THE POTENTIAL OF THE SOLID OXIDE ELECTROLYSER FOR THE PRODUCTION OF SYNTHETIC FUELS

S. H. JENSEN, A. HAUCH, and M. MOGENSEN

Materials Research Department, Ris National Laboratory, DK-4000 Roskilde, Denmark

Improper energy storage systems as well as inefficient conversion technologies are major barriers for a wider application of renewable energy such as wind, photovoltaic and hydropower. Reversible Solid Oxide Cells (SOC) that can be used both as Solid Oxide Fuel Cells (SOFC) and as Solid Oxide Electrolyser Cells (SOEC), have the potential to become a cost effective way to solve the conversion problem: SOEC can split H2O into H2 and O2. When need is H2 can be utilized in a SOFC with high efficiency. SOEC has also the potential of splitting carbon dioxide into carbon monoxide and oxygen. Hence electrolysis using a SOEC on a mixture of steam and CO2 produces syngas, which can be used for synthetic fuel production. Here estimations on production price of H2, CH4 using high temperature electrolysis of steam and CO2 are investigated.

1. Introduction.
The principle of a SOC is sketched in figure 1. The cell basically consists of three different layers. The middle layer (white) is an oxide ion-conducting electrolyte that is gastight. The topmost layer is the positive electrode and the down most is the negative electrode. The electrodes are porous, electron and oxide ion conducting in order to get the gasses into the reaction sites and to get a high three phase boundary where the three species (gas molecules, oxide ions and electrons) can meet and react. A cell voltage is established over the electrodes when gasses with different oxygen partial pressures are fed to the electrodes as described by Nernst equation.1

O2

+
2e-

O2

+
2e-

2O2-

2O2-

2H2O

2H2

2H2O

2H2

Figure 1: Working principles of a Solid Oxide Cell (SOC). Figure 1a shows SOC in fuel cell mode, where H2 is fed to the cell and reacts with oxide ions to form H2O. The reaction continues as long as electrons are allowed to pass through the light bulb in the external circuit and gasses are fed to the electrodes. Figure 1b shows SOC in electrolysis mode where the reaction is the reverse as in fuel cell mode. Here electrons are

forced to the negative electrode by an external voltage supply, indicated as a windmill. This forces oxide ions (taken from H2O) to migrate through the electrolyte from the negative electrode to the positive. During the last two decades intensive research in SOFC has taken place due to a potential of high electricity efficiency (60%) as compared to ordinary gas turbine power plants (30%40%). SOEC were under development as an interesting alternative to ordinary alkaline electrolysis during the 1980'es. The discussions focussed on the use of heat from solar concentrators or waste heat from power stations for this purpose2. Due to the low energy price this development was stopped around 1990, but is now revived by the renewed interest in hydrogen in general and the higher oil prices in particular.

2. Theoretical background
An important advantage of the high working temperature of SOEC compared to that of alkaline electrolysers is the possibility of obtaining a substantial part of the free energy required for water splitting in the form of high temperature heat, and thus the electrolysis is performed with lower electricity consumption, see figure 2a. The thermodynamical trends for steam splitting are also valid for CO2 splitting into CO and O2 as shown in figure 2b. This means that high temperature (850C -1000C) electrolysis of steam and CO2 provides an extremely efficient way of converting electricity into synthesis gas, which may be converted into synthetic fuel using an appropriate catalyst, which may be stored in large quantities in caverns. Besides the thermodynamic argument for high temperature electrolysis the kinetics of a SOC gets increasingly better with temperature, the internal polarisation resistance following an exponential decreasing Arrhenius expression.3 SOC kinetics for different temperatures is presented in Figure 3.
Energy demand for H2O electrolysis
300 Energy demand (kJ/mole) 250 200 150 100 50 0 278
300 Energy demand (kJ/mole) 250 200 150 100 50 0 278 Total energy demand Electric energy demand Heat demand

Energy demand for CO2 electrolysis

H2O liquid

H2O gaseous

478

678

878

1078

1278

1478

478

678

878

1078

1278

1478

Temperature (K)

Temperature (K)

Figure 2: Thermodynamics of steam and carbon dioxide electrolysis. Both steam electrolysis (figure 2a) and CO2 electrolysis (figure 2b) gets more endothermic with temperature. This provides an opportunity to utilise the inevitably produced Joule heat due to the passage of electrical current through the cell and hence reduce the overall electricity consumption and in turn the production price.

1600 1400 Celvoltage [mV] 1200 1000 800 600 400 200 0 -2 -1.5 -1 -0.5 0 0.5 1 1.5 2 2.5 i [A/cm 2] 1000 C 850 C

Electrolyser mode (H2O H2 + O2)

Fuel cell mode (H2O H2 + O2)

Figure 3: Kinetics of a SOC working as an electrolyser cell (negative current densities i) and as a fuel cell (positive current densities i) The tested SOC is a DK-SOFC 2nd generation cell4,5 with a working area of 16 cm2. The internal resistance (slope of the curve) is almost as good in electrolyser mode as in fuel cell mode. Degradation and passivation is a problem of the tested SOC in electrolysis mode so far. Another type of SOEC has proven high sustainability: (1000 oC, i = 0.3 A/cm2 for 1000 h) without degradation.6 It should be noted that the kinetics is far slower for these cells than for the DK-SOFC 2nd generation cell that we tested. The degradation of DK-SOFC 2nd generation cells tested in fuel cell mode is far less than in electrolysis mode. Long-term test (1 year) in fuel cell mode has shown limited degradation.4 Investigations into the reason for the degradation of the DK-cells in electrolysis mode are in progress.

