Journal of Power Sources 296 (2015) 433e439

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Journal of Power Sources

journal homepage: www.elsevier.com/locate/jpowsour

Direct power generation from waste coffee grounds

in a biomass fuel cell
Hansaem Jang a, Joey D. Ocon a, c, Seunghwa Lee a, Jae Kwang Lee b, Jaeyoung Lee a, b, *
a

Electrochemical Reaction and Technology Laboratory (ERTL), School of Environmental Science and Engineering, Gwangju Institute of Science and
Technology (GIST), Gwangju, 500-712, South Korea
b
Ertl Center for Electrochemistry and Catalysis, Research Institute for Solar and Sustainable Energies, GIST, Gwangju, 500-712, South Korea
c
Laboratory of Electrochemical Engineering (LEE), Department of Chemical Engineering, College of Engineering, University of the Philippines Diliman, 1101,
Philippines

h i g h l i g h t s

g r a p h i c a l a b s t r a c t

Waste biomass is directly employed

as a fuel with no any special
treatment.

Waste coffee ground is a fuel for
SOFC-based
carbon
fuel
cell
technology.

Carbonization and gasication take
place
under
experimental
temperature.

Produced in-situ gaseous compounds
highly
enhance
electrochemical
reaction.

a r t i c l e i n f o

a b s t r a c t

Article history:
Received 8 June 2015
Received in revised form
9 July 2015
Accepted 19 July 2015
Available online 1 August 2015

We demonstrate the possibility of direct power generation from waste coffee grounds (WCG) via hightemperature carbon fuel cell technology. At 900  C, the WCG-powered fuel cell exhibits a maximum
power density that is twice than carbon black. Our results suggest that the heteroatoms and hydrogen
contained in WCG are crucial in providing good cell performance due to its in-situ gasication, without
any need for pre-reforming. As a rst report on the use of coffee as a carbon-neutral fuel, this study
shows the potential of waste biomass (e.g. WCG) in sustainable electricity generation in fuel cells.
2015 Elsevier B.V. All rights reserved.

Keywords:
Direct carbon fuel cell
Solid oxide fuel cell
Carbon fuel cell
Biomass
Waste coffee ground

1. Introduction
The worldwide clamor towards less dependence on fossil fuels,
due to the emission of greenhouse gases and energy security issues,
* Corresponding author. Electrochemical Reaction and Technology Laboratory
(ERTL), School of Environmental Science and Engineering, Gwangju Institute of
Science and Technology (GIST), Gwangju, 500-712, South Korea.
E-mail address: jaeyoung@gist.ac.kr (J. Lee).
http://dx.doi.org/10.1016/j.jpowsour.2015.07.059
0378-7753/ 2015 Elsevier B.V. All rights reserved.

has led to the strong interest in using biomass energy [1]. As an

alternative, renewable energy source, biomass absorbs the same
amount of carbon dioxide (CO2) during plant growth, contributing
less to global warming. The only remaining issue, however, is how
to produce energy from biomass without competing with food
supply over the use of arable lands [1]. As such, utilization of waste
biomass byproducts, especially from the food and beverage industry, is key to solving this problem.

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H. Jang et al. / Journal of Power Sources 296 (2015) 433e439

