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Performance of NiO/YSZ anode-supported solid

oxide fuel cell fueled with landfill gas stream

Cevat Yaman and Yusuf Kucukaga

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April 23, 2020

 Performance of NiO/YSZ anode-supported solid oxide fuel cell
(SOFC) fueled with landfill gas stream
Cevat Yaman1*, Yusuf Kucukaga2
1Environmental Engineering Department, Imam Abdulrahman Bin Faisal University, Dammam, Saudi Arabia
2Environmental Engineering Department, Gebze Technical University, Kocaeli, Turkey

Abstract. Generating electrical energy from landfill gas (LFG) is a challenge due to its low conversion
efficiency. In this study, performance of a NiO-YSZ anode-supported cell operating with LFG feed stream
were evaluated. This study investigated the potential of solid oxide fuel cells (SOFC) to produce electricity
from LFG generated in pilot scale anaerobic municipal solid waste bioreactors. During the initial
experiments, power generation was achieved in the SOFC with direct feeding of the LFG. Different feed
flow rates (10 - 25 mL/min) and varying temperature conditions (700 - 800 °C) were also investigated to
define the optimal conditions. Experiments were carried out at different feed rates and the successful results
obtained from 10 mL/min and 20 mL/min feed speeds. It was also observed that the maximal power values
were between 0.10 - 0.11 Watt/cm2 for all experiments. This study showed that SOFCs can provide
significantly higher energy efficiencies than steam engines for LFG conversion into electrical energy.

Keywords: Landfill gas, solid oxide fuel cells, municipal solid waste, waste to energy

1 Introduction Fuel cells, which are also called electrochemical energy

converters, generate electricity and heat through
At conventional waste disposal sites, the aim is both to electrochemical reactions by combining gas fuel with an
benefit economically from the landfill and re-open the oxidizing gas through an ion-conducting electrolyte.
landfill area at the earliest for beneficial use by Their efficiency is higher than conventional internal
eliminating the environmental risks. In a closed landfill, combustion conversions and they produce very little
the landfill should be monitored by recirculating the emissions. The difference between the fuel cells of many
leachate back to the waste mass until all the toxic types depends on the materials used such as electrolyte,
compounds that are harmful to the environment are anode, cathode and the temperature of use.
completely removed. This is possible if the landfill is
operated as a landfill bioreactor. Landfill bioreactors The main advantage is the flexibility of the fuel. A
increase the moisture content of the waste, thus the waste variety of biofuels with natural gas, alcohol and
is decomposed and stabilized faster. The moisture is hydrocarbons can be used. Fuel cells release electrons,
usually supplied from the leachate produced in the protons, energy and water by using a specific fuel such
landfill. By recirculating of leachate, water content, as hydrogen, methane, methanol, and natural gas. There
nutrients, enzymes and the bacteria are evenly is no direct combustion in fuel cells. Simply a fuel cell
distributed in the landfill. Landfill gas production will operating principle is based on a simple oxidation-
increase, and economic benefit will be gained because reduction reaction as given in the following equation
landfill bioreactors accelerate the decomposition and the (Eq-1).
stabilization.
H2 + O-2 → H2O + 2e- (1)
Today, the two most important issues related to energy
In this reaction, unlike direct combustion, electrons are
systems are energy efficiency and environmentally
switched on in a regular and controlled manner, while
friendly energy production with low emission values.
oxygen ions are passed through a membrane called
These justifications necessitate the use of a high
permeable ions but not permeable to molecules or metal
efficiency technology in electricity generation and
ions. Generally, fuel cells are composed of membranes,
transmission. Solid Oxide Fuel Cells (SOFC), which
such as electrolytes and electrodes. In these electrodes,
generate electrical energy from hydrocarbons with about
oxygen and fuel are ionized to produce electrons and
70% efficiency, are among the most important
water, and oxygen ions are transmitted through the
technologies to be used in the future with various design
electrolyte while electrons are transmitted through
and mechanical improvements. The SOFC systems have
current collectors. The wider the surface of the
higher energy efficiency than the other types of fuel cells
electrodes, the more they show catalytic activity.
(up to 85% with the use of heat released during energy
Therefore, it is very important that the surface area of the
production). These systems are environmentally friendly
electrodes is high. Because the oxygen ions move in the
especially with very low emissions and very quiet
membrane (the electrolyte), the shorter the distance
operation.
between the electrodes, the lower the resistance across
*
Corresponding author: cyaman@iau.edu.sa
the electrolyte. The high-porosity electrodes and the fuel 40%, it can reach 90% in low temperature solid oxide
cell, which consist of a finely stable electrolyte, help to fuel cells. Recently, the SOFC market has been growing
achieve optimum values for high energy. Various significantly [1-8]. Figure 1 shows a typical solid oxide
reactions take place on the anode and cathode sides of fuel cell [9].
solid oxide fuel cells. These reactions produce different
stresses in these regions. The difference between these As one of the hydrocarbon fuels, CH4 is the main
voltages makes it possible to use solid oxide fuel cells as component of natural gas, which can be used directly in
a battery. The reactions taking place at the anode and SOFCs. Previous studies have shown that when CH4 is
cathode are as follows (Eq. 2 through 7). used as fuel, several chemical and electrochemical
reactions occur on the anode side of the fuel cell [10-12].
The result of these reactions consists of six species,
which are deposited carbon (C), H2, CO, CO2, H2O and
H2 + O-2  H2O + 2e- (Anode) (2) residual CH4. A probable reaction in the anode is
methane decomposition (Eq. (8)):
CO + O-2 CO2 + 2e- (Anode) (3)
CH4  C + 2H2 (8)
CH4 + 4O-2 CO2 + 2H2O + 8e- (Anode) (4)

