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Novel materials for energy applications

A decade of EU-funded research

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Directorate-General for ResearchDirectorate G – Industrial technologiesUnit G3 ‘Value – added materials’E-mail: [email protected]: http://ec.europa.eu/research/industrial_technologies/

EUROPEAN COMMISSION

Directorate - General for Research, Industrial technologies2008 Unit G3 ‘Value – added materials’

Novel materials for energy applications

A decade of EU-funded research

I. Vouldis, P. Millet and J.L. Vallés

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Table of contents

4 Materials technologies vital to meet future energy needs

7 Materials for energy in FP5

8 Process advances improve wires for high temperature superconductors (2000-2003)

9 Superconductivity network unites academia and industry (2002-2006)

10 Sun-rechargeable smart cards a step nearer (2000-2003)

11 Novel sol gel technology for long length superconducting coated tapes (2001-2005)

12 Tough transparent alumina ceramics lighten energy drain (2000-2003)

15 Materials for energy in FP6

16 New polymer electrolytes and non-Pt catalysts

extend PEM fuel cell performance (2006-2009)

17 Non-noble catalysts cut fuel cell costs (2007-2010)

18 Thin-film solid electrolytes find optical and energy storage applications (2005-2008)

19 High capacity nickel-metal hydride batteries could boost European industry (2006-2009)

20 Nanostructured superconductors pave the way to high temperature,

high magnetic field applications (2005-2008)

21 MgB2 composite superconductors break new ground (2004-2007)

22 ‘New’ carbon for in-car hydrogen storage? (2006-2009)

23 Al-C composite cables lower electricity transport costs (2004-2006)

24 Novel materials for silicate-based fuel cells (2006-2009)

25 EU-Turkey-China cooperation advances intermediate temperature

fuel cell technology (2006-2009)

26 Si nanofilm process potential for photovoltaics and optoelectronics (2005-2008)

27 Nanocomponents integrated in rechargeable microbatteries (2006-2009)

28 Nanostructured fuel cells as industrial chemicals producers (2004-2007)

N O V E L M AT E R I A L S F O R E N E R G Y A P P L I C AT I O N S4 N O V E L M AT E R I A L S F O R E N E R G Y A P P L I C AT I O N S

Materials technologies vital to meet future energy needs

Reliable and sustainable energy supply is fundamental to the economic and social fabric of nations, and to the wellbeing and quality of life for their citizens. In an age when the demand for traditionally exploited natural resources is outpacing supply, conventional industrial practices are contributing to undesirable climatic change and developing regions are competing for a greater share of finite fuel stocks, the search for innovative ways to meet this need becomes more urgent than ever.

Currently over 80 % of Europe’s energy use is based on oil, gas and coal. Overall consumption continues to increase, but the growth of renewable sources is lagging, resulting in a possible 5 % increase on 2006 levels of greenhouse gas emissions by 2012. In addition, the EU’s dependence on external suppliers is growing. Today, 50 % of requirements are met by imports – including products from potentially insecure regions. Forecasters predict a rise to around 70 % over the next 20-30 years.

Policy for research in this critical area is framed within the strategic context of what the European Commission describes as a ‘Kyoto-Lisbon-Moscow triangle’:

the Kyoto corner of the triangle represents sustain-• ability – including technologies to improve energy efficiency, tackle global warming and reduce green-house gas emissions;

Lisbon recalls the Lisbon Council commitment to work-• ing together for growth, jobs and global competitiveness – via industrial transformation, process enhancements and the fostering of human creativity;the Moscow corner refers to the security of energy • supply – implying the development of new modes of energy generation and storage, and diversification into sustainable, locally abundant energy sources.

In January 2008, the Commission announced a package of measures with 2020 targets of cutting EU greenhouse gases by at least 20 %, increasing the share of renewable energies to 20 % and, finally, obtaining a 20 % reduction in global primary energy use through energy efficiency – collectively described as the ‘three 20’s’. The emissions reduction target is likely to be increased to 30 % when a new global climate change agreement can be reached.

The instruments to implement these policies include the Action Plan for Energy Efficiency, the Renewable Energy Roadmap, the N&N (nanosciences and nanotechno-logies) Action Plan for Europe 2005-2009, and the European Strategic Energy Technology Plan (SET-PLAN), together representing a comprehensive set of actions leading to a low- carbon future.

FP6€27.6 million16 projects

FP5€21.3 million13 projects

EU funding on Novel materials for energy applications under FP5 and FP6

5A D E C A D E O F E U - F U N D E D R E S E A R C H

hydrogen. New energy-efficient devices also call for improved processing technologies for materials elabor-ation and integration. This is the case for superconductor tapes formed with complex thin-film architectures where there is a need to control each step of the fabrication – the final product being tape of several hundred metres in length with a nanostructured superconducting active layer of 1 to 3 μm thickness.

Support for projects in this field has therefore featured strongly in the successive RTD Framework Programmes, which are the main vehicles for EU funding of collabora-tive transnational research. The following pages highlight successful projects funded within this research area by the NMP Theme.

Although not named as a topic in its own right under the Fifth Framework Programme (FP5 –1998-2002), 14 projects relating to materials for energy applications received contri-butions totalling around €23 million within the GROWTH (Competitive and sustainable growth) programme.

In FP6, the area was more clearly addressed with a spe-cific topic in the three calls for proposals under Priority 3 (Nanotechnologies and nano-sciences, knowledge-based multifunctional materials and new production processes and devices).

Important role for materials scienceWhile materials science is only one aspect of the response to these daunting challenges, it nevertheless has a cru-cial part to play in achieving the ambitious goals. In the past, it has contributed significantly to advances in the safe, reliable and efficient use of energy and available natural resources.

With the advent of nano-materials, materials research is expected to play an increasing role in sustainable techno-logies for energy conversion, storage and savings. Principal areas of interest are: solar cells, batteries and supercap-acitors; fuel cells, thermoelectrics, superconductors, more efficient lighting and hydrogen technologies.

In most of these areas, incremental improvements of cur-rent technologies are not sufficient to address the important issues of durability, efficiency and costs. New materials research avenues are therefore needed to design, elaborate and integrate materials for energy applications. Nanotechnologies and modelling activities have been instrumental in this respect; for example, in the development of new electrocatalysts for fuel cells membrane electrode assembly (MEA) and in the devel-opment of new materials for solid state storage of

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4

2

11

1

1

3

5

2

2

2

1

1

Total number of projects in FP6 per subarea (€27.6 million)Total number of projects in FP5 per subarea (€21.3 million)

Superconductors

Fuel cells

H2 storage

Photovoltaics

Batteries

Catalysts

Energy distribution

Superconductors

Fuel cellsLighting

Photovoltaics

Batteries

Energy distribution

Energy production

✹ Materials for energy in FP5

Types Number of EC funding contracts RS 11 €18.0 millionTN 2 €3.3 million Grand Total 13 €21.3 million

RS = Research ProjectsTN = Thematic Networks

N O V E L M AT E R I A L S F O R E N E R G Y A P P L I C AT I O N S8

The overall objective of the BIG-POWA project was to pro-vide the R&D base for fabrication of Bi-2223 conductors for eventual incorporation into commercially produced high temperature superconductor (HTS) systems.

In recent years, remarkable progress in the development of materials has led to a continuous increase in the cur-rent capacity of HTS wires and tapes. Compared with other HTS systems, however, Bi-2223 was seen as the most promising candidate. Its easy processing qualities facilitate the industrial fabrication of conductors at liquid nitrogen temperature.

✹ New conductor forms

Over the course of the four-year initiative, the aim was to produce HTS conductors in a square or round shapes that would be more appropriate than the existing flat tapes for the construction of cables, coils and other sys-tem components. The work was to be supported by new 3D modelling and characterisation studies, aiding the design of better geometries and permitting quantification of the conductor benefits.

