................................................................................................................................. 51

4.2. Exploitation actions ..................................................................................................................... 58


ABBREVIATIONS

APU Auxiliary Power Units

CHP Combined Heat Power

FC Fuel Cell

FCH Fuel Cell Hydrogen

GDE Gas Diffusion Electrode

GDL Gas Diffusion Layer

MEA Membrane Electrode Assembly

MPL Microporous Diffusion Layer

PEEK Poly-Ether-Ether-Ketone

PEMFCH Polymeric Electrolyte Membrane FCH (also Proton Exchange Membrane FCH)

PES Poly-Ether-Sulfone

PFSA Perfluoro Sulfonic Acid

PPSU Poly-Phenyl-Sulfone

PTFE Polytetrafluoro Ethylene

RH Relative Humidity

SAP Sulfonic Aromatic Polymer

SPG Stationary Power Generation


1. INTRODUCTION

“Plan for the Use and Dissemination of the Foreground (PUDF)” as a contractual Deliverable is an important

document summarizing the consortium’s strategy and concrete actions to protect, disseminate and exploit

the foreground generated by a project.

The “preliminary” PUDF was presented to the EC in the actual project proposal itself (in the Part B

Application, then in “Description of Work”). During the implementation of the project, the project team

reported periodically to the Commission on any activities carried out in relation to the PUDF.

At the moment - the “final PUDF” (Deliverable 4.9.) is presented at the end of the project and describes

detailed plans for the management of foreground, which enables the EC to evaluate the success of a

project1.

The PUDF clearly outlines convincing plans and intentions of the research consortium to use and

disseminate the project results. The plan is divided into two sections:

A section related to the publishable results and to the corresponding dissemination activities. This

section, which is public, summarizes:

o how participants plan to reach their target public,

o the communication strategy,

o a specific set of dissemination actions presented in a verifiable way to ensure that the EC can

keep track of them.

A section that describes exploitable results and related activities, which remain confidential, at least

until protection and economic exploitation of the results have been implemented. This section, which is

partly confidential, includes:

o verifiable list of all intellectual property rights that have been applied for or registered (e.g., a

European patent has been applied for);

o a list of all the results that may have commercial or industrial applications (e.g. software,

inventions, prototypes, compiled information and data, etc.);

o an outline of the owner of each particular element of foreground, whether it is a single

participant or several of them (in a situation of joint ownership);

o an explanation of how the foreground has been or is going to be used, in either further

research or commercial exploitation activities, including elements such as the following:

purpose, main features and benefits of each technology or product, derived from the

research results: innovative aspects in comparison with technologies and products

already available, needs for further R&D activity (and implied risks), collaboration

needs for exploitation (technology transfer activities);

customer detection: identification of the potential customers and the factors that

affect their purchasing decisions;

features of the target market: size, growth rate, share that the

1 “Make Research Work for Your Company - Strategic Guide to Successfull Use and Disseminiation of the Research anfd the Development Project”. The Guide has been produced as part of Coordination and Support Activities being carried in the “USEandDIFFUSE” Project (Support of dissemination and exploitation of results obtained in research projects realized with the participation of the SME sector), that is funded under the European Commission’s 7th Framework Programme (FP7), and more specifically under “Research for the Benefit of SMEs”. Cracow University of Technology (CUT) was a project partner responsible for preparation of the Guide.


technology/product.could reach, driving factors likely to change the market, legal,

technical and commercial barriers, other technologies likely to emerge in the near

future;

positioning: how the participant (or other entity) entitled to the technology

exploitation is positioned (or should be positioned) in the market, competing

businesses/applications/technologies.

Figure 1: General strategy of Use and Dissemination of Foreground. Exploitation is made after the

timeframes of the project.

All project partners have signed a Consortium Agreement before the start of the project, setting the

principles of the consortium management and placing the relationship between the partners and their

responsibilities on a legal basis for the duration of the work. In particular, the agreement includes

specific arrangements concerning intellectual property rights to be applied among the participants and

their affiliates, in compliance with the general arrangements stipulated in the contract. It thus specifies

the rules for dissemination and use (confidentiality, ownership of results, patent rights, exploitation of

results, protection and dissemination of knowledge), as well as financial and legal provisions.

Consortium Agreement, Grant Agreement and FP7 general rules are a base for dissemination activities

and professional (incl. commercial) use of the results (see Chapter 4.1., as well).


2. THE LoLIPEM PROJECT: ASSUMPTIONS, METHODOLOGY & RESULTS

2.1. Introduction / Assumptions

Previously developed stationary power generation & combined heat and power systems (SPG&CHP) based

on fuel cells can use different types of fuel cell (FC). Depending on FC type they represent different

temperature of operation: 70-80 °C for Polymeric Electrolyte Membranes FC, 150-190 °C for

Polybenzoimidazole-Phosphoric Acid FC, 400-600 °C for Molten Carbonates FC, and 600-1.000 °C for

Ceramic Oxide FC.

The LoLiPEM project was aimed to perform advanced R&D of SPG&CHP systems based on Polymeric

Electrolyte Membrane FC Hydrogen (PEMFCH). PEMFC technology is used in a range of application

segments, for instance in transport and stationary applications, and has a power range up to hundreds of

kilowatts. Therefore PEMFC has dominated the shipments by megawatt since 2008.

Project idea was based on the foreseen assumptions that the SPG&CHP systems based on FCs can help

reducing pollution, especially in large towns. As it was underlined in the project proposal expected results

are intended to be useful for reducing the petrol dependence and for reducing CO2 emissions in the

atmosphere. Finally, utility of the project results in the case of electrical black out could be also considered.

Mentioned co-generation systems based on PEMFCHs are of great interest because they can use very thin

and flexible ionomer membranes exhibiting high proton conductivity at relatively low temperature without

any addition of mineral acids. The peculiar characteristics of the ionomer membranes make easier the

development of small co-generation systems very suitable for small buildings and for mobile (automotive)

applications. The absence of free acids in the membranes avoids lowering of conductivity due to its loss and

poisoning of electrode catalysts. Furthermore, their low operating temperature reduces insulating and

corrosion problems as well as risks for their management. Finally, being noiseless, very small systems could

be provided even for single flats if an easier management is developed.

The proton exchange membrane fuel cell (PEMFC) uses a water-based, acidic polymer membrane as its

electrolyte, with platinum-based electrodes. PEMFC cells operate at relatively low temperatures (below 100

degrees Celsius) and can tailor electrical output to meet dynamic power requirements. Due to the relatively

low operating temperatures and the use of precious metal-based electrodes, these cells must operate on

pure hydrogen. PEMFCs are currently the leading technology for light duty vehicles and materials handling

vehicles, and to a lesser extent for stationary and other applications.

Hydrogen fuel is processed at the anode where electrons are separated from protons on the surface of a

platinum-based catalyst. The protons pass through the membrane to the cathode side of the cell while the

electrons travel in an external circuit, generating the electrical output of the cell. On the cathode side,

another precious metal electrode combines the protons and electrons with oxygen to produce water,

which is expelled as the only waste product; oxygen can be provided in a purified form, or extracted at the

electrode directly from the air.


Chemical Equation:

Anode: 2H2 → 4H+ + 4e-

Cathode: O2 + 4H+ + 4e- → 2H2O

Figure 2: General scheme of PEMFC2

A variant of the PEMFC which operates at elevated temperatures is known as the high temperature PEMFC

(HT PEMFC). By changing the electrolyte from being water-based to a mineral acid-based system, HT

PEMFCs can operate in 120°C (the limes of 200°C is expected to be achievable in the nearest future)3. This

overcomes some of the current limitations with regard to fuel purity with HT PEMFCs able to process

reformate containing small quantities of Carbon Monoxide (CO). The balance of plant can also be simplified

through elimination of the humidifier.

HT PEMFCs are not superior to low temperature PEMFCs; both technologies find niches in where their

benefits are preferable. The table below summarises differences between the two PEMFC variants:

Table 1. Main differences between Low- and High-temperature PEMFC4

Parameters Low Temp. PEMFC High Temp. PEMFC

Operating temperature 70-80 (up to 90)°C 100-120 (up to 200)°C

Electrolyte Water-based Mineral acid-based

Pt loading 0.2-0.8 mg/cm2 1.0-2.0 mg/cm2

CO tolerance <10 ppm 1 - 5 % volume

Other impurity tolerance Low Higher

Power density Higher Lower

Cold start? Yes No

Water management Complex None

Data compiled by the US Department of Energy demonstrate that platinum loading on PEMFC has

decreased by more than 80% between 2005 and 20105 and further reduction reductions in platinum

loadings for fuel cell catalysts are foreseen by 2015. It is widely expected that these targets are feasible,

2 The ”Fuel Cell Today” Industry Review 2011 3 Article “FCT - Fuel Cell Technologies – PEMFC” , www.fuelcelltoday.com, page visited IX’2011 4 ibidiem 5 The ”Fuel Cell Today” Industry Review 2011


and “Fuel Cell Today”6 believes they are essential to achieving the necessary cost reductions to enable the

widespread use of fuel cells in both new and existing applications. However, in PEMFC, DMFC and PAFC,

platinum offers superior performance compared to other catalyst materials in terms of the balance

between power density, durability, activity and cost, and is unlikely to be fully removed from fuel cells for

these reasons.

A variant of PEMFC which operates at higher temperatures is emerging in the stationary sector where it is

finding application in both micro-CHP and UPS. Running at temperatures over 100°C HT PEMFC use

different materials, such as polybenzimidazole, in their membranes and are more tolerant to impurities in

the fuel streams. When fuelled by methane or other hydrocarbons, the higher stack operating temperature

means the stack is more tolerant to the impurity carbon monoxide in the reformed fuel. As a result, the fuel

processing system can be much simpler. The additional by-product heat produced by HT PEMFC can also be

used as part of an integrated installation, increasing the overall efficiency of these units.

The negative aspect of these systems was that the operating temperature of state-of-the-art PEMFCHs (70-

80°C) is too low for efficient cogeneration7. It is well known that the temperature of the cooling fluid in co-

generation systems must be preferably ≥100°C. Such high temperature facilitates both the warm water

distribution in the buildings and renders an additional heating of the water unnecessary otherwise

requested by the temperature-air conditioner systems. Furthermore, the higher temperature decreases the

anode poisoning due to small amounts of carbon monoxide, always present in the hydrogen obtained by

reforming processes, and improves the fuel oxidation kinetics leading to an enhancement of fuel cell

efficiency. Thus, an enhancement of at least 20-30°C of the state-of-the-art operating temperature of

PEMFCHs is highly desirable and it could be decisive for the development of SPG&CHP systems based on

PEMFCHs.

In this type of co-generators, the operating temperature limits are essentially due to the decay of

performance of the PEMs used. A decay of the conductivity of the ionomer used in the catalytic electrodes

can lead to a decrease of the cell performance.

Detailed information & discussion is reported in the section “Progress beyond the-state-of-art” of the

Project Proposal Annex I -”Description of Work”.

2.2. Project objectives

The main objective of the LOLIPEM project has been the development of a long-life SPG&CHP systems

based on PEMFCHs operating at temperatures greater than 100°C. In order to reach this main objective,

various sub-objectives of the project have been identified:

Development of new stable Perfluoro Sulfonic Acid (PFSA) membranes operating at least 20°C

higher than that of the state-of-the-art and fulfilling the requirements in terms of long term

durability for stationary fuel cell operation.

6 ibidiem 7 This is not the only inconvenience. The activation losses are lower at high temperature and the tolerance of contaminants increases!


Development of new stable non perfluorinated ionomers, such as sulfonated aromatic polymers

(SAPs), much less expensive than PFSA and exhibiting a lifetime comparable to that of modified

PFSA membranes, in order to reduce the cost of the co-generation systems, investigating

innovative thermal and chemical treatments for promoting the cross-linking reactions between

adjacent ionomer chains.

Development of new catalytic electrodes more stable at the operating temperatures that have

been used in MEA.

Preparation and texting of MEAs based on these innovative materials.

Reducing the cost of the high temperature FCH by facilitating the replacement of MEAs (“use and

discard” MEAs).

Establishment of accelerated test techniques and lifetime prediction methods for MEAs testing.

Development of a procedure for “post mortem” analysis on MEAs, to identify the main parameters

and conditions affecting the MEA performance and durability.

Development of a prototype of a Modular multi-PEMFCHs system for Combined Heat and Power

(MoPEM) based on Polymer Electrolyte Membrane Hydrogen FC (PEMFCH) for facilitating the

replacement of the single PEMFCH and hence the MEA.

Exploitation of the results in terms of patents for the industrial partners, publications in high impact

international journals and top international conferences, reaching out to the public and increasing

the awareness of this technology.

2.3. Methodology and materials

These main areas of innovation were foreseen for the LoLIPEM project:

Novel polymer membranes. Research focused on the development of a membrane with sufficient proton

conductivity in order to allow huge system simplification and, in consequence, a significant reduction in

cost of manufacturing.

The primary task was to develop proton exchange membranes able to operate in the temperature

range up to 130 °C, at high relative humidity, and without any degradation. The innovative and cutting-edge

approaches included both the improvement of existing systems by new processing methods, and the

development of new polymers.

The new polymers and membranes were characterised for all properties of relevance to fuel cell

application, and preliminary, screening level, in situ single fuel cell tests were performed. URoma2

advanced in existing perfluorosulfonic polymer technologies by modification of the existing Nafion

ionomer; new polymers new compositions and new processing methods were used in the fabrication of

new composition perfluorosulfonic, sulfonated polyaromatic membranes; membranes were developed and

the ionomer were also supplied for application in the catalyst layer.

