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1 Energia salvestamine ja genereerimine. Kütuseelemendid ja elektrolüüserid Enn Lust Tartu Ülikool Keemia Instituut Füüsikalise keemia ja Rakenduselektrokeemia õppetoolid Ettekanne: TEUK 20, EMÜ, 8. nov

2 170 participants from 30 countries! Elektrolüüser H 2 H 2 H 2 salvestamine Sünteetilise kütuse reaktor Tuule ja Päikeseenergia tootmine ja salvestamine E Eestis genereeritakse summaarselt momendil 1.9 GW (76-84% põlevkivi) Kondensaator (Skeleton, NT Bene) Li- ja Na-ioon akud PEMFC; SOFC Q SOFC;MCFC E E 2

3 Novel high voltage graphene ionic liquid capacitor technology mesoporous RGO based anode ( um thick), RGO based cathode ( um thick), BMPDCA electrolyte. First time voltages over 4 V for a C C electrochemical capacitor times faster than a supercapacitor. First results: energy densities much higher than for electrolytic capacitors how far can we go? New polymer polydicyanamide was characterized, structure resolved. [1] T. Romann et al V capacitors with graphene based electrodes and ionic liquid electrolyte. J. Power Sources 208 (2015) [2] T. Romann, E. Lust, O. Oll, Method of forming a dielectric through electrodereril position on an electrode for a capacitor, patent application WO A1, From electrochemists to society Hydrogen energy and economy news/news/09 18 Informal meeting of energy ministers.html 3

4 Vesinikku toodetakse 70 miljonit tonni aastas B. Pivovar, N. Rustagi, S. Satyapal, Interface Vol. 27, No. 1, Spring 2018, pp. 47. Erinevad elektrienergia salvestamise võimalused 4

5 Erinevate energiaallikate Ragone graafikud Kütuseelemendid, W. Ostwald, 1896 ΔE 0 ΔG/nF ΔG ΔH TΔS RT / nf ln Ka H 2 O 2 Fuel cell die Brennstoffzelle Toпливний элемент H 2 O + elekter 5

6 Erinevate kütuseelementide võrdlus Polümeerelektrolüüt kütuseelement Fosforhappe kütuseelement Sulakarbonaadi kütuseelement Tahkeoksiid kütuseelement PEFC PAFC MCFC SOFC Electrolyte Elektrolüüt Nafion H3PO4 Na2CO3-Li2CO3 ZrO2-Y2O3; Ce1-xGdxO2- Operating Töötemperatuur temp. / C Fuel H2 H2 H2, CO, CH4 Kütus H2, CO, CH4, H2S CH3OH, C3H8, NH3, gasoline Expected Prognoositav efficiency effektiivsus (HHV) / % Power, Koguvõimsus, current instaleeritud status / kw Efficiency Effektiivsus / % O. Yamamoto, Electrochimica Acta 45 (2000) Madal temperatuur Kõrge effektiivsus Noble and non noble metal catalyst for PEM in 0.1 M KOH For PGM catalysts the specific active kinetic current densities increase: ORR catalysts synthesized based C(SiC) + FeSO 4 7H 2 O + various organic ligands: j s 3.1/6.8wt% IrPt C(Mo 2 C) 3.5/4.1wt% RuPt C(Mo 2 C) 20wt% Pt Vulcan 3.5wt% Pt C(Mo 2 C) E 1/2 RDE 10mV/s Measured by P.E.Kasatkin, R.Jäger, E.Härk and P.Teppor current and further work 6

7 R.Kanarbik,G.Nurk, I.Kivi, P.Möller, K.Tamm,etc. Pr 0.6 Sr 0.4 CoO 3-δ Ce 0.9 Gd 0.1 O 2-δ Zr 0.85 Y 0.15 O 2-δ 0.6NiO-0.4Zr 0.85 Y 0.15 O 2-δ 97 % H 2 + 3%H 2 O 20 % O 2 in N 2 Joonis 1.4 Elementide suhteline sisaldus maakoores ja sõltuvus aatomi järjenumbrist. Kõige haruldasemad elemendid (kollane ala) ei ole ilmtingimata kõige raskemad vaid on laamade liikumise tõttu liikunud sügavamale maa põude. Selenium ja Telluur on maa koorest lenduvate hüdriididena kadunud. 7