✹ Project successes

Square wires. Ag-sheathed multifilamentary Bi-2223 square wires were produced in lengths exceeding 200 metres. These exhibited high current density and mark-edly reduced ac losses. New deformation procedures, including two-axial rolling, were developed in order to fabricate wires with special configurations.

New processes. A process for industrial manufacture of encapsulated precursor rods with highly homogeneous density has been established. Loading the rods into silver tubes prior to rolling or drawing produces wires and tapes with greater uniformity of electrical transport prop-erties over long lengths than is possible with conventional powder packing processes.

A technique was also developed for the replacement of silver by an inexpensive alloy, leading to a substantial reduction in the cost of fabrication.

Properties modelled. New anisotropy models of cur-rent density, field distribution, and ac losses have been established.

Coils produced. Secondary winding coils were pro-duced using a cable based on the new conductors, which showed a nominal ac peak current of 200 A.

Process advances improve wires for high temperature superconductors (2000-2003)

The development of superconducting wires and tapes brings improved efficiency, smaller size, and reduced weight for applications in ac power transportation, transformation and storage.

G5RD-CT-2000-00219 – BIG POWA High current Bi-2223 conductors with innovative wire geometry for power applicationsTotal cost: €3 863 631 | EC contribution: €1 199 944 Project duration: March 2000 – May 2003 (39 months)Coordinator: René Flukiger – University of Geneva, Switzerland

Transformer during tests.

Cross sections of

mono-core wire 0201dm17.

A D E C A D E O F E U - F U N D E D R E S E A R C H 9

SCENET-2, the FP5 Thematic Network on Superconduc-tivity, built on the groundwork of two previous European networks: SCENET & SCENET-Power, run jointly up to 2001 under the Esprit and Brite-Euram programmes. The objectives were to continue and extend the links between academic and industrial laboratories interested in super-conductivity and its applications, and to promote the exchange of know-how.

Particular targets were to: achieve rapid commercialisation of products; • study new superconducting materials; • develop and apply advanced nanotechnologies to HTS; • create an advanced education and training program. •

✹ Special working groups

Six working groups were created to promote pilot projects and compile specific road maps, respectively covering: ‘Thin films for microelectronics’; ‘Materials for power applications and new materials’; ‘High current superconductors for applications’; ‘Processing of coated conductors’; ‘Superconducting electronics’; and ‘Energy-related power systems’. A shared aim was to master materials and processing on a nanometre scale.

To encourage the dissemination of information, a com-mon education and training program organised advanced schools and exchange visits, while newsletters and web pages formed an active channel of communication.


World recognition. SCENET-2 acquired a truly European scale, and was well recognised worldwide. By its close, the network comprised 87 nodes, of which 24 were industrial, distributed over 22 countries. It became a very powerful agency for bringing together researchers and industries, and for setting an agreed strategy for future R&D in the multidisciplinary field of HTS. The partners delivered a comprehensive strategic vision document, which has been hailed as a very valuable contribution to the sector.

Workshops and exchanges. Two topical workshops each attracted more than 100 participants, while four annual tutorial schools were organised. In addition 40 exchange visits were awarded to young researchers during the four years of activity, with priority given to international transfers and exchanges between industry and academia.

Dissemination. Twelve newsletters were published and sent to more than 800 recipients worldwide. SCENET-2 also produced a series of video lectures by world experts on superconductivity; these were made available on a set of DVDs.

Work goes on. To maintain the momentum, a similar activity is foreseen under the umbrella of ESAS (the European Society of Applied Superconductivity).

Superconductivity network unites academia and industry (2002-2006)

EU-supported networks have enabled dozens of European academic and industrial laboratories to collaborate for more than a decade on the challenges of high temperature superconductors.

G5RT-CT-2002-05077 – SCENET-2The European Network for SuperconductivityTotal cost: €1 869 600 | EC contribution: €1 866 400Project duration: April 2002 – July 2006 (52 months)Coordinator: Massimo Marezio – Centre National de la Recherche Scientifique, Consortium de Recherches pour l’Émergence de Technologies Avancées (CRETA),Grenoble, France

Fault current limiter

demonstrator based

on /EHTS/ YBCO coated

conductor tapes. Very short

quenching time of 0.01 ms

and short recovery time

of 0.5 ms are achieved.

/EHTS/coated conductors

after gold deposition.

This CC-s are based on

a non-magnetic stainless

steel substrate that

determines their high

mechanical performance

(axial stresses of 650MPa

and 6mm bending radii).


In the early part of the present decade, growing interest in the use of smart cards, identification tags, intelligent packaging and similar thin, flat data-carrying devices highlighted a need for greater information-carrying capacity, lifetime and autonomy. At the time, the batter-ies available in a suitable format to power such products were not rechargeable, and no European company was able to produce them.

✹ Complete system

To address these two needs, the consortium of the SERPHO project proposed to build a rechargeable pho-tovoltaic battery-coupled system with appropriately adapted dimensions and flexibility. The 2D solar battery concept comprised three integrated modules: a thin rechargeable battery and an associated solar cell on a flexible substrate, plus an electronic module for power management. Each module would be specified to deliver a complete product matching the demands of the smart card and hotel security markets in terms of technical and economic performance.

As well as the modules themselves, the aim was to develop roll-to-roll processes and equipment for their manufacture, and to demonstrate the integration of the components into a smart card and smart label.


Modules completed. Within the three-year funded peri-od, a flexible micro-battery fulfilling most of the application requirements was realised. Remaining critical issues were its encapsulation and resistance to moisture, the charge current and the temperature range for operation. A success-ful example of a thin, flexible solar mini-module was also designed and produced, able to charge the mini-battery and fulfilling all other specification requirements.

New knowledge. The partners gathered valuable new knowledge about the UV-stability of transparent thin plastic films.

Despite important progress in the development of the two main modules, further work remains necessary to demonstrate the industrial potential of a fully integrated package for the intended applications.

Sun-rechargeable smart cards a step nearer (2000-2003)

Ultra-thin batteries rechargeable by solar energy could herald new versatility for smart cards and identification tags.

G1RD-CT-2000-00194 – SERPHOSelf rechargeable photovoltaic microbattery coupled system (SERPHO)Total cost: €2 389 927 | EC contribution: €1 254 828 Project duration: September 2000 – August 2003 (36 months)Coordinator: Jean-Paul Terrat – Hydromécanique et Frottement R&D SAS, Andrezieux-Boutheon, France

Flexible ultra-thin

rechargeable lithium

batteries underneath

the PV module.


Large scale industrial deployment of high temperature superconductors is critically dependant on the ability to produce long coated conductors at an affordable price. Prior to the start-up of the SOLSULET project, the best available methods for this were costly physical vapour deposition techniques.

The partners aimed to develop a radically new method of depositing coatings of the widely used HTS compound YBa2Cu3O7 (YBCO) onto long thin tapes using sol-gel technology. The principle is to pass the precursor YBCO compounds through a transitional liquid and colloidal phase – when they are present in aerosol form (the ‘sol’ phase) – to arrive by thermal treatment at a solid ‘gel’ state, an intermediate nanostructured state and finally forming an epitaxial superconducting film on the support.

✹ Underexplored field

Such chemical solution techniques were well established industrial practices for the preparation of coatings in the optical, electro-ceramics and biomaterials sectors, but had hardly been explored for the fabrication of supercon-ducting tapes. Research in this area would pave the way for manufacturing second-generation superconducting tapes that could be used in the construction of new, more efficient power devices.

Specific objectives for SOLSULET were to: develop sol-gel methodology for fabricating YBCO-• based superconducting tapes that could be exploited at 77 K in magnetic fields up to 4-5 T;produce high performance coated conductors – critical • current density (Jc) = 1-3MA/cm2 at 77 K – at low cost, and to demonstrate their suitability in the fabrication of power devices;

derive novel sol-gel and/or metal-organic precursors to • prepare buffer and YBCO layers, together with a coating system for continuous deposition.


