Thermoelectric activities in Germany and at Fraunhofer IPM

© Fraunhofer IPM / Folie 1 Réunion GDR Thermoélecricité, 05./06. 2012, Lyon, France "Thermoelectric activities in Germany and at Fraunhofer IPM" Harald Böttner

Réunion GDR Thermoélectricité 05.-06. 2012, Lyon, France 16.11.2012 Harald Böttner, Fraunhofer IPM, Freiburg, Allemagne

"Thermoelectric activities in Germany and at Fraunhofer IPM"

Thermoelectric in Germany: overview

European Projects

DFG SPP1386 Nanothermoelectric

BMBF Thermopower

BMWI projects

?

Thermoelectric at Fraunhofer IPM


Technologies for energy harvesting: Thermoelectricity Organic Rankine Cycle (ORC) Kalina Cycle Heat exchanger Industrial heat pumps

Recommendations for public R&D funding: Evaluation of usable waste heat source New thermoelectric materials Industrial production technologies for thermoelectric

generators Improvement of heat exchanger New concepts for ORC New refrigeration substances for heat cycle

Result: TE is within the focus for public R&D

H. Bradke, Berlin, 05/2009

Scenarios and Strategies towards 2050: Energy efficiency in Industry


Political aspects, „The German transformation of energy system“


International

EU

Carnot

National

DFG

BMBF

BMWI

Regions Saxony, Baden-Württemberg, NRW

Research organisations FhG, Max-Planck, Helmholtz, Leibniz


Columns of R&D


Industrial funded R&D

Siemens/Infineon Micropelt

Industrial R&D (few examples)

BASF (PbTe, materials, TE-batteries)

BMW (TE-engine integration)

Bosch (TE-engine integration)

IAV (TE-engine integration)


R& D in industry

Columns of R&D


Producer/developer (devices and systems)

Micropelt (micro-TE-batteries)

O-flexx (TE-Batteries)

Peltron (classical TE-batteries)

Quick Ohm (custom solutions)

Inheco (custom solutions)

Teccom (custom solutions)

Gentherm (materials , TE-Engines)


Thermoelectric companies

SMEs

large


Karlsruhe

Kiel

Berlin Frankfurt/Oder

Cottbus

Dresden

Chemnitz

Selb Bayreuth

Regensburg

München Freiburg

Stuttgart

Würzburg

Illmenau

Halle Leipzig

Göttingen

Braunschweig

Magdeburg

Hanau

Ladenburg Ludwigshafen

Mainz

Jülich Köln

Münster

Karlsruhe

Wien

Dübendorf

Dresden

Halle

Köln

Freiburg

R&D 1989

R&D 2012

> 46 research facilities: Universities, Max-Planck, Fraunhofer, Helmholtz , (DLR, KIT,FZ Jülich), Leibniz (IFW) > 33 companies

Nürnberg


TE-map

Augsburg


PR CN

JP DE FR

web of science: 12-12-04, inhabitants: wikipedia 12-12-04

Germany 890 France 718

USA 3501 Japan 2373 PR China2311


Comparison to world wide leading countries

Korea 269

Papers per mio. inhabitants

10,98

10,92


International

EU

Carnot

National

DFG

BMBF

BMWI




Columns of R&D


publications 2002-2012 (> 30)

scientific society/ consortium/group (3)


Activities in Europe, a snapshot

TE

TE

TE TE

TE TE

TE

TE

TE

TE

TE

TE

TE Funded by FP 7 (17)

TE

TE

TE

TE TE

TE TE

TE

TE

TE

TE

TE

TE

TE

/


Country Participation Coordinator Publicationen

2008-2012

1 Germany 13 1 562 2 France 8 3 422 3 Spain 8 131 4 Sweden 7 1 76 5 Italy 7 2 113 6 UK 6 1 175 7 Austria 2 84 8 Greece 2 53 9 Russia 1 192

10 Turkey 1 68 11 Poland 1 168 12 Switzerland 1 110 13 San Marino 1 0 14 Cyprus 1 12 15 Czech Republic 1 56 16 Israel 1 46 17 Liechtenstein 1 0


