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Study of cell component materials to produce hydrogen using high temperature solid oxide steam electrolyzer
Report of Summer research fellowship Indian Academy of Sciences 14th May -11th July 2012
Supervised by Dr. Indranil Mann, Director Dr. R. N Basu, Head of Fuel Cell & Battery Division Central Glass & Ceramic Research Institute, Kolkata
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Table of Contents
1 Introduction .4
1.1 Theory of electrolysis.5 1.2 Thermodynamics of HTSE.......6 1.3 Polarization loses in SOEC.....6
1.3.1 Ohmic losses ....6 1.3.3 Activation polarization..8 1.3.4 Electrolysis efficiency8
Experimental12
2.1 Equipment used in the experiment ...13 2.1.1 Heating system.13 2.1.2 Steam generating system...13 2.1.3 Measuring system...14 2.2 Experimental procedure..15 2.2.1 Loading of cell into furnace......15 2.2.2 Reduction of cell ...16 2.2.3 Hydrogen production....16 2.2.4 Testing of produced gas..17 2.3 Precaution to be taken..17
4 5
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Abstract
In the recent years, rise in price of fossil fuel has pushed researchers to focus on renewable sources of energy. Hydrogen, the most abundant element in the universe, is the most promising secondary energy carrier because it is storable, transportable, and environmental friendly. So to produce hydrogen with low cost and with high efficiency is a major area of interest today. High temperature steam electrolytic (HTSE) through a solid oxide electrolytic cell (SOEC) has been receiving increasing research and development attention worldwide because of its high conversion efficiency (about 45% 59%) and its potential usage for large-scale production of hydrogen We have tested three solid oxide electrolytic cells and the hydrogen production rate at different voltages. The cells are made of Ni-YSZ as a cathode YSZ as electrolyte and LSCF as anode material and CGO interlayer. This cell is operated by applying voltage, and steam. The steam breaks down to produce hydrogen.
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1. Introduction
In the recent years, rise in price of fossil fuel has pushed researchers to focus on renewable sources of energy. As renewable energy is promising and fulfill the demand of new generation. But renewable energy source like wind solar energy cannot bear the interest of next generation. Now a days research has exploited hydrogen gas efficiency as an efficient energy carrier, this can attend our future energy demands. Hydrogen is directly used up in a fuel cell, producing hydrogen and leaving water as an only by product. We are not fortunate enough to have hydrogen gas readily available as in case of fossil fuel. But we have lot of water which can be used to produce hydrogen. So we have to give input energy to break water to get hydrogen and oxygen as by product. This makes hydrogen gas a good energy carrier not an energy source. Today most part of the hydrogen is produced from natural gas. This makes its costly and leaving carbon print. Now a days it has become important to bring up new technology to produce hydrogen efficiently with low cost. High temperature steam electrolysis (HTSE) is a reliable technology. This technology uses solid oxide electrolyzer cell (SOEC) to break down high temperature steam into hydrogen and oxygen using electrical and thermal energy. High temperature electrolysis is more efficient economically than traditional room temperature electrolysis because some part of the energy is supplied as heat, which is cheaper than electricity, and because the electrolysis reaction is more efficient at higher temperature. At 2500C, electrical energy input is unnecessary because water breaks down to
hydrogen and oxygen through thermolysis. But such high temperature is impractical to attend. Hence proposed HTSE systems operate between 850C -1000C. [1]
The efficiency improvement of high-temperature electrolysis is best appreciated by assuming the electricity used comes from a heat engine, and then considering the amount of heat energy necessary to produce one kg hydrogen (141.86 mega joules), both in the HTSE process itself and also in producing the electricity used. At 100C, 350 mega joules of thermal energy are required (41% efficient). At 850C, 225 mega joules are required (64% efficient).