Goals met. The objectives of the project were achieved in all critical aspects: the technology was studied in depth, and original solutions made it possible to reach the benchmark performance goals.

Substrates and coatings. Biaxially textured Cu-based metallic substrates were prepared, and extensive investi-gation of electrodeposited coatings was carried out. A large number of metal-organic trifluoroacetate precur-sors were tested for the preparation of oxide buffer layers, and many were used successfully for the preparation of epitaxial buffer layers.

Five architectures. Sol-gel conductors produced with five different architectures showed varying levels of performance.

Interface role determined. The nano-scale characteri-sation of interfaces in the multilayers proved especially important, as they were found to have a very significant relevance in determining the quality of MOD (metal organic deposition) layers grown on them.

Industrial scale-up. Use of the gained knowledge to establish a scale-up strategy for tape fabrication placed industrial partner Nexans in a strong position to face the most advanced global competitors in this field.

Novel sol gel technology for long length superconducting coated tapes (2001-2005)

Sol-gel process developments put Europe at the forefront of a key superconductor technology.

G5RD-CT-2001-00550 – SOLSULETNovel sol gel technology for long length superconducting coated tapesTotal cost: €3 592 404 | EC contribution: €2 000 000Project duration: October 2001 – March 2005 (42 months)Coordinator: Xavier Obradors – CSIC-ICMAB, Universitat Autonoma de Barcelona, Bellaterra, Spain

Superconducting tape

produced by means of

chemical solution deposition

using a reel-to-reel system.

Transmission electron

microscopy image of an

superconducting layer of

YBa2Cu3O7 obtained by

means of chemical solution

deposition on a single crystal

substrate of LaAlO3 (LAO).


In most industrialised countries, artificial lighting accounts for a large, and until recently steadily increasing, share of the overall electricity consumption. Growing environmental concerns have brought the realisation that replacing tra-ditional incandescent and fluorescent light bulbs by more efficient lighting systems could bring huge energy savings – up to 7 billion kWh/year in Europe, corresponding to a 4.5 million tonne reduction in CO2 emission.

The role of the STARELIGHT project in tackling this issue was to develop alumina ceramics with high mechanical strength and transparency, for use as durable, corrosion-resistant lamp envelopes and windows. As well as solving problems in pre-existing metal halide lamps, thus ena-bling them to replace energy-wasting halogen lamps on a greater scale, the improved material would also lead to new uses – e.g. as scratch-resistant replacements for sapphire windows in bar-code scanners.

✹ Focus on high purity

To produce the desired characteristics, research was required to focus on the development of high-purity alu-mina ceramics with greatly reduced grain size narrowly distributed around the 100 nm level. Targeted property enhancements were an increase in mechanical strength from around 300 MPa to 700 MPa, high transparency compared with former translucent or opaque grades, and higher resistance to corrosion by metal halides.

As the optical, mechanical and chemical properties of a ceramic envelope are strongly influenced by the shape as well as the microstructure of the ceramics used, a suit-able shaping method and sintering technique to produce complex hollow forms was also needed.


Ultra-fine grained alumina. Better understanding of the γ to δ to α alumina phase transformations, and of the annealing parameters to minimise α-alumina coalescence, made it possible to obtain high purity α-alumina powder with ultra-fine sub-micrometre grain size.

Processes developed. Slip- and gel-casting processes were developed, to prepare alumina having an average grain size between 0.4 and 0.6 μm and a residual poros-ity below 0.05 %. The transparency, as quantified by real in-line transmission, was around 60-65 %.

Lamps tested. Semi-transparent (due to residual poros-ity) and transparent (no residual porosity) 20W, 70W and 400W envelopes (undoped and doped with magnesia) were produced by slip- and gel-casting. Burners made from these showed efficacies up to 96 lumen/Watt, with a colour rendering index (CRI) up to 93. Although trans-parency degraded over time, partly due to grain growth, it was expected that the use of dopes developed in the project would bring significant improvements.

Tough transparent alumina ceramics lighten energy drain (2000-2003)

Efficient metal halide lamps incorporating highly transparent alumina ceramic envelopes could cut European CO2 emissions by up to 4.5 million tonnes/year.

G5RD-CT-1999-00088 – STARELIGHTSuperstrong transparent alumina ceramics for energy-efficient lightingTotal cost: €3 799 869 | EC contribution: €1 899 935 Project duration: January 2000 – April 2003 (40 months)Coordinator: Michel Van Bruggen – Philips Electronics Netherland B.V., Eindhoven, the Netherlands

Example of translucent polycrystalline alumina tube for ceramic gas discharge

metal halide lamps.

Scanning electron

microscope picture

of polycrystalline

alumina ceramic

microstructure.

✹ Materials for Energy in FP6

Types Number of EC funding contracts SSA 1 €0.5 millionSTREP 15 €27.1 million Grand Total 16 €27.6 million

SSA = Specific Support ActionsSTREP = Specific Targeted Research Projects


Proton exchange membrane (PEM) fuel cell technology has recently received increased attention as an efficient and environment-friendly means of power generation, with great potential for market penetration in both sta-tionary and mobile applications. Major challenges facing the development of efficient high temperature PEM fuel cells are the design, construction and testing of new components to cut cost by simplifying system manufac-turing and operation. This demands the integration and combination of theoretical calculations and several physicochemical methods, as well as engineering and technical substantiation.

✹ Wide-ranging development

APOLLON-B, a follow-up to the FP5 project APOLLON, is aiming specifically to:

develop new materials for high-temperature PEMFCs • functioning at temperatures 130-200 °C;optimise and synthesise novel high temperature poly-• mer electrolyte membranes;develop electrodes and non-noble electrocatalysts for • acid- and base-doped PEMs (the concept of base-doped PEMs allows for the proposal of a variety of alternative electrocatalytic materials as cathodic electrodes).


Novel polymers. During the first eighteen months, novel polymers for H3PO4-imbibed systems, comprising aromatic polyethers with pyridine units in their main structures, were synthesised and evaluated. New aromatic polyethers having one or two imidazole groups in the main chain have been characterised, showing increased thermal and oxidative stability. Polymers with side phos-phate groups have been synthesised in combination with aromatic difluorides and a pyridine-bearing aromatic diol for the preparation of acid-based composite materials.

Membranes prepared. Four samples of nanocomposite sol-gel membranes containing differing compositions of heteropolyacids were prepared with thickness between 30 and 150 μm, and shown to exhibit high conductivity at temperatures up to 140 °C.

New catalysts synthesised. A number of non-Pt elec-trocatalysts have been modelled and synthesised. Several Density Functional Theory (DFT) calculations have been carried out on the oxygen reduction reaction (ORR) in LaMO3 oxide perovskites.

New compositions based on La-perovskites were synthe-sised by combustion. A series of Fe-containing carbon aerogels and xerogels have been prepared by applying the pyrolysis method to produce FeNx-C structures. Car-bon nanotubes have also been found to be active and promising materials for ORR.

Catalyst supports produced. Titanium and iron nitrides prepared from nanocrystalline TiO2 and Fe2O3, respectively by precipitation and combustion methods, have been optimised for use as conductive catalyst supports.

High temperature performance. Measurements on Fe-C electrocatalysts prepared by pyrolysis of organic resins have demonstrated good ORR activity in the temperature range of 140-160 °C in commercial membrane electrode assemblies (MEAs). An improvement of the membrane properties led to an increase in the operating temperature to as much as 200 °C, with good performance under H2/air.

Batch production. A mini-pilot plant has made it pos-sible to synthesise the monomers/polymers in large batches, and to avoid time-consuming and low-yield synthetic steps.