FP 7 Projects: participation, coordination, publication

web of science: 12-11-30


Acronym Start date End Date Coord. ? Funding Project

1 NEAT FP7-NMP 01.04.2011 31.03.2014 France 2882506 4008286

2 E2PHEST2US FP7-ENERGY 01.01.2010 31.12.2012 Italy 1977724 2697100

3 HEATRECAR FP7-TRANSPORT 01.11.2009 31.12.2012 Italy 2513250 4240834 NANO-TEC FP7-IDEAS-ERC 01.03.2010 28.02.2015 Spain 1228000 1228000

THERMO-SPINTRONIC FP7-PEOPLE 01.09.2012 31.08.2016 Spain 100000 100000

4 GREEN SILICON FP7-ICT 01.08.2010 31.07.2013 UK 1660000 2205303

5 NANOHITEC FP7-NMP 01.12.2011 30.11.2014 Liechtenstein 3750000 5287380 SPARKNANOTE FP7-PEOPLE 15.10.2011 14.10.2013 UK 210092 210092

6 THETAGEN FP7-JTI 01.01.2010 30.09.2011 France 474971 1016877 7 NEXTEC FP7-NMP 01.06.2011 31.05.2014 Sweden 3931929 6365779

8 THERMOMAG FP7-NMP 01.05.2011 31.10.2014 France 3986980 5996252

NANOSICON FP7-PEOPLE 01.08.2008 31.07.2010 Germany 159828 159828 COMPTHERM FP7-PEOPLE 01.04.2009 31.03.2012 Sweden 45000 45000

22920280 33560731


FP 7 Projects

participation Fh IPM

participation other Fh I

TE /

http://cordis.europa.eu/fetch?CALLER=PROGLINK_NEWS_EN&QF_PGA=FP7-NMP













NMP.2010.1.2-3 Thermoelectric energy (TE) converters based on nanotechnology aspects of the manufactured nanoparticles as well as the composites that would be part of the researched TE converters.

Expected impact : through improved TE materials ZT > 3

running from ~01/11 until ~ 10/2014

volume ~ 22 Mio€, funding ~ 15Mio€

(NMP) Nanosciences, nanotechnologies, materials and new production technologies


FP 7 NMP Projects: keyword Thermoelectric


planar thermoelectric converters, materials: Bi2Te3, Si/SiGe/ B4C/B9C

http://nanohitec.eu/

http://www.neat-project.eu/

http://www.eu-nextec.eu/index.php

nano particle embedded in alloy thermoelectric, Mg2Si in n-Mg2(Si,Sn) alloy matrix

"Next Generation Nano-engineered Thermoelectric Converters – from concept to industrial validation".

http://www.thermomag-project.eu/index.html

n- and p-type Mg2Si, ZT > 1.5, operational temperature up to 550°C; raw materials <15€/kg




companies 20 universities 14 non gov 9 FhG 4

SMEs 10 large scale industry 10




250 500 750 1000 12500,0

0,5

1,0

1,5

2,0

Temperature [K]

"ZnO" Ohtaki 2008

"MgSi" Zaitev 2006

"MgSi" Fukano 2008

"CoSb3" Zhang 2009

"CoSb3" Shi 2011

"HH" Yu 2009

"HH" Yu 2009

ZT

some best published n-typeSkutterudites S ilicides Half-Heuslers (TiNiSn) Oxides

Theodora Kyratsi (Cyprus); hot pressed samples; Mg2Si0.4Sn0.4Ge0.185Bi0.015 ZT 1.4 @500°C!, Patent application

Nanostructured energy-harvesting thermoelectrics based on Mg2Si



High Temperature Nanocomposite Materials for Thermoelectric Power Generation (THERMO-PRESS), Cyprus Research Promotion Foundation, € 380.000, 2009-2013

Optimized Thermoelectric Nanocomposites (ΝΑΝΟ-THERM), Cyprus Research Promotion Foundation, PENEK, €90.000, 2009-2012

"Thermoelectric Nanosensor Networks", University of Cyprus, "Internal Research Programme of Large Size", Duration 1/6/2006 - 31/5/2010, MME Budget 120.000 CYP (210.000 Euro) (Total Budget of Project: 240.000CYP, 420.000 Euro)

Optimized Thermoelectric Materials and Technology, Cyprus Research Promotion Foundation (130.000 Euros)

Research and Education in Nanomaterials and Nanotechnology: Design, Development and Applications - Energy Generation and Storage - Thermoelectrics and Hydrogen Storage. INTERREG, Greece-Cyprus (300.000 Euros)