Catalyst and MEAs. Project developed novel catalyst materials that are capable of stable performance at

the higher operating temperatures afforded by the new membrane developments and to measure and

identify the optimum kinetic performance from the interaction of the catalysts and electrolytes. This has

required materials development, study of high temperature decay processes and kinetic studies of

catalyst/ionomer interactions.


MEA preparation

The MEA preparation was the key-step in the preparation of a fuel cell system with high performance and

life-time. In this step the PEM and the GDEs were brought together in order to form the MEA being itself

the centre piece of the fuel cell. The developed MEA preparation process included two steps. The first step

was dedicated to the preparation of the catalytically active GDEs, these were assembled in an additional

hot-pressing step with the proton conducting membrane in order to form the MEA.

GDE preparation

In this project we focused on the preparation of 50 cm² GDEs, starting from commercial available GDLs

(Torray). The therefore used process implies the following steps:

(a) ink preparation and its coating on the GDL via spiral blade,

(b) impregnation with SPEEK solution (only for MPL Type 2)

(c) impregnation with Pt precursor followed by its electrochemical deposition

(d) leaching of the GDE.

For the preparation of SPEEK containing inks (MPL Type 1) a dispersion consisting of PTFE, high surface

carbon support and SPEEK was ultrasonicated under vigorously stirring. The so prepared ink was

homogeneously coated onto the GDL using a spiral blade process. After evaporation of the remaining

solvents the sample was allowed to cool down to room temperature before the further utilization. In 3a &

3b a representative MPL Type 1 is shown.

SPEEK free inks (MPL Type 2) were prepared analogously, but in contrast to the latter method, SPEEK

solution was not introduced directly in the ink but was added via an additional step after coating of the GDL

with a MPL consisting of the high surface are carbon support and the PTFE. In this case PTFE sintering was

achieved by heating the coated GDL at 220°C, 280°C and 360°C. The ionomer solution was brought then

into the carbon/PTFE layer using dip-coating technique. Elimination of residual solvent was achieved, at

room temperature over desiccant under vacuum [8]

Nafion® containing inks (MPL Type N) were prepared by the method described in our paper [9]. The

method basically consists of dispersing the ionomer solution and the carbon black in an appropriate

dispersion agent by the use of an ultra-sonic bath. The resulting precursor ink was coated onto a GDL by

using an airbrush, inkjet or a coating-knife. Typical compositions of PFSA – and SPEEK-consisting CLs are

summarized in Table 22.

Table 2: Typical dry composition of PFSA- or SPEEK containing CLs.

PFSA ink SPEEK ink

compound wt.% compound wt.%

C 55 C 75

Nafion 35 SPEEK 15

PTFE 10 PTFE 10

8 F. Arena, J. Mitzel, R. Hempelmann, Zeitschrift für Physikalische Chemie 2013 9 J. Mitzel, F. Arena, H. Natter, T. Walter, M. Batzer, M. Stefener, R. Hempelmann, International Journal of Hydrogen Energy 2012, 37, 6261-6267.


Figure 3: SEM images of the prepared MPL Type 1, a) with a 100-fold magnification and b) with a 1900-

fold magnification.

The Pt precursor (solution of hexachloroplatinic acid) was brought into the so prepared MPLs by means of

dip-coating. To avoid hygroscopically induced migration of the Pt ions after immobilization in the MPL, all

samples were stored over desiccant under vacuum. The GDL including MPL and Pt precursor, arranged as

cathode, was pressed in a fuel cell like setup onto a half MEA consisting of Nafion® 115 and a commercial

Johnson Matthey GDE acting as hydrogen depolarized anode (HDA). During the electrodeposition, the HDA

was fed with hydrogen and serves thus simultaneously as dynamic hydrogen electrode. The cathode side

was purged with nitrogen. The technique implies furthermore the use of a potentiostatic double pulse.

Further experimental details concerning the pulsed potentiostatic electrodeposition for precursor

reduction by a HDA have been described previously. Activation of the Pt surface as well as removing of non-

reduced Pt precursor was realized by several purification steps after catalyst deposition. For this purpose

the GDE was immersed alternately in diluted sulfuric acid and deionized water at room temperature. The so

prepared GDEs were used as gas diffusion anode as well as cathode. For all prepared MEAs a Nafion-based

ELE0162 GDE from Johnson Matthey was used for the counter side.

2.4. Experimental setup and measurement principles

The aim of project was to provide a down-selection of materials for a more focused practical electrode and

MEA design using a selected set of new ionomers, electrolytes and catalysts as well. It delivered newly

developed and improved catalysts for high temperature operation.

Moreover, it was required to develop and elaborate new membrane electrode assemblies

(including membrane and catalyst layer) suitable for high temperature operation and demonstrate and

evaluate such membranes in a fuel cell stack. The selection of the materials has been done also on the basis

of new protocols of materials preparation and properties measurements developed to make the selection

more reliable.

Mass transport properties evaluation

Among the various characterization of the membrane one of the main important in the evaluation of mass

transport properties to correctly estimate the proton conductivity of the membrane but also its permeance

that, in other terms, represents a measure of the cross over phenomena that can occur in the PEMFC.


Within LOLIPEM project a new approach for the systematic evaluation of the mass transport

properties of a PEM was proposed. A protocol for permeation measurements has been elaborated to

rightly compare the transport properties of different membranes as a function of the same operating

conditions due to the strict dependence of the membrane performance on the relative humidity (RH) and

temperature. The method has been proven on various membranes developed during the research activity

by the various partners.

The proton conductivity represents the other transport property of the membrane was considered

together with the gas permeation properties. The ideal/desired membrane had to exhibit low gas

permeability and high proton conductivity. Thus, a new parameter called Transport Performance Index has

been defined as the ratio of hydrogen permeability and proton conductivity. This leads to an immediate

idea of the whole mass transport performance of the membrane. The mass transport properties, proton

conductivity and Transport Performance Index were measured for the various membranes as function of

temperature, pressure, relative humidity feeding different gaseous streams.

The elaborated protocol took into account the strict dependence of the membrane performance on

the RH and temperature. The mass transport measurements (permeation tests) started feeding H2 at 80°C

and RH=50%. Then hydrogen was replaced by N2 keeping the same temperature and RH. Afterwards,

nitrogen was replaced by O2, always at 80°C and RH=50%. An analogous sequence (H2, N2, O2) was repeated

once for higher RH (75%) and again for RH=100%, at the same temperature. A total of nine steps complete

this first part. The same sequences were repeated at the higher temperature values of 100°C and 120°C.

The experiments were performed continuously and the membrane was left overnight under a gaseous

stream at 2 bar. Figure 4 shows more about the specific sequence and combination of these variables. The

use of this protocol in the testing of the various membrane samples significantly contributed in the

evaluation of the membrane performance and, thus, on its suitability for further use in MEA.

H2 N2 O2

O2 N2 H2

H2 N2 O2

N2 H2 O2

O2 N2 H2

H2 N2 O2

N2 H2 O2

O2 N2 H2

H2 N2 O2

RH=50%

RH=50%

RH=50%RH=75%

RH=75%

RH=75%

RH=100%

RH=100%

RH=100%

80°C

100°C

120°C

1 1918171615141312111098765432 26252423222120 27

STEPS

TEM

PER

ATU

RE,

°C

80

100

120

140

Figure 4. Mass transport measurements – Experimental procedure.


Hot-Pressing

GDEs and proton conducting membrane were assembled in an additional step to form the MEA. For this

purpose a hot-pressing step was used to assure good contact between GDE and PEM and therefore to

maximize the “3-phase zone”. Figure 5 shows a typical cross-section of hot-pressed MEA. From the image

typical MPL thicknesses of 18-25 µm were revealed.

Table 33 summarizes the optimized hot-pressing parameter (temperature, pressure and time)

depending the used PEM. Where T represents the hot-pressing temperature, p the corresponding pressure,

t the time and CR the cooling rate. In the case of a slow cooling rate (SCR) MEA is cooled down to room

temperature with approximately 1 °C min-1. Whereas in the case of a fast cooling rate (FCR) the MEA is

allowed to cool down from 125°C to room temperature within 3 min.

Table 3: Optimized hot-pressing parameter for Nafion® and cross-linked SPEEK (XL-SPEEK).

Parameter Nafion® SPEEK

T / °C 125 160-190

p / kNcm-2 0.5 0.5

t / s 300 300

CR FCR SCR

Figure 5: Cross-sectional SEM image of Nafion 212 membrane with SPEEK containing GDEs.

MEA development

The use of alternative PEMs materials necessitate apart from the development of appropriate GDEs also

the development of the MEA in order to satisfy high life-time in addition to competitive performance. In

order to assembly MEAs possessing cross-linked SPEEK as centrepiece life-time and performance relevant

factors like hot-pressing parameters, MEA pre-conditioning and performance testing are screened and

optimized.

Hot-pressing temperature

Interfacial contact between the SPEEK material and the GDEs was improved using a hot-

pressing temperature close to the glass transition point of the used membrane. Corresponding

measurements revealing the change of the glass transition temperature Tg with depending on the


SPEEK membranes of cross-linking degree were performed by Prof. P. Knauth (University of Aix-

Marseille).

The influence of the MEA hot-pressing temperature was therefore investigated in the range of 160°C to

250°C. For all prepared MEA a cross-linked SPEEK membrane (thickness: 30 µm, provided by Fumatech &

URoma2) and commercial GDEs from Johnson Matthey are used. Figure 6 and Table 44 revealed that best

results in terms of fuel cell performance abd MEA life-time were obtained using a hot-pressing temperature

in-between 160°C and 190°C respectively.

Table 4: Summarizing table for MEA performance and life-time as function

of the applied hot-pressing temperature.

Hot-pressing EOL j-peak @ 650 mV

C h A cm-2

160 25 1.1

190 > 4.5 1.0

220 26 0.8

250 1.5 0.04

Figure 6: Polarization curves at 80°C for MEAs prepared

using different hot-pressing temperatures.

Variation of heating and cooling rate during hot-pressing

Cross-linked SPEEK being more brittle than PFSA material reacted more sensitive to the

applied mechanical stress introduced in the MEA by the hot-pressing step. Therefore different

heating and cooling rates were investigated in order to minimize the aforementioned. For this

purpose different MEAs based cross-linked SPEEK membrane (20 µm of thickness) were hot-

pressed with commercial GDEs from Johnson Matthey.

Figure 7 summarizes the results in terms of polarization curves for the variation of heating

and cooling rate by representing the last polarization cycle before the beginning of degradation.

From the plot the positive influence of using a slow heating as well as a slow cooling rate during the

hot-pressing can be deduced. This result is underpinned by the analysis of the MEA life-time

summarized in Table 55.

EX-330(180/7) hot-pressing @ 250°C



0,0 0,2 0,4 0,6 0,8 1,0 1,2 1,4

0,5

0,6

0,7

0,8

0,9

1,0

50 cm² / Tcell

= 80°C / RH = 95% / H2

= O2

= 1.2

vo

lta

ge

(V

)

current density (A/cm²)



Figure 7: Polarization curves for the applied heating and cooling rates

during the hot-pressing process.

Table 5: Results in terms of fuel cell performance and MEA life-time investigating the influence of the used

heating and cooling rate during the hot-pressing process.

EOL j-peak @ 650 mV

h A cm-2

FH/FC 6.0 0.85

FH/SC 6.5 0.70

SH/SC 12.0 1.00

Cross-linking degree

A series of membranes differing in cross-linking conditions during their preparation process were

used to prepare MEAs. In all cases commercial Johnson Matthey GDEs were used.

SE detector

BSE detector

SH & SC

0.0 0.2 0.4 0.6 0.8 1.0 1.2 1.4

0.5

0.6

0.7

0.8

0.9

1.050cm² / T

cell= 80°C / RH = 95% /

H2= 1.1

O2= 1.2

volta

ge [V

]

current density [A/cm²]

FH & FC

FH & SC


Figure 8. SEM analyses: not used (delaminated) MEA-EX 330.

Table 66 lists the membranes (thickness: 30 µm) used for these tests. They differ significantly in the

annealing temperature time (t2) correlated to the degree of cross-linking.

Figure 8. SEM analyses: not used (delaminated) MEA-EX 330.

Table 6: Summary of the prepared MEA based on an EX-330 membrane thermally annealed for different

times.

Name T2 t2 Supplier

°C h

EX-330 180-9 180 9 URoma2

EX-330 180-7 180 7 FUMATECH

EX-330 180-3 180 3 FUMATECH

EX-330 180-9

Figure 9 shows the time-dependent signals for current (black), voltage (blue), and OCP (red).

The representation clearly shows the initial increase of the MEA performance during the first 5 h of

operation followed by a decrease of both the maximum current and the OCP.

SE detector

BSE detector


0 2 4 6 8 10 12 14 16 18 20 22 24

0

10

20

30

40

50

60

70

80

50 cm² / Tcell

= 80°C / RH = 95% / H2

= O2

= 1.2

current

voltage

OCP

time

cu

rre

nt (A

)

0,0

0,1

0,2

0,3

0,4

0,5

0,6

0,7

0,8

0,9

1,0

vo

lta

ge

(V

)

Figure 9: Graph showing the time-dependent signals

for current, voltage, OCP and Ohmic resistivity.

EX-330 180-7

Figure 10 represent the quasi-stationary polarization curves reached after 5, 15, and 5 h at

operation temperatures of 80°C, 90°C and 95°C respectively.

The loss in performance at 95°C is attributed to the notable dew point accompanied by high

water vapour partial pressure and resulting reactant starvation on the GDEs. Accordingly a

chronopotentiometric measurement at 95°C using a decreased RH (80%) was performed after a

total operation time of around 25 h. During this measurement a similar decrease of the OCP

concomitantly with a significant drop of performance was observed.

