Magnets as enablers for renewable energy and resource efficiency

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1 Magnets as enablers for renewable energy and resource efficiency Oliver Gutfleisch TU Darmstadt, Material Science, Functional Materials Fraunhofer Project Group for Materials Recycling and Resource Strategy IWKS Hanau, Germany DPG Magnetism School 2017 IWKS

2 Contents Material criticality in green energy Finiteness of strategic metals and resource strategy Rational design of novel magnetic materials Reduction - Recycling - Substitution Permanent magnets for E-mobility and wind turbines Magnetocaloric materials for solid state refrigeration Mastery of hysteresis Efficient utilisation and substitution on different levels Oliver Gutfleisch 2

Distribution of CO 2 emission Sept 2014, Fossil Fuel Data Assimilation System (FFDAS) http://hpcg.purdue.edu/ffdas/index.

3 Distribution of CO 2 emission Sept 2014, Fossil Fuel Data Assimilation System (FFDAS) closing the carbon cycle for CO 2 neutral fuel and electricity Global Carbon Project: Total Billion tonnes (28 % China, 14% USA, 10%EU, 7% India) increase every year 2.5% (2.0t/person, 4.5t/person, 1.9t/person, 0.5t/person) Oliver Gutfleisch 3

4 TOWARDS 100% RENEWABLE EUROPE Typical winter week in Germany Renewable Energy 50 (2013) 826 More efficient conversion Intermittent and volatile renewable power production from wind and sun requires significant backup generation and storage Oliver Gutfleisch 4

GROSS POWER PRODUCTION IN GERMANY IN 2016 BY SOURCE 0.6 33.8 0.8 Total 648 TWh [Mrd. kwh] 30.4 14.9 USA in 2016 19.

5 GROSS POWER PRODUCTION IN GERMANY IN 2016 BY SOURCE Total 648 TWh [Mrd. kwh] USA in Oliver Gutfleisch 5

Rapid deployment of strategic metals in energy and

applications (gallium, germanium, selenium, indium,

praseodymium, dysprosium, terbium) for offshore

catalysts in fuel cells, chemical energy conversion

tellurium) magnetic cooling (neodymium, gadolinium,

cobalt) yttrium for high TC superconductors alloying

hafnium, and rhenium) https://en.wikipedia.

6 Rapid deployment of strategic metals in energy and related technologies electronic and solar energy applications (gallium, germanium, selenium, indium, and tellurium) rare earth elements (neodymium, praseodymium, dysprosium, terbium) for offshore wind, e-mobility, lighting platinum group metals for catalysts in fuel cells, chemical energy conversion thermoelectric conversion of waste heat (cadmium, tellurium) magnetic cooling (neodymium, gadolinium, germanium, indium, cobalt) batteries (lithium, cobalt) yttrium for high TC superconductors alloying elements in high-temperature turbines (cobalt, hafnium, and rhenium) Oliver Gutfleisch 6

Critical materials and supply Fraunhofer IWKS, Armin Reller

century English economist who noticed that as people began

7 Critical materials and supply Fraunhofer IWKS, Armin Reller Ever increasing complexity Jevons Paradox, after the 19th century English economist who noticed that as people began to use coal more efficiently, they began to use more coal, not less. Contemporary economists talk about what they call the rebound effect." Efficiency or Jevons Paradox Oliver Gutfleisch 7

8 Factors for criticality of metals Technical Development (Need for Raw Materials, Primary Production, competing technologies) Geological Availability (Range, Reliance on by-product production) Geopolitical Factors of Influence Ecological Consequences (Extraction, Application Disposal) Substitution, Recycling possible? Economical Development (Pricing, Offering, Demand) Fraunhofer IWKS, Armin Reller (possibly reduced cost and performance vs sustainability) Criticality is dynamic! Oliver Gutfleisch 8

Abundance of elements in the Earth crust per million of Si atoms Abundance of the chemical elements in Earth s upper continental crust (1) Rock-forming elements (major elements in green field and

9 Abundance of elements in the Earth crust per million of Si atoms Abundance of the chemical elements in Earth s upper continental crust (1) Rock-forming elements (major elements in green field and minor elements in light green field); (2) Rare earth elements (lanthanides, La Lu, and Y; labeled in blue); (3) Major industrial metals (global production > kg/year; labeled in red); (4) Precious metals (purple); (5) The nine rarest metals the six platinum group elements plus Au, Re, and Te (a metalloid). US Geological Survey Oliver Gutfleisch 9