Waste coffee grounds (WCG) are an abundant resource for

biomass-to-energy conversion technologies. The worldwide coffee
consumption has steadily increased over the past decades, reaching
an annual consumption of 8.8 million metric tons and leading to
enormous amounts of organic wastes [2]. There have been various
attempts in using WCG but most of these methods generate byproducts that should be discarded in landlls or eventually incinerated [3e8]. For example, Sena da Fonseca et al. [3] found that
WCG can be added to clay ceramics to enhance the mechanical
strength due to increased water absorption and porosity. Several
research groups [4e8] investigated the adsorption properties of
polyhydroxy polyphenol functional groups in WCG and WCGderived char on heavy metals. In addition, some researchers
[9,10] studied WCG reforming with pyrolysis in order to produce
bio-oil, which can then be processed to synthesize high value
chemicals. Recently, biodiesel was produced from WCG [11,12],
with the oil content, saponiable lipids, and lipid prole varying
according to the regional location and brewing technique [12].
On the other hand, using WCG as fuel in a carbon fuel cell
technology with a solid oxide electrolyte renders multiple advantages. This electrochemical technology offers higher efciency
because it is not subject to Carnot limitations [13]. It mainly produces CO2, which could be captured and reused, and a small
amount of ashes, from which metals and/or other materials could
be retrieved [14,15]. Additionally, it does not require intermediate
conversion steps or pretreatment, improving the overall process
efciency relative to conventional methods [16e19]. Biomassbased carbon fuel cells can be categorized by a fuel treatment
method: i. fuel as a carbonized biomass [14,15,20e22], ii. fuel as a
gasied biomass (similar technique to that of integrated gasication fuel cell, IGFC) [23e26], and iii. fuel as an untreated biomass
[27]. While there have been previous studies using biomass-based
carbon fuel cells as recapitulated above, this is the rst report on
the performance of WCG-powered fuel cells, without the need for
pre-treatment or gasication.
In this study, we showed the direct electrochemical oxidation
performance of WCG-powered anodes, in comparison with that of
carbon black (CB). A detailed analysis on the chemical composition
and nature of WCG and carbonized WCG was performed in order to
explain its electrochemical behavior.
2. Experimental

Fig. 1. Current-potential (j-V) and -power (j-P) curves of carbon fuel cells using
(a) carbon black and (b) waste coffee grounds at different temperatures: - 750  C, C
800  C, : 850  C, and ; 900  C.

temperature. When the temperature reaches up to 600  C from

room temperature, the anode chamber was purged out by ushing
pure Ar gas (99.999%) at a rate of 30 mL min1 to eliminate internal
O2, which could oxidize the fuel. Meanwhile, pure O2 (99.99%) gas
was continuously fed at a rate of 50 mL min1 to the cathode side.

2.1. Preparation of biomass fuel cells

Waste coffee grounds (WCG, Tanay Hills Coffee Beanery,
Hazelnut Arabica, Philippines) were dried at room temperature for
three days (<50% relative humidity). Carbon black powder
(ENSACO 350G, Timcal) was used as reference fuel due to its high
carbon purity. The commercially available anode-supported button
type cell was xed to a Pt (99.9%, 52 mesh, Alfa Aesar) current
collector using Ag paste (Fujikura Kasei). The cell, which is
composed of Ni-YSZ as anode, 8YSZ as electrolyte, and LSM as
cathode, was air-sealed using sealants (Thermiculite 866, the USA;
Aremco ceramabond 668) to prevent combustion of fuels during
the electrochemical reaction.
2.2. Electrochemical characterization
The fuel cell experiments were performed using an optimally
designed apparatus consisting of an alumina ceramic reactor, a
furnace and an electrochemical workstation (NARA Cell-Tech). The
power performance tests were carried out at different temperatures: 750  C, 800  C, 850  C, and 900  C. The reactor was heated up
at a ramping rate of 5  C min1 up to the desired reaction

Fig. 2. The measured high frequency resistance of carbon black (black solid line with
circles, C) and waste coffee grounds (red dash line with squares, -) (For interpretation of the references to color in this gure legend, the reader is referred to the web
version of this article.).

