1. Energy sustainability vs materials availability. Equivalence and differences Igor Lubomirsky and David Cahen Dept. Materials and Interfaces Weizmann Institute of Science Rehovot, 76100, Israel all knowledge starts from wonder Aristotle 1

2. There are lot studies about sustainability of materials … What can we add to it? This is the Man all tattered and torn, That ……………………………………………….. ………………………………………………… That lay in the House that Jack built

3. What happens if energy becomes more expensive? How will it affect materials production and consumption? Do we have the technological abilities to adapt? If yes, how? 3 Energy availability defines the range of materials that can be used

4. World Oil Energy Consumption by Sector, 1973-2010 Why do we have to think about these questions ? Because energy consumption is highly specialized.

5. More than 90% of coal is used for three purposes only: Electricity Steel Cement

6. Energy prices are not interdependent If one energy source becomes more expensive, then other sources follow. 6 Despite high specialization…

7. http://www.metalprices.com/pubcharts/Public/Aluminum_Price_Charts.asp http://www.moneyweek.com/news-and-charts/market-data/oil No oil is used for aluminum production Should the price of aluminum correlate with the price of oil? Why? High energy price diverts some electricity used from aluminum production to other uses 7

8. If a technologically and economically viable alternative exists, can it be implemented quickly?

9. http://energyalmanac.ca.gov/gasoline/margins/index.php http://www.methanex.com/products/methanolprice.html 9 Methanol vs Gasoline price Price of Methanol on Nov. 2012: $1.45/gallon Ratio of Methanol to Gasoline Energy Content (w/w) = 0.55 Density of Methanol: 0.79 gm/cm 3 Density of Gasoline: 0.72 gm/cm 3 Cost of the amount of Methanol equivalent to 1 US gallon (= 3.785 l) of gasoline: Gasoline costs, before taxes & distribution, on Nov. 2012: $3.0 / gallon, which includes price of crude oil @ $2.44 /gallon price of refining (including profits) ~$0.55 /gallon (slightly varies from state to state) Why arent we driving on MeOH?

10. Gasoline consumption in the US alone is ~130 billion gallons Total production of methanol in the world is 16 billion gallons Total installed production capacity is ~20 billion gallons (<8% of US gasoline equivalent) Methanol production capacity cant match demand in foreseeable future

11. Questions: 1.How much energy can be diverted without major disrupting living standards? (How flexible is the energy consumption structure?) 2. Can materials availability limitations affect technological changes? Starting point: Transition to new technologies requires diversion of energy and materials

12. What is energy used for? 12

13. Can some of this energy be redirected? Transportation? Only ~8% of personal fuel consumption is purely recreational (1.6% of total)! Gasoline consumption rises ~ 30% per decade Hidden costs of energy Unpriced consequences of energy production and usethe national academies press, Washington, D.C. Energy usage in transportation in the US

14. Can some of this energy be redirected? Residential? Major fraction (>85%) is for heating and air conditioning. Commercial services? Energy consumption can be cut but … at the expense of important services Hidden costs of energy Unpriced consequences of energy production and usethe national academies press, Washington, D.C.

15. Can some of the energy for materials processing be redirected?

16. Since, these five materials are vital, only a small portion of the energy used for industry can be really diverted Five materials use more than half of all energy for materials production 16

17. Can the energy expenses for materials production decrease with time? Not likely

18. The fraction of materials in the total energy balance will grow because improvement in extraction technology is offset by decreased quality and exhaustion of ores 18 Gupta and Hall.. Energy cost of materials.. Gordon, R. B., Bertram, M., and Graedel, T. E.: Metal stocks and sustainability, PNAS, 103(5), 1209 (2006).