10 Global estimates of end-of-life recycling rates for 60 metals and metalloids (2008) T. E. Graedel et al., J. Ind. Ecol. 15, 355 (2011). Oliver Gutfleisch 10

11 The cobalt pipeline Tracing the path from deadly hand-dug mines in Congo to consumers phones and laptops Oliver Gutfleisch 11

12 AMNESTY INTERNATIONAL JANUARY 2016, INDEX: AFR 62/3183/2016 Oliver Gutfleisch 12

13 General Context of the Rare-Earth Market supply, criticality and applications Oliver Gutfleisch 13

14 Which are the 17 rare earths? Light and heavy rare earths lighter RE are more incompatible (as they have larger ionic radii) and therefore more strongly concentrated in the continental crust than the heavier RE RE with even atomic numbers (58Ce, 60Nd, ) have terrestrial abundances than adjacent RE with odd atomic numbers (57La, 59Pr, ) Oliver Gutfleisch 14

5 kg Ce China FOB 4Q2016: Nd US$ 40, La US$ 2, Ce US$ 1, Dy US$ 185, Tb US$ 425 EU 2015: Critical raw

15 Rare earth balance Utilisation of earth abundant rare earths Ce La Production 2020: every kg Nd yields 1.5 kg La and 2.5 kg Ce China FOB 4Q2016: Nd US$ 40, La US$ 2, Ce US$ 1, Dy US$ 185, Tb US$ 425 EU 2015: Critical raw materials for the EU Gauss and Gutfleisch, The resource basis of magnetic refrigeration, J. of Industrial Ecology, images: prices: metal pages Oliver Gutfleisch 15

16 Rare earth market and production K.-H. Müller, S. Sawatzki, R. Gauss and O. Gutfleisch, Permanent magnetism, in Springer Handbook of Magnetism, ed. by J.M.C. Coey and S. Parkin, book in preparation. Oliver Gutfleisch 16

With an adequate, one-off investment, REE supply could have been diversified and supply security been guaranteed.

17 Rare earth crisis was not only predictable, it was also preventable 2002 USGS estimates proven reserves of REEs at 800 times of current demand. Technologies for mining, beneficiation and separation of REE are available outside China. With an adequate, one-off investment, REE supply could have been diversified and supply security been guaranteed. A single REE mine would meet all Europe s current rare earth requirements. Import reliance rate of Europe is 100% EU communication on the 2017 list of Critical Raw Materials for the EU, Brussels, REPORT BY THE EUROPEAN RARE EARTHS COMPETENCY NETWORK (ERECON), 2015 Oliver Gutfleisch 17

Electric, Data: US DOE) 37m 1990 450kW 154m Today 6-8MW 240m 2020 94m Big

18 Direct drive wind turbine per 1 MW windpower +/- 600 kg Nd-Dy-Fe-B 4% Dy = 24 kg 28% Nd = 168 kg Average turbine rotor diameter (image General Electric, Data: US DOE) 37m kW 154m Today 6-8MW 240m m Big Ben Oliver Gutfleisch 18

19 Global refrigeration Global residential energy demand 3 billion refrigeration, air-conditioning and heat pump systems in operation worldwide 300 billion USD global annual sales 12 million people employed worldwide in the refrigeration sector 17% of the overall electricity used worldwide consumed by refrigeration IIR 29 th Informatory Note on Refrigeration Technologies 02/12/2015 Heating versus cooling (air conditioning) reference scenario as modelled by Isaak and van Vuuren 2009 Oliver Gutfleisch 19

20 Numbers of household versus numbers of refrigerators for Germany, USA, China and India (in million units) The size of the spots correlates with the amount of energy spent for domestic refrigeration in each country per year (estimates for the years 2013/2014). refrigeration revolution Gauss and Gutfleisch, The resource basis of magnetic refrigeration, J. of Industrial Ecology, Oliver Gutfleisch 20

21 Demand for Nd-Fe-B by different applications in 2015 K.-H. Müller, S. Sawatzki, R. Gauss and O. Gutfleisch, Permanent Magnetism, bookchapter in Springer Handbook of Magnetism, ed. by Coey and Parkin, to be publ.. Oliver Gutfleisch 21

22 REE Permanent Magnets towards mastery of coercivity Oliver Gutfleisch 22

NdFeB magnets dominate the permanent-magnet

23 NdFeB magnets dominate the permanent-magnet market by value, ferrites dominate by mass Market shares by value, 2016* NdFeB 68% Ferrite 28% Alnico 1% SmCo 2% Market shares by mass, 2016* Ferrite 84% Adv. Mat. (Review) 23 (2011) 821 NdFeB 15% SmCo <1% Alnico <1% *2016 forecast estimates Constantinides, Magnetics Conference 2016 Oliver Gutfleisch 23

Permanent Magnet Growth World production of sintered NdFeB in 2012: ~100.