H. Jang et al. / Journal of Power Sources 296 (2015) 433e439

Table 1
The proximate analysis of waste coffee grounds and carbon black as a reference,
performed along with the method in ASTM D3172.
Sample

Moisture
Volatile matter Ash
Fixed carbon
/% as received /% dry basis
/% dry basis /% dry basis

Carbon black
2.02
Waste coffee ground 6.09

3.46
84.86

0.03
1.29

96.50
13.85

The gases entering the reactor were preheated and kept at 100  C to
prevent a dramatic temperature drop, which could inuence the
cell resistance [28,29]. During operation, the internal cell resistance
was measured with an AC-impedance meter (3560 AC mU HiTester,
Hioki) at 1 kHz.
2.3. Characterization
Proximate analysis (ASTM D3172) of WCG showed a high
amount of volatile matter, which could be continuously ventilated
out by Ar gas up to 600  C in the experiment. Hence, the carbonization was performed at 950  C under the presence of atmospheric
oxygen without any inow in order to foster a similar atmosphere
with that in the reactor for characterizing and understanding the
behavior of the fuels. Characterization with FE-SEM (S-4700, Hitachi) and XRD (MiniFlex II, Rigaku) exhibited that carbonization

435

process left a carbon backbone after volatilization of WCG.

To better understand the gasication and oxidation reactions,
TGA was carried out in the experimental temperature range at a
ramp setting of 5  C min1 from room temperature to 900  C. To
reect the real experimental condition, TGA was done in air (TGA50H, Shimadzu) and N2 gas (SDT Q600, TA Instruments Ltd.). The
results of TGA indicated that the WCG experiment displayed unique
trends, which were not found in the test with pure carbon. Thus,
elemental analyzers were employed for estimating organic matter
composition (CHN-S: Flash 2000, Thermo Fisher; O: EA-1110,
Thermo Quest). The result showed the presence of hydrogen and
heteroatoms even after carbonization, which implies various reactions including gasication are available to occur in the range of
experimental temperature since the carbonization was proceeded
at 950  C. These various reactions could happen due to gasication;
therefore, gas analysis was performed to gure out the gas
composition of the anode chamber at the experimental condition
and to identify the gasication reactions. WCG was placed in a
horizontal furnace and then heated at the same temperature
setting with that in the electrochemical tests. The furnace was put
in a vacuum condition and then was fed with Ar gas at a rate of
50 mL min1 until the sampling was nished. At the each pause,
product gas was sampled and then analyzed with GC (7590A,
Agilent Technologies)/MS (5975C, Agilent Technologies). In addition, surface area analysis (Belsorp max, BEL Japan. INC.) was also

Fig. 3. Scanning electron microscope (SEM) images of (a) carbon black, (b) coffee ground, (c) waste coffee ground, (d) 7-min-carbonized waste coffee ground, (e) 15-min-carbonized
waste coffee ground and (f) 30-min-carbonized waste coffee ground.

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H. Jang et al. / Journal of Power Sources 296 (2015) 433e439

Fig. 4. Mass loss curves of carbon black (black solid lines), waste coffee grounds (red
dotted lines) and carbonized waste coffee grounds (red dashed lines), under (a) air and
(b) N2 gas. The TGA measurements were taken at a ramping rate of 5  C min1 (For
interpretation of the references to color in this gure legend, the reader is referred to
the web version of this article.).

sites is low relative to gaseous fuels. For instance, even in gaseous

fuels, reactions can only happen in the adjacency of no more than
10 mm [30e37]. For this reason, the indirect electrochemical carbon
oxidation preceded by the reverse Boudouard reaction might have
been more dominant than the direct carbon oxidation [17]. In
addition, the production of gaseous products during fuel cell
operation could lower the polarization resistance since the gaseous
reactants can easily reach the active sites in contrast to solid carbon
fuels.
The cell ohmic resistance was measured in the high frequency
region (1 kHz) to investigate the possible reactions in the anode. As
shown in Fig. 2, the reverse Boudouard reaction was dominant in
CB, evident from the dramatic drop in cell resistance as the reactor
temperature was increased beyond 700  C. The reverse Boudouard
reaction spontaneously occurred over 800  C, as seen from the
converging cell resistances of all samples. At this point, carbon
monoxide (CO) is the thermodynamically dominant species [38].
On the other hand, WCG exhibited simultaneous gasication reactions other than the reverse Boudouard reaction (e.g. pyrolysis) in
the temperature range considered.
In order to investigate the morphology, crystallinity, and gasication tendencies of the samples, different characterization
techniques (e.g. proximate analysis, scanning electron microscope
(SEM), X-ray diffraction (XRD)) were used. The results (Table 1)
showed that WCG contains more than 80% volatile matter, most of
which could be removed by Ar gas purging up to 600  C while the
rest can be utilized as gaseous fuels. Furthermore, WCG has relatively low xed carbon content (~14%) relative to carbon black
(~97%), yet the former exhibited better fuel cell performance than
the latter. To improve our understanding on the reactions in the
anode, we also used carbonized WCG (cWCG) for comparison with
the pristine WCG, since the carbonization removed volatile materials. It could be expected that the actual WCG-powered carbon fuel
cells have characteristics in between to that of WCG and cWCG. As
shown in the SEM images in Fig. 3, the WCG samples have the same
morphologies, characterized by a honeycomb-shaped structure.
Nonetheless, the removal of volatile materials resulted to a
smoother surface and thinner walls of the structure in cWCG.