19. the energy cost of extraction increases steeply with decrease of ore quality Energy and greenhouse gas implications of deteriorating quality ore reserves; T.Norgate and S. Jahanshahi; CSIRO Minerals/Centre for Sustainable Resource Processing; URL : http://www.minerals.csiro.au The fraction of materials in the total energy balance will grow

20. discovery of new ores does not compensate for exhaustion 20 Gupta and Hall.. Energy cost of materials.. Gordon, R. B., Bertram, M., and Graedel, T. E.: Metal stocks and sustainability, PNAS, 103(5), 1209 (2006).

21. Can materials consumption be restricted by increased efficiency of their use? 21

22. Material intensity increases steadily ( quantity of materials per unit of product decreases) USA UK Japan Does it mean that materials consumption will decrease? 22 Krausmann et al…

23. Mineral/fossil Biomass Materials consumption per capita INCREASES because living standards rise 23 Krausmann at al… 2009

24. Absolute materials consumption accelerates exponentially 24 F. Krausmann, S. Gingrich, N. Eisenmenger, K. H. Erb, H. Haberl, and M. Fischer-Kowalski, Growth in global materials use, GDP and population during the 20th century, Ecological Economics, 68(10), 2696-2705 (2009).

25. Conclusion 1 Current structure of the energy/materials production/consumption does not allow for large flexibility

26. Availability of materials produced as byproducts 26

27. Price scales as a power law with abundance John R. Boyce, Biased Technological Change and the Relative Abundance of Natural Resources

28. from Cu from Zn from Cu-Mo Low price relative to abundance from Zn from Zn, Cu, Pd Price scales as a power law with abundance

29. Production volumes should also scale with abundance Source of data: USGS, EIA, CRC Handbook of Chemistry and Physics, others

30. 30 Can the supply of a byproduct be increased rapidly if a technological need arises?

31. 31 Listed energy cost of the byproducts (does not include the price of the primary) product pr Approximate energy cost production (GJ t -1 ) Primary products Aluminum188 Steel29 Copper135 Cement6 Iron ore3 Lead31 Zinc76 Phosphate0.35 Secondary products Gallium50 Germanium40 Indium40 Selenium116 Tellurium116 Cadmium4.5 Gupta and Hall.. Energy cost of materials..

32. Increase in production of byproducts requires increase of production of the corresponding primary product 32 The problem

33. How does it affect abilities to switch to renewable energy sources? 33

34. than that of materials for solar cells For Never Was A Story Of More Woe 34

35. Nayak Bisquert, Cahen. AM, 2011, updated 2012 Solar cells are as good as they can be Cell type (absorber) [%] of theoretical efficiency sc-Si ~90 GaAs ~90 InP ~80 CdTe ~ 75 Cu(In ~0.7 Ga ~0.3 )Se~78 a-Si:H~67 DSSC (black dye) (red N719) ~55? ~75? Org. polymer (P3HT- PCBM-based) ~55? 35

36. 36 Annual production of Te in 2010 is only 150 tonne (from Cu refinement) Current recovery rate is 33–40% Increasing installed capacity from current 0.07 TW to 0.7 TW requires a few times increase in copper production. In 2008 Cu production used 0.08% of world energy. Increasing production by a few times is not feasible. Data from Minerals Yearbook ( US Geological survey) and Fthenakis, V.: Sustainability metrics for extending thin- film photovoltaics to terawatt levels, MRS Bulletin, 37(4), 425 (2012).

37. ResourceAvailability, in metric tonsYears to exhaustion with the current consumption rate and technology Annual production including recycling Known resources Indium (2010)574N/AProbably <10 Gallium (2008)184N/AProbably <10 Tellurium (2010)15522,000140 Selenium (2009) (US declined to disclose) 2,28088,00039 Cadmium (2010)22,000660,00030 Similar calculation can be done for other materials Increase in Ga or In production requires increase in Al production 37 Si, Ti and organics… are available in really large quantities Data from Minerals Yearbook ( US Geological survey) How big is the increase? Only 10% of Al producers extract Ga Practically impossible