New designs of wind generators use NdFeB magnets at a rate of ~600 kg per mega-watt.

production. Hard disc drives cannot function without RE permanent magnets.

24 Permanent Magnet Growth World production of sintered NdFeB in 2012: ~ t (estimated 80% China, ~18%Japan, 2%Europe) The motor/generator in a hybrid electric vehicle contains 1 kg of NdFeB. Set to grow to between 10 million and 20 million vehicles by New designs of wind generators use NdFeB magnets at a rate of ~600 kg per mega-watt. This application alone has potential to increase RE demand by 25% per year above current production. Hard disc drives cannot function without RE permanent magnets. Formerly 70% of the NdFeB market this is now diluted by the other major applications. Solid state energy efficient cooling: Magnetocalorics 1kg MCE and 4 kg NdFeB per kilo-watt cooling power Adv. Mat. (Review) 23 (2011) 821 Oliver Gutfleisch 24

25 Intrinsic and extrinsic magnetic properties intrinsic properties + microstructure 100µm > l > 1nm extrinsic properties saturation magnetisation, M s anisotropy field, H A fit µ-magnetic length scales remanence, J r coercivity, H c Curie temperature, T C energy density, (BH) max exchange length, l k critical single domain particle size, D c exchange stiffness, A domain wall width δ w and energy γ hardness parameter κ M r or B r H c bh c M or B Oliver Gutfleisch 25

26 Hysteresis at the heart of all magnetic materials physics and material science of hysteresis efficiency and reversibility Phil. Trans. R. Soc. A, 374: (2016) Oliver Gutfleisch 26

27 Nd 2 Fe 14 B Nd 2 Fe 14 B structure has a tetragonal crystal structure. It is largely composed of Fe which is abundant and has a large FM moment. Relatively small amount of abundant light rare earth provide anisotropy. Tetragonality stabilised by B occupying only 2 vol. % alternating layers of soft and hard Oliver Gutfleisch 27

28 Magnetism in Nd 2 Fe 14 B Element M S K 1 T C Fe 3d high low high Nd 4f low high low Magnetisation curves for a Nd 2 Fe 14 B single-crystal at room temperature (from Chikazumi 1997) Oliver Gutfleisch 28

29 Magnetism in Nd 2 Fe 14 B Herbst et al Oliver Gutfleisch 29

30 Principal processing routes of Nd-Fe-B magnets based on coarse grained and nanocrystalline powders K.-H. Müller, S. Sawatzki, R. Gauss and O. Gutfleisch, Permanent magnetism, in Springer Handbook of Magnetism, ed. by J.M.C. Coey and S. Parkin, in preparation. Oliver Gutfleisch 30

31 NdFeB sintered magnets Nd 2 Fe 14 B - φ Video Oliver Gutfleisch 31

32 NdFeB sintered magnets 1,5 1,0 polarisation J (T) 0,5 0,0-0,5-1,0-1, applied field µ 0 H (T) 5µm Oliver Gutfleisch 32

33 Brown s paradox (W.F. Brown, 1945) - an unsolved problem in physics - Nd-Fe-B intrinsic Nd-Fe-B sintered Nd-Fe-B as-cast =H A H C (real) << H A Reduction is principally attributed to local magnetic softening by chemical, structural or geometrical irregularities. Oliver Gutfleisch 33

34 Fundamental coercivity mechanism Initial magnetisation curve and field dependence of coercivity in nucleation and pinning-type magnets Nd-Fe-B Sm(CoFeCuZr) z Skomski and Coey 1999 Oliver Gutfleisch 34

Magnetisation reversal in sintered NdFeB the weak link Perfect

Nucleation + propagation K 200 nm crystalline or amorphous

continuous or discontinuous H activation volume H c = H A H c <<

35 Magnetisation reversal in sintered NdFeB the weak link Perfect materials: Coherent rotation K Nucleation-type magnet Defects : Nucleation + propagation K 200 nm crystalline or amorphous metallic or oxidic FM or PM microchemistry, structural defects continuous or discontinuous H activation volume H c = H A H c << H A efficient use of Dy by grain boundary diffussion process Oliver Gutfleisch 35