performed.
3. Results and discussion
In order to demonstrate the possibility of using WCG as fuel in
high temperature carbon fuel cells, we assembled the cells
comprised of CB and WCG. Expectedly, the overall cell performance
of the carbon fuel cells improved with the increase in the operating
temperature. WCG generally has higher operating voltages with
increasing current density than the CB, as seen in Fig. 1. For
instance, WCG-powered fuel cells exhibited a power density of
87.2 mW cm2 at 900  C, which is almost twice higher than CBpowered anodes (46.3 mW cm2). In addition, the open circuit
potential (OCP) of WCG is noticeably higher than that of CB, which
could suggest that not only carbon electrochemical oxidation occurs in the WCG-powered cells but other oxidation reactions as
well.
The predominance of anodic half reactions occurring at the
triple phase boundary (TPB), where fuel, electron-conducting material (current collector) and ion-conducting material (electrolyte)
meet, strongly inuences the carbon fuel cell performance [17]. In
solid fuels, however, the probability of forming these TPB reaction

Fig. 5. The X-ray diffraction analysis of carbon black (green solid line), carbonized
waste coffee grounds (red solid line) and waste coffee grounds overlapped with
representative monomers and bimer of lignin (black bar, 4-Methoxyphenol), cellulose
(red bar, a-D-Glucose; green bar, Cellobiose) and hemicellulose (blue bar b-DL-Arabinose) (black solid line). (For interpretation of the references to color in this gure
legend, the reader is referred to the web version of this article.)

H. Jang et al. / Journal of Power Sources 296 (2015) 433e439

437

Table 2
Elemental analysis of carbon black, waste coffee grounds and carbonized waste coffee grounds.
Elementa

Sample

Carbon black
Waste coffee ground
Carbonized waste coffee ground

7 min
15 min
30 min

94.996
51.896
71.467
75.914
75.574

0.148
7.249
1.036
1.112
0.618

0
1.651
2.235
1.730
1.719

0
0.083
0
0
0

0.662
21.361
6.128
5.193
5.176

All values tabulated here are in weight percentages.

Thermal gravimetric analysis (TGA) under air condition was

carried out on CB, WCG, and cWCG. As shown in Fig. 4a, the onset of
CB oxidation into either carbon dioxide (CO2) or carbon monoxide
(CO) occurred at around 550  C. On the other hand, WCG was
readily oxidized at a considerable lower temperature, with the gap
between WCG and cWCG at 300e400  C representing difference in
degree of volatilization. While the XRD patterns of cWCG and CB
are similar (Fig. 5), the oxidation initiation temperature of cWCG
(350  C) was notably lower than CB (550  C). The heteroatoms and
hydrogen contained in WCG and cWCG, which are low in concentration in CB, could lead to gasication reactions that form additional oxidizable fuels. By heteroatoms, we refer to elements and
components aside from carbon and ash. As shown in the generalized pyrolysis reaction below, the heteroatoms are crucial in
explaining the behavior of WCG and cWCG during carbon fuel cell
operation [39].