0.0 0.2 0.4 0.6 0.8 1.0 1.2 1.4

0.5

0.6

0.7

0.8

0.9

1.0

50 cm² / H2

= O2

= 1.2

volta

ge [V

]


EX-330 (180/7) @ 80°C / 95 % RH

EX-330 (180/7) @ 90°C / 95 % RH

EX-330 (180/7) @ 95°C / 95 % RH

Figure 10: Polarization curves of a MEA collected at 80°C, 90°C and 95°C.

EX-330 180-3

Best results in terms of fuel cell performance as well as mid-term stability were obtained

using a membrane with shortest thermal annealing time (3 h). The obtained polarization results for

80°C and 90°C are represented in Figure 11. In both cases the quasi-stationary curves are obtained

after 5 h (Tfc = 80°C) and after 7 h (Tfc = 90°C).


0.0 0.2 0.4 0.6 0.8 1.0 1.2 1.4

0.5

0.6

0.7

0.8

0.9

1.0

50 cm² / H2

= O2

= 1.2

EX-330 (180/3) @ 80°C / 95 % RH

EX-330 (180/3) @ 90°C / 95 % RH


volta

ge [V

]

Figure 11: Polarization results for 80°C (brown) and 90°C (red).

Table 77 summarizes the results for the test in terms of fuel performance at 650 mV and as well as

mid-term stability using Tfc = 80°C and 95 % RH. Highest current densities were obtained for SPEEK

membranes with a thermal annealing time of 7 h and 3 h. Besides the performance increasing effect the

reduction of annealing time increases the MEA life-time.

Table 7: Characteristic values of fuel cell performance and life-time as function of thermal annealing time

for the used SPEEK EX-330 membrane.

EX-330 (180/9) EX-330 (180/7) EX-330 (180/3)

j at 650 mV / A cm-2 0.65* 1.1 1.1

EOL / h 8-10 25 - (> 39)

* no quasi-stationary conditions were reached during measurement

Influence of Reinforcing Frame and Pre-Conditioning Method

The border-region between GDE and SPEEK membrane was identified as “weak-point” and

therefore as possible source of mechanical failure. Hence the reinforcement of this region was

investigated in order to increase the MEA life-time. As additional parameter the type of the MEA

pre-conditioning was studied in the same set of experiments. In this context the liquid water pre-

conditioning and the chronopotentiometric pre-conditioning were analysed with regard to their

beneficial effect on the MEA performance and life-time. In all cases MEAs consisting of cross-linked

SPEEK membrane (30 µm of thickness) and JM GDEs were used.

Figure 12 summarizes the polarization curves obtained at 60°C and 80°C. Figure 12a clearly

shows that the use of a reinforcing frame in combination with a chronopotentiometric pre-

conditioning has the most beneficial effect on fuel cell performance. Unexpectedly the MEA pre-

conditioned with liquid water without any reinforcing frame offered good fuel cell performance

however featuring a very short life-time (cf. Table 8).

The obtained polarization curves at 80°C (cf. Figure 12b) confirmed the before mentioned

results. From 8 the life-time increasing effect of the used reinforcing frame is obvious.


Table 8: Results of the screening of the pre-conditioning methods as well as reinforcement frame.

Pre-Conditioning Framing EOL / h j-peak at 650 mV / A cm-2

60°C 80°C

LW1 YES 32* 0.5 0.6

CP YES > 56 1.0 1.1

LW1 NO 25 1.0 --

CP NO 15 -- 0.8

*EOL probably caused by thermal shock

a)

b)

Figure 12: Influence of the variation of the pre-conditioning method

and the use of a membrane reinforcing frame

on the polarization curves at 60°C (a) and 80°C (b).

0.0 0.2 0.4 0.6 0.8 1.0 1.2 1.4 1.6 1.8 2.0

0.5

0.6

0.7

0.8

0.9

1.0

chronopot pre-cond., with frame

50cm² / Tcell

= 80°C / RH = 95% / H2

= 1.1 O2

= 1.250cm² / Tcell

= 80°C / RH = 95% / H2

= 1.1 O2

= 1.2

volta

ge [V

]


liquid water pre-cond, with frame

chronopot. pre-cond., no frame

0.0 0.2 0.4 0.6 0.8 1.0 1.2 1.4 1.6 1.8 2.0

0.5

0.6

0.7

0.8

0.9

1.050cm² / T

cell= 60°C / RH = 95% /

H2= 1.1

O2= 1.2

chronopot pre-cond, with frame

volta

ge [V

]


liquid water pre-cond, with frame

liquid water pre-cond, no frame


Evaluation of MEA development

The optimized parameters obtained from the screening were used for the

preparation/operation of MEAs based on cross-linked SPEEK membranes. Short- and intermediate-

term performance test were carried out. The chronopotentiometry was identified as the most

powerful technique for testing at operational temperatures ≥ 100°C without the use of

backpressure.

An intermediate performance test was carried out using a reinforced MEA based on a

cross-linked SPEEK membrane (30 µm of thickness, thermally annealed at 180°C for 7 h) and JM

GDEs (0.4 mg-Pt cm-2 of platinum loading). Hot-pressing was performed at 160°C and using the

optimized heating and cooling parameters. The MEA was pre-conditioned using the

chronopotentiometric method. An operation temperature ranged between 60°C and 95°C was

investigated using both chronopotentiometric and polarization techniques. In this context a

chronopotentiometric measurement was carried out initially (cf. Figure 1313). For each current the

corresponding voltage signal was collected (black curve). Characteristic points of operation were

summarized in Table 99. Dewpoints on anode and cathode side (light blue and green curves) were

adjusted to maintain 95 % of RH up to an operational temperature of 90°C. At 95°C a dewpoint of

90°C was used representing the limiting dewpoint of the gas humidifier.

Up to 90°C a constant fuel cell performance was observed up to a maximum current

density of 1.5 A cm-2.

6 8 10 12 14 16 18 20 22 24 260.0

0.2

0.4

0.6

0.8

1.0

50cm² / Tcell

= 60-95°C / H2

= 1.1 O2

= 1.2

t [h]

U [V]

j [A/cm²]

T(fuel cell) [°C]

dp(anode) [°C]

dp(cathode) [°C]-0.2

0.0

0.2

0.4

0.6

0.8

1.0

1.2

1.4

1.6

20

40

60

80

100

Figure 13: Chronopotentiometric measurement of an MEAs based on a SPEEK EX330 membrane (180/7)

with stepwise increase of operational temperature from 60°C up to 95°C.

Table 9: Listing of characteristic points of the chronopotentiometric measurement.

t Tfc RH j U

h °C % A cm-2 mV

2

80

95

0.7 683

1 629

1.5 515

90 0.7 664

1 562

Figure 144 represents the polarization measurement at different operation conditions carried out after the

chronopotentiometric experiment. The corresponding operational conditions are mentioned on top and


inside the graph. For all investigated temperatures (60°C-90°C) a quasi-stationary behaviour was reached

after several hours of operation. A summary of the current densities obtained at a reference voltage of

650 mV are represented in 10. Noticeable is the increase of mass transport limitations with increasing

operational temperature probably due to the non-optimized microporous layer of the commercial GDE.

Table 10: Current densities as function of operational temperature of the fuel cell at a reference voltage of

650 mV.

Tfc / °C

at 650 mV

j / A cm-2 w / W cm-2

60 1.0 0.6

80 1.1 0.7

90 0.8 0.5

0.5

0.6

0.7

0.8

0.9

1.050cm² /

H2= 1.1

O2= 1.2

wa

tta

ge

de

nsity [

W/c

m²]

vo

lta

ge

[V

]

60°C; 95% RH

80°C; 95% RH

90°C; 95% RH


0.0 0.2 0.4 0.6 0.8 1.0 1.2 1.4 1.6 1.8 2.00.0

0.2

0.4

0.6

0.8

1.0

Figure 14: Polarization results in a temperature range from 60°C up to 90°C.

The produced MEA was used in total for 56 h under reverse load without indicating the EOL.

2.4.1. Test bench for long term durability measurements and advanced control strategies

Within the LoLiPEM project a single-cell test bench has been designed and constructed at MATGAS (Figure

15) specifically to carry out performance and lifetime tests on the developed MEAs. The test bench was

designed to allow long term experiments, thus, all safety issues related to unsupervised operation were

implemented on the system. In addition, a flexible operation was established, being able to monitor and

control pressure and temperature at the different parts of the system; a precise control of relative humidity

of gases; and the possibility of operating with oxygen and air. Moreover, a centralized and modular control

system allowed a precise control and a continuous data acquisition; on this system advanced control

techniques were implemented.


Figure 15: Piping and instrumentation diagram of the fuel cell testing bench designed and constructed at MATGAS for

the long-term tests on the developed PEM membranes.

The system is required to test high-temperature PEM fuel cells and to study durability by means of long-

term experiments. As mentioned above, the fuel cell test bench has been implemented to run long-term

single-cell testing which allows a precise control on humidity, gas flow and temperature. This is

accomplished by a system (see Figure 16) which includes a series of sensors (for temperature, pressure, and

humidity) and actuators at the different lines of gas supply, humidification, and fuel cell housing, providing

a flexible set-up that can work at a different range of conditions and which is operated by a central unit

that continuously monitors, controls and records the operation parameters.


Figure 16 Overall picture of the long term test bench at MATGAS

(safety features added to the system are highlighted).

Related to safety, the test-bench includes safety requirements in accordance with legal regulations and also

internal safety compliance at MATGAS to allow uninterrupted unsupervised operation. Figure 16 contains

an overall picture of the system highlighting the main safety elements added to the system: (1) fume hood

control, (2) UV flame detector, (3) explosivity detector, (4) thermostats and sensors, (5) alarm control (PC).

The alarm control was implemented in Labview along with the software to monitor and control remotely

the test bench system and record all operation data during tests. Figure 17 shows the main window of the

program were the different process variables can be set-up from the computer. The program has been

developed to allow easily implementations of the control algorithms. The control algorithms enable to

optimize the performance of the fuel cell by using semi-empirical models of the high temperature fuel cell

system.

Figure 17 Main window of the visual interface of the monitor and control of MATGAS test bench.

The design of this apparatus has been strongly linked to the specifications of the membranes developed in

the project by other partners, in order to achieve the best performance and to appropriately determine the


degradation rate and lifetime of the new membranes. It is important to remark the difficulties found to

measure some critical variables inside the fuel cell stack such as the relative humidity. Therefore, a detailed

model based on the work presented in ‘A. J del Real, A. Arce and C. Bordons, development and

experimental validation of a PEM fuel cell dynamic model, Journal of Power Sources 173, 2007, 310-324’

has been developed in order to estimate immeasurable variables. In addition, this model has been used in

the design step. Specifically, the model is a semi-empirical model which mixes first principle equations and

empirical correlations. The new contributions of this model are the two-phase fluid dynamics, the effects of

the flooding on the stack voltage, the start-up dynamics, the thermal dynamics and the novel mathematical

description of the polarization curve. The model has been tailored for a stack comprised by a membrane of

25 cm2 (the membranes used in the project) and it is divided in different blocks: electrochemical equations,

fluid-dynamics equations, thermal-dynamics equations and ancillary devices.

A correct design of the humidification system was essential in a test bench constructed to test high

temperature PEM fuel cells. The humidification inside the fuel cell is a critical parameter since it was

strongly linked to the degradation rate of the membrane. First, the time response of the humidification

system had to be fast enough to allow load changes without achieving high relative humidity values inside

the fuel cell for a long period of time. We incorporated to our system two humidifiers based on membrane

humidification. Moreover, an appropriate gas heating system was very important to achieve the desired

relative humidity inside the fuel cell when we operated at high temperature. Thus, MATGAS incorporated

to its system heater lines which can quickly heat the gases to the desired temperature before passing

through the humidifier and maintain a controlled temperature after the humidifier and before entering in

the fuel cell housing.

On the other hand, a fuel cell system that includes an advanced control strategy can dynamically

ensure the optimal operation in terms of efficiency and lifetime.

Figure 18: Control scenario of the high temperature PEM fuel cell test-bench.

We proposed a control scenario composed by two different control levels, the lower level comprises the

local control of the equipments and the higher level is an optimal control strategy which has the objective

to maximize the lifetime and the efficiency simultaneously. We proposed a controller based on Model

Stack temperature

controller

Air flow controller

Humidifier and heater controller


Hydrogen flow

controller

Back pressure regulators

Relative Humidity control loop

Efficiency control loop


Predictive Control technology since it has been successfully implemented in fuel cell systems (A. Arce, A. del

Real, C. Bordons and D. R. Ramírez. ‘Real-time implementation of a constrained MPC for efficient airflow

control in a PEM fuel cell’, IEEE Transactions on Industrial Electronics, 57, 6, 2010, 1892-1905).

Figure 18 shows the control scenario scheme of the test-bench where the local controllers which

are in the lower level are related to one of the two objectives of the higher controller. Thus, the humidifiers

and heater controller and the stack temperature controller are related to the lifetime objective which in

turn is related to the relative humidity inside the fuel cell. The air and hydrogen flow controllers are related

to the efficiency. Finally, the back pressure regulators are related to both objectives. Figure 19 shows the

control architecture where the two levels are represented.

Finally, for long-term testing purposes, it is necessary to implement an appropriate and robust Data

Acquisition program. Our system was implemented by using Labview RT platform due to its flexibility and

powerfulness in laboratory applications.

Figure 19: Control architecture of the test-bench.

Stack temperature

controller

Air flow controller



Hydrogen flow

controller

Back pressure regulators

Supervisor Controller

Set-points- Simulations


2.4.2. Durability measurements

A method10 to predict membrane lifetime consisting of an in situ accelerated test was developed previously

to the LoLiPEM project.