oxygen ion is being conducted by the electrolyte and hydrogen ion is reduced to hydrogen gas. Conducted oxygen ion reaches the anode where oxygen ion is oxidized to oxygen molecule. The cathode and anodic reaction of the cell are given below; Cathode reaction: Anode reaction: Overall reaction: H2O +2e- -2 O 0.5O2 + 2eH2 + O-2 (ii) (iii) (i)
H2O H2 +0 .502
Figure 1 main operating parts of the solid oxide electrolytic cell. [2]
In the figure 1 the upper layer is the porous cathode. This is a negative electrode with is made of NiO-YSZ. The cathode layer has good ionic and electronic conductivity. Its porous structure provides large three phase boundary for reaction. And the middle layer is electrolyte made of 8-YSZ. This layer is a ionic conductor and an insulter for electronic conduction. This layer transports the oxygen ion to anode surface. The anode is made of LSCF. This anode is a positive electrode where oxygen ion loses there electron to from
oxygen gas.
In the above plot we can see that total electric energy (G) demand decreases with the increase in temperature. Other part of splitting energy is supplied by thermal energy. As TS increase with temperature thermal energy supplied for electrolysis. As a part of energy is thermally, it increases the overall efficiency of the system. High operating temperature gives good electrode reaction kinetics.
1.2
H2O H2+1/2O2 (vi) This is the electrolytic reaction occurring in solid oxide electrolytic cell. For Gibb's free energy (G) is related to potential difference, E, by the following equation; E=/ Or zEF=G (vii)
where F is the Faraday constant (96,487C/mole ) and z denotes the number of electron participating in the reaction, in the case for steam electrolysis is, z =2. The electromotive force (EMF) at standard pressure and temperature is E. In electrolysis reaction, standard Gibbs free energy change in the reaction is given as follow;
G=Go +RT ln(PH2PO2/PH2O) (viii) Or zEF=zEoF +RT ln(PH2PO2/PH2O) (ix) Or E=Eo + ln (PH2PO2/PH2O)
(x)
Equation (x) gives potential in terms of product and reactant partial pressure are known as Nernst equations, and the potential calculated is called the Nernst potential . The Nernst potential, also called open circuit volt age (OCV). Open-circuit voltage is produced by the difference in oxygen partial pressure from one side of the cell to the other. The open-circuit voltage depends on the temperature, the gas partial pressure of H2, H2O at cathode and O2 at anode.
=ohm +con+acti
1.3.1 Ohmic losses
(xi)
An ohmic loss is caused due to resistance to the electron flow and ionic transfer though the cell material. There are also losses in electric metal contact, interconnections, nickel wires and electrodes. The ohmic polarization is linearly depended system (ohm =current X resistance of cell). The ohmic polarization can be written as; 6|Page
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Figure 3 different polarization loses in different part of the cell. [2] Figure 4 Voltage versus current density plot illustrating [4] th e d if fe re n t ty p e s o f p o l a ris a tio n s in th e o p e ra t in g
e le c tro ly s is c e ll .
The activation polarization is defined as the external energy required overcoming the maximum activation energy barrier in order to maintain the electrode reaction. Activation polarization is caused due to activation energy required for the charged ion to transfer trough the electrolyte and electrode materials at triple phase boundary. On the electrode surface first adsorption of gaseous species occurs then it dissociates to adsorbed atoms. Dissociated atoms go for surface diffusion in triple-phase boundaries. There is formation of ions by electron transfer and incorporation of ions into the electrolyte. The activation polarization is a function of:
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material properties microstructure of electrode, operating temperature of cell, reactant and product concentration , Current density.
1.3.4 Electrolysis efficiency Efficiency of the cell is determined as energy supplied to the cell and amount of hydrogen produced from the reaction which carries the energy supplied. This can be calculated by Gibbs free energy change, using the following equation: =
2()
Where; E is the applied voltage , is the cell polarization, Q is the hydrogen production rate in mole/s , is the energy efficiency of cell, I and E are current and voltage respectively.