Cx Hy Oz sH2 gCH4 gC2 H4 gCOgCO2 gCs

(1)

In the same manner, the TGA under inert gas condition supports
the observations above (Fig. 4b). Without any oxidants, CB was
stable, as shown by the absence of any mass loss up to 800  C. This
is consistent with the high stability of the almost heteroatom-free
CB in inert gas. In the region between 400  C and 700  C, both
cWCG and CB have parallel mass loss curves, with slightly
decreasing mass as the temperature was increased. Table 2 displays
the difference in the elemental composition between CB, WCG, and
cWCG at various carbonization times. After only 7 min of carbonization, the hydrogen content of WCG dropped from 7.25 wt.% to
1.04 wt.%, which could lead to formation of water and small organic
molecules. Consequently, water could initiate the gasication (e.g.

Fig. 7. Thermodynamically calculated mole fraction of CO (red dash line) and CO2
(black solid line) as a function of temperature at 1 atm (For interpretation of the references to color in this gure legend, the reader is referred to the web version of this
article.).

water-gas shift reaction) [39,40] that improves the oxidation kinetics and lowers the cell polarization. As observed in Table 2,
sulfur seemed to be volatilized rst, and then followed by the other
elements. Then, Ni-YSZ anode could deteriorate with sulfur, which
can be utilized as a possible fuel in liquid tin anode solid oxide fuel
cell system [41]. Thus, this system could be considered in biomass
fuel cells in order to prevent the sulfur poisoning to anode surface
and to enhance cell performance. In addition, carbon, hydrogen and
oxygen are all involved in the gasication reactions, as shown in the
change in their concentrations, consistent with the reaction in
eqn. (1).
Unlike CB, both WCG and cWCG were gasied due to the presence of the intrinsic heteroatoms and its high hydrogen content. To
better understand the reactions in the fuel cell, WCG was gasied
under the same conditions, except that the gasication was carried
out in the absence of O2 ion supply. The presence of O2 ion during
gas production can further oxidize the gaseous products and thus
hide the effect of the intrinsic heteroatoms and hydrogen. The exit

Table 3
Surface area of carbon black, waste coffee grounds and carbonized waste coffee
grounds.

Fig. 6. Gas composition of the gasied waste coffee ground as a function of the reactor
temperature. The gasication products are CO (solid), CO2 (dash), CH4 (short dot), C2H4
(dash-dot), and C2H6 (dot).

Sample

Analytic modela

Surface area/m2 g1

Carbon black
Waste coffee ground
Carbonized waste
coffee ground

BET eq.
BET eq.
Langmuir eq.
Langmuir eq.
Langmuir eq.

782.23
3.14
288.47
511.27
807.54

7 min
15 min
30 min

A proper model is applied in terms of the shape of isotherm.

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H. Jang et al. / Journal of Power Sources 296 (2015) 433e439

Fig. 8. The X-ray diffraction (XRD) analysis of ash retrieved from waste coffee grounds,
including C MgO, : KCaPO4 and A K6Fe2O5.