A set of accelerated tests was performed to predict a value for membrane lifetime measuring the

number of cycles, following the procedure and the experimental conditions established in this test

protocol. It consists of two steps: (1) the determination of the value of a coefficient alpha according to the

following equation

𝜶 = 𝒇𝒖𝒏𝒄𝒕𝒊𝒐𝒏 (𝑬𝒙𝒑𝒆𝒓𝒊𝒎𝒆𝒏𝒕𝒂𝒍 𝑬𝒏𝒅𝒖𝒓𝒂𝒏𝒄𝒆 𝒗𝒂𝒍𝒖𝒆

𝑳𝒐𝒂𝒅 𝒄𝒚𝒄𝒍𝒊𝒏𝒈 𝒗𝒂𝒍𝒖𝒆|

@ 𝒔𝒆𝒕 𝒐𝒑𝒆𝒓𝒂𝒕𝒊𝒏𝒈 𝒄𝒐𝒏𝒅𝒊𝒕𝒊𝒐𝒏𝒔

)

where alpha is the accelerated degradation coefficient, and (2) the evaluation of the life time of the

membrane through the following relation

𝑳𝒊𝒇𝒆𝒕𝒊𝒎𝒆 = 𝜶 ∗ 𝑵𝒖𝒎𝒃𝒆𝒓 𝒐𝒇 𝑪𝒚𝒄𝒍𝒆𝒔

The alpha coefficient strongly depends on operating conditions (e.g., protocol) and membrane material.

Literature values for Nafion and sPEEK are reported in the following table.

Membrane type Nafion® Sulfonated polyetheretherketone (sPEEK)

Lifetime coefficient 16.7 17.7

It was utilized to predict the life time of other membranes once it was evaluated by experimental

measurements on some samples of a specific material.

Thus, the starting point for the evaluation of the lifetime of the produced membranes as the

calculation of the α values following the mentioned method which are reported below.

Using the literature protocol, 2400 cycles were experimented for Nafion. This leads to a lifetime of ca.

40000 hours.

Table 111 lists the parameters of the LoLiPEM protocol and, for comparison, the ones of the

literature protocol. In addition, the alpha value for the LoLiPEM protocol is reported as function of the one

of the literature protocol. Considering the different cycling conditions (e.g., longer time of each cycle), the

alpha value of the LoLiPEM protocol, when the latter is operated at 75°C and RH=85%, could be at least 2

times higher than the literature one, as shown in

Table 111 and Table 122 for Nafion and sPEEK, respectively.

Table 11: Values for the alpha coefficient for the LoLiPEM protocol for NAFION membrane.

Literature protocol LoLiPEM protocol

Conditions 30 min@X Amp 60 min@X Amp

30 sec@OCV 300 sec@OCV

10 M. Marrony, D. Beretta, S. Ginocchio, “Durability study and lifetime prediction of Advanced High Temperature proton exchange membranes”, 2nd CARISMA International Conference on "Progress in MEA Materials for Medium and High Temperature Polymer Electrolyte Fuel Cells", 19-22 September 2010, La Grande Motte, France


α minimum 16.7 2*16.7 = 33.4

Table 12: Values for the alpha coefficient for the LoLiPEM protocol for Sulfonated

polyetheretherketone (sPEEK) membrane.

Literature protocol LoLiPEM protocol

Conditions 30 min@X Amp 60 min@X Amp

30 sec@OCV 300 sec@OCV

α minimum 17.7 2*17.7 = 35.4

Description of the experimental apparatus

The MEA, having an active membrane area of 25 cm2, was assembled in a single PEMFC between two flow

fields with a serpentine configuration (Figure 20). The MEA was sealed among the two flow fields by means

of a gasket type BASF LT250EWCUSTSI (Figure 21). Further assembling details are reported in Table 133.

Figure 20 Flow field design of the fuel cell

Figure 21 Gasket type

Table 13: Fuel cell characteristics

Gasket thickness 0.25 mm

Cell technology (collectors) Gold-plated plates

Cell tightening 5 Nm

Heating/cooling system Heating strips

Lowest cell voltage allowed 0.3 V


Figure 22 Set up used for accelerated tests. (1) Bubbler, (2a) Capacitive humidity sensors

(inlet gases), (2b) Capacitive humidity sensors (outlet gases), (3a) Capacitive pressure sensors (line),

(3b) Capacitive pressure sensors (back pressure).

Figure 22 shows the set up used for the accelerated tests performed on the developed MEAs. The feeding

gases are circulated through the bubbler to be humidified at the desired level of relative humidity. Relative

humidity was tuned by modulating the temperature of the bubbler and the fuel cell. After the

humidification section, the relative humidity of the feeding gases was measured by various capacitive

humidity sensors. The same sensors were placed at the outlet gases of the fuel cell to monitor the variation

of the relative humidity. In the case of measurements carried out with an imposed pressure difference on

the two MEA sides the capacitive pressure sensors were used. The data were collected with an automatic

acquisition data device.

After the assembling, a leakage test was performed on the fuel cell before the operation

(preconditioning) starts with a current density of 0.4 A/cm², at 65°C as cell and line temperature, and 60°C

in the bubbler for obtaining a RH≈85% at 1 bar.

Measurements on Nafion and Nafion thermal annealed membranes

Experiments were performed on commercial Nafion at 75°C using the LoLiPEM test protocol in order to

verify the lifetime hypothesis exposed above. As previously mentioned, the expected lifetime for this type

of Nafion membrane is 40.000 hours.

Figure 23 shows the obtained results measured under a pressure and relativity humidity of the inlet

gasses of 1 bar and 85%, respectively.

1

2

b

3

a

2

a

3

b


Figure 23: Accelerated test with Nafion. Cell temperature 75°C, pressure 1 bar, RH=85%

The test lasted about 830 number of cycles and was then stopped by the operator for service reasons. In

spite of the considerable number of cycles, and as can be seen from the performance of the fuel cell, the

MEA suffered a very low level of degradation.

Thus, starting from the Nafion lifetime found out in literature (40.000 hours) and the number of

cycles (ca. 830) a new and refined value was calculated using the mentioned equations. It was estimated as

48. This value is higher than the minimum value 33.4 reported in table 1. This means the value of 33.4 can

be considered as a lower limit for the coefficient and may be used as conservative value for lifetime

evaluation in the LoLiPeM protocol.

To evaluate the lifetime of the membranes developed in the project, the LoLiPEM protocol was

applied to a MEA assembled with a membrane supplied by a project partner, the Nafion NRE 212 thermally

annealed in DMSO at 140°C for 48h, and 120°C for 15h. The test was carried out at the temperature of

110°C, significantly higher than the operating temperature that can be used with a commercial Nafion. The

pressure and relativity humidity of the inlet gases were 1 bar and 95%, respectively. The results are shown

in Figure 24.

Figure 24: Accelerated test using Nafion NRE212 (thermally annealed, in DMSO at 140°C for 48h,

and 120°C for 15h). Operating conditions: 1 bar, RH=95% and 110°C


In these conditions, the MEA operated for a number of cycles of approximately 250. Using the mentioned

equation, it is possible to evaluate the lifetime of this sample which is the product of the number of cycles

and the evaluated alpha value, for instance, alphaminimum = 33.4.

However, it has to be pointed out that the lifetime of the MEA is also strictly related to the

operating conditions used in the protocol. In this sense, the difference between 75°C of the test carried out

on commercial Nafion and the 110°C for the thermally annealed Nafion and the higher relative humidity

used for the latter membrane, lead to the presence of another coefficient in the equation that takes into

account the temperature and relative humidity differences. The equation aforementioned thus becomes:

𝑳𝒊𝒇𝒆𝒕𝒊𝒎𝒆 = 𝜶𝒎𝒊𝒏𝒊𝒎𝒖𝒎 ∗ 𝑻_𝑹𝑯𝑪𝒐𝒆𝒇𝒇𝒊𝒄𝒊𝒆𝒏𝒕 ∗ 𝑵𝒖𝒎𝒃𝒆𝒓 𝒐𝒇 𝑪𝒚𝒄𝒍𝒆𝒔

𝜶 = 𝜶𝒎𝒊𝒏𝒊𝒎𝒖𝒎 ∗ 𝑻_𝑹𝑯𝑪𝒐𝒆𝒇𝒇𝒊𝒄𝒊𝒆𝒏𝒕

The new coefficient took into account the dependence on the operating temperature and relative

humidity. The relative humidity affected the membrane stability in a higher degree than the temperature.

Alberti et al. stated that any 1% for relative humidity had the same effect of 5°C. Thus, these effects had to

be taken into account in the evaluation of the membrane lifetime as they leaded to higher degradation

processes and therefore values of T_RH above 1 should have been expected under these conditions.

Table 14: Lifetime as function of T_RH coefficient for a thermally annealed Nafion membrane.

α minimum Number of cycles T_RHCoefficient α Lifetime predicted

(hours)

35.4 250

1 35.4 8850

2 70.8 17700

3 106 26550

4 142 35400

5 177 44250

Table 144 reports some estimation of the possible lifetime values for the Nafion thermal annealed as

function of the coefficient just introduced that takes into account the temperature and relative humidity

effects.

The predicted lifetimes for this MEA based on Nafion thermally annealed membrane is 8850 if no

effect of the higher temperature and relative humidity was taken into account (T_RH=1, most conservative

situation). However, as discussed above, it had to be noticed the measurement was done at 110°C (35°C

more than usual) and at 95% of relative humidity (10% more). Therefore, if these so stronger conditions (a

temperature and relative humidity higher of 35°C and 10%, respectively) were taken into account then a

value of T_RHCoefficient higher than 1 had to be considered. Thus, an value of the ones previously reported

as hypothesis becomes realistic and therefore a higher membrane lifetime should have been expected. For

a precise determination of the value of the coefficient at these conditions further experiments would

have been required, however we estimated that this value can lay above 1 and up to 5, as shown in

Table 144. Analogous analysis has been performed for MEAs with SPEEK membranes


MOPEM-CHP Design and building up

Within the project an important role has been covered by the design and building of a modular multi-cell

system able to allow the MEA replacement in an easy way, so- called MOPEM, developed by ITM-CNR.

In the typical stacks the electrical connection between two consecutive cells was given by bipolar

plates and the eventual replacement of a MEA, that could usually occur due to unexpected failures in the

membrane, flooding of the electrodes, etc., requires the disassembling of the whole stack including bipolar

plate; However this latter belonged to the various adjacent cells; therefore in the case of MEA failure also

the other cells of the stack were open and the operation has to be necessarily interrupted.

The MoPEM is characterised by a high flexibility degree since the cells assembling was designed and

build in such a way that the disassembling of the whole system was not anymore necessary for removing a

single cell and thus the typical drawbacks of traditional stack are overcome.

Since the MEAs developed in the LOLIPEM project allowed to operate at temperatures higher than

the ones currently used in traditional stacks, it came more and more pressing the necessity to cool the

system, when the an excess of heat was produced during the reaction. This allows assuring a constant

performance of the system, recovering in the meantime the heat produced by the stack itself. On the basis

of these considerations, the MOPEM was designed to allow adiabatic operations maximizing the recovery

of heat produced by cogeneration.

Figure 25 shows the frontal view of MoPEM-CHP system. It is constituted by four drawers, each of

them containing a single fuel cell that can be easily removed.

Both the case and the drawers have been made in aluminium. This choice has been done since this

material even light assures good mechanical resistance. The external structure as well as each drawer can

be simply opened allowing several access options to the system to the operator.

Figure 25: Frontal view of MoPEM-CHP system.

Figure 26 shows a detailed photo of a single drawer in frontal and rear view. In this latter the

fast&lock connections which permit the reduction of the time necessary for connect a single cell to the feed

and output tubes and every electrical cables can be seen. In addition, it is possible to observe the presence

of the connections for hydrogen, oxygen and water.

The heat recovery of the system is done by circulating liquid water on an external circuit very close

to the MEA. When the reaction occurs, the cold water fed to the system is heated in dependence on the

reaction conditions.


Figure 26: Single fuel cell hosting module, frontal and rear view.

Each single cell is connected to the stack using the connections illustrated in Figure 27 which shows the rear

view of the whole system. In case of problem occurring on a single cell, the caps are placed and the system

continues to operate without any interruption.

Figure 27: MOPEM-CHP system rear view.

Figure 28: shows the software developed for acquisition of the data of the MoPEM-CHP system. The

software runs on a dedicated PC and allows the easy control of all the parameters of each single fuel cell

permitting to intervene immediately if there are any kinds of problems.


Figure 28: Details of MOPEM software.

As it is shown in Figure 28: the software permits to detect the volt, current and temperature of every single

fuel cell. Furthermore it allows the control of hydrogen and oxygen gas lines humidity. These lines are

common for all the system, and then we need only two humidity sensors.

The whole MOPEM-CHP system is shown in Figure 29 where it is possible to observe every single

part constituting the system.

Figure 29: Whole MOPEM system.


2.5. Results

Following project deliverables were foreseen (including public and restricted to the consortium partners –

foreseen for protection as IPR):

Table 15. List of some LoLIPEM project deliverables11

Del.

No. Deliverable name Nature

Dissemination

level

Delivery date

(project month) Commercialization

WP-1. Long-life membranes for PEMFCH

1.1. PFSA membranes P CO 12 See chapters 3 and 4

1.2. SAP membranes P CO 18

1.3. Set-up for permeation

measurements P PU 12 See chapter 4

WP-2. New concept MEA with improved durability

2.1. MEAs suitable for temperature

higher than 100°C P CO 18

See chapters 3 and 4

2.2. MEA use and discard P CO 32

WP-3. Lifetime test and prediction techniques, establishment of accelerated test techniques

3.1. In situ accelerated ageing test

protocol R PP 24 See chapters 3 and 4

3.2. Results of in situ accelerated aging

tests R CO 24

See chapters 3 and 4 3.3.