1/2O2 + 2e- O-2 (Cathode) (5)

CO + H2O H2 + CO2 (Anode) (6)

CH4 + H2O 3H2 + CO (Anode) (7)

The anode portion of the solid oxide fuel cell is supplied

with pure hydrogen, hydrocarbons (gasoline, natural gas-
CH4) or alcohols as fuel. These fuels undergo a
processing step to obtain molecules used in the fuel cell
for reactions in equations (2), (3) and (4), such as H2, CO Fig.1: A typical methane-fed solid oxide fuel cell [9]
and CH4. Equations (3) and (4) don’t really occur Removal of carbon using H2 gas was studied in detail by
because the equations (6) and (7) are realized much several authors. It was reported that the separation of
faster. If the equation (3) is realized, carbon monoxide surface carbon from Ni-YSZ causes less damage to the
(CO) in the hydrogen gas is also used as fuel, but if the Ni-YSZ structure compared to removal of carbon with
equation (6) is realized, this CO provides H2 from water oxygen [13]. One study investigated the carbon
and is used as fuel. The same applies to methane (CH4). gasification with H2 in a Ni-YSZ cell and concluded that
The cathode side is supplied with oxygen or another gas the gasification rate varied greatly depending on the H2
such as oxygen-containing air. concentration [14]. Pure H2 gas was observed to
There are several advantages of solid oxide fuel cells. completely gasify the carbon on the surface of the cell.
For instance, fuel processing and desulphurization are Cell stability is an important criterion for SOFC working
improved due to thermal compatibility. Another with hydrocarbon based fuels. Tao et al. [15] added an
advantage of fuel cell is that less cell sintering is additional functional Ce1-xNixO2-y layer to enhance Ni-
required when preparing cell materials and time- SDC (nickel samaria-doped ceria) cell stability using
dependent deformation is reduced, thus increasing the hydrocarbon fuels. This cell exhibited resistance to
geometric tolerances. Furthermore, less thermal stresses carbon deposition and showed a partially stable open
occur at low temperatures, which will reduce the circuit voltage with 0.8% degradation with dry ethanol.
resistance density of the fuel cell. A wide variety of
alternatives are provided for the insulating layers used Landfill gas (LFG) is a product of anaerobic degradation
for sealing in the fuel cell. and mainly consists of methane (CH4) and carbon
dioxide (CO2). Thus, LFG is known as a renewable
Today, fuel cells are one of the most important elements energy source. Waste-to-energy is a well-known concept
for the widespread use of hydrogen energy and other for landfill sites; however, the high energy content of
clean and renewable energy sources. Fuel cells are an LFG is typically converted to electricity by using gas
electrochemical device that directly converts chemical engines. This phenomenon has been proved as a low
energy into electrical energy and releases heat only as a efficient process and has many problems, such as
by-product. Compared to conventional energy siloxane contamination inside the engine.
converters, fuel cells have superior features such as high
efficiency, reliability, modularity, and noise-free The LFG produced in this study is used in the production
operation. Since it generates both electrical energy and of electricity with modular and high technology fuel cell
heat, SOFC systems can meet all the electricity needs of systems which are completely environment friendly and
a house while meeting the heating and cooling needs. produce water vapor only as an end-product. Within the
While the efficiency in current energy systems is 30- scope of this study, this will be a unique study on
converting landfill gas into electrical energy with fuel conversion. Under actual operating conditions, not all
cells instead of using steam engines. In this study, LFG fuel sent to the fuel cell can be converted into energy. In
from a pilot scale anaerobic landfill bioreactor, which this case, the fuel and some of the oxidant supplied to the
contains 900 kg of municipal solid waste (MSW), was system leave the fuel cell before it converts into energy.
used as energy source for a solid oxide fuel cell. Accordingly, fuel use is expressed as the ratio of the fuel
flow corresponding to the electrical current generated in
the system to the actual fuel flow sent to generate the
2 Methodology same current.