First fuel cell tests. Tests were conducted on conven-tional MEAs and catalyst systems. A new polymer from partner Advent revealed exceptional continuous operating stability, with no decay in performance for over 2,000 hours at 180 °C under H2/air feed.

New polymer electrolytes and non-Pt catalysts extend PEM fuel cell performance (2006-2009)

Cost-cutting fuel cell materials pave the way for increased stationary and mobile application.

NMP3-CT-2006-33228 – APOLLON-BPolymer electrolytes and non noble metal electrocatalysts for high temperature PEM fuel cellsTotal cost: €2 899 701 | EC contribution: €1 800 000Project duration: October 2006 – September 2009 (36 months)Coordinator: Stylianos Neophytides – Foundation of Research and Technology HellasInstitute of Chemical Engineering and High Temperature Processes, Heraklion, Greece

High temperature polymer

electrolyte membrane.


Reducing the cost of catalyst systems is one of the ways in which fuel cells can be brought closer to full commer-cialisation. Currently, pure platinum (for pure H2 fuel) or 50:50 platinum/ruthenium alloy (for reformate gas, used where pure H2 is not available) supported nanoparticle catalysts are used for the hydrogen oxidation reaction at the anode of PEM fuel-cells. Their replacement by cheap-er non-noble alternatives would bring valuable savings. Currently, for fuel cell-powered vehicles, the platinum catalyst alone has a comparable cost to an entire petrol combustion engine.

The FCANODE project has set up a novel route involving a multi-disciplinary approach, covering the full range from theoretical design through to the final operating membrane electrode assembly, to find non-noble metal based systems. Its goal is to achieve a significant reduction in noble metal content – or, ideally, its total elimination. Modelling exercises and combinatorial screening of new materials have been conducted in an initial search for potential candidates suitable for use with both pure hydrogen and reformate gas.

✹ Realistic competitor to platinum

The resultant systems must show sufficiently high density of hydrogen oxidation to make them a realistic com-petitors to current platinum-based catalysts, while remaining stable in the humidified fuel cell environment

at potentials of up to +400 mV, and exhibiting the neces-sary tolerance to CO and CO2. Large-scale production of the newly developed carbon-supported nanoparticles must be possible by practical industrial methods – and in addition they should be suitable for use at higher tem-peratures than the current PEMFC operating range, since the focus is now on higher temperature membranes for increased performance.


Preliminary ‘library’ of potential novel materials. Density Functional Theory calculations have identified potential catalysts to be applied to the hydrogen oxida-tion reaction (HOR). Combinatorial fast screening has been performed on these potential systems regarding hydrogen oxidation and CO tolerance.

Advanced platinum-based catalyst standards. State-of-the-art platinum-based catalyst standards have been developed; while benchmarking for the adsorption, electrochemical and single-cell testing programmes has been performed.

Novel systems with lower noble metal content. So far, several systems with lower noble metal content and consequently lower cost have been developed. Further-more, a number of entirely non-noble systems are currently being investigated, some of which have already shown interesting properties.

Non-noble catalysts cut fuel cell costs (2007-2010)

The cost of noble-metal catalyst systems for proton exchange membrane fuel cells (PEMFC) is driving research to find less expensive non-noble alternatives.

NMP-STREP-32175 – FCANODENon-noble catalysts for proton exchange membrane fuel cell anodesTotal cost: €1 951 857 | EC contribution: €1 492 866Project duration: February 2007 – January 2010 (36 months)Coordinator: Ib Chorkendorff – Technical University of Denmark, Department of Physics, Lyngby, Denmark

Image of a catalyst nanoparticle

by high-resolution transmission

electron microscopy.

Image of catalyst nanoparticles

on a new support material

by transmission electron microscopy.


In recent years, thin-film science has grown into a major global research field, following recognition that the prop-erties of thin surface layers differ greatly from those of the same materials in bulk. Promising areas for exploiting these phenomena are in microbatteries, micro-superca-pacitors and electrochromic devices such as smart windows or displays. Here, the challenge lies in the development of solid electrolytes in the form of glasses and crystallised materials – which, in thin-film form, provide new physical properties such as very high ionic conductivity together with very low electronic conductivity, as well as increased chemical and mechanical stability.

In the HI-CONDELEC project, the central area of interest is to develop electrolytes with a high conductivity towards lithium ions, for use in the above-mentioned application areas.

✹ Demanding combination

Because thin-film solid electrolytes require rather specific properties that are sometimes difficult to combine, the first objective is to assemble the fundamental knowledge needed to optimise the design of solid lithium-conducting glasses with the appropriate physical and chemical char-acteristics. A multidisciplinary RTD approach combining simulation, theory, experiment, validation and testing has been chosen, in order to maximise the understanding of conductivity and thermo-electro-mechanical interactions in such materials.


Modelling tools. Powerful computational tools for mod-elling materials behaviour, processing and use have been developed, based on and supported by extensive meas-urement of electrical, mechanical, thermal, environmental and optical properties of the films.

New synthesis directions. Following the determination of key factors regarding basic structural-property rela-tionships and the influence of process parameters and conditions, new directions for the synthesis of thin-film electrolytes have been proposed.

Theoretical advances. A novel theory of non-linear conductivity in disordered structures has been derived, as well as an algorithm for the optimisation of mechani-cal parameters such as the stresses and strains of Li-ion thin-film assemblies under an elastic regime.

Properties measured. Several critical aspects (modulus, Poisson´s ratio, thermal conductivity, thermal behaviour, yield, density, deflection, etc.) of glasses for microbattery,micro-ultracapacitor and electrochromic applications have been identified and measured experimentally on deposited films.

Promising performance. Newly developed families of material – including nitrided lithium borate – offer performance at least similar to that of existing materials.

A new key parameter for nitrogen incorporation during the sputtering process was found to be the nitrogen flow rate, adjustment of which enabled the stability of the electrolyte to be increased.

Process innovation. An innovative process to fabricate large-sized targets for thin film electrolyte deposition as well as a target bonding procedure were developed. The latter is subject to a French patent application.

Industry-ready product. The project produced an exploitable LiSiPON-type electrolyte with some improve-ment in conductivity, excellent chemical stability and better thermomechanical stability for microbatteries. Another electrolyte composition should promise for smart windows, but will require considerable effort to reduce film defects.

Thin-film solid electrolytes find optical and energy storage applications (2005-2008)

Theoretical and experimental studies bring solid-state electrolytes closer to commercial exploitation.

NMP3-CT-2005-516975 – HI-CONDELECDesign of highly conductive solid thin film electrolyte for stack integration within optical and energy storage applicationsTotal cost: €2 830 253 | EC contribution: €2 100 000Project duration: April 2005 – March 2008 (36 months)Coordinator: Michel Martin – HEF R&D, Andrezieux-Boutheon, France

Example of calculated Mises

stresses in a microbattery

when heated up due to

thermal cycling load up to

240 °C. Each layer thickness

of the battery is comprised

between 100nm and 3μm.

Total thickness is 5μm.

Atomic configuration of

the optimal LISON cluster

as deduced from ab initio

electronic structure

calculation. Oxygen atoms

are marked in red (large

spheres), sulfur atoms in

yellow (mid-size spheres),

nitrogen atoms in blue

(mid-size spheres), and

Li atoms in cream (small

spheres).


The market for electrical storage batteries is a global battle field, in which European manufacturers are falling behind Far Eastern suppliers. Development of the tech-nology for higher capacity nickel-metal hydride (NiMH) batteries could help to redress this balance by providing more ecologically benign replacements for NiCd types in such high-current-density applications as power tools, hybrid vehicles and small portable devices.

✹ High gains possible

Large gains in the current storage capacity of NiMH bat-teries can be achieved by reducing the size of the active particles from a few hundreds of microns down to the nanometre range – and thus increasing the surface/volume ratio. However, the high surface energy of such extremely small particles makes them extremely flam-mable in contact with air, which is very difficult to manage in production processes.