Results of long term single cell

tests R CO 28

3.4. Results of post mortem analysis. R CO 24

3.5

Optimized operating conditions

protocol for multi-cell system

performance

R PP 33 See chapters 3 and 4

P – Product, R – Report,

PU - Public, PP - Restricted to other project participants, CO - Confidential, only for members of the consortium

(including the Commission Services)

11 LoLIPEM Project Proposal Annex I -”Description of Work”.


3. DISSEMINATION OF KNOWLEDGE

3.1. Introduction

The dissemination of knowledge in the project is implemented via three forms of social communication:

oral (spoken), documentary (print, written) and electronic. These forms interact with each other resulting in

hybrid communication forms. A short description of the seven combinations obtained as a result of this

interaction is as follows:

a) Oral (spoken) communication [O] involves the personal contacts of scientists with colleagues at

conferences, seminars and lectures, etc. Oral communication plays a substantial role in informal

communication of academics. Spoken communication is localized in time and space, rich in information

saturation, and quite expensive to organize.

b) Documentary (written, print) communication [D] uses artificially created print documents to transfer

meanings in time and space. Documentary communication is the basis of formal communication for

scientists through publication in books and journals.

c) Electronic communication [E] is based on transferring information through telecommunication

networks including wireless communication. One of the most important electronic communication

channels is the Internet. The emergence and development of the Internet has had a considerable

impact on the advancement of scientific communication in recent years. Scientists are utilizing such

forms of electronic communication as e-mail, e-groups, etc.

d) Oral – Electronic. [OE] This combination provides such communication tools as telephone, radio and TV.

Relatively new communication channels which show the potential to win popularity in academic

societies include videoconferencing, electronic notebooks and IP-telephony. In the context of the

globalization of science the combination of oral and electronic forms of communication will play a

progressively more important role.

e) Documentary – Oral. [DO] This rather old combination includes video or audio recording.

f) Documentary – Electronic. [DE] This grouping gives birth to electronic journals, dissertations, books,

and new formats such as e-prints. The potential for this combination to gradually displace documentary

communication is sufficiently high.

g) Documentary – Oral – Electronic. [DOE] This combination allows the creation of new forms of scientific

organization such as co laboratories.

3.2. Dissemination strategy

The dissemination activities are performed among three main target groups:

researchers,

industry and

policy makers.

Tools and methods of dissemination used by the project team include: establishment of the project web

page [E-channel], brochures and printing materials development [D, DE – channels], publication of research

papers [D, DE – channels] and participation in thematic conferences [O, OE, DOE – channels] (Annex I -

„Description of Work” Chapter B3. Impact; B.3.2 Plan for the use and dissemination of foreground).


Creating appropriate communication channels between the project consortium and external audiences (EU

community, the European Technology Platforms, Industrial Clusters, Fuel Cells technology experts) enables

the effective transfer of knowledge. The dissemination activities for LoLiPEM project are covered by WP-4.

The overall objective of the WP4 is to disseminate and exploit new paths leading to development of highly

innovative technologies for SPG & CHP systems based on PEMFCs.

The specific objectives of the WP4 are following:

To ensure communication of project results towards the EU policy makers;

To ensure promotion of the project results to the EU community;

To assess the impact of promotion activities carried out within the project as a whole.

All information to be disseminated is managed, and has to receive prior clearance, to ensure compliance

with intellectual property rights (IPR) issues. The management of IPR is described in detail in consortium

agreement. Thereafter, dissemination made via communicates were addressed directly to stakeholders and

potential clients.

The project partners apply a policy of confidentiality regarding the contents of the research carried out and

the results achieved. Therefore any proposed publication, communication or presentation was subjected to

the a screening/evaluation of the Coordinator and in case also of other involved partners, who were free of

approving the disclosure of the results, being also allowed to modify or suppress details that could harm the

exploitation of the results of the project. The dissemination was made via newsletters to clients, leaflets on

mature industrial topics or other channels of information, publication of articles in appropriate scientific or

trade journals, conferences, exhibitions etc.

3.3. Dissemination actions – activities undertaken

3.3.1. Project Website

Information on the results of the project are listed on the home page of the Project www.lolipem.eu.The

project web page, has been implemented and it is operative. The project web page consists of different

sections:

Project

Consortium

Contacts

Consortium meeting

Events

News

Publications

Download

Links

The project website content includes12:

12 For December 31st, 2012

http://www.lolipem.eu/


10 consortium meetings, including one “mid-term review”;

3 workshops;

4 researches exchanges between partners.

The project achievements presented in publication section13:

three books published,

21 papers already published

41 oral presentations, some also as invited talks

5 poster presentations presented at conferences, and

3 seminars took place.

Download section (This section contains brochures, leaflets about the project and workshops in pdf format.

Printable copies are available for dissemination activity.)14:

3.3.2. Events

The project events took place in for of three workshops:

1) ”Membrane materials: preparation and characterization” took place on March 17-18, 2011 in

Grottaferrata (Roma), Italy. The workshop was organised by the University of Roma ”Tor Vergata”.

The 1st International Workshop on “Long life membranes based on PFSA & SAPs: Preparation and

Characterization” aimed to bring together scientists and students interested in the study and

development of new Polymer Electrolyte Membrane Fuel Cells. The workshop was attended by

well-known scientists from 8 countries: Italy, Germany, France, Switzerland, Spain, Poland, UK,

USA. 44 participants were present, with 17 oral presentations and 2 invited lectures. 9

presentations were held by member of the Lolipem consortium and 10 by external scientists.

Abstracts of the lectures from the WORKSHOP 17-18 March 2011 “Long life membranes based on

PFSA & SAPs: Preparation and characterization”, Grottaferrata (Rome), Italy were included in PDF

format on web site www.lolipem.eu in the download section.

2) “Electrochemistry and Electrocatalysis” took place on March 25-27, 2012 in Saarbrucken,

Germany. The workshop was organised by the University of Saarbrucken. The scientific organization

of the workshop was done by a three-membered committee chaired by Professor Rolf

Hempelmann. The workshop Electrocatalysis featured important aspects of electro-chemistry with

focus on electro-catalysis. Main topics were fuel cells, redox flow batteries, electro-enzymatics,

(bio-) electro-sensors as well as electrolysis of NaCl or HCl for chlorine production. The workshop

aimed to bring together scientists and students in the above outlined field and in particular to

gather the national and international collaboration partners of LoLiPEM.42 Participants form 5

different European countries were present. In the course of the workshop18 oral presentations

were held, two of them as invited keynote lectures. In addition 11 poster contributions were

presented. Interestingly, also participants from 3 industrial companies actively participated in the

worhshop.

3) “Fuel cell stack assembly” took place on May 29-31, 2012 in Altafulla, Spain. The third workshop

was organised by MatGas. This workshop, the third of the series, brought together scientists as well

as fuel cell manufacturers interested in the study and development of new Polymer Electrolyte

13 As above. 14 As above


Membrane Fuel Cells, with emphasis on Fuel Cell Stacks Assembly. It included keynote lectures and

oral presentations. The workshop was held over two days. The program comprised plenary (45mn +

15 discussion) and oral communications (20mn+ 10 discussion). The scientific program focused on

those aspects at the frontier of new progresses in the field of high temperature membrane for Fuel

Cells, other topics devoted to Fuel Cells from a broad perspective, as well as practical relevant

aspects of Fuel Cells development and implementation, with particular emphasis on Fuel Cell

Stacks. 19 Participants from 5 different EU countries were present. In the course of the workshop 2

plenary lectures and 6 oral presentations were held. We also had participants from industry and

academia.

3.3.3. Researchers exchanges between partners

1) Dr. E. SGRECCIA of University of Roma “Tor Vergata” to University of Provence, March 2010

2) Dr. B. MARANESI of University of Roma “Tor Vergata” to University of Provence, February - May 2011

3) Pr. P. KNAUTH of University of Provence to University of Roma “Tor Vergata”, June 2010

4) Pr. M. L. DI VONA of University of Roma “Tor Vergata” to University of Provence, November 2010

The exchange of personnel was by expanding knowledge transfer within the consortium, increase

connectivity between the different laboratories.The exchanges of personnel was to overcome the gaps

between the groups by building bridges of knowledge transfer and integrate and unify know-how, and

increase strengths.

Permanent cooperation and exchange of knowledge and experience is taking place among LoLiPEM

partners’ institutions which results in numerous common publications and presentations.


3.3.4. Publications related to the project results

List of books:

1) J-F Chailan, M. Khadhraoui P. Knauth, Chapter 6: Mechanical and Dynamic Mechanical Analysis of Proton-Conducting Polymers, Solid State Proton

Conductors. Properties and Application in Fuel Cells. Eds. P. Knauth and M. L. Di Vona, Wiley, (2012)

2) G. Alberti, R. Narducci, M L Di Vona, Chapter 8: Perfluorinated Sulfonic Acids as Proton Conductor Membranes, Solid State Proton Conductors.

Properties and Application in Fuel Cells. Eds. P. Knauth and M. L. Di Vona, Wiley (2012)

3) R. Hempelmann, Chapter 4. Structure and Diffusivity in Proton-Conducting Membranes Studied by Quasielastic Neutron Scattering, Properties and

Application in Fuel Cells. Eds. P. Knauth and M. L. Di Vona, Wiley, (2012)

List of the papers (also including submitted or in preparation, for full version-of table see the Final report)

Type of audience Countries addressed

Journal Title Responsible

Scientists, competitive companies

Worldwide ChemSusChem 2011, 4, 1–12; DOI: 10.1002/cssc.201000415

Durability of Sulfonated Aromatic Polymers for Proton-Exchange-Membrane Fuel Cells

H. Hou, M. L. Di Vona, P. Knauth


Worldwide Journal of Analytical and Applied Pyrolysis 92 (2011) 361–365 doi:10.1016/j.jaap.2011.07.012

Thermogravimetric analysis of SPEEK membranes: Thermal stability, degree of sulfonation and cross-linking reaction

P. Knauth, H. Hou, E. Bloch, E. Sgreccia, M. L. Di Vona


Worldwide Journal of The Electrochemical Society, 158 (2) B159-B165 (2011)

Water activity coefficient and proton mobility in hydrate acidic polymers

P. Knauth, E. Sgreccia, A. Donnadio, M. Casciola, M. L. Di Vona


worldwide Journal of Membrane Science 369 (2011) 536–544 doi:10.1016/j.memsci.2010.12.044

Composite polymer electrolytes of sulfonated poly-ether-ether-ketone (SPEEK) with organically functionalized TiO2 l

M. L. Di Vona, E. Sgreccia, A. Donnadio, M. Casciola, J.F. Chailan, G. Auer, P. Knauth





worldwide

Journal of membrane science, 423–424, 113–127 dx.doi.org/10.1016/j.memsci.2012.07.038

Building Bridges: Crosslinking of Sulfonated Aromatic Polymers – a Review

H. Hou, M.L Di Vona, P Knauth


worldwide Solid state ionics 225, 255-259 http://dx.doi.org/10.1016/j.ssi.2012.01.043

Sulfonated aromatic ionomers: Analysis of proton conductivity and proton mobility

P Knauth; ML Di Vona


worldwide Journal of Material Research 27, 1950-1957 (2012).

Crosslinked SPEEK membranes: Mechanical, thermal and hydrothermal properties

H. Hou, B. Maranesi, JF Chailan, M Khadhraoui, R. Polini, ML Di Vona, P Knauth


worldwide

International Journal of Hydrogen Energy 37, (2012) 8672-8680 doi:10.1016/j.ijhydene.2012.02.159

High Performance Sulfonated Aromatic Ionomers by Solvothermal Macromolecular Synthesis

M. L. Di Vona,G. Alberti,bE. Sgreccia, M. Casciola,P. Knauthc


worldwide

International Journal of Hydrogen Energy 37 (2012) 6302-6307 doi:10.1016/j.ijhydene.2011.07.134

New Results on the Visco-Elastic Behaviour of Ionomer Membranes and Relations Between T-RH Plots and Proton Conductivity Decay of Nafion 117 in the Range 50-140°C

Alberti, ML. Di Vona , R. Narducci


Worldwide Electrochimica Acta 66 (2012) 164– 172 doi:10.1016/j.electacta.2012.01.074

Influence of the preparation conditions on the properties of polymeric and hybrid cation exchange membranes

Fontananova E., Cucunato V., Curcio E., Trotta F., Biasizzo M., Drioli E., Barbieri G.


Worldwide Journal of Power Sources 205 (2012) 222– 230 doi:10.1016/j.jpowsour.2012.01.108

New approach for the evaluation of membranes transport properties for polymer electrolyte membrane fuel cells

Brunetti A., Fontananova E., Donnadio A., Casciola M., Di Vona M.L., Sgreccia E., Drioli E., Barbieri G.