gas distribution during gasication depends mainly on the reactor

temperature. The gaseous stream is composed of H2, O2, CO, CO2
and various C1 to C3 hydrocarbons, as expected from the biomass
pyrolysis reaction in eqn. (1). The yields of some of the pyrolysis
products from WCG are plotted in Fig. 6. Hydrocarbon products
were predominant at 750  C, proving that the hydrogen content
difference between WCG and cWCG played a crucial role in the
pyrolytic reactions. Upon reaching 800  C, the sample seemed to
have been oxidized by the elemental oxygen within the sample.
Furthermore, at higher temperatures, the CO/CO2 ratio increased
and became well-matched with the thermodynamically computed
COeCO2 speciation (Fig. 7). Regardless of the reactor temperature,
formation of oxidizable gases (e.g. CO and hydrocarbons) provided
additional fuel in the electrochemical system. This is advantageous
due to the higher accessibility of the gaseous reactants to the TPBs,
leading to sustained electrochemical oxidation in the cell. This is
reected in the decrease in the anodic polarization and lowering of
the cell resistance in Fig. 2.
The gasication reactions in Fig. 4b occurred vigorously at
temperatures higher than 800  C, resulting to a steeper mass loss
slope in cWCG than in WCG. This is due to the difference in the
specic surface area (SSA) of the samples, as shown in Table 3.
During carbonization, the SSA of WCG sharply increased with heattreatment time. For instance, the SSA of WCG (807.54 m2 g1) approaches that of CB (782.23 m2 g1) after only 30 min of carbonization. Thus, increased SSA from gasication could provide more
reaction sites between the solid fuels and gases.
Unlike the ash contents of most carbon materials [17], the
amount of ash in WCG is more than 1% (Table 1) and the ash consists not of silicate but mostly of MgO, KCaPO4 and K6Fe2O5 (Fig. 8

Scheme 1. Illustration on a biomass fuel cell powered by waste coffee grounds (WCG).
The gasication of the WCG components is crucial in the production of easily oxidizable gaseous fuels, leading to good electrochemical conversion in the carbon fuel cell.

and Table 4). The impact of these minerals in the fuel cell operation should be considered in future studies. Generally, the presence
of ash in solid oxide fuel cells is not as serious as that in molten
carbonate fuel cells (MCFC) due to the easier separation of ash [17].
Nevertheless, the accumulation of ash onto anode surface and pore
could eventually lead to fuel cell activity degradation by hiding
TPBs.
4. Conclusion
In this paper, we rst report on the characteristics and performance of waste coffee grounds (WCG) as fuel in carbon fuel cell
technology. At a cell operating temperature of 900  C, WCGpowered fuel cells exhibited a maximum power density that is
almost twice than that of carbon black. Using various characterization techniques (e.g. TGA, XRD, GCeMS), we show that the
heteroatoms and hydrogen initially contained in WCG were crucial
in the in-situ gasication of WCG to produce electrochemically
oxidizable products (i.e. H2, CO and hydrocarbons), see Scheme 1.
The gaseous products of gasication could then easily access the
TPB reaction sites, resulting to decreased cell polarization. While it
would be relevant to study in detail the gasication reactions in
WCG-powered fuel cells, the complexity of gasication reactions in
this setting is limiting. Future studies should focus in looking at the
possible effects of the ash composition in WCG in its long-term fuel

Table 4
Energy-dispersive X-ray spectroscopy of carbon black, coffee grounds, waste coffee grounds and carbonized waste coffee grounds (TEM-EDS; Oxford, INCAx, England).
Samplea

Mg

Ca

Fe

Carbon black (Timcal 350G)

97.08
97.79
91.13
94.43
89.72
93.36
91.66
94.42

2.92
2.21
5.48
4.27
6.83
5.34
6.12
4.73

1.16
0.45
0.72
0.28
0.06
0.02

0.64
0.33
0.62
0.32
0.56
0.29

0.35
0.14
0.39
0.16
0.43
0.17

0.75
0.24
0.75
0.24
0.94
0.30

0.45
0.14
0.95
0.30
0.23
0.07

0.03
0.01
0.01
0.00
0.01
0.00

Coffee ground
Waste coffee ground
Carbonized waste coffee ground
a

The upper values in each space are in wt.%-basis and the lower ones are at.%-basis.

H. Jang et al. / Journal of Power Sources 296 (2015) 433e439

cell performance. Nevertheless, this work provides sufcient evidence that WCG can indeed be used as fuels in a high temperature
fuel cell technology.
Acknowledgment
This work was supported by the New & Renewable Energy
Development Program of the Korea Institute of Energy Technology
Evaluation and Planning (KETEP) grant funded by the Korea Government Ministry of Knowledge Economy (No. 20113020030010).
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