2.1 Theoretical Background Three different efficiencies are expressed for fuel cells.
These efficiency statements affect the overall operating
status of the fuel cell. Therefore, the actual efficiency of
The energy conversion efficiency of the fuel cells is not the fuel cell is equal to the three efficiency expressions,
limited to Carnot efficiency and can reach up to 90% the theoretical efficiency, the voltage efficiency, and the
with the combined heat and power system. One of the multiplication of the fuel usage efficiency (Eq. 13).
expressions of efficiency for fuel cells is theoretical
efficiency. Theoretical efficiency is the expression of the
maximum efficiency a fuel cell can achieve and is ereal  eideal .evoltage .eusage (13)
expressed as follows [16] (Eq. 9);
The stoichiometric ratio, which is the inverse of faradic
efficiency, is defined for fuel cells. Stoichiometric ratio
G S
eideal   1 T (9) is a type of expression that is often used to prevent
H H excess oxidant from being sent during the
electrochemical reaction (Eq. 14 and Eq. 15):

Where, ΔG, ΔH and ΔS represents Gibbs free energy, 1

enthalpy and entropy, respectively. Assuming that all c  (14)
Gibbs free energy is converted to electricity for fuel
c
cells, the maximum possible theoretical efficiency can be
calculated as follows (Eq. 10); 1
a  (15)
a
G 237.34kj.kg 1
eideal    83% (10)
H 286.02kj.kg 1 Anode and cathode stoichiometry for fuel cells is usually
more than 1. In other words, more fuel and oxidant is
Generally, the lower thermal value of hydrogen is used provided above 100% fuel usage value. In the literature,
in theoretical fuel cell efficiency calculations. Thus, the stoichiometric ratio of hydrogen is between 1.2 and 2,
yield is more than 83%. The purpose of this here is not while air stoichiometry ranges between 1.5 and 4. In
to increase the efficiency numerically, but to compare it addition, there are many misleading data in the literature
with internal combustion engines (Eq. 11). regarding fuel efficiency. Fuel usage efficiencies vary
according to the flow rate and fuel cell operating voltage
[16].
G 228.74kj.kg 1
eideal    94.5% (11)
H lowerheat 241.98kj.kg 1
2.2 Design of LFG-SOFC system
In fuel cells, cell potential decreases during operation
due to polarizations. Therefore, the net yield depends on
the cell potential Vcell. The voltage efficiency can be LFG was collected from the pilot scale landfill
defined as follows (Eq. 12); bioreactor (LBR) to a flexible gas sampling bag. Then it
was slightly pressurized to sustain a constant flow during
the SOFC energy conversion experiment. Inlet flow of
Vcell
evoltage  (12) LFG was controlled with a gas flowmeter, and different
Vmax flow rates were investigated to identify the maximal
current produced in the SOFC system. Solid oxide fuel
cells were first reduced with hydrogen gas to allow
Where, Vmax is the Nernst potential, or the maximum nickel oxide-nickel conversion. Then, when the
voltage potential, and Vcell is the actual cell potential. operating temperature reached 775 °C, the input LFG
was fed into the fuel cell at different speeds (10 - 20
Another efficiency expression in fuel cells is called fuel mL/min). The gas balloon was gently pressurized and
usage efficiency. Fuel utilization is an expression of how fed at constant speed with the help of rotameter. During
much fuel and oxidant is supplied to the system during SOFC experiments, voltage, power and current values
were recorded instantaneously on computer assisted The current-voltage (i-V) and the corresponding power
system in order to monitor the efficiency of energy density current density figures when the SOFC is fueled
obtained from LFG. with pure CH4 and landfill gas are shown in Fig. 3 and
Fig. 4, respectively. The open circuit voltage (OCV)
values for the Ni-YSZ cells at 775 oC were measured as
Anode supported micro tubular solid oxide fuel cells
0.42-0.90 V with pure methane as the fuel and 0.21-1.00
were used in this study. The cells were developed in a
V with landfill gas as the fuel with feeding speed of 20
nanotechnology laboratory. Anode electrolyte and
mL/min and 0.14-0.98 V with feeding speed of 10
cathode materials were NiO-YSZ (50/50, weight/weight)
mL/min (Fig. 3 and Fig. 4). The open circuit voltage
composite powder, 8YSZ (%8 Y2O3 doped with ZrO2)
values for the Ni-YSZ cells at 750 oC were measured as
and LSM (lanthanum strontium manganite),
0.09-0.97 V with landfill gas as the fuel with feeding
respectively. Anode support layers were prepared via
speed of 15 mL/min and 0.08-0.98 V with feeding speed
thermoplastic extrusion. The active surface of cathode
of 20 mL/min (Fig. 5).
was 3 cm2.