1.4.1 Electrolyte Electrolyte of an SOEC works as an ionic transporter between two electrodes. Electrolyte should have the following properties to be selected as an electrolyte material. It should be dense and gas tight to prevent mixing of product gases. The electrolyte should be thin so that there is less loses in cell. High ionic conductivity and zero electronic conductivity at working temperature. Must be stable in both oxidizing and reducing environments at high temperature.
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ZrO2 doped with 8 mole % Y2O3, commonly called 8-YSZ or yttrium stabilized zirconia. It has all the properties of the electrolyte. YSZ has a fluorite structure. Zirconia has fluorite structure at high temperature, which is stabilized by yttrium to have fluorite structure at low temperature. As yttrium (Y+3) a trivalent ion is replacing Zr+4 makes oxygen ion deficiency to maintain electric neutrality. Thus, oxygen vacancies are oxide-ionic conducting. 1.4.2 Anode The required properties of anode are as follow:
Mixed electronic and ionic conductivity, Catalytic activity for anodic reaction, Compatibility with electrolyte material (thermal expansion coefficient) Non-reactive with electrolyte at high temperature. LSCF is a ferrite perovskite (La0.8Sr0.2Co1-yFeyO3-) acceptor-doped cobaltite perovskite-type oxides are characterized by enhanced oxygen ion vacancy. High oxygen ion vacancies make the material ionic conductor.
1.4.3 Cathode Cathode material should have catalytic activity for water splitting which is necessary for the kinetics of the reaction. Cathode must have the following properties also: High ionic conductivity which allows the transportation of oxygen ions. High electric conductivity. The cathode should be pours for diffusion of steam.
NiO-YSZ is a cathode material that has good catalytic activity at triple phase boundary to break steam.
Table 1 alternative component material that can be used in solid oxide electrolytic cell.
Porous cathode
Ni-YSZ cermet, Sc0.15Zr0.62Y0.05Ti0.18O1.9 (SZYT), La0.25Sr0.75Cr0.5Mn0.5O3 (LSCM), Zr0.62Y0.2Ti0.18O1.9 (ZYT).
Thermal expansion coefficient of all three cathode, anode and electrolyte should match, otherwise there will be mechanical failure of the cell There some time need of interlayer between electrode and electrolyte so that there no chance of formation of insulating phase.
1.5 History
First use of high temperature steam electrolysis was done by the German Dorniersystem GmbH and Lurgi GmbH in cooperation with Robert Bosch GmbH in the process called high operating temperature electrolysis, HOT ELLY. This experiment was carried out in 1980s they relatively focused on tubular SOEC and assembly technology. They also demonstrated a pilot plant. They has aslo proposed the exothermic and endothermic behavior
of the cell at different voltage ,which graph can be seen in figure 6.
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This figure shows the exothermic and endothermic behavior of the solid oxide electrolysis cell (SOEC). Cell reaction is exothermic when applied voltage is more than 1.3volt (thermoneutral voltage) and cell reaction is endothermic when voltage is less than 1.3 volt. This is graph was given in popular Hot Elly experiment.
Some of the important progresses in HTSE are given in the following table 2. Table 2 history of important HTSE experiments.
by Ni-YSZ
HTSE by Ni-YSZ Westinghouse Electric. Co. HTSE by JAERI Ni-YSZ (Tube SOEC) HTSE by JAERI Ni-YSZ (Planar SOEC)
400 mA/cm 2
1000
LaMnO3
YSZ (Y2 O3 mole fraction 8%) YSZ (Y2 O3 mole fraction 8%)
-----------
950
------------
850
2. Experimental
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Existing electrochemical setup was modified for carrying out the solid oxide electrolytic cell testing. The schematic of the solid oxide fuel cell is given below in following figure. This setup is temporary setup, which has been used for testing only button cell of 16mm diameter. Some of the important instrument which has been used to test SOEC is given in next section.
Figure 7 is the schematic diagram which has been used in SOEC testing experiment .
2.1.1 Heating system Furnace The solid oxide electrolytic button cells are loaded in the furnace. This provides operating temperature for working of SOEC. In the figure we can see the furnace and its controller. Controller controls the operating temperature and current drawn by the furnace to maintain operating temperature.
