www.cea.frwww.cea.fr

Etienne BOUYER

Burgos, 25th June 2015

CRM a challenge for R&D and Innovation

29 JUIN 2015 | PAGE 2

29 JUIN 2015

CEA General Direction

Tech

no

log

yS

cien

ce

DefenceSecurity

MilitaryApplications

Division

NuclearEnergy

NuclearEnergyDivision

TechnologicalResearch

TechnologicalResearch Division

DAM goal: strategic independency of France

DEN goal: energetic independency of France

DRT goal: contribute to the economical competitivity of France

Basic Research

Siences of Matter Division

Life Science Division

Fench Atomic & Alternative Energy Commission at a glance

> 2050Control the environmental impact

climate

Strategic raw materials resources

Technical and economic studies

CEA acting to prepare energy transition towards a carbon-free energy mix

Efficency / sobrietyAvoidedEnergy use

Basic Research for Energy

Technologies by 2020-2030

Fusion

Generation IV

> 2040- 2050

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EU – Nov. 2013« Report on CRM »

Genesis

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Warning signals : increasing price tension and multiplication of report/studiesidentifying and about (non energetic) « critical materials »

EU – June 2010« Report on CRM » EU JRC –2011

« Critical Metals in Strategic Energy Tech. »

DoE – Dec 2010« Critical materials strategy »

Cou

rt te

rme

0-5

ans

Moy

en te

rme

5-15

ans

BGS – Sept 2012« Risk list 2012 »Rapport OPECST – Août 2011

Rapport Assemblée Nationale – Nov 2011

Finding : the new technologies for energy are more particularlyimpacted since they need CRM

Two objectives:Anticipate tensions on the avaibility of CRM for the actual need andfor the technologies under developmentSecure CRM supply for our key technologies thanks to research &innovation

EU – June 2015« Strengthening the

European RE supply chain »

Establish a SoA of the uses of CRM in our technologicaldevelopment and quantify our strenghts and weaknesses

Identify the area of expertise where CEA can act through its R&Dmeans:

(Bio-)Chemistry - synthesisMaterial science & engineering (processing, modelling,…)Process engineering, Chemical engineering (e.g.pyro/hydro/iono-metallurgy)Separative chemistryDigital intelligent systems (e.g. sensors, signal processing)Ecodesign (Life Cycle Analysis,…)…

Act as support for industry on the full CRM value chain in proposingadvanced solutions through research capabilities & know how ofCEA

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Strategy

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CRM in the low carbon energy technologies (focus on non energetic materials)

Nuclear

Gen IIIFusion

Permanent

magnets

Wind , EV

PV Si PV thin

filmsBatt. Li-ion PEMFC H2 storage LED Thermoelectricity

Renewable EnergiesNuclear Other

Ag

In

Nb

W

Nb

REE:

Nd

Pr

Dy

Tb

Sm

Ag

In

In

Ga

Te

(Li)

Co

PGM

Co

Mg REE:

Y

Ga

Ge

Mg

Primary resource

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Primary ressources are there but their extraction beco me more difficult (deposit of lower quality)…

… with environmental consequences that could be locally imp ortant

Each ton of RE produced in Baotou (China) is associatedwith:

• production of: � 8,5 kg of fluor � 13 kg of dust

• generation of 9 600 to 12 000 m3 acid water • one ton of (low) radioactive waste

55 ton ore 1 ton copper 125 ton ore 1 ton copper

« …the Minister wishes that a demonstration project for responsiblemining would be implemented. »

« …the Minister wishes that a demonstration project for responsiblemining would be implemented. »

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Towards a re opening of mine in France ?

Symposium – Strategic metals: challenges & solutions for industry16/10/2012, Paris

Mining code has to be dusted off (Imperial Law, April 21st 1810) to:1. Modernize the French mining model, bringing it near to

the environmental code and to the ICPE-17 regulation,2. Improve public participation, 3. Develop working conditions, public safety and

environmental protection, 4. Reduce the time of the preliminary procedure.

Deep ocean ?

-71% of the planet surface (60 % > 2000 m)

- under explored , not yet exploited

- potential ressources for several metals (Cu, Zn, Pb, Co, Ni, and also Pt, In, Ge, Au, Ag, REE…)

- deposit mineralization on seabed

- country strategy in response to current priority issues(scientific, environmental, legal, geopolitical)

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- Scientific expertise (BRGM, IFREMER & universities)- Underwater exploration technologies (IFREMER)- Industrial technologies deep oil (Technip)- Mining operators (Areva, Eramet)- 2nd worldwide EEZ (exclusive economic zone) 11 035 000 km2- Commitment for a national strategy

French assets for offshore mineral ressources

•Pilot zone: Wallis et Futuna (Pacific Ocean)

•French permit in international waters

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Secondary resources: urban mine

29 JUIN 2015 | PAGE 11

Legal & regulation aspects

« Extended Responsability to Producer » principleREACHIncrease the ratio recycled/landfilled or throughenergy recovery