The composition of LFG produced from pilot scale

anaerobic bioreactors was measured by Agilent 6890N
gas retention detector gas chromatography (GC-TCD).
In GC-TCD analysis, Agilent HP-PLOT/Q model
capillary column was used for CO2 capture and Agilent
HP-MOLSIEVE capillary column was used for
separation of other gases. Detailed content of LFG used
in this study is presented in Table 1. To determine the
energy conversion efficiency of the SOFC experiment,
voltage, power and current were recorded during the
experiment by computer-based control system (Fig. 2).

Table 1. LFG content used in SOFC experiments Fig.3. Electricity production from pure methane gas with fuel
cell with feeding speed of 20 mL/min at 650 oC

Gas Unit Value

CH4 % 51,04
CO2 % 27,48
N2 % 12,68
O2 % 3,53
Others % 5,27
H2S ppm 1105

Fig.2. Experimental set up with fuel cell

2 Results

LFG is a mixture of gas with high energy value, which

mainly contains CO2 and CH4 produced by anaerobic
biodegradation of organics in landfills. LFG is converted Fig. 4. Electricity generation from LFG with fuel cell with
into electrical energy with very low efficiency (30-40%) feeding speed of 10 mL/min and 20 mL/min at 775 0C
by conventional internal combustion gas engines.
Producing electrical energy from chemical energy with
an efficiency of approximately 60% from hydrocarbons, Experiments were carried out at different feed rates and
SOFCs will be among the most important energy the successful results obtained from 10 mL/min and 20
conversion technologies to be used in the future. mL/min feed speeds and the results of the pre-test
performed with pure methane gas at 650 °C were 3 Discussion
compared in Table 2. It was also observed that the
maximal power values were between 0.10 - 0.11
Watt/cm2 for all experiments. It can be seen from Fig. 3, Fuel cells are an efficient, combustion-free, virtually
Fig. 4, and Fig. 5 that the highest power densities for the pollution-free power source for a green energy
Ni-YSZ cells were achieved at the highest temperature production that is perfectly environment-friendly,
of 775 oC tested. completely silent and has a few moving parts. The desire
for solid oxide fuel cells to be manufactured at larger
sizes, with more power, less emissions and lower costs
has led to new developments. It was estimated that the
fuel cell production has grown by 44% since 2014 -
parallel to the increase in solar and wind energy in
previous years. This rapid growth is driven by increased
demand for energy diversification and the employment
of alternative energy sources. Because of increased
carbon emissions and extreme climatic events,
businesses and communities demand three things: more
affordable electricity, more durable power and cleaner
energy.