38. Materials for wind energy: economy and materials limitation 38

39. Nd 2 Fe 14 B magnets Made ONLY in China (80%), Japan (17%), and Germany (3%). A 3MW windmill requires 700 kg of Nd (A hybrid car requires 3 kg of Nd) Nd 2 Fe 14 B lose 50% coercivity @100 C New Nd-Dy-YFe-B magnet works to 200 C and uses less Nd. Wind energy. Materials aspect ResourceAvailability, in metric tonsYears to exhaustion with the current consumption rate and technology Annual production including recycling Known resources Nd7.0008 million tonnes Using ALL available Nd may add 35 TW With current production one can add 13 GW /year 39

40. However….. many materials have very limited number of producers. Sometimes one producer. The problems are often political… 40

41. ~80% of wind- electricity produced in Denmark is sold with economic loss 41 Danish center for political studies (CEPOS) report of Sep. 2009: WIND ENERGY THE CASE OF DENMARK

42. because there is no good way for large-scale energy storage 42 Danish center for political studies (CEPOS) report of Sep. 2009: WIND ENERGY THE CASE OF DENMARK

43. Electricity to fuel. Materials aspect 1 1. Water electrolysis: low temperature electrolysis (alkaline process ) requires Pt to reach > 80% efficiency Taking 1/10 of world Pt production (U 1.5 V potential (82% efficiency), 100 nm thick coverage, J=0.1 A/cm 2 ) can convert 135 GW of electrical energy into H 2. ResourceAvailability, in metric tonsYears to exhaustion with the current consumption rate and technology Annual production including recycling Known resources Platinum (2010)180 tonne ( 9 m 3 ) 14,000NA Without Pt, the efficiency is < 50% ( 1 atm), ~ 80% @ (high pressure) This is < 0.3 % of the energy required for transportation. 43

44. Electricity to fuel. Materials aspect 2 2.Water electrolysis: high temperature electrolysis (reversed fuel cells) 3.Materials are not restricted (Y, Zr, Ni, Co) Efficiency 120 C 45%; 850 C <65%; theoretically FEASIBLE. Susceptible to sulfur poisoning Practically not tested ResourceAvailability, in metric tonsYears to exhaustion with the current consumption rate and technology Annual production including recycling Known resources Yttrium (2010)8900540,00060 Ziconium (2010, ktons)11905600047 Cobalt (2010)88,0007,300,00082 44

45. The method: CO 2 to CO conversion by electrolysis of molten Li 2 CO 3 -Li 2 O mixture Operating temperature: 900 o C; Current density range: 0.05-2 A/cm 2 ; Cathode: Titanium; Anode: Carbon; Container: Titanium or Ti-plated steel 3. CO 2 CO electrolysis in melts (Kaplan & Lubomirsky, 2010) 45

46. 1000 hrs of continuous operation without degradation Current density: 0.1-2 A/cm 2 Cell voltage: 1.0-1.5 V Faradaic efficiency 100 %; Thermodynamic efficiency 100% 46

47. Small scale (5 kA) prototype was successfully tested 47

48. Why is this better than other schemes? 1.No precious (Pt, Ag, Au, Pd) metals required 2.No materials limitations: Ti and Li 2 CO 3 -Li 2 O 3.No hazardous chemicals involved, no pollution 4.Continuous operation is possible 5.One can use flue gas as a source 6.The system is fully tolerant to SO 2 and No x 7.Capture of CO 2 from air is possible 8.The system is VERY COMPACT >50 kW/m 3 9.CO can be easily converted into liquid fuel (CH 3 OH) 48

49. Can recycling help? Yes, but only partially! Current recycling levels Pb >90% Fe 55-65% Al 40-50% Sn >50% Mg >40% Cu >25% 49

50. Large fraction of materials cannot be recycled Recycled already >50%

51. 1.there is very little flexibility in the ability to divert energy resources to new technologies 2.production of those materials that are by-products cannot be increased rapidly 3.recycling can provide only a partial relief Optimism and Realism We need new ideas NOW 51