Thermoelectric funding in Cyprus

:1,32 Mio €


n- and p-type Mg2Si, ZT > 1.5, operational temperature up to 550°C; raw materials <15€/kg

Typ Material price in $/kg metals (metric tons)

2008 2012

V2VI3 Bi2Te3 140 81

IV-VI PbTe 99 59

Zn4Sb3 4 4

Silicides

p-MnSi1.73 24 3,5

n-Mg2Si0.4Sn0.6 18 20

Si0.8Ge0.2 660 415

Si0.94Ge0.06 270 152

Skutterudites CoSb3 11 10

Half Heusler TiNiSn 55 34

Clathtrate Ba8Ga16Ge30 1000 866

Oxides p-NaCo2O4 17 26

n-type Mg2Si, ZT ~ 1.5

operational temperature: ZT max @ 500°C

Raw materials ~ 20$/kg ~ 15€/kg

Nanostructured energy-harvesting thermoelectrics based on Mg2Si

FP 7 projects (“thermoelectric call”)


International

EU

Carnot

National

DFG

BMBF

BMWI




Columns of R&D


International

EU

Carnot


WATTS

coordinators Name of the

Institute e-mail address

Principal Coordinator: Dr. Alexandre

Jacquot

Fraunhofer Institute Physical

Measurement Techniques

alexandre.jacquot @ipm.fraunhofer.

de

National Coordinator

Dr. Anne Dauscher

Institut Carnot Énergie et

Environement en Lorraine

anne.dauscher @ijl.nancy-

universite.fr

Wafers based thin thermoelectric systems development


Nr. Result Assessment criteria 1 n and p type metal/skutterrudite/metal

wafers with the thermoelectric material is as thin as 200 µm. Preparation methods: melt spinning spark plasma sintering

In this project there will be no requirement on the size of the wafers. Wafer as large as possible will be produced. Wafers must be produced with the thermoelectric material is as thin as 200 µm.

2 Thin thermoelectric converters with a power range between 0.5 and 2 Watts and a footprint of 1 cm2

The power produced must be at least 0.5 Watt The footprint must be 1 cm2

3 System that demonstrates actuation, sensing, power management and data transmission at an electrical power level of 1 Watt.

The systems must cover its electrical energy needs (at least 1 Watt) by drawing thermal energy from its environment.


WATTS


International

EU

Carnot

National

DFG

BMBF

BMWI




Columns of R&D


Materials Dr. Harald Böttner ( Fraunhofer IPM, Freiburg) Dr.-Ing. Gabi Schierning -Deputy- (Univ. of Duisburg-Essen)

Characterisation Prof. Dr. Christian Jooß (Univ. of Göttingen) Dr. Raphael Hermann -Deputy- (FZ Jülich)

Theory Prof. Dr. Ingrid Mertig (Martin Luther Univ. Halle/Wittenberg) Prof. Dr. Christian Elsässer -Deputy- (Fraunhofer IWM, Freiburg)

Three areas


DFG priority programm „Nanothermoelectric“

Principle investigator distribution:

1st 2nd

on topics


Nanostructure, thermoelectric properties

and transport theory of V2VI3 and V2VI3 /

IV-VI based superlattices (Break and

Beyond)

Fraunhofer IPM projects (2009-2015) Break / Break and Beyond

a hard nut to crack

Comprehensive Clarification of the Physical Reasons of the Breakthrough of ZT~2.4/1.7 for p/n-V2VI3-Superlattices (Break)

H. Böttner (Freiburg), W. Bensch (Kiel ), L. Kienle (Kiel )

R. Venkatasubramanian, E. Siivola, T. Colpitts, B. O'Quinn., Nature 2001, 413, 597


First method:

Nanoalloying

MBE: low thermal

stability, no efficient

reduction of l by „SLs“

Sputter deposition:

better thermal stability,

but no efficient

reduction of l by „SLs“

and good PF

key point for high ZT ! better thermal

stability: should give

high PF and low l

Fabrication of SLs by nanoalloying -> results

TEM Sputtered

TEM MBE

0 50 100 150 200 250 300 350 4000.35

0.40

0.45

0.50

0.55

0.60

0.65

0.70

0.75

0.80

SLs 2h

homogen. 2h

SLs 24h

l [W

/mK

]