The production of electricity as a result of an

electrochemical reaction rather than fuel combustion
shows that fuel cells are much cleaner and more
sustainable than conventional combustion-dependent
technology. Fuel cells are more environmentally friendly
in two ways: first, they avoid spreading harmful
impurities such as NOx and SO2, which are associated
with respiratory diseases and poor air quality throughout
the world, and the second they reduce greenhouse gas
(GHG) emissions. Fuel cells are continually proving to
be the most efficient, resilient, and sustainable form of
alternative energy generation. As an energy solution that
provides both sustainability and power security, fuel
Fig. 5. Electricity generation from LFG with fuel cell with 15 cells are the leading power generation technology for
mL/min and 20 mL/min at 750 0C businesses and communities now and in the future.

Solid oxide fuel cell fueled with landfill gas has the
potential to generate electrical energy, which seems to be
an alternative to incineration and landfill applications.
Table 2. Electrical voltage, current and power values obtained
from SOFC experiments at 775 oC
However, separating renewable hydrogen from biomass
and landfill gas is not an easy task. Furthermore,
construction and operation costs are quite high, which
Feeding gas

can cause customers to avoid risk. Today, those who

Maximum
Feeding

started using solid oxide fuel cells early started to use

Voltage

Current
density

density
Power

power
speed

government tax incentives and sustainability program

grants.
mL/m Volt A/cm2 W/cm2 W/cm2

20 0,700 0,125 0,088 0,114

Some of the systems that use direct fuel cells generally
%100 CH4
operate at 538 °C and use biogas produced by anaerobic
LFG 20 0,705 0,121 0,085 0,110 digesters. In most projects, the purified landfill gas can
(%51 CH4) be injected into an existing natural gas pipeline that
LFG 10 0,709 0,104 0,074 0,099 directs it to direct fuel cell units elsewhere. However, it
(%51 CH4) is a fact that landfill gas contains moisture, sulfur and
CO2. For landfill gas-fueled fuel cell systems,
desulphurization and moisture removal is required, while
stricter pipeline quality is required for bio H 2, thus CO2
must be removed for directed biogas systems.
4 Conclusions 8. Williams, M. C., Strakey, P. S., Surdoval, W. A.,
Wilson, L. C. (2006). Solid oxide fuel cell
technology development in the U.S., Solid State
Nickel-based anodes are suitable for SOFC technology Ionics 15: Proceedings of the 15th International
when hydrogen gas is used as fuel. Biogas-SOFC energy Conference on Solid State Ion, Part I., 177, 2039-
system, which uses landfill gas as a feed source, can 2044.
meet both electrical and thermal energy needs for homes
away from the grid. However, the obligation to clean up 9. Jelvehnaz M. and Steven C. (2014).
biogas can have a major impact on the total investment La0.6Sr0.4Co0.2Fe0.8O3 Perovskite: A Stable
and operating costs and thus complicate the procurement Anode Catalyst for Direct Methane Solid Oxide
of technology among non-rural communities. Therefore, Fuel Cells, Catalysts, 4(2), 146-161.
the choice of a cleaning system technology, in particular 10. Jiang L., Scott A B. (2003). Operation of anode-
for the small-scale biogas-SOFC energy system, should supported solid oxide fuel cells on methane and
also meet the impurity levels required by SOFC, natural gas, Solid State Ion, Volume 158, Issues 1–
typically less than 2 ppm for H2S. For small-scale 2, Pages 11-16.
biogas-SOFC systems, a suitable gas cleaning unit must 11. Hongxin Y., Hongjie G., Gang C., Abuliti A.,
be very efficient to maintain low pollution levels and Xinwei D. (2011). The conversion among reactions
also economical for small-scale systems. at Ni-based anodes in solid oxide fuel cells with low
concentrations of dry methane, J. Power Sources,
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landfill gas was successfully conducted on anode 12. Marco A. B. and Josephine M. H. (2012). Methane
electrolyte and cathode materials of NiO-YSZ composite Electrochemical Oxidation Pathway over a Ni/YSZ
powder and LSM at 775 0C. This study showed that and La0.3Sr0.7TiO3 Bi-Layer SOFC Anode J.
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