Figure 9 it is an image of flow meter used in experiment showing different part of flow meter.
. 2.1.2 Steam generating system Humidifier Humidifier is a device, which is used to feed steam into the system. It has a controller which is coupled with thermocouple. Thermocouple provides the temperature of the steam inserted into the system. We can also increase the temperature of steam with the help of the controller. With increase in temperature the amount of steam also increase in with flow of gas.
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Flow meter is a mechanical device, which us two balls to indicate the flow of gas inside the system. This device can provide 10-950 sccm (standard cubic centimeter per minute) flow. Flow knob is used to control the flow of input gas. An image of flow meter used in the experiment
can be seen below.
Gas chromatographer
Gas chromatography is a gas separation technology. The sample mixture is injected and vaporized, if a liquid, at the beginning of the column. The sample mixture is carried through the column by a carrier gas.
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Different gases has different moving rate and gas reach the detector at different time. Lower mass gas reach the detector first then the higher mass gas. We used nitrogen as a carrier gas. In our experiment we used tattler bags to collect the sample gas from outlet of setup. This gas is inserted in the gas chromatographer. Computer software calculates the different time taken by the gas to reach the detector .The peaks formed at different time gives information about the gas.
The data from gas chromatographer is used for making changes in experiment and taking dissection for further experiment. 2.2.1 Loading of cell into furnace Three solid oxide electrolytic cells with 1.5mm thickness and 16 mm diameter are fabricated. Each cell is made of Ni-YSZ cathode, YSZ as electrolyte, LSCF as anode and CGO as interlayer between electrolyte and anode.
6 mm 16 mm
Figure 12 the image in left is cell without Cell holding alumina glass ring, image on right is cell with glass rod ring.
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This cell is fixed with glass rings upper glass ring is 1.5mm thick and lower glass ring is 1mm thick. Upper glass ring is thicker because upper glass ring will melt and come down due to gravity. And more effectively contribute to sealing.
mm
Figure 13 showing the cell with glass ring and its thickness.
1 mm
The cell with glass ring is loaded into the furnace. The furnace has to concentric alumina rods which hold the cell in the place. Through this concentric alumina rods steam and argon is channeled to cell.
Figure 14 image of inside the furnace and the concentric alumina rod.
olding cell
After the cell is loaded into the furnace the temperature of furnace is raised to 1000 in 6 hours. Slow heating will reduce the thermal shock on cell. 1000 is maintained for 1 hour so that glass ring will melt and seal the glass with alumina ring. This ensures that there is no leak of gas. After sealing the cell temperature is brought down to 800 in 2 hours and the temperature is maintained, to carry out reduction of cell.
2.2.2 Reduction of cell While fabrication of Solid oxide electrolytic NiO-YSZ is used as a cathode material. But we need Ni-YSZ for experiment; hence we have reduced the cell to convert NiO-YSZ to Ni-YSZ. Cell is reduced by passing hydrogen to cathode and increasing the flow of hydrogen from
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10 sccm to 358 sccm with argon flow of 50 sccm. To conform the cell is reduced we passed oxygen on other side of cell and measured the OCV (open circuit voltage). OCV starts to increase once the cell start to reduce. We stop reduction once we OCV reach near 1.0 volt. After reduction cells both the side argon gas is passed to conform that there is no hydrogen is present in the pipe line. The argon flow is maintained at 50 sccm for an hour. After an hour the furnace temperature is raised to 925 to start high temperature steam electrolysis. 2.2.3 Hydrogen production A voltage of 1.5 volt is applied across the cell; voltage drop across the cell and current drawn by the cell is measured. Steam is also feed into the cathode using argon flow into the humidifier. Argon took steam with its flow to cathode. Humidifier has a controller which is used to heat the steam to 100. Steam flowing pipe is preheated and its temperature is maintained 5 above humidifier temperature. In the given condition cell starts to work and produce hydrogen.