Annealing temperature [°C]

(Bi,Sb)2Te

3

PF ~ 40

ZT 0.6-1.9

PF ~ 15

µW / cmK²M. Winkler, et al., J. Electron. Mater. 41, 2012, 1322

U. Schürmann et al, Adv. Eng. Mater. 2012, 14, No. 3

MBE

Sputtered


Colors: MBE – Sputtering – Theory – new review

Accepted for publication in ZAAC

recent papers concerning Break /Break and Beyond

P. Zahn, Dresden B. Yu. Yavorsky , Karlsruhe I. Mertig, F. N. Hinsche,Halle


International

EU

Carnot

National

DFG

BMBF

BMWI




Columns of R&D


Aims

Coordinated by industry

Exploitation of the potential of thermoelectric heat to current conversion

Application of this technology for increased efficiency in energy comsuming equipment

Complete value chain from material over module to specific systems including thermoelctric

Key application: automotive

Funding

17 proposals

11 funded (Vol.: ~ 45 Mio. €, funding ~ 27 Mio. €)

> 30 companies, 26 research facilities


Thermopower I


Topics of funded projects:

Materials- and modules based on: Silicides, oxides, chalkogenides, Skutterudites, Half-Heuslers, Zintls

Application in systems: self powered sensor systems, cooling of electronic devices, industrial waste heat, automotive industriy

Expected results

modul-prototyps based on better materials

prototyps in automobils and industrial equipment

Feasibility is proved : new materials in modules and systems!


Thermopower I


activities Fraunhofer IPM:

SiGe thin films , Micropelt technology for 8”

Silicide modules,

automotive systems

metrology (round robin test)


Thermopower I


ThermoElectric-Standardisation „TESt“ Start: 01.01.2011


Thermopower I

http://www.netzsch.com/de/home/

http://www.dlr.de/


TESt

Public funded projects in Germany

German Thermoelectric

Society

EURAMET

International Thermoelectric

Society

European Thermoelectric

Society

Round Robin Tests For high temperature materials and thermoelectric generators


Thermopower I

ThermoElectric-Standardisation „TESt“

http://www.netzsch.com/de/home/

http://www.dlr.de/


International

EU

Carnot

National

DFG

BMBF

BMWI




Columns of R&D


ThermoHeusler Coordinator: Bosch Isabellenhütte Heusler GmbH (Friedrich Heusler 1903) Fraunhofer IPM (responsible for modules) Johannes Gutenberg University Mainz

HighTEG Coordinator: Behr Evonik CeramTEC AG Leoni (founded 1496) DLR Köln Otto von Guericke University Magdeburg ZAE Bayern

1901 the director Friedrich

Heusler (1866 – 1947),

discovered the later named

„Heuslerschen

Legierungen“ Heusler alloys

(alloys of non ferreous

metals). These alloys are

ferromagnetic, although

the constituents are non

magnetic metals.

Christmas tree decoration using leoni type wires (~1920)

Volume ~19Mio; funding ~11 Mio


Thermoheusler


Start of large scale production (n-material) Isabellenhütte, Dillenburg ~3kg (p-material) Vacuumschmelze, Hanau~5 kg


Thermoheusler


200 300 400 500 600 700 800 900 1000 11000.0

0.5

1.0

Fig

ure

of

mer

it Z

T

Temperature T [K]

thermoHEUSLER

LSR JGU Mainz

A

B

C

Yu et al.,

ActaMater 2009

A B

C

n-material

Benjamin Bahlke, priv. comm. 19.11. 2012


Thermoheusler


0 100 200 300 400 500

0,0

0,1

0,2

0,3

0,4

0,5

0,6

0,7

ZT

Temperature [°C]

IPM_SPS_Thermoheusler_141 LFA M01 cp + Thermoheusler_141 IPM-SRX M01 ip

IPM_SPS_Thermoheusler_142 LFA M01 cp + Thermoheusler_142 IPM-SRX M01 ip

ZT p-material

300 400 500 600 700 8000,0

0,2

0,4

0,6

0,8

1,0

N10_klein LFA M01 cp + IPM-SRX M01 ip

Literatur

ZT

Temperature [K]

ZT n-material

Literature


Thermoheusler


0.85 W/cm2 @Thot 530°C, Tcold 30-50°C basis TE-material


Thermoheusler


long-term objective 100T/a, in within two years 30 kg/batch, VC Kapital 20 Mio. $