36 Sintered NdFeB magnets for electro motors Design light-weight, high torque-to-weight ratio motors, using permanent magnets with adequate temperature stability torque scales linearly with remanence Hirosawa et al. J. Appl. Phys. 59, 873, 1986 Crystal M s at 300K / µ B /f.u. H a at 300K / koe T c / K linear motor Nd 2 Fe 14 B Dy 2 Fe 14 B Pr 2 Fe 14 B Adv. Mat. 23 (2011) 821 Oliver Gutfleisch 36

37 Grain boundary diffusion processes (GBDP) Heavy rare earth Dy or Tb in sintered Nd-Fe-B magnets Increase by 420 ka/m (0.52 T) at 0.11 wt.% Dy Acta Mater. 83 (2015) Oliver Gutfleisch 37

38 In-situ Magnetisation reversal in GBDP processed sintered Nd-Fe-B magnets Remanent State ( 0 Tesla) local switching by Kerr vs MFM 20 µm 10 µm 0 T -0.1 T -0.2 T -0.3 T Acta Materialia 127 (2017) 498 Oliver Gutfleisch 38

39 Atomic-scale characterisation and modelling 3D Atomprobe, TEM and EELS analysis of SmCo pinning magnet Adv. Mat. (Review) 23 (2011) 821 Oliver Gutfleisch 39

40 Atomic-scale characterisation and modelling SmCo pinning magnet Nature Communications, 2017 TEM STEM Characterisation of the Zr-rich phase HAADF-STEM I ~ Z 2 Oliver Gutfleisch 40

41 REE Recycling The Integration of Recycling into the REE Supply Chain Oliver Gutfleisch 41

42 Rare earth value chain for magnets Advanced Functional Recycling of EoL products no radioactivity not all RE are present simplified separation much higher concentration very different LCA R. Gauß und O. Gutfleisch, Magnetische Materialien Schlüsselkomponenten für neue Energietechnologien" Springer Spektrum Verlag, 2016 Oliver Gutfleisch 42

43 From EOL products to the pure RE oxides Almost same long value chain with some important differences! Collecting & Sorting Sorted product cracking Pure RE salts or oxides Pure RE solutions RE mix concentrate RE finishing RE Separation Oliver Gutfleisch 43

44 Recycling using Hydrogen Decrepitation (HD) of Nd-Fe-B after HD Advanced Energy Materials 3 (2013) 151 cast ingot, t x 4, 1bar, RT 10 μm sintered magnet, t x 90, 1bar, RT Videos Oliver Gutfleisch 44

45 Anisotropic sintered NdFeB magnets with X % recycled material % recycled 10 % recycled 20 % recycled 30 % recycled J[T] H[kA/m] Oliver Gutfleisch 45 IWKS

46 Magnetic refrigeration From fundamentals to application Oliver Gutfleisch 46

47 Magnetocaloric effect T adiabatic apply field H T+ T S m T = = H M T 0 H H T C dh M T 0 H,p H, p dh absorb heat expel heat isothermal Large H T- T adiabatic remove field T H Large M T Small C H,p H Large MCE Maxwell equation applies to equilibrium thermodynamics coupled magnetostructural transitions, related latent heat, hysteresis ΔS iso = ΔS mag + ΔS lat + ΔS el Oliver Gutfleisch 47

48 Active Magnetic Regenerator Video adiabatic magnetisation A B entropy D C adiabatic demagnetisation temperature AMR first proposed by J.A. Barclay,1982 Oliver Gutfleisch 48

49 1 st order transition 2 nd order transition µ 0 H = 2T Nature Mater. 11 (2012) 620 Oliver Gutfleisch 49

50 LaFeSi a substitute for Gd Adiabatic temperature change of La(FeMnSi) 13 H 1.53 µ 0 H = 1.93 T Scripta Mat. 67 (2012) 584 Cooperation Vacuumschmelze Hanau Oliver Gutfleisch 50

LaFeSi a substitute for Gd V, % 1,2 1,0 0,8 0,6 Acta 0,4Materialia 125 (2017) 506 0,2 LaFe 11.74 Co 0.

67 (2012) 584 J. Appl. Phys. 115 (2014) 17A941 µ 0 H = 1.9 T LaFe 10.71 Co 1.30 Si 1.