Figure 15 showing the schematic of working Figure 15 the schematic of working SOEC SOEC.
2.2.4 Testing of produced gas Tattler bags are used to collect sample gas from the SOEC outlet. The tattler bags are marked according to the temperature and voltage at which sample has to be collected. The bags are flushed many times with argon gas. Before collecting sample tattler bags are taken to the gas chromatography test to check whether there is any presence of hydrogen trace in the tattler bag. Once ensured that there is no hydrogen in the tattler bag we used this bag to collect sample gas from the outlet. Sample gas is taken the gas chromatographer. This device detects the presence of gases with different gases. And plots graph count versus time. We compare the standard plot of hydrogen with the plot from the sample. If hydrogen is present we will get peak at same time. In our cause we
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get peak at 0.73 minute. This same procedure was carried out on the different sample and different temperature.
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Sl.no
Sample ID
1. 2. 3.
3.1 Testing of cell 3.1.1 First cell (ID 1057/8) This cell tested for four days, gas sample from cell can only be tested on the 3rd and 4th day only. Given below is the plot from gas chromatographer at different voltage. The entire test is carried out at 925. Table shows the hydrogen production rate increase with applied voltage.
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Table 4 hydrogen production rate at different voltage. Applied voltage 1.3 V 1.5 V 1.6 V Hydrogen production 0.122 sccm 0.150 sccm 0.264 sccm Figure 17 shows the plot of current density vs. voltage and current density vs. power.
We see from the plot power drawn by the cell increases all most linearly with increase in voltage. There little fluctuation in current density vs. voltage this might be due to oxidation of Ni to NiO and reduction caused by produced hydrogen.
Figure 18 is the plot from gas chromatographer showing 0.63% hydrogen in sample.
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ccm
m2
Figure 19 is the plot from gas chromatographer showing 0.63% hydrogen in sample.
3.1.2 Second cell (ID 1057/7) This cell could only be tested for single day only due to cracking of cell. This cell is tested at 925 and 850. At 850 there was no hydrogen found in the sample.
Table 5 showing current density hydrogen production rate at different temperature and applied voltage.
1.5V 1.5 V
As from the table we can see that more hydrogen is being produced at lower voltage. This is an unexpected behavior of cell. As we know that cell has been cracked due which we have stop our experiment. This behavior of cell may be due damage caused to cell while testing of cell. No hydrogen is being produced at 850. Electrolysis is an endothermic reaction so high temperature is needed. As high specific heat capacity of steam may cool down the cell locally. This will reduce hydrogen production and may cause micro cracks due to localized cooling.
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3.1.3 Third cell (ID 1043/2) This cell is tested only at 925 at different voltage. The hydrogen production rate is given in a table below:
Table 6
Hydrogen production rate has first increased with increase in voltage. Up to 1.5 volt but the production rate changed randomly in higher voltage. The possible causes of this behavior are: Oxidation of the Ni YSZ to NiO-YSZ. In our experiment the cell OCV starts fall suddenly. This indicated the oxidation of Ni to NiO. Cell was reduced again by using H2. This increased the OCV. And we continued our experiment. Partial oxidation of cell will give less hydrogen production.
Figure below shows the gas chromatography result of sample (ID 1043/2). In plot (a) 1.3V; (b) 1.8V; (c) () 1.7V; (d) 1.8V.
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Hydrogen production rate: 0.905sccm Current density 1.326/cm2 Applied voltage 1.3 V Voltage drop across cell 0.935 V Power drawn by cell 1.24 watt/cm2
Hydrogen production rate: 0.484sccm Current density 1.89/cm2 Applied voltage 1.8V Voltage drop across cell 1.33V Power drawn by cell 2.63watt/cm2
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Hydrogen production rate: 0.3211sccm Current density 1.83A/cm2 Applied voltage 1.7 V Voltage drop across cell 1.21 V Power drawn by cell 2.213 watt/cm2
Hydrogen production rate: 2.127 sccm Current density 1.942A/cm2 Applied voltage 1.5 V Voltage drop across cell 1.05 V Power drawn by cell 2.039 watt/cm2
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Sample ID 1057/8 was given for XRD analysis. XRD shows other phases formed in the cell. The unmarked peaks show that there are other unknown phases present in the sample. This has been formed due to reaction of cell material at high temperature. Peak of NiO shows that cell has partially been oxidized by high temperature steam.