Worldwide Journal of Power Sources 205 (2012) 145– 150 doi:10.1016/j.jpowsour.2011.12.060

Conductivity and hydration of sulfonated polyethersulfone in the range 70-120°C: effect of temperature and relative humidity cycling

A. Donnadio, M. Casciola, M.L. Di Vona, M. Tamilvanan


Worldwide MRS Proceeding 2012,

dx.doi.org/10.1557/opl.2012.439 Proton-Conducting Cross-Linked Sulfonated Aromatic Polymers for Fuel Cells Application

B. Maranesi, L. Pasquini, M. Khadhraoui, P. Knauth, M. L. Di Vona


Worldwide Fuel Cells, 2013, 13(1), 58-64

dx.doi.org/10.1002/fuce.201200116 Permeability and Diffusivity Measurements on Polymer Electrolyte Membranes

F. Arena, J. Mitzel R. Hempelmann


Worldwide International Journal of Hydrogen Energy DOI: 10.1016/j.ijhydene.2011.09.063

Electrodeposition Of PEM Fuel Cell Catalysts By The Use Of A Hydrogen Depolarized Anode

J. Mitzel, F. Arena, H. Natter, T. Walter, M. Batzer, M. Stefener, R. Hempelmann



dx.doi.org/10.1002/fuce.201200123

Stabilization of Sulfonated Aromatic Polymer (SAP) Membranes Based on SPEEK-WC for PEMFCs

E. Fontananova, A. Brunetti, F. Trotta,M. Biasizzo, E. Drioli,G. Barbieri



dx.doi.org/10.1002/fuce.201200126

Annealing of Nafion 1100 in the Presence of an Annealing Agent: A Powerful Method for Increasing Ionomer Working Temperature in PEMFCs

Alberti, G.; Narducci, R.; Di Vona, M. L.; Giancola, S



dx.doi.org/10.1002/fuce.201200120

Proton Mobility in Sulfonated PolyEtherEtherKetone (SPEEK): Influence of Thermal Crosslinking and Annealing

Knauth, P.; Pasquini, L.; Maranesi, B.; Pelzer, K.; Polini, R.; Di Vona, M. L.

http://dx.doi.org/10.1557/opl.2012.439





Worldwide Fuel cells, 2013

in press dx.doi.org/10.1002/fuce.201200010

Cross-linking of sulfonated poly ether ether ketone by thermal treatment: how does the reaction occur?

B. Maranesi, H. Hou, R. Polini, E. Sgreccia,G. Alberti, R. Narducci, P. Knauth, M. L. Di Vona


Worldwide Industrial & Engineering Chemistry Research, 2013 In press

More on NAFION conductivity decay at temperatures higher than 80°C: preparation and first characterization of in-plane oriented layered morphologies

Alberti, G.; Narducci, R.; Di Vona, M. L.; Giancola, S.


Worldwide Zeitschrift fur Physikalische Chemie In press

Sulfonated Aromatic Polymers as Proton-Conducting Solid Electrolytes for Fuel Cells: a Short Review

Maria Luisa Di Vona Philippe Knauth


Worldwide Z. Phys. Chem, 2013

in press dx.doi.org/10.1524/zpch.2013.0346

Electrocatalyst–Membrane Interface and Fuel Cell Performance with Sulfonated PolyEtherEtherKetone as Ionomer

F. Arena, J. Mitzel R. Hempelmann

List of the oral presentations at conference

Publishing date Conference title Type of audience Countries addressed Title presentation Responsible

29 August - 3 September 2010

XII International Symposium on Polymer Electrolytes (ISPE12), Italy


Worldwide Development of stabilized SPEEK-WC membranes

E. Fontananova, G. Barbieri, F. Trotta, E. Drioli




Worldwide from Gas Diffusion Layers to Gas Difdfusion Electrodes directly by Electrodeposition

J. Mitzel, F. Arena, H. Natter, R. Hempelmann




Worldwide Aspects of Physical Chemistry of Aromatic Ionomers for Fuel Cells

P. Knauth, M. L. Di Vona

http://www.oldenbourg-link.com/doi/abs/10.1524/zpch.2013.0346






Worldwide

A new representation of the instability maps of an ionomer at medium temperature: plots T-RH at constant values of the counter-elasticity index of Nafion 117 in the temperature range 50-140°C

G. Alberti, M. L. Di Vona, R. Narducci

4-6 June, 2010 7th Italy-Korea Workshop “Membranes for a clean environment”, Italy


Italy Korea

Membrane operations in the energy field

E. Fontananova, G. Barbieri, F. Trotta, E. Drioli

June 2010

EMRS 2010 Spring Meeting June 2010 Palais des Congrès, Strasbourg, Symposyium O: Solid state ionics: exploring chemical and structural complexity of novel ionic conductors, France


Worldwide New Generation Proton-Conducting Polymers For Fuel Cells

M. L. Di Vona (Invited lecture)

19-22 September 2010

2nd CARISMA International Conference on Progress in MEA Materials for Medium and high Temperature Polymer Electrolyte Fuel Cells, France


Worldwide

Water-vapour sorption isotherms of Nafion 1100 membranes taking into account the permanent deformations provoked by some standard pre-treatment procedures usually performed before their use in fuel cells

G. Alberti, M. L. Di Vona, R. Narducci

November 7- 11, 2010

6th international symposium on high-tech polymer materials synthesis, characterization and applications, China


Worldwide Advanced Thermal Treatments for High Durability Sulfonated Aromatic Polymers




March 17-18, 2011

Workshop on “Long life membranes based on PTFA & SAPs: preparation and characterization”, Italy


Worldwide Development of long life SAP membranes for PEMFCs based on SPEEK-WC

E. Fontananova, A. Brunetti, H. Hou, P. Knauth, F. Trotta, E. Drioli, G. Barbieri

March 17-18, 2011



Worldwide Study and Implementation of Advanced Control Technologies to Maximize PEM Fuel Cell Durability

A. Arce, J.O. Ossó, C. Bordons and L. F. Vega

March 17-18, 2011

Workshop on “Long life membranes based on PTFA & SAPs: preparation and characterization” , Italy


Worldwide

Gravimetric determination of the water uptake of ionomeric membranes as a function of temperature at controlled relative humidity

M. Casciola, M. L. Di Vona and A. Donnadio

March 17-18, 2011



Worldwide Ex-situ stability test of Sulfonated Aromatic Polymers by Thermogravimetric Analysis

P. Knauth and H. Hou

March 17-18, 2011



Worldwide Mechanical analysis of Polymers M. Khadhraoui, H. Hou and P. Knauth

March 17-18, 2011



Worldwide Permeability and Diffusivity Measurements on Membranes for H2-PEMFC’s

F. Arena, R. Szamocki and R. Hempelmann

March 17-18, 2011



Worldwide Hybrid approach for improved SAP membranes

E. Sgreccia, P. Knauth and M. L. Di Vona



March 17-18, 2011



Worldwide Permeability and Diffusivity Measurements on Membranes for H2-PEMFC’s

F. Arena, R. Szamocki and R. Hempelmann

24-27 May 2011 Nanomeeting 2011, Belarus Scientists, competitive companies

Belarus Membranes Based on SPEEK for Polymer Electrolyte Membrane Fuel Cells

M. L. Di Vona, P. Knauth, G. Auer

July 3-8, 2011 18th International Conference on Solid State Ionics Warsaw


Worldwide Strategies for improvement of Sulfonated Aromatic Ionomer

P. Knauth (Keynote) and M. L. Di Vona

August 1-5, 2011 Thermec 2011, Quebec City, Canada


Worldwide

Proton consucting sulfonated aromatic polymers: relation between macromolecular structure, water activity and proton mobility

P. Knauth (Keynote)

August 1-5, 2011 Thermec 2011, Quebec City, Canada


Worldwide Proton-conducting high ionic exchange capacity aromatic ionomers for fuel cells application

M. L. Di Vona (Invited)

August 1-5 2011 Thermec 2011 Quebec City, Canada


Worldwide Proton-Conducting High Ionic Exchange Capacity Aromatic Ionomers For Fuel Cells Application


March, 2012 International Workshop on “Electrocatalysis”, Germany


Worldwide Thermally Annealed SPEEK and Its Application for Medium Temperature Hydrogen PEM Fuel cells

F. Arena J. Mitzel, M. L. Di Vona, G. Alberti, R. Hempelmann

May, 2012 International Workshop on “Fuel Cell Stack Assembly”, Spain


Worldwide

Permeability and Diffusivity Measurements on Polymer Exchange Membranes for Hydrogen PEM FUEL CELLS

F. Arena M. L. Di Vona, R. Hempelmann



May, 2012 E-MRS Spring 2012 – Symposium F , France


Worldwide Solid State Proton Diffusion and Quasielastic Neutron Scattering

R. Hempelmann

May 29-30, 2012

3rd LoLiPEM International Workshop Fuel Cell Stack Assembly, Spain


Worldwide New approach to control fuel cell stacks under variable loads

Alicia Arce,alCarlos Bordons and Lourdes F. Vega

May 29-30, 2012



Worldwide Model predictive control for fuel cell systems

Carlos Bordons

May 29-30, 2012



Worldwide Evaluation of membranes mass transport properties of polymer electrolyte membranes for PEMFC

Adele Brunetti, Enrica Fontananova, Enrico Drioli and Giuseppe Barbieri

May 29-30, 2012



Worldwide Hurdles on the path to the hydrogen economy

Pedro Gómez-Romero

May 29-30, 2012



Worldwide

Cross-linked proton-conducting membranes: an efficient strategy to improve sulfonated aromatic polymers for fuel cells

Maria Luisa Di Vona, Emanuela Sgreccia

May 29-30, 2012



Worldwide

Static and dynamic mechanical measurements: what information can they provide for pem fuel cell technology?

P. Knauth, M. Khadhraoui



July 9-10, 2012 8th International Symposium on Advanced Polymeric Materials, Kuala Lumpur


Worldwide Proton Conducting hydrated acidic polymers: relation between proton mobility and proton concentration

P. Knauth (invited)

July 9-10, 2012 8th International Symposium on Advanced Polymeric Materials, Kuala Lumpur


Worldwide Proton-conducting cross-linked sulfonated aromatic polymers for fuel cells application

M. L. Di Vona (Invited)

August 26-31, 2012

XIII International symposium on polymer electrolytes, Selfoss, Iceland


Worldwide Proton-mobility in proton-conducting polymers

P. Knauth (invited) and M. Luisa Di Vona

August 26-31, 2012

XIII International symposium on polymer electrolytes, Selfoss, Iceland


Worldwide Proton-conducting cross-linked sulfonated aromatic polymers for fuel cells application

M.L. Di Vona, B. Maranesi, L. Pasquini and P. Knauth

August 12-17, 2012

International Material Research conference, Cancun, Mexico


Worldwide Proton-conducting hydrated acidic polymers: relations between polymer microstructure and proton mobility

P. Knauth and M. L. Di Vona

August 12-17, 2012

International Material Research conference, Cancun, Mexico


Worldwide Sulfonated Aromatic Polymers for Fuel Cells

M. L. Di Vona and P. Knauth

November 21-23, 2012

Congreso Nacional de Pilas de Combustible


Spain In-situ characterization of PEM membranes by AFM

I. Torres, A. Arce, J. O. Ossó, M.L. DiVona, L. F. Vega

November, 2012 GDCh Workshop – Energy transformation


Germany Gasdiffusionselektroden für SPEEK-Elektrolytmembranen in Brennstoffzellen

F. Arena, D: Durneata; J. Mitzel, M. L. Di Vona, R. Hempelmann


List of the poster presentations at conference

Publishing date

Conference title Type of audience Countries addressed

Title poster presentation Responsible

4-6 June, 2010 7th Italy-Korea Workshop “Membranes for a clean environment”, , Italy


Italy Korea

New strategies to improve membrane durability for PEMFCs

E. Fontananova, A. Brunetti, G. Barbieri, F. Trotta, E. Drioli

19-22 September 2010

2nd CARISMA International Conference on Progress in MEA Materials for Medium and high Temperature Polymer Electrolyte Fuel Cells, France


Worldwide Annealing of proton-conducting ionomers based on SPEEK

M. L. Di Vona, E. Sgreccia, P. Knauth, R. Narducci, G. Alberti

July 23-29, 2011

International Conference on Membranes and Membrane Processes, The Netherlands


Worldwide Design and development of non-fluorinated polymer electrolyte membranes with improved stability

Fontananova E., Brunetti A., Hou H., Knauth P., Trotta F., Drioli E., Barbieri G

May, 2012 E-MRS Spring 2012 – Symposium F , France


Worldwide

Permeability and Diffusivity Measurements on Polymer Exchange Membranes for Fuel Cell Applications

F. Arena, A. Brunetti, G. Barbieri, R. Hempelmann

September, 2012

Euromembrane 2012, England Scientists, competitive companies

Worldwide

Permeability and Diffusivity Measurements on Polymer Exchange Membranes for Fuel Cell Applications

F. Arena, J. Mitzel, D. Durneata, R. Hempelmann

Seminars

1) Arce. Advanced Control Technologies: Applications on Fuel Cell and CO2 Capture Sytems. Matgas Resarch Center. 11 February 2011. Barcelona.

2) Arce. Modeling of PEM fuel cell systems. Institut de Robòtica i Informàtica Industrial. Universidad Politécnica de Cataluña. 4 March 2011. Barcelona

3) Arce. On the Exploitation of MPC-based Formulations for Performance Enhancement of Fuel Cell Systems. Institut d’Organització I Control de sistemas

Industrials. Unversidad Politécnica de Cataluña. 4 May 2011. Barcelona.


Other Issues

1) The LoLiPEM project partner: Cracow University of Technology – Bogna Grochola, LoLiPEM project

webpage: www.lolipem.eu, Webpage ,2010

2) The LoLiPEM project partner: Cracow University of Technology – Bogna Grochola, The LoLiPEM

project leaflet, Leaflets, 2010

3) The LoLiPEM project partner: Cracow University of Technology – Bogna Grochola, LoLiPEM project

short press release in Granty Europejskie (04.2010)

3.3.5. Summary

Finally, the dissemination methods were summarized in table below.

Constituency Dissemination methods Form of

comm

Examples

Media

Send press releases to journals, magazines,

and electronic publications

Post on list serves and websites

all See 4.3.1. (website)

Other

universities’

scientists and

students

Host or attend seminars O, D, E,

OE, DE

See 4.3.3, and 4.3.4., and

4.3.5. (books, publication,

conferences, posters,

seminars, website)

Policymakers

[EU]

Distribute summary document

Draft and send policy position statements

Send press releases

D, DE See 4.3.2 and 4.3.5.

Companies

Send a e-newsletter summarizing research in

progress

Host or attend seminars

Host community forums to discuss the

research

all

See 4.3.3, 4.3.4., and

4.3.5. (books, publication,


seminars, website)

Local

communities

Host of attend seminars


research

Appeal for articles in local media sources

Participate in local events or conferences

all

See 4.3.3 and 4.3.5.