The consortium of the HYDRONANOPOL project is exploring the application of polymeric nanocoatings as a solution to this problem. This entails studying the behaviour of suitable polymers in terms of their ability to prevent combustion without impairing the ion conduc-tivity of the dispersed nanoparticles. In addition, it requires the development of novel multifunctional hydride storage alloys for the negative electrodes of the batteries. These must also be assessed for electrochemical connection efficiency and stability in the alkaline medium.


Functional system. An early-stage advance was the synthesis of Ormocer® inorganic-organic hybrid polymers in which the organic part provides the necessary passiva-tion and ion conduction properties. Samples were characterised for particle size distribution, structure, shape, composition and density.

Various nickel alloys (H(La, M) Ni5) were nano-encapsu-lated using milling and coating processes, after which the coatings were optically analysed and tested for solu-bility in KOH solution.

Mechanism confirmed. The mechanism of hydrogen absorption/desorption and the influence of the state of charge (SOC) on the hydrogen diffusion were determined.

Test protocol. A standard electrochemical testing pro-tocol allows reliable characterisation of hydride-forming powders prepared in the course of the project.

Optimisation continues. It has been shown that Ormocer® does not affect charge transfer kinetics; nor does it influence double layer capacitance. However, in order to eliminate small losses in the hydrogen storage capacity of milled and coated materials (probably because of electrical insulation of some particles by the polymer), optimisation of the Ormocer® coating is being pursued.

Low energy milling is found to facilitate activation of the materials, but accelerated self-discharging requires further investigation and remedying. Refinement of the small-particle preparation procedure is also being undertaken to compensate for a less-than-expected improvement in the hydrogen diffusion rate for milled samples, compared with unmilled particles.

High capacity nickel-metal hydride batteries could boost European industry (2006-2009)

Polymer-coated hydride storage alloys increase battery capacity while solving production problems.

NMP3-CT-2006-32517 – HYDRONANOPOLAdvancement in storage capability and hydrogen kinetics of hydride storage alloys through nanocoating with multifunctional hybrid polymerTotal cost: €2 228 586 | EC contribution: €1 866 792Project duration: October 2006 – September 2009 (36 months)Coordinator: Martin Krebs – Varta Microbattery GmBH, R&D Nickel Metal Hydride Button Cells, Hanover, Germany

The MH electrode process.

New limited volume electrode

(LVE) for study of metal

hybride materials.


High temperature superconductivity is a key enabling technology for the development of efficient electrical energy management incorporating renewable energy sources, for use in new medical technologies based on magnetic resonance imaging or, in the longer term, in fusion generators. This vision relies on achieving cost-effective conductors with high performance at high temperatures in high magnetic fields.

The goal of mass fabrication of superconducting tapes at low cost can be achieved with innovative chemical solution deposition methodologies, where a multilayered structure is generated on a metallic substrate, leading to new types of tape known as ‘coated conductors’.

The architecture of these conductors needs to be as simple as possible to minimise manufacturing costs, but supercon-ducting layers based on the compound YBa2Cu3O7 must be nanostructured in order to achieve high perform-ance. Currents 100 times higher than with Cu wires can be achieved.

In order to achieve these goals, the HIPERCHEM project focused on four main areas:

advancing the knowledge of the growth of epitaxial • superconducting layers based on two chemical solution

deposition methodologies – metal-organic decomposi-tion and hybrid liquid phase epitaxy;preparing nanostructured interfacial oxide templates, • based on strain-induced self-assembling or track-etched polymer coatings, which can generate a network of artificial defects in the superconducting layer, acting as vortex pinning centres;developing innovative chemical solution processing • methodologies for the preparation of epitaxial super-conducting film nanocomposites ensuring vortex pinning at high film thickness;generating simple coated conductor architectures • integrating the most promising nanostructuration approaches for scaled-up production with excellent specifications.


World-beating nanocomposites. YBa2Cu3O7-BaZrO3 nanocomposite superconducting films produced by chem-ical processing achieved world record performance in terms of vortex pinning efficiency.

Structures compatible with epitaxial growth. Oxide nanostructures were prepared by self-assembling and by track-etched polymer template growth based on chemical solution methods. Both interfacial structures are compatible with the growth of epitaxial superconducting layers.

Rapid growth rates. Superconducting films (above 1 μm), were produced at high growth rates (above 1 nm/s) with high quality epitaxial structure and high critical currents by chemical solution processing methods.

Large-scale manufacture possible. Simplified conductor architectures have been obtained for different types of flexible metallic substrates that enhance the large-scale manufacturability of the coated conductors.

Nanostructured superconductors pave the way to high temperature, high magnetic field applications (2005-2008)

Coated conductors may be the answer to mass fabrication of high temperature superconductors.

NMP4-CT2005-516858 – HIPERCHEM High performance nanostructured coated conductors by chemical processing Total cost: €2 314 350 | EC contribution: €1 700 000Project duration: April 2005 – December 2008 (44 months)Coordinator: Xavier Obradors – ICMAB – Consejo Superior de Investigaciones Científicas, Barcelona, Spain

TEM image of a YBCO/BZO

nanocomposite where

a BZO particle embedded in

the YBCO matrix is observed

together with a high density

of planer defects and a sever

buckling of the CuO2 planes.

Pinning Force, Fp(H), curves of

a nanocomposite film at 65 K

and 77 K, compared with a

standard YBCO-TFA film at

65 K and NbTi wires at 4.2 K.


Prototype MgB2 conductors have already demonstrated the potential of this material for existing and future applications, but there is still considerable scope for per-formance improvements that could be pioneered by innovative European researchers.

A key advantage of MgB2 is its relatively high operating temperature (39 K), reachable with cryogenic cooling methods that are cheaper and more user-friendly than liq-uid He. This lowers cooling cost, simplifies system design and increases safety. Within a decade, MgB2 is expected to be the material of choice in many applications involv-ing medium-range magnetic fields. One of these is medical magnetic resonance imaging, a substantial market in which EU companies have a dominant position.

✹ Breakthrough in energy?

Potentially about ten times less expensive than high tem-perature superconductors, MgB2 could also play a pivotal role in the breakthrough of superconducting technology into the energy domain, where it would offer substantial monetary and ecological advantage.

To keep Europe at the forefront of these developments, the HIPERMAG project is developing a scalable, cost-effec-tive and reproducible processing route for MgB2-based conductors with controlled nano-structure, leading to sig-nificantly enhanced magnetic flux line (vortex) pinning properties and optimised composite micro-structure, while assuring full thermal stability.


Studies of precursor powders and bulk samples provided the know-how needed for optimised powder processing. The excellent properties of carbon-doped nanosized

precursor powders were demonstrated in monofilamen-tary wires with world-record performance in magnetic field.

Process conditions established. The conditions for obtaining higher critical current densities in MgB2 wires were well defined – although further improvements could be achieved through a better powder quality, new addi-tive combinations, a higher density after deformation and increased control over the high temperature reaction.

Powder production options. Scalable, cost-effective and reproducible routes to MgB2 precursor powders have been established. These appear to be highly suitable for producing large powder batches of high quality MgB2 for the fabrication of superconducting wires and tapes.

Design parameters specified. Investigations have shown that, for low ac losses and optimal thermal and mechanical stability, a multifilament conductor should be designed with high electrical and thermal conductivity, barriers to prevent interdiffusion of elements, a strong sheath component to ensure good compaction, and a high thermal expansion coefficient.

Property correlation modelled. Specialised structural and physical analyses of the superconducting wires and tapes have been carried out, leading to a coherent under-standing of the correlation between JC (critical current density) and microstructure.