Today, only 5% of mobile phone sold inEurope are recycled

WEEE

Our waste contain the raw materials of tomorrow

A large potential for recycling

29 JUIN 2015 | PAGE 12

Recycling rate of 60 metals

UNEP International Resource Panel (2011)Recycling Rates of Metal, a Status Report

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R&D-technical strategies with different timescale

1/Materials- Minimization- Replacement (partial or total)

3/Operation conditions- Operating point optimization- Increasing lifetime

2/Processes saving matter- Direct fabrication (additive techniques) - Coating technologies- Production scrap recycling

4/End of life treatments- Dismantling/crushing- Physical separation(smart/fast/efficient sorting)- Chemical separation- Qualification of secondary RM vs virgin RM 5/Mineral treatments

- Separation- Purification

ReduceReplaceRecycleReinvent

29 JUIN 2015 | PAGE 14

educe

eplace

ecycle/ euse

Pt reduction(PEMFC)

RE reduction

Batteries recycling

Criticalityassessment

of rawmaterials in NTE & NTIC

PV recycling

Project typology

Catalystbio-inspiredchemistry

Pt recycling(PEMFC)

WEEERecycling

(RE)

Ashesrecycling

Nanomaterialsrecycling

Effic. shapeforming

processes(PV)

Substitute identification

method

Effic. shapeforming

processes(RE)

ITOsubstitute

Cu substitute

3D printing

Magnetremanufacturing

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An example: Pt in PEMFC

Use : optimize operation point

Manufacturing :production scrap recycling

Design : reduce Pt content

- through nanostructuration- through adapted shape forming process

or

substitute Pt - by means of non noble metals- by novel materials (e.g. bio-inspired materials, N-CNT)

End of life :Pt recycling with other component

Minimization Pt in PEMFC

29 JUIN 2015 | PAGE 16

Mat

urity

leve

l

Optimisation of platinum utilisation: Structuration of platinum supported electrode by physical deposition and electrode formulation

Example: MEA with 0.2 mgPt/cm²total loading (vs 0,5 mg/cm² ref, loading)

� no significant degradation after more than 2500 hours of operation in representative transportation conditions

Non platinum catalyst • Nitrogen doped catalyst,

A. Morozan, et al., Energy Environ. 2011 ; A. Morozan et al., ChemSusChem 2012.

• Bio-inspired Ni catalyst,….

Nanos-structured platinum catalyst• Core-shell structure,Galbiati et al., Electrochemica Acta 2014, 125, 107-116.

• Platinum nanotubesLepesant M. thesis 2014

PEMFC: catalyst development on MEA

29 JUIN 2015

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n-Pt deposition by advanced CVD techniques

Same performances with a third of platinum quantity(0,2 g Pt/kW vs DOE 2015 target 0,15 g Pt/kW)

PEMFC for transportation

29 JUIN 2015

| PAGE 18

EPICEA 2 kWComposite

stack

GENEPAC 20 kW

Metallic stack

SPACT 8030 kW

Composite stack

GENEPAC 80 kW

Marathon Shell200 W

Graphite stack

RobotPAC200 W

Graphite stack

• Optimization of nanomaterials and membrane electrode assembly

• Membrane degradation mechanisms analysis

• Development of electrochemical constitutive equations coupled with thermohydraulic analysis

• Development of materials and nanomaterials for bipolar plates

• Design, manufacture and tests of stacks

Bipolar plates

DuBois et al. J. Am. Chem. Soc. 2006

Hydrogenase NiFe

Bio-inspired catalyst

European patent application EP-08 290 988.8Le Goff et al. Science 2009Tran et al. Angew. Chem. Int. Ed. 2011

Bio-inspired catalytic nanomaterials

First Pt-free electrocatalytic materials-bidirectional (production & oxydation of H2)-no overpotential-good stability (>100.000 cycles)-Nafion compatible (pH 0)

Performance optimisation:Nano-CAT project (FCH-JU 2012)Caroucell project (ANR BioME 2013)

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Li-ion batteries recycling : Complete recycling process

New cells

pack

Pack EoL

Safe dismantling

Cells/modules crushing& sieving

separation

Stirring slurry& separation

Organic materials (binders, carbon

Powders)

Active mineral materialsleaching

Chemical separation & metal salts synthesis

for new active materials

LCA & Cost analysis

Production scrapes

Al, Cu, steels &polymer membrane

packaging& electronics cards

2nd LifeApplications

Hydrometallurgy routeTo maximize the recycling rateTo reduce hazardous emission

To promote sorting andSeparation

before leaching

Promote the reintroductionof low cost recovered

materials in the production line

WEEE

29 JUIN 2015 | PAGE 21

29 JUIN 2015

Synthesis through polyol process

High transparency (>80%), high conductivityFlexibleLow temperatureNo vacuum, neither plasmaPrintable/ conformable / patternableIR transparentLow cost

Nanowire percolatingnetwork obtainedby spray coating

OPV cell

OPV: Replacement of ITO by Ag nanowire network

CNT CABLES

29 JUIN 2015 | PAGE 22

The A380 contains ~500 km electric cables representingapproximately…4 Tons

Fibers drawing from carpets

Drawing device

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Various cables obtained:

��

��

ratio define the degree of

torsion θ of the cableWeb formation during drawing

L: up to 10 m, Ø: from 6 to 15 µm, θ: from 4 to 27°

Results: - setting up of a drawing protocole

Drawing of cables up to 10 m

Resistivity of CNT is not frequency dependant

CRM_Innonet project (2012-2015)

Coordination & Support action focussing on critical m aterial substitution -

CRMs are potential risks for EU economy… risk mitigation research is relevant !