(books, publication,


seminars, website)

“green energy”

advocacy groups

and NGOs

Distribute flyers, brochures & research briefs

Participate in local events or conferences

Host or attend seminars


research

Ask agencies to feature the research project

in their newsletters & websites

all See 4.3.5. (website)

http://www.lolipem.eu/


3.4. Dissemination actions – plans for the future

Partners plan additional dissemination actions beyond project time-frames. These activities are performed

mainly at the conferences. Forthcoming dissemination activities are focused on scientists – as a group of

audience – and are addressed to worldwide scientific community. Plans are summarized in Table below:

Table 16. Project deliverables – planned for publication:

Planned

date

Dissemination

methods

Type of action /

event

Constituency

/ type of

audience

Countries

addressed

Expected

size of

audience

Partner

/Beneficiary

responsible*

8-13

September

2013

O, D

Congress,

EUROMAT,

SEvilla, Spain

Scientists International 100

2 & 3

December

2013 O, D

Congress,

Thermec, Las

Vegas USA

Scientist International 100

2 & 3

August

2014 O, D

Congress, IMRC,

Cancoon, Mexico Scientist International 100

2 & 3

July 2013 D Publication Scientist International 2 & 3

* Beneficiary 1: CNR; Beneficiary 2: URoma2; Beneficiary 3: UProvence; Beneficiary 4: USaar; Beneficiary 5:

Edison; Beneficiary 6: Fumatech; Beneficiary 7: MatGas; Beneficiary 8: CUT


4. STRATEGY OF EXPLOITATION

4.1. Introduction

The technology component consists of tools and techniques to implement effective knowledge

management practice which provides values to its business, employees, customers and partners. The tools

can further be classified into knowledge creation, knowledge integration, knowledge sharing and

knowledge utilization.

Figure 30. Technology strategy.

The various steps are described here:

Knowledge Creation - Knowledge is created either as explicit or tacit knowledge. Explicit

knowledge is put in paper or electronic format. It is recorded and made accessible to others. Tacit

knowledge is created in minds of people. This knowledge resides within individuals. This knowledge

needs to be transformed into explicit knowledge so that it can recorded and shared with others in

the organization.

Knowledge Storage - Knowledge is stored and organized in a repository. The decision on how and

where lies with the organization. But the objective of this phase to enable organization to be able

to contribute, organize and share knowledge with.

Knowledge Sharing - Knowledge is shared and accessed by people. They can either search or

navigate to the knowledge items.

Knowledge Utilization - This is end goal of knowledge practice. The knowledge management does

not have any value if knowledge created is not utilized to its potential. The more knowledge is

created as knowledge is applied and utilized.

And Measuring knowledge benefits (not shown) - No process can be improved if it is not measured

for success. The key to success of knowledge management is the ability to measure the

effectiveness of the implementation and narrowing it down to returns through revenue. The

monitoring and control on processes are necessary to identify opportunities for eliminating

redundancy and allow for continuous improvement.

Knowledge is utilized and commercialized in many ways. Many of these involve some form of codification

from tacit knowledge to knowledge in more explicit forms such as documents databases and computer

software. What starts as uncodified knowledge, often a set of ideas, is gradually shaped through dialogue

and expression into something more tangible, such as a process description or a product design, that finally

http://2.bp.blogspot.com/_3jsesw2yfMI/Ro11jBaeE1I/AAAAAAAAALY/Pm0DIkhFMZY/s1600-h/km.gif


emerges as products for sale.

Figure 31. Knowledge commercialization process.

Much knowledge in organizations is neither explicitly codified nor commercialized. thus many knowledge

management initiatives identify important tacit knowledge, held by a few experts, that is capable of

codification and would benefits many other people. knowledge can be commercialized in several ways:

selling it as part of an advisory service; developing methodologies as part of a consultancy; developing

training courses; converting it into information products such as databases or publications etc

Details on knowledge management and on IPR are provided by the Consortium Agreement that all

partners signed. Some of the major aspects concerning confidentiality, ownership of knowledge, patents

and access rights are shortly reported below:

Confidentiality: each partner treats information from other partners as confidential and not

disclose it to third parties unless it is obvious that the information is already publicly available.

Ownership of knowledge: knowledge is owned by the partners who carried out the work

generating the knowledge.

Patents: Partners who own patentable knowledge may, at their own expense, make applications

for patent or similar form of protection and shall supply details of each such application to the

other partners.

Access rights: Partners grant to each of the other partners royalty-free access right to knowledge

generated in the project to the extent needed to successfully perform the project.

The protecting intellectual assets highlights two-fold challenge. From a legal/contractual perspective,

nothing substitutes for a well -crafted Consortium Agreement. Those document contains the intellectual

asset terms and conditions each project partner must abide by during the collaboration. They also ensure

that collaborating researchers have the necessary rights to carry out the collaboration and take the fruits of

the work into the marketplace.

From the human behavior perspective, partners must ensure that collaborating researchers (esp.

working for Public Research Organizations like Universities) have an understanding of the relevant terms of

the contract, including what information must and must not be shared. The real challenge with protecting

intellectual assets is that they are both “leaky” and “sticky”. They leak out of the organization with every

visit of an outsider (defined as “third parties” – see section 8.4 of Consortium Agreement), and they stick in

the minds of anyone who hears them. It takes “a while” for the person who just learned interesting

information to convince themselves that they always knew that information, and therefore have a right to

use it. Providing and repeating the information to members of both sides of R&D process (researchers and

commercializing staffs in companies involved), with a specific focus on protecting sensitive information

during the course of the collaboration, pays enormous dividends in saving commercial potential of


discoveries and findings.

Protection of know-how. The nature of intangible assets such as know-how and trade secrets is a barrier to

their protection. They are easily shared, travel effortlessly in peoples' minds, and resist being categorized

into neat little piles labeled proprietary and non-proprietary knowledge. To complicate matters further,

know-how is hard to talk about.

Consortium doesn’t distinguish between “know how”, which is information or skills required to do

something useful, or “trade secrets”, which are valuable information the firm takes specific actions to

protect. The real issue is protecting proprietary information, i.e., valuable knowledge a firm taking a part in

R&D project wishes to protect from unintended use.

The reality of the collaborative R&D process is that different legal agreements build on one another

as the collaboration moves through various phases. The Non-Disclosure Agreement (NDA) is normally the

first agreement in the series. It may be followed by an agreement covering development of new technology

such as a collaborative research agreement, a joint development agreement, or an agreement to purchase

developments from one of the parties. If the collaboration is successful, they are followed by agreements

that enable the operation of a business such as purchase agreements, joint marketing agreements, and

various types of licenses to assure each party has the necessary rights to operate their business.

In the LoLIPEM project majority of issues mentioned above is covering by “Consortium agreement” which

defines management of the background (section 11.3), and joint invention and foreground knowledge

management (section 11.2) as well.

[Joint invention] If, in the course of carrying out work on the Project, a joint invention, design or work is

made ‐ and more than one Party is contributor to it ‐ and if the features of such joint invention design or

work are such that it is not possible to separate them for the purpose of applying for, obtaining and/or

maintaining the relevant patent protection or any other Intellectual Property Right, the Parties concerned

agree that they may jointly apply to obtain and/or maintain the relevant right together with any other

Parties.

[Applying the results of joint invention and licensing to the third parties] The Parties concerned shall seek

to agree amongst themselves arrangements for applying for, obtaining and/or maintaining such right on a

case‐by‐case basis. As long as any such right is in force, each Party concerned shall be entitled to use and to

license such right without the consent of the other Parties, provided that the Party concerned shall be

informed in advance of any licensing to third parties. In case of licensing to third parties, appropriate

financial compensation shall be given to the other Parties concerned.

[Access rights] All Access‐rights {to background and foreground knowledge} granted in accordance with

{Consortium Agreement} are granted on a nonexclusive basis, expressly exclude any rights to sub‐license

and shall be made free of any transfer costs. (…) Foreground and Background shall be used only for the

purposes for which Access‐ rights to it have been granted and only for so long as is necessary for those

purposes.

Protecting the explicit knowledge by patenting. Protection of research results can be an important step in

the valorisation and commercialisation of LoLIPEM project results. Patent protection is the “strongest”

intellectual property right and also the most widely used for project results.

Before initialization of the patent procedure partners has to contact the patent attorney or other


interface office and together try and asses the valorisation potential of research results. They shall examine

whether it is possible ornecessary to protect the research results e.g. through patenting and try to asses the

market value of the technology.

Subsequently university project partners shall contact companies which take a part in the project -

they might be interested in applying the technology into their products and services and they need a patent

or other formal tool of IP protection.

The way to best proceed, shall be decided on a case by case basis. When making the decision,

which of the following is the most important factor to consider for patenting: patentability (prior art, stat

bar issues, etc.), technical viability, or market factors?

Figure 32. Patenting decision. The most important factors.

As can be seen by the pie chart, the vast majority chose market factors. It means that technologies

recognize that can be patented, doesn’t mean it should be patented. If there is no market for the

technology, there is little point in spending time and resources determining whether it is technically viable,

what prior art exists, or whether a stat bar deadline has been passed.

So the trend is in the right direction. Some companies worry that, even if the technology has no

market potential, they need to obtain a patent in order to protect their right to use the innovation

themselves.

For a government lab or research organization (not a company), this is totally erroneous. Filing a

patent solely for the purpose of protecting your right to practice is a waste of money, because there is a

perfectly legal and inexpensive way to protect your rights: publish.

One trap that universities and government labs are particularly susceptible to is prestige patents.

These occur when policies create incentives for having as many patents as possible, regardless of their

commercial viability. Many institutions have “refereed papers or patents” as a metric. Yet sometimes the

patent is easier to obtain than the refereed paper. Solutions to this problem include:

If a technology doesn’t have market potential, stick to your guns and do not patent. Instead,

encourage and support the inventor in submitting a paper to a peer-reviewed journal.

Look for other venues for publication and reward them for that recognition.

Submit the technology for an external award.

In a screening, technology developers do a rapid analysis of market research and intellectual property (IP)

information to figure out if a technology has enough commercial potential to warrant the more in-depth

step of an assessment.

Has the technology been publicly disclosed and, if so, when (i.e., have you missed the 1-year

statutory bar deadline for filing for a patent)?

http://1.bp.blogspot.com/-I1DAMXixJno/TdFvSbsQfyI/AAAAAAAAAFA/gqtYundx_Ww/s1600/2011-05-16_blog-211-patenting-decision-pie-chart.png


Is it evolutionary or revolutionary?

Is it broadly applicable or relevant only to a few (or even a single) industries?

What is the estimated market size and how fast is it growing (or is it shrinking)?

Will it be easy/inexpensive or difficult/costly for licensees to adopt it?

What is the technology’s level of development?

How mature is the market? Has the window of opportunity closed, is it open now, or has it not yet

opened?

These are questions that can be answered well enough in a rapid screening to say either “Yes, this should be

studied more closely” or “No, it’s too unlikely that this will be successful” This type of rapid screening is

particularly important when you have a backlog of technologies in IP/patent portfolio.

In 2010, the US and European patent offices published a combined total of 1,801 granted fuel cell

patents. A comparison of this number to the total number of granted patents published in 2000 and 2005

(Figure 1) shows significant growth in intellectual property between 2000 and 2005, and again from 2005 to

2010. The increase equates to 347% growth in annual patent numbers over the decade15.

To determine to what extent the increase in fuel cell patents exceeded underlying growth in general

patent activity, we have estimated the number of fuel cell patents that would have resulted from no more

than average growth. These have been calculated from a 2000 baseline using overall patent growth rates

from WIPO . Had fuel cell patenting grown in line with general patenting, the number of fuel cell patents in

2005 would have been just 494 (compared to 861 actual) and in 2010 almost three times fewer at 627.

Figure 33. Increase in fuel cell patents number.

Baseline (average) = overall patent growth rates from WIPO.

Since applications for patents are only granted if they satisfy the requirement for novelty, the growth in

granted patents reflects substantial levels of innovation in fuel cell technology. It also underscores the rapid

progress of the industry towards commercialization in the first decade of this millennium, as granted

patents are only pursued and maintained by the assignee if a profit is expected from the invention.

The number of patents granted to each country by the US and European patent offices, collectively,

is shown in following figures (top ten countries, and countries with fewer than 100 patents in each year).

15 The 2011 Fuel Cell Patent Review [www.fuelcelltoday.com] Patents and applications relating to fuel cells were located by searches carried out on Thomson Reuters’ Aureka® IP analysis platform, using relevant keywords and the International Patent Classification (IPC) code H01M0008* for ‘Fuel Cells, Manufacture Thereof.


Figure 34. Clean energy patents (granted 2000.2005.2010) per country.

Figure shows Japan and the USA leading the field, as we would expect. There have been significant

increases in absolute terms for both these countries, but fuel cell patenting in Japan accelerated sufficiently

during the decade to put Japan ahead of the USA by 2010.

This may be ascribed in part to a more widespread acceptance of fuel cells as commercial

technology in Japan, aided by government support for the Ene-Farm project (amongst others). After the

demonstration phase, which ran from 2005 to 2009, this support took the form of a ‘pull’ subsidy, with the

Japanese Government providing a significant percentage of the purchase cost of the Ene-Farm system. The

result has been thousands of fuel cell units sold to residential customers in Tokyo and elsewhere in Japan.

The number of patents from South Korea has also increased markedly from 2005 to 2010 –almost

putting it on a par with Germany, which has been active in this area for some time.

Large Korean corporations are responsible for pushing it to prominence, particularly Samsung and

to a lesser extent Hyundai and LG, but again significant support from the South Korean authorities for fuel

cell technology should be counted as a spur to innovation.

