energia salvestamine ja genereerimine. kütuseelemendid ja...

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Energia salvestamine ja genereerimine.

Kütuseelemendid ja elektrolüüserid

Enn [email protected]

Tartu Ülikool

Keemia Instituut

Füüsikalise keemia ja Rakenduselektrokeemia

õppetoolid

Ettekanne: TEUK 20, EMÜ, 8. nov. 2018

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170 participants from 30 countries !

Elektrolüüser

Eestis genereeritaksesummaarselt momendil

1.9 GW (76-84% põlevkivi)

H2salvestamine

PEMFC; SOFC

QE

E

Sünteetilise kütuse reaktor

H2 H2

SOFC;MCFC

Kondensaator (Skeleton, NT Bene)Li- ja Na-ioon akud

Tuule ja Päikeseenergia tootmine ja salvestamine

E

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• First time voltages over 4 V for a C‐C electrochemical capacitor• 2 000 times faster than a supercapacitor.• First results: energy densities much higher than for electrolyticcapacitors – how far can we go?

• New polymer polydicyanamide was characterized, structure resolved.

[1] T. Romann et al. 4‐10 V capacitors with graphene‐based electrodes and ionic liquid electrolyte. J. Power Sources 208 (2015) 606‐611.

[2] T. Romann, E. Lust, O. Oll, Method of forming a dielectric through electrodereril 3.12.2018

position on an electrode for a capacitor, patent application WO2016050761 A1, 2016.

• Novel high voltage graphene|ionic liquid capacitor technology –mesoporous RGO‐based anode (50‐200 um thick), RGO‐based cathode (0.1‐10 um thick), BMPDCA electrolyte.

From electrochemists to society –Hydrogen energy and economy

https://www.eu2018.at/latest‐news/news/09‐18‐Informal‐meeting‐of‐energy‐ministers.html

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B. Pivovar, N. Rustagi, S. Satyapal, Interface Vol. 27, No. 1, Spring 2018, pp. 47.

Vesinikku toodetakse 70 miljonit tonni aastas

Erinevad elektrienergia salvestamise võimalused

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Erinevate energiaallikate Ragone graafikud

Fuel cell

die Brennstoffzelle

Toпливний

элемент

Kütuseelemendid, W. Ostwald, 1896

H2 O2

H2O + elekter

aKnFRTG/nFE ln/ΔΔ 0

STHG ΔΔΔ

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PEFC PAFC MCFC SOFC Electrolyte Nafion H3PO4 Na2CO3-Li2CO3 ZrO2-Y2O3;

Ce1-xGdxO2-

Operating temp. /C 70-80 200 650-700 500…1000 Fuel H2 H2 H2, CO, CH4 H2, CO, CH4, H2S

CH3OH, C3H8, NH3, gasoline

Expected efficiency (HHV) / %

30-40 35-42 45-60 45…90

Power, current status / kW 12.5 100 1000 10…2500 Efficiency / % 40 40 45 50…85

O. Yamamoto, Electrochimica Acta 45 (2000) 2423.

Madal temperatuur

Kõrge effektiivsus

Polümeer-elektrolüüt

kütuseelement

Fosforhappe kütuseelement

Sulakarbonaadi kütuseelement

Tahkeoksiid kütuseelement

Erinevate kütuseelementide võrdlus

Elektrolüüt

Kütus

Töötemperatuur

Prognoositav effektiivsus

Koguvõimsus, instaleeritud

Effektiivsus

Noble and non‐noble metal catalyst for PEM in 0.1 M KOH

• For PGM catalysts the specific active kinetic current densities increase:

3.1/6.8wt% IrPt‐C(Mo2C)

3.5/4.1wt% RuPt‐C(Mo2C)

20wt% Pt‐Vulcan

3.5wt% Pt‐C(Mo2C)

• ORR catalysts synthesized basedC(SiC) +FeSO4∙7H2O +various organic ligands:

• Measured by P.E.Kasatkin, R.Jäger, E.Härk and P.Teppor current and further work

js

E1/2

RDE 10mV/s

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R.Kanarbik,G.Nurk, I.Kivi, P.Möller, K.Tamm ,etc. Pr0.6Sr0.4CoO3-δ|Ce0.9Gd0.1O2-δ|Zr0.85Y0.15O2-δ|0.6NiO-0.4Zr0.85Y0.15O2-δ

97 % H2+ 3%H2O20 % O2 in N2

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.

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Diagram of co-electrolysis of CO2

and H2O 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) 398–403.

