Molten Carbonate Fuel Cell

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Molten Carbonate Fuel Cell

Introduction

 Molten carbonate fuel cells (MCFCs) use a molten carbonate salt suspended in
a porous ceramic matrix as the electrolyte. Salts commonly used include
lithium carbonate, potassium carbonate and sodium carbonate.
 They operate at high temperature, around 650 0C and there are several
advantages associated with this. Firstly, the high operating temperature
dramatically improves reaction kinetics and thus it is not necessary to boost this
with a noble metal catalyst.
 The higher temperature also makes the cell less prone to carbon monoxide
poisoning than lower temperature systems. As a result, MCFC systems can
operate on a variety of different fuels, including coal-derived fuel gas, methane
or natural gas, eliminating the need for external reformers.

Working

 In a molten carbonate fuel cell (MCFC), carbonate salts are the electrolyte.
Heated to 650o C (about 1,200o F), the salts melt and conduct carbonate ions
(CO3) from the cathode to the anode. At the anode, hydrogen reacts with the
ions to produce water, carbon dioxide, and electrons. The electrons travel
through an external circuit, providing electrical power along the way, and
return to the cathode. There, oxygen from air and carbon dioxide recycled from
the anode react with the electrons to form CO3 ions that replenish the
electrolyte and transfer current through the fuel cell.
 High-temperature MCFCs can extract hydrogen from a variety of fuels using
either an internal or external reformer.
Chemical Reaction

Figure 10. Configuration of molten carbonate fuel cell (MCFC) system.

 The half-cell reactions of the MCFC are:

 Merging the half-cell reactions of the anode and the cathode yields the overall
reaction of the fuel cell:

 In MCFC fuel cells, the reactant essential by the fuel cell is not limited to
hydrogen like other most fuel cells. Here, CO can also act as a fuel through the
following electrochemical reaction at the anode,

 The cathode reaction would be the same as when hydrogen is supplied to the
anode.
Components

Electrolyte

 The electrolyte used for MCFCs is a molten mixture of potassium carbonate


(K2CO3) and lithium carbonate (Li2CO3). In order to improve the pore size
delivery and performance of the electrolyte, a small quantity of sodium
carbonate (Na2CO3) and carbonate of earth-alkaline metals is added to the
mixture.
 Because of the high conductivity of molten carbonates, there is no need for a
supporting electrolyte like those needed when using water or organic solvents
as electrolytes.
 The use of immobilized molten carbonate suspended in lithium aluminum
oxide as electrolyte allows for the direct use of fuel mixtures with high
concentrations of carbon monoxide and carbon dioxide

Electrodes

 Nickel-based electrodes and can be constructed as a stack of bipolar plates. The


system must include a system for recycling carbon dioxide in gaseous phase
that includes a water separation process. The simplified configuration diagram
of a MCFC is shown in Figure 10.
 At the high operating temperature, a Nickel anode and the Nickel oxide
cathode is able to promote the electrochemical reaction. This means lower
production costs compared to low temperature fuel cell, where the catalyst
electrode is usually made of platinum. The Ni electrodes are less prone to CO
poisoning, hence coal-based fuel can be used, especially since internal
reforming can take place.
 The main problem with the electrodes is their solubility in the electrolyte by
Ostwald ripening, which is a dissolution/reprecipitation process. It decreases
the internal surface of the porous nickel oxide cathode, causing it to deteriorate.
The solubility of nickel oxide (cathode material) is dependent on the cathode
potential and temperature. The solubility of Ni and NiO in Li/Na was found to
be lower than in Li/K melts.
 Although Li/Na melts have been found to have superior performance compared
to Li/K melts, the lower oxygen solubility reduces the cathode performance on
lean gas with a low oxygen partial pressure (below 0.1 bars).

Figure 11. Solubility of electrode in electrolyte

Catalysts

 Since they operate at extremely high temperatures of 650 °C (roughly 1,200 °F)
and above, non-precious metals can be used as catalysts at the anode and
cathode, reducing costs.
 The materials for the anode that are used must withstand a reducing
environment. Copper, cobalt, and nickel with additives such as aluminum or
chromium can be used as an electrocatalyst for the oxidation of hydrogen at the
anode. The additives increase the life and stability of the anode when subjected
to sintering and creeping under compression forces of the stack.

Advantages

 These fuel cells can work at up to 60% efficiency for fuel to electricity
conversion, and overall efficiencies can be over 80% in CHP or CCP
applications where the process heat is also used.
 they are more resistant to impurities than other fuel cell types and are not prone
to poisoning by CO2 or CO. Thus, MCFCs can use gases derived from coal or
carbon oxides as fuel.
 MCFCs work well with catalysts made of nickel, which is much less expensive
than platinum.
 High operating pressure, which results in lower irreversibility.
 Suitable for use as combined cycle
 High operating temperature, which results in improved reaction kinetics and
lower irreversibility.

Disadvantages

 The primary disadvantage of current MCFC technology is durability. The high


temperatures at which these cells operate and the corrosive electrolyte used
accelerate component breakdown and corrosion, decreasing cell life.
 Disadvantages associated with MCFC units arise from using a liquid electrolyte
rather than a solid and the requirement to inject carbon dioxide at the cathode
as carbonate ions are consumed in reactions temperature corrosion and the
corrosive nature of the electrolyte but these can now be controlled to a achieve
a practical lifetime.
 Several commercialization challenges exist for MCFCs such as corrosion, short
lifetime, relatively slow oxygen reduction reaction, low power density, and
high cost; therefore, efforts to resolve these and further improve efficiency are
ongoing.
 Not suitable for portable applications

Applications

 MCFCs are used in large stationary power generation. Most fuel cell power
plants of megawatt capacity use MCFCs, as do large combined heat and power
(CHP) and combined cooling and power (CCP) plants. the long start-up time
due to the high occupied temperature, which makes the MCFC more suitable
for stationary and continuous operation applications.
 The high operating temperature opens the opportunity of using waste heat to
make steam for space heating, industrial processing, or in a steam turbine to
generate more electricity. Many modern gas-fired power plants exploit this
type of system, called cogeneration.
 In the early 1990s, Ishikawajima Heavy Industries in Japan successfully
operated a 1,000-watt molten carbonate fuel cell power generator for 10,000
continuous hours.
 M-C Power Corporation of Illinois installed a 250 kw MCFC unit at the
Miramar Marine Corps Air Station in San Diego (figure 12) in 1997.
 The fuel cell ran briefly, producing about 160 mwh and generating steam for
use on the base. In spring 1999, the company installed a new 75 kw stack at
Miramar and began a test program intended to gradually scale up the
installation--ultimately intending to test a 300 kw prototype commercial plant.
 Institutions such as hospitals, schools, and some larger commercial operations
that can use both electricity and high-grade heat are potential customers. In
South Korea several large MCFC power plants have been built, including a 59
MW facility that provides both power and district heating to the city of
Hwaseong. Meanwhile in Europe, MCFC units are being developed for marine
use. However, the technology remains relatively expensive and cost reductions
will be necessary to appeal to more than niche or government supported
markets.
Figure 12. MC-Power molten carbonate fuel cell power plant at Miramar, 1997

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