1 X=0.2 X=0.3 X=0 T ad, K 0,0 5 4 3 2 200 250 300 350 Temperature,K LaFe 11.6-x Mn x Si 1.4 H X=0 x X=0.

51 LaFeSi a substitute for Gd V, % 1,2 1,0 0,8 0,6 Acta 0,4Materialia 125 (2017) 506 0,2 LaFe Co 0.13 Si 1.13 LaFe Co 0.52 Si 1.09 LaFe Co 0.91 Si 1.04 Acta Mat. 59 (2011) 3602 Scripta Mat. 67 (2012) 584 J. Appl. Phys. 115 (2014) 17A941 µ 0 H = 1.9 T LaFe Co 1.30 Si 1.00 T ad, K JAP 114 (2013) J. Magn. Magn. Mater. 396 (2015) 228 LaFe 11.6-x Mn x Si 1.4 X=0.1 X=0.2 X=0.3 X=0 T ad, K 0, Temperature,K LaFe 11.6-x Mn x Si 1.4 H X=0 x X=0.1 X=0.4 X=0.3 X= Temperature, K Temperature, K Oliver Gutfleisch 51

52 Demonstrator 2nd generation 2nd generation demonstrator Δµ 0 H: 1.1 T Mass of magnet: 3.9 kg Active Volume: 63.6 cm³ Frequency: up to 5 Hz Fluid: water Temperature span: 26 K Gd mass: 76 g Sphere diameter: µm Improvements compared to 1 st generation: Use of recycled Nd 2 Fe 14 B Less permanent magnet mass 124% higher active volume 18% higher magnetic field change 50% lower torque smaller motor Less heating of magnets 50% higher maximum thermal span Oliver Gutfleisch 52

53 Ni-Mn based Heusler compounds Ni Mn X M [emu/g] T T [K] dilemma of inverse magnetocaloric materials Oliver Gutfleisch 53

Mastering hysteresis in NiMnInCo M (emu/g) 100 80 60

3 kbar S (J/kgK) 30 25 20 15 10 5 Aging at 573 K for

µ 0 H (T) 0 290 300 310 320 330 T (K) Adjusting the

range Large thermal irreversibility can be overcome

54 Mastering hysteresis in NiMnInCo M (emu/g) kbar 1.3 kbar S (J/kgK) Aging at 573 K for x min µ 0 H (T) T (K) Adjusting the transition temperature Increasing the operating range Large thermal irreversibility can be overcome by the combination of magnetic and mechanical forces Nature Mater. 11 (2012) 620 Oliver Gutfleisch 54

Comparison of barocaloric effects Heusler alloys

106 (2015) 021901 Gottschall et al., Phys. Rev.

, J. Appl. Phys. 115 (2014) 17A941 Radulov et al.

55 Comparison of barocaloric effects Heusler alloys Gottschall et al., Appl. Phys. Lett. 106 (2015) Gottschall et al., Phys. Rev. Applied 5 (2016) dt t dσ ΔV Skokov et al., J. Appl. Phys. 115 (2014) 17A941 Radulov et al., J. Magn. Magn. Mater. 396 (2015) 228 La(Fe,Si) 13 Oliver Gutfleisch 55

56 Solid-state caloric effects ERC Advanced Grant Cool Innov Using a multi-stimuli and hysteresis-positive approach Advanced Functional Materials, 2017 Oliver Gutfleisch 56

57 Efficient utilisation and substitution on different levels Example: Magnetic Refrigeration Energy and resource efficiency Environmental footprint gas vapour compression Magnetic Cooling sintering & cutting 3D printing or extrusion Gd La(FeSi) 13 Heusler Oliver Gutfleisch 57 IWKS

58 Conclusions Post-fossil society is not possible without rare metals REPM based motors are the best technological solution big demands in E-mobility, wind turbines, maybe magnetic refrigeration are still to come currently no equivalent substitutes for Nd-Fe-B magnets in many applications; a new RE free PM would be technologically disruptive RE balance needs to be explored, utilisation of free rare earths environmental indicators of a product would be drastically improved if recycled REPMs were used magnetic refrigeration FORWARD by high through-put modelling materials database rational synthesis advanced characterisation identification of replacement material (earth abundant materials) Oliver Gutfleisch 58

UNITED NATIONS CONFERENCE ON TRADE AND DEVELOPMENT MULTI-YEAR EXPERT MEETING ON COMMODITIES AND DEVELOPMENT April 2014 RARE EARTH METALS

UNITED NATIONS CONFERENCE ON TRADE AND DEVELOPMENT MULTI-YEAR EXPERT MEETING ON COMMODITIES AND DEVELOPMENT 9-10 April 2014 RARE EARTH METALS by Ms. Alexandra Laurent Statistician, UNCTAD The views expressed