World first. Applications for MgB2 conductors in several different forms have been realised. Current leads for valves and an ADR (adiabatic demagnetisation refrigera-tion) magnet on the x-ray astronomy satellite Suzaku were made as thin monofilament wires with an Fe/SS composite sheath. Ultra-thin monofilament wires with stainless-steel sheath serve as liquid-hydrogen level sen-sors, and Cu-stabilised multifilament tapes with Ni sheath were used to build the world’s first MgB2-MRI magnet.

MgB2 composite superconductors break new ground (2004-2007)

Early application successes put Europe ahead in low-cost superconductor technology.

NMP3-CT-2004-505724 – HIPERMAGNano- and micro-scale engineering of higher-performance MgB2 composite superconductors for macro-scale applicationsTotal cost: €3 318 076 | EC contribution: €2 499 996Project duration: September 2004 – August 2007 (36 months)Coordinator: Andries den Ouden – University of Twente, Faculty of Science and Technology, Enschede, the Netherlands

Some of the MgB2 composite prototype

wires developed within the HIPERMAG

project.

World-first MgB2-based MRI system,

realised by the European companies

Paramed Medical Systems, ASG

Superconductors and Columbus

Superconductors.


The operating requirements for efficient onboard H2 stor-age in hydrogen-powered vehicles include appropriate thermodynamics, fast kinetics for H2 uptake/release, high storage capacity, effective heat transfer, high gravimetric and volumetric densities, long cycle lifetime, high mechan-ical strength and durability, safety during use and acceptable risk under abnormal conditions.

Current technology, using tanks in which H2 is stored as compressed gas or cryogenic liquid, fall far short of the targets for mobile applications. Solid storage (in metal and complex hydrides, chemical storage materials or nanostructured materials) holds considerable promise for meeting the goals, but fully satisfactory materials have yet to be identified.

The HYCONES project is investigating a radical new form of material: carbon cones (CC), which are fundamentally different from all previously known carbon structures. CCs can be produced economically in industrial quanti-ties via the so-called Kværner carbon black and H2 process, which yields a mix of soot and carbon micro-structures, namely disks and cones.

✹ Room-temperature H2 release

CCs are curved graphite sheets, in which five different conical angles have been observed, in accordance with the occurance of 1-5 pentagons at the tip of the cones (a graphene sheet has zero pentagons while the C60 fullerene curvature is produced by six pentagons). Previ-ous experiments clearly demonstrate H2 release at near ambient temperatures, implying a new form of interaction between carbon and H2 that differs from conventional physi- and chemi-sorption.

This behaviour is explained by computational calcula-tions, which indicate that the special topology of CCs confers unique electronic properties not shared with any other form of activated or nanostructured carbon.

The consortium is pursuing the development, characteri-sation and modelling of this new ‘unexplored’ carbon form in order to provide enhanced understanding of the interaction mechanism between CCs and H2. During the project lifetime, it intends to construct and test a prototype CC-based lab-scale storage system.


Bench-scale production. During the first year, an oper-ational bench-scale CC production unit has been built. Intense testing is still going on to optimise and control the set-up and the conditions of production.

Purification strategies. A large number of purification strategies have been evaluated and purification work will continue, particularly with regard to the selective chemi-cal modification of cones.

Properties characterised. Intense experimental charac-terisation complemented by advanced predictive multiscale (atomistic to mesoscopic) computer simula-tions have verified the unique CC properties (including H2 release at room temperature), and revealed non-dissociative hydrogen sorption.

High capacity derivatives. Moreover, a novel metal doping approach has been considered for CCs. The met-al decorative cone derivatives have shown remarkable hydrogen storage capacity reaching to 3 wt % at room temperature and moderate pressure (20 bar), denoting a performance well above the current state-of-the-art in hydrogen solid storage based on nanostructured materials.

‘New’ carbon for in-car hydrogen storage? (2006-2009)

A recently discovered carbon microstructure shows great promise as the H2 storage medium for future mobile applications.

NMP3-CT-2006-032970 – HYCONESHydrogen storage in carbon conesTotal cost: €2 564 000 | EC contribution: €1 550 000Project duration: November 2006 – October 2009 (36 months)Coordinator: Theodore Steriotis – Institute of Physical Chemistry, National Centre for Scientific Research ‘Demokritos’, 15310 Aghia Paraskevi-Attikis, Greece

Degenerate E1 HOMO orbitals

of the conic anion.

Coulomb potential

of the anion.


Metal matrix composites (MMCs) form an interesting new class of materials, in which metal bulk is reinforced with other materials to improve mechanical, electrical or thermal properties. MMC aluminium wires known as EFRA (endless fibre-reinforced aluminium) would have major advantages in many specialised electricity trans-port applications that demand high strength, low weight and low thermal expansion.

For such purposes, carbon fibre offers far better proper-ties than the ceramics often used to reinforce EFRA wires. Carbon/aluminium composite wire exhibits all of the desirable properties, as well as high conductivity. How-ever, extreme processing difficulties have hindered its commercial introduction.

The purpose of the MACE project was to resolve these problems with a new conductor design that could help Europe to meet growing electricity demand with reduced environmental impact.

✹ New techniques required

A basic requirement was to overcome the interfacial problems between carbon and molten aluminium, which had hitherto prevented continuous production of the wire. Also essential was the development of advanced conductor stranding techniques, to deliver a product of high reliability and capacity, with high mechanical strength, low losses, and low sag over long spans. This would facilitate expansion of the overhead electricity net-work, with fewer new lines and lower towers.

A second thread of the research was to promote exploitation of the composite in a wide range of other applications, such as robotics and aerospace.


Process optimised. A plasma-flux-assisted infiltration method that satisfactorily achieves the required wetting of carbon fibre by molten aluminium has been devised and refined, yielding considerable understanding of the process. Wires with the required combination of low porosity, high fibre fraction, high tensile strength and modulus were satisfactory produced.

Plasma pre-treatment. Initial trials to establish suitable conditions for the production of coatings with accepta-ble physical properties were carried out on carbon discs, in order to allow convenient x-ray photoelectron spectro-scopic analysis of the deposited material. The mechanical performance of composites incorporating plasma-treated fibres was found to be the best criterion for accurate assessment of the benefits of the process. Several long lengths of treated fibre were processed into composite wire for mechanical testing.

Control of molten aluminium. Different methods have been used to control molten aluminium, in particular the use of various combinations of permanent magnets or electromagnets, with application of either ac or dc current. One additional passive system, using a multi-layer coil and a ferrite core, proved to generate the highest magnetic field per unit area.

Wire rounding and process integration. An experi-mental version of an integrated rig permitted the production of small-diameter wires with a circular-cross section. Continuous lengths of up 350 m were achieved.

Quality assessment. New techniques for quality assess-ment of the specialised materials have been established, including practical on-line void monitoring. Mechanical measurements showed that the EFRA wire achieved the required properties.

Computer modelling confirmed the potential of EFRA wire as an advanced conductor core material. A crucial area for improvement was to find a means of ensuring consistent roundness without generating breakages.

Al-C composite cables lower electricity transport costs (2004-2006)

Solving composite conductor production problems offers the prospect of a simpler, cheaper power infrastructure.

NMP3-CT-2003-505463 – MACEMultifunctional advanced carbon aluminium composite for electricity transportTotal cost: €2 908 065 | EC contribution: €1 049 896Project duration: January 2004 – December 2006 (36 months)Coordinator: Neil Philip Wright – C-Tech Innovation Limited, Chester, United Kingdom

Stranding of EFRA wire –

Lumpi-Berndorf.

EFRA wire section –

ARC/Armines.


Intermediate-temperature solid oxide fuel cells (SOFC) operating at around 600-700 °C would compete with existing systems running at much higher temperatures (typically 900-1 000 °C). To achieve this temperature tar-get there is a need to develop new solid-state electrolytes with appropriate ionic conductivity.