8 Diagram of co-electrolysis of CO 2 and H 2 O in a solid oxide cell, as part of a renewable fuel cycle:contract with Elering AS C. Graves et al. / Solid State Ionics 192 (2011)

9 Energia salvestustehnoloogiate hinnad O. Schmidt et al., Nature Energy 2 Article No (2017) ( Energia salvestustehnoloogiate hinnad tulevikus (1TWh tootmismahu korral) O. Schmidt et al., Nature Energy 2 Article No (2017) ( 9

10 Energia salvestustehnoloogiate hindade muutused ajas O. Schmidt et al., Nature Energy 2 Article No (2017) ( Energia salvestusmeetodi sõltuvus summaarsetest investeeringutest O. Schmidt et al., Nature Energy 2 Article No (2017) ( 10

11 Põhijäreldused ehk Euroopa eesmärgid 2050 aastaks Vesiniku kui kütuse massiline kasutamine nii tööstuses, transpordis kui ka individuaalelamutes ja asumites. Süsiniku asendamine redutseeriva agendina vesinikuga terase (15 25 %) haruldaste muldmetallide ja alumiinimumi tootmises (20 25%). Elektri genereerimine põhiliselt tuule ja päikeseenergia (PV ja CSP) abil. Elektri salvestusvõimsuste arendamine: vesiniku elektrolüüs ja redoks ning erinevad suure mahtuvusega (ka superkondensaatorid) patareid. Energia interneti väljaarendamine ja ilmaennustuse arvestamine energiasalvestuse seadmete juhtimisel. Finantseerida baasuuringuid uute odavamate materjalide ja seadeldiste (suurem mahtuvus, pikem eluiga, suurem laadimis/tühjenemise tsüklite arv) loomiseks. Ringmajanduse kasutuselevõtu stsenaariumide väljatöötamine. Energiajulgeoleku tõstmine hajutatud energia (elektri) genereerimise ja salvestamise vahendusel. Luua seadusandlik baas nn energiaühistute loomiseks. (Väga populaarsed USAs). Toetajad: Euroopa Regionaalarengu Fondi toetatud projektid: Eesti tippkeskus , Energiatehnoloogia programmi projekt , Materjalitehnoloogia programmi projekt , Institutsionaalne uurimistoetus IUT

12 Impregnation method used to prepare Ni-free H2 electrodes electrolyte paste C Lamination Tape casting 2 μm Calcination Porous electrolyte scaffold after the calcination Catalysts O2 electrode H2 electrode C 900 C 2 μm Impregnation Ni-free H2 electrodes analysed: La0.7Sr0.3VO3-δ activated with CeO2 and Pd nanocatalysts in SOFC mode La0.8Sr0.2Cr0.5Mn0.5O3- activated with CeO2 and Pd nanocatalysts in SOEC mode Sr2Fe1.5Mo0.5O6 in SOFC and SOEC mode Sr2Fe1.4Ni0.1Mo0.5O6 in SOFC and SOEC mode Impregnated electrode La0.7Sr0.3VO3-δ -SDC+CeO2+Pd Ce0.8Sm0.2O2-δ SDC-La0.8Sr0.2CoO3-δ 1 T = 600 C ; Fuel = 97%H2 3%H2O LSV+Pd 0.2 LSV 0 0 E/V 0.03 LSV+CeO T = 600 C Fuel = 97% H2 3% H2O j / A cm T = 600 C 300 E = 0.6 V Fuel: humidified 0.2 atm H2 and 0.8 atm Ar T = 700 C Δi ~ 3% Δi ~ 5% T = 700 C T = 600 C j /A cm-2 i / ma cm LSV+CeO2+Pd P / W cm Time / h % porous SDC scaffold r50(pore) = 2000 nm P / mw cm-2 E/V % porous SDC scaffold r50(pore) = 2200nm 57% porous SDC scaffold r50(pore) =1550 nm K. Tamm, R. Küngas, R.J. Gorte, E. Lust, Electrochimica Acta, 106 (2013) 398. K. Tamm, R. Raudsepp, R. Kanarbik, P. Möller, G. Nurk, E. Lust, ECS Transaction, 57(1) (2013) K. Tamm, P- Möller, G. Nurk, E. Lust, Journal of the Electrochemical Society, 163 (2016) F