2. System studies
A heat exchanger is used in order to save expenses for heating the feed gas to working temperature of the SOC as shown in figure 4.
e-

Nickel
H2 + CO H2O + CO2 O2

650C
O2-

400C Heat exchanging Heat exchanging

CH4 + H2O H2O + CO2 O2

25C 25C 25C

O2

Figure 4: Sketch of a SOEC system for CH4 production by electrolysis of steam and CO2. CO2 and H2O are fed through the heat exchanger to the cell. Here it is split into H2 and CO (syngas) and O2. On the way out, the synthesis gas is catalysed into CH4 and H2O using a Nicatalyst.

Demineralised water and CO2 are fed through the heat exchanger to the cell. Here it is split into H2, CO and O2 where O2 has migrated trough the gastight electrolyte. On the way out, H2 and CO is catalysed into CH4 and H2O, if a Ni-catalyst is used. This exothermal process gives off heat that is used for steam rising in the inlet part of the heat exchanger. Other types of fuels can easily be made from the produced syngas, by simply inserting another catalyst. The negative electrode of a SOC is made of Ni, which is the preferred CH4 catalyst, but at 0.1 Mpa and 650 oC only small amounts of CO and H2 is catalysed into H2O and CH4.7 Therefore a Ni catalyst is placed downstream in the heat exchanger, where the temperature is lower. If the pressure is increased, more CH4 can be produced at the negative electrode.8 The exothermic formation of CH4 from syngas produces heat that can be utilised within the system. If the heat is produced at the negative electrode, the heat can be converted into free energy in the form of H2 and CO. If the heat is produced downstream at the catalyst the heat can be used for steam rising.

3. Economical assumptions
Table 1 gives the economical assumptions to make an estimate of synthetic fuel production price using the SOEC kinetics at 1000 oC as presented in figure 3 (electrolyser mode). Assuming CO2 is captured from air, the produced synthetic fuel will be CO2 neutral. For this reason the CO2 cost per tonne is taken to 20 US$, since the technology for wind-scrubbing is quite new. The Gibbs free energy to capture CO2 from air is only 0.50 GJ/tonne equivalent to 1.8 US$ per tonne assuming an electricity price of 1.3 US/kWh Table 1. Input assumptions for calculation of synthetic fuel production costs. Etn is thermo neutral potential where the produced joule heat in the cell equals the heat consumed by the electrolysis process and steam rising. Fuel cell stack Investment cost Interest rate Depreciation time Operation time Water cost CO2 cost Electricity price Cell temperature Cell voltage H2O utilization Energy loss in Heat Exchanger 2100 US$/m2 cell area 6300 US$/m2 cell area 5% 10 years. 5 years 2.3 US$/m3 20 US$/tonne 1.3US/kWh (3.6US$/GJ) 1000 C 1.48 V (Etn) 71% 5%

4. Results of economical calculation

Using Table 1 as input for a calculation of production prices for H2 and CH4 we found: H2: 4.8 US$/GJ equivalent to a crude oil price of 29 US$/barrel using the higher heating value.

CH4: 7.8 US$/GJ equivalent to a crude oil price of 48 US$/barrel crude oil using the higher heating value.9,10 Figure 5 shows the parts of H2 and CH4 production price given the assumptions in table 1. It is seen that electricity costs for electrolysis and steam rising is the largest part of the production price. Hence the main dependence of production price is that of electricity price. Note that these production prices are calculated at Etn, which means that the efficiency * is 98% for H2 production and 76% for CH4 production!

CH4 58%

H2 19%

Loss in heat exchanger Reversed osmosis water Investment depriciation Electricity for electrolysis Electricity for evaporation CO2 capture

17%
66%

3% 2% 10%

1% 1% 14% 9%

Figure 5: Parts of H2 and CH4 production price. It is seen that electricity costs dominates investment cost, losses in heat exchanger and water costs. In Figure 6 the H2 and CH4 production price dependency of the electricity price is shown. Since the reversible SOC, can work both, as a SOEC and SOFC only small investment cost is to be included when converting the fuel back to electricity. Hence the resulting buffered electricity price can be estimated to 4.8 US$/GJ/0.6 = 8 US$/GJ or 2.9 US/kWh. It should be noted that this calculation does not include costs for storage or distribution of H2, which will of course increase the buffered electricity price.

= H 25 C /El , where El is the electric energy used to form 1 mol H2. El is calculated as the sum of losses in
o
o

the heat exhanger, evaporation electricity and reaction electricity.

160 equiv. crude oil price [US$/barrel] 140 120 100 80 60 40 20 0 0 1 2 3 4 5 Electricity cost [US/kWh] H2 CH4 H2 (low temp. electrolysis)

Figure 6: H2 and CH4 production price given as equivalent crude oil price vs. electricity price. For comparison is presented the estimated H2 production price estimation from alkaline electrolysis.11

5. Conclusion
If low electricity is available as for instance Norway or Iceland, there is a potential for synthetic fuel production at prices that are comparable with todays prices for conventional fuel. Better thermodynamical conditions due to the high working temperature gives SOEC an important advantage compared to low temperature alkaline electrolysis. Using a catalyst downstream in the heat exchanger for CH4 production makes it possible to save expenses for steam rising, which is a significant part of the production price.

6. Acknowledgement
Thanks to NEFP and the entire Ris National Laboratory SOFC group for assistance in this work.

7. Reference List
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