The MATSILC project is exploring the use of electrolytes based on apatite-type silicates, some of which are uniquely suited to the transport of interstitial oxygen ions. By changing the acid-basic nature of the electrolyte phase, it is possible to enhance the electrocatalytic performance of related ceramic/metallic composite (cermet) anodes, and to minimise critical limitations of sulphur contamination and carbon deposition in contact with hydrocarbon fuels. In addition, silicates have the potential to overcome some degradation problems associated with SOFCs based on alternative electrolytes, such as yttria-stabilized zirconia (YSZ) or gadolinia-doped ceria (CGO) with silica.

✹ Total fuel cell concept

The aim is to develop a complete SOFC concept, includ-ing materials and processing technologies for the core components, as well as compatible electrodes. The latter aspect entails devising synthetic procedures for the fabrication of nano-architectured micro-/meso-porous electrodes of catalyst-doped oxide matrix by a templat-ing approach, plus investigation of the influence of doping and surface nanoengineering on their working parameters.

A novel fuel cell design incorporating catalytic inter layers and diffusion-blocking nanolayers along grain boundaries will be constructed and tested against the LSM/YSZ/Ni-Cermet system at temperatures in the region of 700 °C.


Materials prepared. During the first year, apatite-type electrolyte materials with various dopants and dopant levels were developed and prepared by several methods. Fe-containing apatites sintered to density values of 97 %, but powders containing Al proved to require longer dwell times to approach full density values.

Superior conductivity demonstrated. The conductiv-ity of new electrolytes was tested and compared with that of similar apatites reported in the literature. One of the formulations showed higher conductivity than state-of-the-art YSZ, particularly at 600-750 °C.

Fast, efficient processing. Powders prepared by a sol-gel technique reduced the time required for sintering compared with those prepared by solid-state synthesis. Besides the well known Pecchini method, mechanochemi-cal activation has been used to prepare active powders for sintering. The sintering temperature of the synthesised apatites was reduced by applying different preparation routes, especially with mechanochemical activation.

Preparation of dense electrolytes (95 % of the theoreti-cal density) at temperatures as low as 1 450-1 500 °C has been achieved. Increasing the sintering temperature to 1 600 °C leads to dense pellets with more than 99 % of the theoretical density.

Cell studies in progress. Investigations of the reactivity of cell materials are in progress, while preparation of cathode layers on electrolyte substrates has been per-formed by means of electrophoretic deposition.

Electrophoretic characterisation of electrolyte powder suspensions has been done, and powder preparation procedures are being scaled up.

Novel materials for silicate-based fuel cells (2006-2009)

New solid-state electrolytes could form the basis of more economical intermediate-temperature fuel cells.

NMP3-CT-2006-33410 – MATSILCNovel materials for silicate-based fuel cellsTotal cost: €2 092 000 | EC contribution: €1 849 869Project duration: December 2006 – November 2009 (36 months)Coordinator: Christos Argirusis – Technische Universität Clausthal, Institut für Metallurgie, Clausthal-Zellerfeld, Germany

SEM micrographs of the

microstructure of the

La2Ni0.5Cu0.5O4+d cathode:

A) powder

B) as deposited electrode

C) and D) electrode

after electrochemical

measuremenrs.

A

B

C

D


High temperature solid oxide fuel cells (HTSOFC) are made costly by the need to use expensive ceramic mate-rials; whereas low temperature fuel cells (LTFC) based on polymer electrolytes suffer the drawback of strong dependence on easily-poisoned catalysts. So-called inter-mediate temperature fuel cells (ITFC) are expected to offer a reasonable compromise, but cell components with the required performance are far from well-defined.

Electrolyte conductivity of 0.1 S/cm is a basic essential, which current single-phase SOFC materials cannot deliver at temperatures below 600 °C. Lowering the operating temperature of SOFCs will only be possible if new, improved materials are developed. Suitable nanocom-posites are believed to offer the potential to reduce the working temperature of conventional SOFCs from 1 000 °C to 300 °C, giving rise to what will be low-cost, readily marketable systems.

✹ East-West collaboration

The main impetus of the NANOCOFC programme is to develop nanocomposites by constructing interfaces that may act as ion conducting ‘highways’ in two-phase materials, and to investigate super-ionic conduction and dual H+/O2 conductors. To assemble a critical mass of human and material resources behind the necessary research, it is extending the Sino-Swedish IT/LTSOFC (Intermediate and Low Temperature Solid Oxide Fuel Cell) network to embrace cooperation between prominent research institutions in the EU, Turkey and China.

Access to the combined facilities of the partners, plus a wide range of disseminational and educational activities, is already enhancing research capabilities in nanotechno-logy, multifunctional materials, applications and next generation fuel cell technology.


Cooperation underway. A number of joint industrial efforts were launched in network’s first year. The con-sortium was also extended to include more associate partners.

Spreading information. An Internet office and website (http://nanocofc.hrbeu.edu.cn/) have been created. Pub-lication of periodic newsletters has begun, and the first seminars and workshops have been organised. Joint PhD, postdoc and scientist training programmes are in place.

Research achievements. Successes to date from the research cooperation include:

Swedish patent on ‘Development on extremely low • cost electrolyte material: industrial grade rare-earth mixed carbonates used successfully in LTSOFCs’; two-phase nanocomposites providing the oxygen and • proton conductivity of 0.1 Scm-1 at 300 °C (comparable to YSZ conductivity at 1 000 °C);material conductivity, fuel cell power outputs and sys-• tem efficiency enhanced by combining or integrating multi-ion functions, typically, H+ and O2

- conduction.

Performance breakthrough. The NANOCOFC method-ology has delivered sensational performance of 1.1 W/cm2 at 500ºC, together with new anode and cathode mate-rials, co-developments of which extend high performance down to temperatures as low as 300 ºC, without the need to use noble metal catalysts.

EU-Turkey-China cooperation advances intermediate temperature fuel cell technology (2006-2009)

International networking is bringing early dividends in the search for reliable low-cost fuel cells.

NMP3-SSA-2003-32308 – NANOCOFCEnhancement of research capabilities on multi-functional nanocomposites for advanced fuel cell technology through EU-Turkish-China cooperationTotal cost: €891 300 | EC contribution: €500 000Project duration: November 2006 – October 2009 (36 months)Coordinator: Bin Zhu – Kungliga Tekniska Högskolan, Department of Chemical Engineering and Technology, Stockholm, Sweden

TEM micrograpghs of the

as-prepared poly-crystalline

SDC nanowires, the inset is

the SAED pattern of an

individual nanowire.

SEM image of the as-

prepared Samarium doped

ceria (SDC) nanowires with

a high aspect ratio, which are

100~200 nm in diameter and

up to 10 μm in length.

SEM for SDC-carbonate

nanocomposites showing

uniformly distributed

composite particle size.


Nanocrystalline silicon (nc-Si) is a promising candidate for second generation solar cells and light-emitting devices, although full demonstration of its potential as a compet-itor to crystalline silicon (c-Si) solar cells is still under debate. Main open questions are whether an adequate deposition rate for industrial applications is possible and which of the available plasma-enhanced chemical vapour deposition (PECVD) techniques is most appropriate.

The NANOPHOTO project has developed and modelled a low-energy variant of plasma deposition (LEPECVD) as a new nc-Si growth process on suitable substrates for both photovoltaic and optoelectronic applications. Calcu-lations also extend to the simulation of nc-Si grain growth in an amorphous silicon (a-Si) matrix, to determine the best a-Si/nc-Si ratio and the elastic/plastic effects of embedding the nanocrystals.

Theoretical studies based on systematic measurement of the optoelectronic properties of nc-Si are providing insight into the role of process parameters on the local nanostructural aspects and associated physical properties.

Practical application knowledge has been acquired with the construction of a prototype device, which is essen-tially a solar cell, but can also work as a light-emitting device under external electrical excitation.


High growth rate. An LEPECVD furnace set up to opti-mise the nc-Si deposition process has demonstrated high rates of growth for high quality and homogeneous nc-Si films on substrates including glass and conductive glasses.