Project objectives : Develop material risk diagnostics, Develop substitution roadmaps & recommandationsNetwork on CRM substitution…

EU funded (FP7)Wide consortium (18 partners)

Performed :CRM materials application mappingEnergy, ICT & Transport sectors analysisfor CRM dependenciesRoadmap for substitution & recommendations(under finalization)Numerous workshops organized

EU Critical Raw Material definition (2014)

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CRM_Innonet : Examples of Results (CEA )

• Supply chain analysis, for economic riskassessment

(example: CRM for Wind energy – REE)

• CRM substitution roadmap for selectedtechnologies at risk

(example : CRM for Batteries – Co, Graphite, REE, Sb, F… )

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RECVAL HPM

29 JUIN 2015 | PAGE 26

Waste ResourcesUsed magnetsCollection & Analysis

Reuse

Recycling

MagnetsMarket

REEs marketREEs extraction

CEA Magnet development Platform

PyrometallurgyElectroreduction in molten saltHydrometallurgy processes- Classical leaching & REEs recovery- Bioleaching

Bonded magnetsSintered magnets

Magnets remanufacturing

Magnets conditioning

Innovative RE-use and Recycling VALue Chain for High-Power Magnets

RECVAL HPM PROJECT

A basic process to recover REEs from used magnets

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REEs extraction & purificationBy oxalic precipitation

Purity>99.5%Recovery Efficiency >90%

CEA patented process WO2014064597

Used permanents magnets& production waste

Nd, Pr, Dy, Fe, B

Acid leaching

Iron extraction Fe(OH)3

Decrepitation & sieving

Low T thermal Treatment

CHALLENGES & INNOVATION IN RECYCLING PROCESSES R. LAUCOURNET

29 JUIN 2015 | PAGE 28

Magnet platform : semi industrial scale for NdFeBmanufacturing

Material saving: Position in 3D printing Value chai n

Materials & StoragePowdersPolymers,

MetalsCeramics

Materials by design

PretreatmentMixture

FormulationPowder surface functionalization

Shaping Process

Post treatmentCleaningDebindingSinteringAnnealing

Characterizationmicrostructure &

properties (mechanical,

thermal, fluidic…)& certification

Multi-physical Modelling (mechanical, thermal, flui dic, optical, …)

• Optical functionalization of materials

• Metal powder oxidation protection

• Formulation & rheology

• Debinding kinetics (thermal or chemical)

• Sintering mechanism study

• Annealing for microstructure / properties

• Control of oxidation constraint of metals

• Non destructive characterization (Acoustic and X Tomography)

• Mechanical, thermal, optical properties measurement

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• Ab-initio Calculation• Alloys Formulation• Mechanical alloying• Thermochemistry• Chemical

characterization

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CEA participation to national and european initiativ es

Research Platform for the Advanced Recycling and Reuse of Rare Earths

Waste2Value: Sustainable recoveryof scarce metals and safe management ofnanowaste

ERECON European Rare Earth CompetencyNetwork

Associate member + activities in the French mirror groups

KIC Raw Material

COMES, French Committee for Strategic Metals(WG1 « Evaluation of French Industrial needs in CRM », WG5 « CRM efficiency & substitution »)

GP2 Strategic Materials

Plat’Inn PLAteform of research &technological INNovation on sorting andrecycling of waste for CRM supply

French cluster of excellence on recycling

KIC Raw Materials

29 JUIN 2015 | PAGE 31

HQ

KIC Raw MatTERS – The CLCs

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Thematic focus of the Central Colocation - Center

1. Substitution (and reduction)

2. Recovery and sorting (automotive, aircraft)

3. Light weight strategies

4. Multi-functional and smart materials

5. Efficient processing and design

6. Economic geology, advanced processes for mineral recovery

KIC Raw MatTERS – The Central CLC

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29 JUIN 2015 | PAGE 34

Increase the awarness of our scientists/engineers who develop technologies on the

tension about CRM and on the impact on the technological R&D

Material risk to be considered in the first step of development, on the basis of a

regularly updated CRM list relevant for our activities

Veille active setting up of a Material Observatory

Integrate a Material intelligency approach for material efficiency all along the life of the

components according to the three main pillars:

Minimization of CRM

Substitution (partial, full) of CRM

Recycling of CRM containing components

Share, disseminate & enrich this approach

with & within industry, strengthen european

partnership.making our activities more visible

Conclusion & perspectives

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Commissariat à l’énergie atomique et aux énergies alternatives

Centre de Grenoble | 38 000 Grenoble

T. +33 (0)4 38 78 96 54

etienne.bouyer@cea.fr

Etablissement public à caractère industriel et commercial | RCS Paris B 775 685 019

Thank you for your attention