hydrogen as a fuel made by electrolysis - zsw-bw.de · -19-advanced alkaline electrolysis...

Energy Science & Technology IIINovember 12th 2015, Ulm

Andreas Brinner, Ludwig Jörissen

Zentrum für Sonnenenergie- und Wasserstoff-ForschungBaden-Württemberg (ZSW)

Hydrogen as a Fuel made by Electrolysis

- 1 -

The Cycle of Energy and Materials

- 2 -- 2 -

Once there is abundant Electricity from Renewables we will need Energy Storage

Warum neue Energieträger ?

- 3 -- 3 -

What do we want / need?Unlimited Energy and Mobility with no harmfull impact to the environment.

We need coupled systems.

Solar

WindGSP / BCHP

CO2 Speicher

ElectricGrid GAS GRID

Electrolysis /H2 Storage

Methanization

H2

CO2

CH4

Electricity Generation

Electricity Storage

CO2

GASTANK

Electric Energy

Hydrogen Synthetih Methane

BEV FCEV CNG-V

Mobility

H2

CO2

Plug-In HEV Plug-In HEV

BEV: Battery Electric Vehicle

FCEV: Fuel Cell Electric Vehicle

CNG-V: Compressed Natural Gas Vehicle

Plug-In HEV: Plug-In Hybrid Electric Vehicle

GSP Gas and steam power plant

BCHP Block-type heating power station

Warum neue Energieträger ?

Or just a Power Gap Filler?

- 4 -

- 5 -

How to “Destroy” water

H2O ⇌ H2 + 1/2 O2∆G(l)25°C = -237,141 kJ/mol º 1,23 V∆H(l)25°C = -285,830 kJ/mol º 1,48 V

Alkaline Electrolysisconventional electrolysisadvanced electrolysis

Membrane electrolysisPolymer electrolyte

High temperature electrolysisSolid state electrolyte

- 6 -

Electrolyzer Operation

Source: Stolten, FZJ

- 7 -

Thermodynamics of Water SplitingH2O Heat of Evaporation

Source: Schnurnberger, DLR

- 8 -

Thermodynamic efficiencies

In water electrolysis one needs to overcom ∆H

Higher heating value of hydrogen (water in liquid form)∆H0 = 285.6 kJmol-1 1.48 V∆G0 = 237.1 kWmol-1 1.23 VT∆S via heat or electricityWater spliting via electricity

Lower heating value of hydrogen (water in vapor form)∆H0 = 241.8 kJmol-1 1.25 V∆G0 = 228.6 kWmol-1 1.19 VT∆S via heat

- 9 -- 9 -

Water Electrolysis (Principles) -1

Verfahren zur Wasserstoffherstellung

- 10 -

Water Electrolysis (Principles) -2

Quelle: T. Smolinka, M. Günther FhG-ISE, J.Garche, FCBAT

Quelle: ELT; www.elektrolyse.de Quelle: E-ON / SWB Quelle: R. Hino / JAERI - Japan (angepasst)

Verfahren zur Wasserstoffherstellung

Technology Temperature Cathode (HER) Charge carrier Anode (OER)

Half-cell reactions, Temperature Range and Charge Carriers of the dominant electrolysis processes

- 11 -

Some Examples globallly

Quelle: M del Pilar, INTA, Spanien, B. Simonsen, IET, Norwegen, S. Schoenung, OA, USA

Projektbeispiele für globale Elektrolyseprojekte

- 12 -

Some experimental / laboratory installations

Quelle: M del Pilar, INTA, Spanien, B. Simonsen, IET, Norwegen, S. Schoenung, OA, USA

Projektbeispiele für globale Elektrolyseprojekte

- 13 -

Water Electrolysis is Known for quite some Timea few examples

ELT, 30bar, 2,4MW

Alkaline Electrolysis (AEL)

PEM-Elektrolysis(PEMEL)

Solid Oxide Electrolysis (SOEL)

Not yet commercially available

Power: 1 kW – 2,5 MWPressure: atmospheric – 100 bar

Power: 0,1 kW – 100 kWPressure: atmospheric – 100 bar

Hydrogenics, 10bar, 320kW

Hydrotechnik, 1bar, 0,6MW

ABB, 1bar, 100kW, bis 2000

Siemens, 50bar, 100kW, ab 2012

FUMATech, 10bar, 1,7kW

Idaho NL, 1bar, 17,5kW

Kommerzieller Stand der Elektrolysetechnik

But lots of promises

- 14 -

Conventional Alkaline Electrolysis

- 15 -

Separators for Water Electrolysis (I)


- 16 -

Separators for Water Electrolysis (II)


- 17 -

Electrode Materials


- 18 -

Reduction of Internal Resistance

- 19 -

Advanced Alkaline Electrolysis

Minimization of electrode gap (zero gap)Electrodes are in direct contact with the separator

Electrode shapePerforated metal sheet as electrode with adapted diameter,

Cathode (Hydrogen evolution: 0,5 mm)Anode (Oxygen evolution: 1 mm)

Special shape of holes (conical shape)

Separator / DiaphragmWettability, thermal StabilityUsed to be asbestous, today oxide (Ni, Zr, …) powder in a microporous polymer

Catalytic electrodesCathode: Nickel (partially alloyed)Anode: Metal oxides (e.g. Ni Co2O4, LaNiO3, LaSrCoO3)

- 20 -

Technologies

Pressurized Electrolysis

AdvantagesVery compact, low piping diameterRoom for further improvementDirect coupling to various industrial applications

DisadvantagesHigh investment costLarge control effortIncreased safety requirementsLower dynamic range (30-100% @ 10 bar)Increased maintenance effort

Atmospheric electrolyzers

AdvantagesSimple and robust systemsSimple controlLarge dynamic range (20% -100%)20%-30% lower capital investment compared to pressurized elecrolyzersReliable, long term experience

DisadvantagesLarger footprintMore effort for gas dryingAdditional cost for additinal compression stageLimited high load capabilioties

Source: Wenske, Enertrag

- 21 -

Advanced Alkaline Electrolysis

- 22 -- 22 -

Alkaline Electrolysis Cell

Quelle: A. Brinner, DLR-TT, Stuttgart

Elektrolyse entscheidend für Erfolg !