Figure 20 shows the XRD of sample ID 1057/8 after electrolysis, indicating the peaks of LSCF, CGO, YSZ, Ni and NiO.
4. Conclusion
Table 7 hydrogen production rate of all samples at different applied voltage.
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Sl.no 1.
Sample ID Voltage applied Hydrogen produced (sccm) 1057/8 1.3V 1.5V 1.6V 0.122 0.150 0.131 0.682 0.623 Nil production 0.905 2.217 0.3211 0.484
2.
1057/7
3.
1043/2
The best sample is 1043/2 with highest production of hydrogen at 1.5V. 1043/2>1057/7>1057/8 are sample with decreasing order of performance. In cathode (Ni-YSZ) side of cell some hydrogen should be passed with steam to prevent oxidation of Ni to NiO. From XRD we see some unknown phases are there which is affecting cell performance. These phases may be insulating and prevent conduction. As NiO is present so of O-2 which are not carried by electrolyte may react with Ni forming NiO. LSCF sintered at 925 performed better than LSCF sintered at 975 . In our setup we did not have control over amount of steam so we use argon flow to control the steam flow. The setup should be modified for further experiment as it contains many leaks and required proper sealant. This setup can only be used for preliminary testing of solid oxide electrolytic cell.
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References
[1]http://www.weltemp.eu/.
[2] M.A. Laguna-Bercero , Recent advances in high temperature electrolysis using solid oxide fuel cells; Journal of Power Sources 203 (2012) 4 16 . [3] R.N. Basu Materials for Solid Oxide Fuel Cells, in Recent Trends in Fuel Cell Science and Technology, Chapter-12, pp.284-389, (2006). [4] Kelcey Lnne Eccleston, Sol id Oxide Steam Electrolysis for High Temperature Hydrogen Production ; https://research-repository.st-andrews.ac.uk/ . [5] Xuedi Yang, Cathode Development for Solid Oxide Electrolysis Cells for High Temperature Hydrogen Production. https://research-repository.st-andrews.ac.uk/ . [6] YU Bo, ZHANG WenQian, CHEN Jing, XU JingMing & WANG ShaoRong, Advance in highly efficient hydrogen production by high temperature steam electrolysis; springer, 2008. [7] G. Schiller, A.Ansar , M. Lang ,O.Patz High temperature water electrolysis using metal supported solid oxide electrolyser cells (SOEC) 7 October 2008,Springer Science. [8] K.W. Harrison, R. Remick, and G.D. Martin Hydrogen Production: Fundamentals and Case Study Summaries; National Renewable Energy Laboratory, January 2010. [9] Sren Hjgaard Jensen Solid Oxide Electrolyser Cell; Ris National Laboratory.
[10] J. H Lee, H. Moon, H.W Lee, J. Kim, J.D Kim, K.H Yoon Quantitative analysis of microsracture
and its related electrical properties of SOEC anode ,Ni-YSZ Cerment;Solid state ionic. [11] J. P EA-Martne, D. M Arrero -L pe , C. Snche - Bautista, A.J. Dos Santos Garca, Effect of a CGO buffer layer on the performance of (La0.6Sr0.4)0.995Co0.2Fe0.8O3- dcathode in YSz-Based SOFC; Cermicay Vidrio. [12] Charusporn Mongkolkachit and Suda Wanakitti, Characterization of (La,Sr)(Co,Fe)O3- Ferrite-Based Cathodes for Intermediate-Temperature SOFCs; National Metal and Materials Technology Center.
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