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O. Schmidt et al., Nature Energy 2 Article No. 17119 (2017) (https://www.nature.com/articles/nenergy2017110)

Energia salvestustehnoloogiate hinnad

Energia salvestustehnoloogiate hinnad tulevikus (1TWh tootmismahu korral)


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Energia salvestustehnoloogiate hindade muutused ajas


Energia salvestusmeetodi sõltuvus summaarsetest investeeringutest


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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 3.2.0101.11-0030, Energiatehnoloogia programmi

projekt 3.2.0501.10-0015, Materjalitehnoloogia programmi

projekt 3.2.1101.12-0019,

• Institutsionaalne uurimistoetus IUT20–13

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electrolyte paste

Tape casting Lamination Calcination

O2 electrode H2 electrodeCatalysts

Impregnation

1400‐1500°C

900°C 700‐1200°C

Impregnation method used to prepare Ni-free H2 electrodes

2 μm

2 μm

Porous electrolyte scaffold after the calcination

Impregnated electrodeNi-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

La0.7Sr0.3VO3-δ -SDC+CeO2+Pd | Ce0.8Sm0.2O2-δ | SDC-La0.8Sr0.2CoO3-δ

57% porous SDC scaffoldr50(pore) =1550 nm

75% porous SDC scaffoldr50(pore) = 2200nm

60% porous SDC scaffoldr50(pore) = 2000 nm

0

60

120

180

240

300

360

0

0.2

0.4

0.6

0.8

1

0 0.2 0.4 0.6 0.8 1

P/

mW

cm

-2

E/

V

j / A cm-2

T = 600 °CFuel = 97% H2 3% H2O

0

100

200

300

400

500

600

700

800

0 20 40 60 80 100 120 140 160 180 200 220

i / m

A c

m-2

Time / h

E = 0.6 VFuel: humidified 0.2 atm H2 and 0.8 atm Ar

T = 700°C

T = 600°C

0100200300400500600700800

0 4 8 12 16 20 24

T = 700°C Δi ~ 3%

T = 600°C Δi ~ 5%

0

0.03

0.06

0.09

0.12

0.15

0

0.2

0.4

0.6

0.8

1

0 0.1 0.2 0.3 0.4 0.5

P /

W c

m-2

E /

V

j /A cm-2

T = 600 °C ; Fuel = 97%H2 3%H2O

LSV+CeO2+Pd

LSV+Pd

LSV+CeO2

LSV

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) 1185.K. Tamm, P- Möller, G. Nurk, E. Lust, Journal of the Electrochemical Society, 163 (2016) F586.

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Nafion content 30 wt%

wt%

wt%

Temperature22oC

60

oCEa = max

Ep = max

E1/2 =max

ORR = max

Tafel slope = const

oC

10

50

5

Tafel slope = max

The best performance was achieved for 20wt% Pt‐C(Mo2C) catalyst intermixed with 30wt% Nafionionomer @ 60oC in 0.1 M KOH

• R.Jäger et.al, ECS Trans. (2015) doi:10.1149/06624.0047ecst • R.Jäger et.al, J. Electrochem. Soc. (2016) doi:10.1149/2.0861603jes• R.Jäger et.al, J. Electroanal. Chem. (2016) doi: 10.1016/j.jelechem.2015.12.018• E.Härk et.al, J. Solid State Electrochem. (2017) doi: 10.1007/s10008‐017‐3521‐7

https://www.theicct.org/sites/default/files/publications/Hydrogen‐infrastructure‐status‐update_ICCT‐briefing_04102017_vF.pdf

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Seade Aku Superkondensaator

Elektroodi protsess Elektrokeemiline oks/red reaktsioon Füüsikaline adsorptsioon

Eluiga (tsükleid) 100…10 000 <1 000 000

Laadimise/tühjenemise aeg Mõni minut kuni mõni tund Mõne sekundi suurusjärgus

Energiatihedus (Wh kg‐1) Kuni 160 0.5 kuni 30

Võimsustihedus (kW kg‐1) 1–3 Isegi üle 50

Efektiivsus (%) 50–90 ~95

Na-ioon

Osaliselt grafitiseerunudSüsinikmaterjal (süsinik nanokerad to-odetud suhkust või jääkidest)

Na‐ioon akud, valmistatud elektrospinningu meetodil, patenteeritud 2015 (USA,World,UK)

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Kõrge pingega grafeen|ioonse vedeliku kondensaator,patenteeritud 2018 ( US,WO, UK)

Tänan kuulamast!

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http://publications.jrc.ec.europa.eu/repository/bitstream/JRC103586/4%20int%20workshop%20on%20h2%20infra%20final%20pdfonline.pdf

46 tk 100 tk

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S.D. Vora et al., ECS Trans. 78 (2017) 3‐19

U. Bünger et al., Chem. Ing. Tech. 2018, 90 , No. 1–2, 113–126

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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 2019.