13 The best performance was achieved for 20wt% Pt C(Mo 2 C) catalyst intermixed with 30wt% Nafion 60 o C in 0.1 M KOH 50 wt % Nafion content 30 wt% Tafel slope = const wt % 5 E a = max Tafel slope = max E 1/2 =max E p = max ORR = max 60 o C Temperature 22 o C o C 10 R.Jäger et.al, ECS Trans. (2015) doi: / ecst R.Jäger et.al, J. Electrochem. Soc. (2016) doi: / jes R.Jäger et.al, J. Electroanal. Chem. (2016) doi: /j.jelechem E.Härk et.al, J. Solid State Electrochem. (2017) doi: /s infrastructure status update_icct briefing_ _vf.pdf 13

14 Na-ioon Seade Aku Superkondensaator Elektroodi protsess Elektrokeemiline oks/red reaktsioon Füüsikaline adsorptsioon Eluiga (tsükleid) < Laadimise/tühjenemise aeg Mõni minut kuni mõni tund Mõne sekundi suurusjärgus Energiatihedus (Wh kg 1 ) Kuni kuni 30 Võimsustihedus (kw kg 1 ) 1 3 Isegi üle 50 Efektiivsus (%) ~95 Na ioon akud, valmistatud elektrospinningu meetodil, patenteeritud 2015 (USA,World,UK) Osaliselt grafitiseerunud Süsinikmaterjal (süsinik nanokerad toodetud suhkust või jääkidest) 14

15 Kõrge pingega grafeen ioonse vedeliku kondensaator,patenteeritud 2018 ( US,WO, UK) Tänan kuulamast! 15

16 46 tk 100 tk 16

17 S.D. Vora et al., ECS Trans. 78 (2017) 3 19 U. Bünger et al., Chem. Ing. Tech. 2018, 90, No. 1 2,

18 Nikola also detailed plans for a North American network of hydrogen fueling stations to support the Nikola One trucks. The web of stations 56 are planned initially will eventually balloon to 364 stations. The first stations will start construction in January 2018 and begin opening in late Hydrogen fuel for the stations will come from solar hydrogen farms owned by Nikola, the company said. The farms are each expected to produce more than 100 megawatts of power using electrolysis and will allow the company more pricing flexibility without having to make long-term hedges against diesel, Milton said. Nikola also exhibited its 107-kilowatt-hour lithium battery pack, which is designed to give its Nikola Zero electric utility task vehicle more than 300 miles of range on a single charge. The company said the 1,000-pound, patent-pending battery can also be inserted into other vehicles starting next year. hydrogen/ 18

19 Fuel Cell ΔE 0 ΔG/nF ΔG ΔH TΔS RT / nf ln Ka H 2 O 2 Fuel cell die Brennstoffzelle Toпливний элемент H 2 O + electricity 19

20 Chair of Physical Chemistry Mixed conducting ceramics and fuel cells Unit cell of perovskites (ABO 3 ) Cell materials Solid oxide cell Oxygen electrode Chemical barrier/electrolyte Electrolyte Fuel electrode Pr 0.6 Sr 0.4 CoO 3 δ PSC Gd 0.1 Ce 0.9 O 2 δ GDC Y 0.08 Zr 0.92 O 2 δ YSZ Ni Y 0.08 Zr 0.92 O 2 δ Ni YSZ

21 AS Elcogen 1kW SOFC Cooperation with Elcogen AS/OY since 2001 (Patents: USA 2005, EU (14 countries) 2005, Russian Fed.2006, etc.). Horizon 2020 Fuel Cells and Hydrogen Joint Undertaken (FCHU II) report data best in EU. HT XRD electrode configuration and porous structures of studied electrodes High porousity La 0,6 Sr 0,4 CoO 3-δ Low porousity La 0,6 Sr 0,4 CoO 3-δ Gd 0,15 Sr 0,85 CoO 3 δ 42 21

22 Expansion of La 0,6 Sr 0,4 CoO 3 unit cell (electrode with low porosity) 43 Diffractogram fragments for La 0,6 Sr 0,4 CoO 3- with high - and low porousity 44 22