Chris Caylor; Zhifeng Ren GMZ, Boston College

current batch for HH is 100 gr, nanosacle-HH nanosacle (ball milling) Hot pressed wafer 2“ p-ZT peak 1.1, n-ZT peak 1.1, module HH and Bi2Te3; 9.0 % efficiency @ DT 700K, contact resistance ~ p:0.6 µ cm2, n:0.7 µ cm2 goal 1kW TEG resulting in 5% „FE increase“


Thermoheusler international competition


Funding project volume

DFG (German Research

Society) 8,7 8,7

BMBF Scientific 5,5 5,5

Fed. Min. of Education

and Research

BMBF applied 25 40

Fed. Min. of Education

and Research

BMWI 11 19

Fed. Min. of Economics

and Technology

total 50,2 73,2

EU FP 7

23

34

Nanoscale TE SPP 1386

Thermopower I 27 45

17,4 17,4

60,9 86,9

Funding in Germany

?


LeGrandeur-Kajikawa-Chen-Böttner-Fairbanks 12-12-04 priv. comm.

Global Investment in TE Technology- November 2012 Snapshot (~ 2008 -2013 5 ~yr bucket)

Region Total Spend, Mio. €

Total Government funds, Mio. €

EU 138 96 North America 41 29 Russia 31 15 Japan 17 17 China 12 12 Worldwide Total 236 166

Worldwide public sector thermoelectric investments


International

EU

Carnot

National

DFG

BMBF

BMWI


Research organisations FhG (10/60), Max-Planck, Helmholtz, Leibniz


Columns of R&D


DFG one one BMBF five two BMWI one one BaWü two Carnot one one EU four one fourteen

Public funded projects



10 scientists 7 engineers 9 technicians 15 students 41 TE-fans

Harald Böt t ner Kilian bart holome Mart in Jägle Jan König Const anze bach Markus Bart el Benjamin Bayer Rol and B i nni nger Olovia Herm Pat r ik Broucke

Alexander bär Mat eusz Cichosz Susanne Drost Elena Felk Norbert Francz Marco Frey Eugen Geczi Est eban Gross Daniel Hauerwas Nikola Henze

Jana Heuer Jonas Horn Jan Horzella Alexandre Jacquot Christ ian Jedrusik Uwe Kruck Andreas Kürzinger Timo Larke Nat alya Mat lakova Frank Menzel

Ulr ikew Nussel Hans-F. Pernau Angela Pf aadt Diet er Rut sch Silvia Rut schinski Sabrina Schwarzer Monika St ef an Karina Tarant ik Julia Tet cau Marc Vergez

Uwe Vet t er Frank Vollmer Markus Winkler Christ of Zäh

Department Thermoelectric Systems



Converters for power generation and cooling

High-Temperature and Nano materials

Bulk and thin film system technology

Development of production processes

Simulation

Metrology for materials, modules and integrated systems

systems development



Materials

High temperature and Nano materials

Using of melt spinning

Development of new production methods (SPS)

Development of Seebeck „standard“ materials and metrology in with PTB and international metrology institutes



Metrology

Metrology on demand

High throughput screening systems

Online measurement of ZT-value

Module characterization

On demand lab: costumer sample characterisation



Source: EADS

Structure control in airplanes

~8mW output power with a 10g system


Energy-autarkic sensors

inside


Source: E.G.O.

TEG

transmitter

Temperature-

sensor

insertion thermometer for cooking and food control

Martin Jägle


inside




Communicating coffee pot





Version 0


Kaffee leer!

Data:

Max. TEG-voltage: 400 mV

Average TEG-voltage: 150 mV

Max. power: 85 mW

Average power: 12 mW




Internet: www.ipm.fraunhofer.de

Quelle: fotolia.de



Never again cold coffee


http://www.ipm.fraunhofer.de/en/ideas-expertise/thermoelectrics.htm

Energy-Autarkic Systems and Thermoelectric Metrology

Thermoelectric Energy Converters

Thermoelectric Systems

Thank you for your attention


Office of German Thermoelectric Society

http://www.ipm.fraunhofer.de/en/ideas-expertise/thermoelectrics.html





Thermoelectric activities in Germany and at Fraunhofer IPM

Documents