Figure above largely accords with the results of a recent patent-based study on clean energy

technology, jointly conducted by the EPO, the United Nations Environment Programme (UNEP) and the

International Centre for Trade and Sustainable Development (ICTSD)5. The study found that almost 80% of

innovation in clean energy technology originates in just six countries: Japan, the USA, Germany, the

Republic of Korea, France and the UK. Figure below excludes the USA, Japan, Germany and South Korea,

and shows those countries from which fewer than 100 patents but more than 5 patents originated in 2010.

Figure 35. Clean energy patents (granted 2000.2005.2010) per country

excl. Japan, USA, South Korea, & Germany.


Steady growth from year to year is seen for the UK, Italy, Denmark and Australia, with progress in these

countries driven almost entirely by a handful of familiar names in the fuel cell industry. Significant growth

in France has seen increases in patents granted to a number of parties, significantly automakers Peugeot

and Renault, and the CEA (Commissariat à l'énergie atomique et aux énergies alternatives; the French

Alternative Energies and Atomic Energy Commission).

Figures confirm the growing dominance of Japan in this area: 20% of the top ten assignees in 2000

were Japanese corporations; this proportion increased to 50% in 2005 and to 70% in 2010. I.e. Samsung has

had a meteoric rise, from no presence in the top ranks in either 2000 or 2005, to number one on the list in

2010. It accounts for the bulk of Korea’s 177 granted patents in 2010 and has been almost solely

responsible for pushing that country into the top ten.

The presence of so many automotive manufacturers in the list for each year is particularly

encouraging, and underlines the determined effort by these companies to push fuel cell electric vehicles to

commercialization by 2015.16

The fuel cell patent numbers reflect the rapid technological progress in the industry from 2000 to 2010, and

the advent of commercialization in that period.

The extent of the growth we have reported, while extraordinary, is supported by statistics on clean energy

patents reported elsewhere. The Organisation for Economic Co-operation and Development (OECD) has

documented a significant rise in ‘green’ intellectual property from 1999 to 2008, with patents in renewable

energy showing the largest increase9. The WIPO 2010 indicators similarly show growth in the number of

PCT applications in four clean energy technologies: fuel cells, solar, wind and geothermal energy. From 584

applications in 2000, this had increased to 3,424 applications in 2009.

For obvious reasons, growth in clean energy technology can be expected to continue outstripping

underlying economic growth and its indicators, such as overall patent numbers.

16 The 2011 Fuel Cell Patent Review [www.fuelcelltoday.com]


Whether there would be a return to the very rapid growth in applications between 2000 and 2005 remains

to be seen; our feeling is that this rate of increase is both unsustainable and unnecessary in the longer

term. More modest growth in patent numbers is a positive indicator if it reflects a progression from

research and development, and the intensive fund-raising phase, to commercial implementation within a

maturing industry.

Some predictions for the next five years we can make confidently: Japan will retain its position of

prominence in fuel cell patents, followed by the USA and Europe. These regions have built up a solid base

of intellectual property over the last decade and are well positioned to reap the benefits of that as

commercialization gains momentum. The most rapid growth in intellectual property will likely be in South

Korea, China and Taiwan, and we expect these to become powerhouses in the industry over the next

decade.

What this analysis has also confirmed is the extent of the commitment to fuel cell technology by

automotive OEMs. The patent numbers show that major manufacturers such as Toyota, Honda and General

Motors have sunk significant resources into this area. For fuel cell vehicles, and for the wide range of other

applications for fuel cells, the rapid increase in patent activity in the decade 2000 to 2010 reflects growing

confidence in fuel cell technology.

4.2. Exploitation actions

As we read in project proposal the following technology and knowledge exploitation models were

considered:17:

Partner 5, FumaTech, is active in the membrane market and is ready to commercialize any improved

ionomer membrane immediately. For this commercialization it is essential to have a demonstrator fuel cell

operating which proves the technical performance and the concerted action of ionomer and electrocatalysts.

FumaTech´s clients are manufacturer of MEAs or perhaps even of complete fuel cell stacks, and these clients

have to convinced. All decisions concerning exploitation have been made by the exploitation manager who

co-operated with technical and commercial staff of all the partners co-ordinating all exploitation issues,

such licences and patents.

FuMA-Tech GmbH “Functional Membranes and Plant Technology” combines the important tasks of

providing energy and water. At the sites in St. Ingbert (Saarland) and Vaihingen (Baden-Württemberg) in

Germany, FUMATECH is engaged in the field of fuel cell technology and membrane separation technology.

The company can look back on more than 15 years’ experience in polymer and membrane production and

in membrane separation technology. FUMATECH is a member of BWT-AG best-water-technology, the

leading water technology group in Europe.

Concerning the exploitation strategy and the intellectual property policy, any significant innovation

developed inside the project shall be protected by patents and any results which might have an EU

competitive advantage will be patented as soon as possible. Patenting cost and maintenance fees shall be

shared (decided on a case by case basis) by the partners having the main interest in the patent and bilateral

agreements concerning the protection of rights shall be made between partners with mutual interests. All

17 Annex I - „Description of Work” Chapter B3. Impact; B.3.2 Plan for the use and dissemination of foreground


licensing issues shall be defined in detail in a Consortium Agreement to be discussed and signed by all the

partners before the end of project negotiation. In addition, the research institutes and universities shall

transfer the knowledge gained in this project both to their teaching activities, updating future engineers

and students, and to their interactions with other industries and research institutes.

Industrial partner show their particular interest in project results as follows:

From a technological viewpoint, FUMATECH ranks as the leading manufacturer of ion exchange

polymers and membranes, having comprehensive skills that range from the synthesis of raw and auxiliary

materials, to the conversion of these materials to membranes and finally to their application in industrial

membrane separation plants.

Polymer synthesis, manufacturing experience in film and membrane production as well as the

reliable operation of these membranes in industrial products have provided the Know-How for the

development and serial production of proton-conductive polymers and membranes for all known electro-

membrane applications including electrodialysis, acid and base dialysis, electrolysis, batteries and fuel cells.

Due to the in-house polymer production and coating plants for continuous membrane production,

FUMATECH is well equipped, even today, as a supplier of membranes for operations at pilot and industrial

level. The main area of FUMATECH’s competence lies at the heart of the fuel cell, namely the proton-

conductive membrane, fumapem®. The fuel cell strategy of FUMATECH is to supply all fuel cell industries

with (a) ionomers in bulk powder or solution, (b) membranes from fluorinated ionomers, non-fluorinated

ionomers and hybrid organic-inorganic composites for electrolysis, hydrogen fuel cells and direct methanol

fuel cells. Furthermore, FUMATECH provides coating services for e.g. toll production of tailored membranes

as well as for the production of catalyst coated membranes.

The main objective of LoLiPEM Project was to give a clear demonstration that long-life SPG&CHP

systems based on PEMFCHs operating at temperatures ≥ 100°C can be developed if stabilized ionomer

membranes and electrodes, prepared with new strategies are used for FCHs. FUMATECH is active in the

membrane market and is ready to commercialize any improved ionomer membrane immediately. For this

commercialization it was essential to have a demonstrator fuel cell operating which proves the technical

performance and the concerted action of ionomer and electrocatalysts. FUMATECH´s clients are

manufacturer of MEAs and complete fuel cell stacks.

The overall strategy of FUMATECH within LoLiPEM was the exploitation of project results for

commercialization of new PEMFC membranes based on:

the synthesis of crosslinked SAP membranes by innovative reactions

the preparation of stabilized PFSA and PFSA-ZrP composite membranes prepared by new tailor-

made annealing procedures.

FUMATECH was considering the following exploitation strategies within LoLiPEM project aiming at

facilitating and accelerating entry of PEMFCs to mass market:

Take licence of patents from project partners on new results regarding polymer and membrane

fabrication

Apply for patents on innovative results regarding polymer and membrane fabrication

Polymer production based on potentially low-cost material

Apply efficient crosslinking strategies on hydrocarbon membrane

Membrane production based on stabilizied PFSA and

Membrane production based on crosslinked SAP material (e.g. sPEEK)

Supply of ionomer and membranes for clients in the field of Fuel Cells


Up-scaling of polymer and membrane production based on low-cost material

FUMATECH has considered the complete production chain starting from non-sulfonated PEEK to the ready-

to-use membrane, as show in the following process flow chart:

Figure 36. Process flow chart of production of sPEEK membranes.

This production chain comprises the following stages:

Scaled-up production of fumion® E (sulfonated PEEK): During the LoLiPEM project, FUMATECH has

developed and optimized the production of highly sulfonated PEEK including industrial scalability, cost and

environmental considerations. The process allows for a cost-effective and process-controlled

manufacturing, and a target-oriented and reproducible achievement of the degree of sulfonation of the

PEEK. The different stages of the production have been considered including the sulfonation as a batch

process versus a conti-process, the isolation by precipitation, the cleaning step by washing with water, the

purification by dialysis, the drying of the product and even the waste treatment.

Optimized solution preparation of sPEEK in DMSO for membrane casting: Optimized solution

composition and preparation have been developed which allow for reproducible and effective casting on

the FUMATECH’s continuous membrane production line. In particular the solvents, the solution

concentration, the solution viscosity, filtration and some important additives have been considered.

Optimized membrane production of sPEEK from optimized DMSO solution FUMATECH has

developed a robust process for the production of sPEEK membranes from optimized DMSO solutions on the

continuous membrane production line. The production process includes the coating of the polymer solution

onto a carrier foil, followed by a three-stage drying process. Process parameters were optimized in order to

obtain defect-free membranes. The process of the pilot-scale membrane production is fully compatible with

the standard large-scale membrane production enabling the rapid transfer and integration of the new

technology into the standard operation of manufacturing processes; and the subsequent exploitation of the

project results. The corresponding cost structure of polymer and membranes preparation has been

evaluated as well, comprising medium-scale polymer and membrane preparation and optionally the use of

ePTFE-reinforcement.

Optimized annealing / crosslinking process of sPEEK cast from DMSO: UROMA and FUMATECH

have developed the DMSO-mediated annealing process for crosslinking the sPEEK membranes in terms of

Polymer

Production

Solution

Preparation

Solution

Filtration

Membrane

Casting

Solvent

Evaporation

Annealing

Crosslinking

Activation

Conditioningblue = batch process

yellow = conti process


temperature, time and procedure. This process is still a batch process and needs further optimization being

cost-effective and reproducible. Also the membrane activation after annealing is still a matter of

optimization.

Transfer of crosslinking concept to alternative highly sulfonated polymers: FUMATECH has

commenced exploring the transfer of the crosslinking concept to alternative highly sulfonated polymers This

concept has already been applied successfully to some sulfonated polymers – e.g. fumion® STO sulfonated

poly(ether sulfide sulfone) and fumion® ST sulfonated poly(sulfide sulfone).

Exploitation and use of crosslinked sPEEK for other applications: FUMATECH is considering the

exploitation and use of the developed crosslinked sPEEK membranes and other sulfonated hydrocarbon

membranes for other applications. Due to the specific properties and the potentially low-cost, these

membranes will be explored for the following applications:

DMFC applications: Due to the crosslinking and the corresponding insolubility, and due to the high

degree of sulfonation, the methanol crossover of these membranes is supposed to be significantly reduced,

while the proton conductivity is still high, leading to high fuel utilization and high performance in DMFC

applications.

Electrolysis for the production of hydrogen: Due to the high proton conductivity and high

mechanical stability, these membranes may be used in electrolysis application for hydrogen generation.

Humidifier: Due to the high degree of sulfonation, the water transfer rate through these

membranes should be high, which renders possible their application for humidifier.

Electrodialysis: These membranes may be used as cation-exchange membranes for water

treatment (desalination) in electrodialysis and other electrochemical processes, due to the potentially high

permselectivity, high conductivity and low-cost structure.

Partner 7, MATGAS Research Center is a strategic alliance, legally registered as a nonprofit Economical

Interest Group, among the company Carburos Metálicos- Air Products Group, the Spanish National Research

Council (CSIC) and the Autonomous University of Barcelona (UAB). The mission is to establish a center of

excellence in material science and gas application by combining the strengths of industrial, academic and

government institutions for the benefits of the founding partners and society.

The objective of MATGAS Research Center, with respect to the exploitation of results, is to develop novel

advanced control techniques for high temperature PEM (HT-PEM) fuel cell in different stationary

applications as combined heat and power systems. This technology will allow operating the systems in a

feasible way during long-term period maximizing the durability while keeping a high global efficiency. This

technology will be generic for high temperature PEM fuel cells and will also be applicable to non-stationary

applications such as transportation. The development of this technology requires a deep knowledge of

different areas such as material science (membranes, gas diffusion layers and catalysts), dynamic models,

control and instrumentation. The knowledge generated in the framework of the LoLiPEM project is a

matter of vital importance for MATGAS purposes and will be protected by proprietary rights. During this

project, different membrane technologies are going to be tested and the generalization of our control

approach for HT-PEM fuel cells will be developed. The technology developed by MATGAS in this project will

be an important innovation in the design of more competitive high temperature fuel cell systems for

combined heat and power applications. Once the technology is protected, development of commercial

systems will be possible in partnership with other participants of the LoLiPEM project, combining improved

membranes with advanced control techniques which will provide competitive FCH systems.


Potential markets of the developed technology for stationary applications are backup systems for

residential power and heat supply and autonomous units for buildings, but this technology could also be

adapted to non-stationary applications, broadening the possible target markets. MATGAS, through its

partner Air Products, a leader in H2 production is involved in the research and development of this

technology due to its aforementioned promising potential.

These exploitations of results have been completed or are intended to be completed in the near future.

lolipem long-life pem-f h &hp systems at ... · tel: ++48 (12) 628 26 60; e-mails:...

Documents