23 Diffractogram fragments for La 0,6 Sr 0,4 CoO 3- with high - and low porousity 45 The peak shift values for studied materials at different oxygen partial pressures and temperatures 46 23

24 S.D. Vora et al., ECS Trans. 78 (2017) 3 19 PEM kütuseelemendi ühikraku mõõtmised PEM kütuseelemendi võimsustihedused eri temperatuuridel 24

25 PEMFC ühikrakk kandja mõju Asümmeetriline rakk: Pt C(Mo 2 C) Nafion115 Pt C(Vulcan) Pindala: 5 cm 2 Katalüsaatori hulk: 1 mg cm 2 kaasaarvatud 0.7 mg cm 2 Pt t cell =60 C S. Sepp, K. Vaarmets, J. Nerut, I. Tallo, E. Tee, H. Kurig, J. Aruväli, R. Kanarbik, E. Lust, Electrochim. Acta 203 (2016) Redox dynamics of sulphur at Ni/GDC anode during SOFC operation at meadium temperatures: An in operando S K-edge XANES study Gunnar Nurk, Thomas Huthwelker, Artur Braun, Christian Ludwig, Enn Lust and Rudolf Struis J.Power Sources.accepted Ni-GDC anode has been treated with methane containing sulphur con taminantes ( H2S, Thiophene,etc.) In operando sulphur K edge studies by XANES method indicate the existence of sulphur componds in various oxidation states (6+; 4+; 0; 2-). Kinetic limitations have been observed and analysed 25

26 Kogemuspõhise hinna rakendamine standardiseeritud seadme hinnale O. Schmidt et al., Nature Energy 2 Article No (2017) ( S.D. Vora et al., ECS Trans. 78 (2017)

27 Erinevate kütuste gravimeetrilised ja ruumalalised energiatihedused Energiatihedus (MJ/dm 3 ) Elektrolüüseri kasutatavus elektrienergia kiireks salvestamiseks 1 kg vesinikku 33,5 kwh elektrit 27

28 PEM elektrolüüser, mis töötab 30 bar (Hz) rõhu all Typical ranges of polarization curves for different types of state of the art water electrolysis cells. E th,water and E th,steam are the thermoneutral voltages for water and steam electrolysis, respectively. E rev is the reversible potential for water electrolysis at standard state. C. Graves, S. D. Ebbesen, M. Mogensen, K. S. Lackner, Renew. & Sust. Energy Rev. 15 (2011)

29 S.D. Vora et al., ECS Trans. 78 (2017) infrastructure status update_icct briefing_ _vf.pdf 29

30 SOFC power systems (hardware demonstrators, prototypes and precommercial systems up to 200 kw, concepts at 1MW and above) Q. Nguyen, M.B. Mogensen, The Electrochemical Society, Interface, Vol. 22, No. 4 (2013) p. 55 Haruldaste muldmetallide esinemine maakoores

31 Electrical energy demand (ΔG) for electrolysis of H 2 O and CO 2 as a function of temperature. X. Sun, M. Chen, S. H. Jensen, S. D. Ebbesen, C. Graves, M. Mogensen, Int. J. Hydrogen Energy 37 (2012)

32 32

33 Wind and solar energy storage and generation complex E Estonia total:1.9gw Capacitor (Skeleton, NT Bene) Li- ion and Na-ion batteries E Electrolyser H 2 H 2 H 2 storage Synthetic fuel synthesis reactor PEMFC;SOFC Q SOFC(Elcog en);mcfc E The characteristics and current status of the different types of fuel cell Polymer electrolyte fuel cell Phosohori c acid fc Molten carbonate fc Solid oxide fc PEFC PAFC MCFC SOFC Electrolyte Nafion H 3 PO 4 Na 2 CO 3 -Li 2 CO 3 ZrO 2 -Y 2 O 3 ; Ce 1-x Gd x O 2- Operating temp. / C Fuel H 2 H 2 H 2, CO, CH 4 H 2, CO, CH 4, H 2 S CH 3 OH, C 3 H 8, NH 3, gasoline Expected efficiency (HHV) / % Power, current status / kw Efficiency / % Low effisiency High efficiency O. Yamamoto, Electrochimica Acta 45 (2000)