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.http://solarhydrogeninc.com/tag/solar‐hydrogen/

https://energy.gov/sites/prod/files/2017/10/f37/fcto_2016_market_report.pdf

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https://www.hydrogen.energy.gov/pdfs/review14/h2in_watanabe_2014_o.pdf

Fuel cell

die Brennstoffzelle

Toпливний

элемент

Fuel Cell

H2 O2

H2O + electricity

aKnFRTG/nFE ln/ΔΔ 0

STHG ΔΔΔ

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Mixed conducting ceramics and fuel cells

Unit cell of perovskites (ABO3)

Chair of Physical Chemistry

Cell materials

Solid oxide cell

Pr0.6Sr0.4CoO3‐δ – PSC

Gd0.1Ce0.9O2‐δ – GDC

Y0.08Zr0.92O2‐δ – YSZ

Ni‐Y0.08Zr0.92O2‐δ – Ni‐YSZ

Oxygen electrode

Chemical barrier/electrolyte

Electrolyte

Fuel electrode

06.06.2017 40

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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 JointUndertaken (FCHU II) report data ‐ best in EU.

HT‐XRD electrode configuration and porous structures of studied electrodes

42

High porousity La0,6Sr0,4CoO3-δ

Low porousity

La0,6Sr0,4CoO3-δ

Gd0,15Sr0,85CoO3‐δ

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Expansion of La0,6Sr0,4CoO3‐ unit cell (electrode with low porosity)

43

Diffractogram fragments for La0,6Sr0,4CoO3-with high - and low porousity

44

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Diffractogram fragments for La0,6Sr0,4CoO3-with high - and low porousity

45

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The peak shift values for studied materials at different oxygen partial pressures and temperatures

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PEM kütuseelemendi võimsustihedused eri temperatuuridel

PEM kütuseelemendi ühikraku mõõtmised

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PEMFC ühikrakk– kandja mõjuAsümmeetriline rakk: Pt‐C(Mo2C) | Nafion115 | Pt‐C(Vulcan) tcell =60°CPindala: 5 cm2

Katalüsaatori hulk: 1 mg cm−2

kaasaarvatud 0.7 mg cm−2 Pt

S. Sepp, K. Vaarmets, J. Nerut, I. Tallo, E. Tee, H. Kurig, J. Aruväli, R. Kanarbik, E. Lust, Electrochim. Acta 203 (2016) 221‐229.

Gunnar Nurk, Thomas Huthwelker, Artur Braun, Christian Ludwig, Enn Lust and Rudolf Struis J.Power Sources.accepted

Redox dynamics of sulphur at Ni/GDC anode during SOFC operation at meadium temperatures: An in operando S K-edge XANES study

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

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Kogemuspõhise hinna rakendamine standardiseeritud seadme hinnale



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Erinevate kütuste gravimeetrilised ja ruumalalised energiatihedused

Energiatihedus (M

J/dm

3)

Elektrolüüseri kasutatavus elektrienergia kiireks salvestamiseks

1 kg vesinikku 33,5 kWh elektrit

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PEM elektrolüüser, mis töötab 30 bar (Hz) rõhu all

C. Graves , S. D. Ebbesen , M. Mogensen , K. S. Lackner, Renew. & Sust. Energy Rev. 15 (2011) 1 – 23.

Typical ranges of polarization curves for different types of state‐of‐the‐art water electrolysis cells. Eth,water and Eth,steam are the thermoneutral voltages for water and steam electrolysis, respectively. Erev is the reversible potential for water electrolysis at standard state.

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https://www.theicct.org/sites/default/files/publications/Hydrogen‐infrastructure‐status‐update_ICCT‐briefing_04102017_vF.pdf

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SOFC power systems (hardware demonstrators, prototypes and pre‐commercial 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

60https://en.wikipedia.org/wiki/Natural_abundance

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https://energy.gov/sites/prod/files/DOE_CMS_2011_Summary.pdf

X. Sun , M. Chen , S. H. Jensen , S. D. Ebbesen , C. Graves , M. Mogensen, Int. J. Hydrogen Energy 37 (2012) 17101 – 17110.

Electrical energy demand (ΔG) for electrolysis of H2O and CO2 as a function of temperature.

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Electrolyser

E Estonia total:1.9GW

H2storage

PEMFC;SOFC

Q

E

E

Synthetic fuel synthesis reactor

H2 H2

SOFC(Elcogen);MCFC

Capacitor (Skeleton, NT Bene)Li- ion and Na-ion batteries

Wind and solar energy storageand generation complex

The characteristics and current statusof the different types of fuel cell

PEFC PAFC MCFC SOFCElectrolyte Nafion H3PO4 Na2CO3-Li2CO3 ZrO2-Y2O3;

Ce1-xGdxO2-

Operating temp. /C 70-80 200 650-700 500…1000Fuel H2 H2 H2, CO, CH4 H2, CO, CH4, H2S

CH3OH, C3H8,NH3, gasoline

Expected efficiency(HHV) / %

30-40 35-42 45-60 45…90

Power, current status / kW 12.5 100 1000 10…2500Efficiency / % 40 40 45 50…85

O. Yamamoto, Electrochimica Acta 45 (2000) 2423.

Low effisiency High efficiency

Polymer electrolyte

fuel cellPhosohoric acid fc

Molten carbonate fc

Solid oxide fc

energia salvestamine ja genereerimine. kütuseelemendid ja...

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