- 23 -- 23 -

Advanced Pressurized Electrolyzer using vacuum-plasma-sprayed Electrodes (CLR-Konzept)

Quelle: Hysolar Final Report, Phase II 1992- 1995, Stuttgart

Comparison at 500 mA/cm2

1,7 kWN alkaline laboratory electrolyzer,atmospheric operation,

22 % energy saving as compared toblank metal electrodes

10 kWN alkaline pressurized electrolyzer,

5 bar operating pressure,18 % energy saving as compared to

im Vergleich zuBlank metal electrodes

Leistungsanpassungsprinzipien

- 24 -

How to Connect Cells

Bipolar Design

CharacteristicCell Electrical series connectionVoltage is the sum of individual cell voltages

AdvantagesMinimization of voltage drop, better efficiencyCompactBetter adaptability to applications

DisadvantagesMore complicateddesignOne dect cellleads to a defect stack

Unipolar Design

CharacteristicCells connected in parallelLow voltage, high current

AdvantageRuggedLow investment costFaulty cells can be mothballed easily

DisatvanragesBukyLittle potential to improve energy efficiency

Source: Wenske, Enertrag

- 25 -- 25 -

Alkaline 0,5 MWN Pressurized Electrolyzer

N2-iner-tization

Elektrolysisstack

H2-Water-Separation

Waterseparator

Waterloop

Causticloop

Quelle: eigene Aufnahme


- 26 -

Alkaline Electrolysis Plants with Long History

Source: Smolinka, ISE

- 27 -

Large Units have been Realized in AEL


- 28 -- 28 -

Electrolyte-cooler

Electrolysis-stack

Gas-Separation

Electrolyte-collection

Electrolyte-loop

Advanced Atmospheric, Alkaline Elektrolyzer having2400 kW Electric Power Input

Weiterentwicklung der Wasserstofferzeugung

- 29 -

And AEL is (Re)-Entering the MW-Class


- 30 -

Membrane Eectrolysis

Polymer electrolyte membranePerflourinated sulfonic acide.g. Nafion

Cathode catalyst: PtAnode catalyst: Ir or Ru-OxideCurent collector: Titanium

[-CF-CF2-(CF2-CF2)n-]mO-CF2-CFO-CF2-CF2-SO3H

CF3

- 31 -

Membrane electrolysis

- 32 -

PEM Electrolyzers gradually Grow


Mainz Energy Park

Hydrogen production from wind-electricity

Pressurized PEM-electrolyzer upto 6 MW

Hydrogen use for vehicles and asfeed-in gas to the natural gas grid

- 33 -Source: Siemens

- 34 -

Advantages Solid Oxide Electrolysis

Decreased amount of electrical energy requiredImproved reaction kineticsHeat from high temperature heat source or internal lossesAdiabatic operation possibleHeat utilizationReduced operating costTypical operating temperatures approximately 850°C.

Source: A. Friedrich, DLR

- 35 -

Solid Oxide Electrolysis (Hot Elly)

- 36 -

Modern SOEC

Source: A. Friedrich, DLR

- 37 -

Comparison of Electrolysis Technologies


- 38 -

Water Electrolysis is a System Issue

Crucial ComponentsCaustic loop (KOH)Gas caustic separator, scrubberGas purification (oxygen removal, drying)Power electronicsHeat management

- 39 -

Electrolyzer Efficiencies


- 40 -- 40 -

Coupling of Energy ConvertersThe Hysolar-ProjectTechnology development, Investigation & Analysis of different ways to couple Photovoltaics and Electrolysis

Principle

Technical Realization



- 41 -- 41 -

350 kWN Photovoltaic-Field Solar Village bei Riyadh, Saudi Arabia

Quelle: eigene Aufnahme


- 42 -- 42 -

Dynamic Coupüling of Photovoltaics and Electrolysis

27.10.89

Optimum Operation

19.09.89

Minimum Operation

19.05.89

Dynamic Operation

Measurements were taken during the German-

Saudi-Arabian ProjectHYSOLAR



- 43 -- 43 -

Dynamic Wind Electrolysis Coupling

1997

Dynamic Electrolysis

Messungen im Rahmendes

Europäischen Joule II-Projektes

JOU2-CT93-0413

1996

Wind Turbine TestQuelle: W. Hug, H. Dienhart, DLR-TT, Stuttgart


- 44 -- 44 -

Coupling of Wind and Hydrogen Systems need Conditioning!

Übertragung der Ergebnisse auf Wind-Elektrolysesysteme

Electronisc Power Conditioning ELA

Electronic Voltage Conditioning ESA

Quelle: W. Hug, H. Dienhart, DLR-TT, Stuttgart

- 45 -- 45 -

Operation of Electrolyzers using Renewable Energies is efficient

Total electrolysis efficiency of 70%for an operating day using activated

electrodes

Total electrolysis fefficiency of 55%for an operating day using non

activated electrodes

10 kW Electrolyzer

350 kW Electrolyzer

Quelle: A. Brinner, DLR-FK, Stuttgart


Thank You Very Much For Your Kind Attention

hydrogen as a fuel made by electrolysis - zsw-bw.de · -19-advanced alkaline electrolysis...

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