Process described. 2D and 3D models of the processes occurring in the reactor chamber were obtained, backed by measurements of the plasma composition and ion distribution. Full modelling of the reactions occurring at the gas/solid phase during nc-Si film deposition was also accomplished.

Properties characterised. Preliminary and conclusive electrical, optical and structural characterisation were carried out on doped and undoped nc-Si films deposited under a range of conditions.

Inlet gas affects structure. The effects of changes in the composition/flow rate of the furnace inlet gas mixture on film microstructure have successfully been determined. The mixture consists of silane, hydrogen and argon for undoped film deposition, while diborane and phosphine are added for doped films. It has been shown that crystallinity decreases with the dilution ratio of the dopants, and that this behaviour is common to films deposited over the temperature range 220-350 °C.

Divergent requirements. It was found that film homo-geneity, which is essential for solar cells, could actually be a limitation to good light-emitting devices. The nature of optical emissions and the possible presence of quantum confinement effects in materials consisting of nanocrys-talline and amorphous areas have been studied.

Si nanofilm process potential for photovoltaics and optoelectronics (2005-2008)

Thorough investigation confirms the promise of a new kind of process for chemical vapour deposition of Si nanofilms structured for solar cells and light-emitters.

NMP3-CT-2003-013944 – NANOPHOTONanocrystalline silicon films for photovoltaic and optoelectronic applicationsTotal cost: €1 968 655 | EC contribution: €1 699 954Project duration: June 2005 – November 2008 (42 months)Coordinator: Sergio Pizzini – University of Milano-Bicocca, Department of Materials Science, Milan, Italy

Composite TEM image

showing the columnar

growth of nc silicon

(on the extreme left the

substrate/nc-Si film interface).

Schematic drawing of

the LEPECVD system

with the main system

components.


Nano-particulate electrode materials, electrode materials modified by surface layers in the nm range (core-shell materials) and nano-structured composite electrodes and electrolytes all offer opportunities to overcome the limi-tations of current lithium polymer microbatteries. They reduce transport limitations within the materials, and decrease the over-potential required for intercalation/deintercalation reactions of the Li ions.

The NANOPOLIBAT project is engaged in the design and fine tuning of active materials, binders and separators for a very long life, high-rating rechargeable polymer micro-battery for low voltage applications. Intelligent composite electrodes require a well-designed spatial distribution of the various components, which cannot be achieved by simple mixing. The alternative being explored is the self-assembly of nano-particles on preconditioned surfaces.

✹ Demonstrator for tomorrow’s technologies

An advanced nano-ceramic/organic hybrid polymer (Ormocer®) combined with a promising new conductive salt is being used to produce a separator with high lithium-ion conductivity and adequate electrochemical stability. The hybrid is also applied as a binder for electrode mate-rials. The goal is to build up a battery with the newly developed nano-materials, in order to deliver a final dem-onstrator proving the concept for future technologies such solar energy storage and the powering of smart cards.


High-capacity blends. Nano-silicon/graphite blends that show higher capacities than standard graphite have been developed. In the opening year, a first sample con-taining 10 % nano-Si was synthesised, showing a specific capacity of 600 mAh/g.

Higher capacity, safer electrodes. A study of the prop-erties of Li-titanate (Li4Ti5O12) as a cathode material is being carried out. This shows excellent capacity retention at various charge/discharge rates and temperatures, and is safer than other common electrode materials. In the form of nano-tubes and nano-fibres, it is characterised by extremely fast Li-ion intercalation/deintercalation.

Components tested. The conductivity of a polymer-salt complex electrolyte was measured at 10-6 Scm-1 at 25 °C and 6 x10-3 Scm-1 at 80 °C. Tests were undertaken to measure the effect of plasticisation by a non-volatile ionic liquid on conductivity and battery performance. Samples of the ionic liquid were also made available to partners for testing with the Li-titanate cathode material, nano-Si/C anode and Ormocer®-based binder.

A first generation solvent-free polymer electrolyte gave conductivity of around 10-5 Ohm-1 cm-1.

Nanocomponents integrated in rechargeable microbatteries (2006-2009)

Nanomaterial combinations could provide the performance required for miniaturised batteries to store solar energy and power smart cards.

NMP3-CT-2003-33195 – NANOPOLIBATNanotechnology for advanced rechargeable polymer lithium batteriesTotal cost: €2 228 586 | EC contribution: €1 793 696Project duration: October 2006 – September 2009 (36 months)Coordinator: Martin Krebs – Varta Microbattery GmbH, R&D Poliflex, Hannover, Germany

SEM image of copper

nano wires – magnification

10 000 X and 50 000 X.


A new approach to industrial production could emerge from the development of a polymer-electrolyte fuel cell reactor technology that synthesises industrial chemicals by oxidation/reduction processes, while simultaneously pro-ducing usable energy. One interesting prospect is that a significant increase in value would be added to chemical streams from the petrochemical industry by harnessing the available energy (Gibbs free energy) of electrosynthetic reac-tions to insert oxygen into alkenes (ethylene, propylene, etc.) of low molecular weight. Moreover, another benefit is that the technology is inherently clean.

For the NENA project, the two applications selected for study were oxygen reduction to yield hydrogen peroxide, the mechanism of which is already well understood, and epoxidation reaction. This required the development of advanced structured materials and components for a reactor capable of co-generating chemicals and energy.

✹ From theory to synthesis

The research sought to establish links between surface structure and reactivity, employing theoretical and compu-tational techniques to predict the course of reactions at the surface of nanosized clusters. Quantum chemical cal-culations were also used to provide guidelines for the selection of potential nanoparticle electrocatalysts. Suitable candidates were then synthesised, followed by reactivity measurements and assessment of the use of redox-catalytic

cycles. The work provided greater understanding of the relationship between crystal orientation of nanocrystalline materials and their electrochemical reactivity.

Novel anionic exchange materials were also synthesised, based both on polymers and on mesoscopic particulate ion exchangers for use in fuel cells. These were then characterised and modelled to predict their behaviour in the membrane electrode assemblies used to separate cell electrodes.


Catalysts selected. Two materials, respectively poly-meric and composite, were shown to be suitable as catalysts for H2O2 production in acidic and basic cathode environments.

High peroxide yield. A new theoretical approach to the analysis of electron and proton transfer mechanisms was also developed. Fuel cells operating with electrocatalysts developed during the project are giving high yields of peroxide.

A prototype that could allow future deployment of decen-tralised production modules for the co-generation of H2O2 and energy in a PEMFC was demonstrated, confirming the feasibility of such dual-purpose reactors.

Nanostructured fuel cells as industrial chemicals producers (2004-2007)

A clean technology using fuel cell reactors for simultaneous production of usable chemicals and energy could bring radical change in important sectors of industrial processing.

NMP3-CT-2004-505906 – NENANanostructures for energy and chemicals productionTotal cost: €2 011 563 | EC contribution: €1 777 496Project duration: July 2004 – June 2007 (36 months)Coordinator: Kyösti Kontturi – Helsinki University of Technology, Department of Chemical Technology/Laboratory of Physical Chemistry and Electrochemistry; Espoo Suomi, Finland

Hydrogen peroxide rig.

Hydrogen peroxide test cell.

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European Commission

Novel materials for energy applications – A decade of EU-funded research

Luxembourg: Office for Official Publications of the European Communities

2008 – 28 pp. – 21 x 29.7 cm

Acknowledgements

The authors express their thanks for the contributions of the coordinators and the programe officers of the projects.Furthermore, the collaboration of Mike Parry, Michael Horgan, Charlotte Andersdotter and Bingen Urquijo Garay is acknowledged.

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Novel materials for energy applications - European …ec.europa.eu/research/industrial_technologies/pdf/novel-materials... · EU funding on Novel materials for energy applications