See discussions, stats, and author profiles for this publication at: https://www.researchgate.

net/publication/336886151

A micro‐Tubular Direct Carbon Solid Oxide Fuel Cell Operated on the Biochar
Derived from Pepper Straw

Article · October 2019

DOI: 10.1002/ente.201901077

CITATIONS READS

0 38

8 authors, including:

Fangyong Yu Weimin Zhang

Shandong University of Technology Shandong University of Technology
23 PUBLICATIONS   125 CITATIONS    54 PUBLICATIONS   1,767 CITATIONS   

SEE PROFILE SEE PROFILE

Xiuxia Meng Jie Xiao

Shandong University of Technology Kunming University of Science and Technology
65 PUBLICATIONS   547 CITATIONS    28 PUBLICATIONS   222 CITATIONS   

SEE PROFILE SEE PROFILE

Some of the authors of this publication are also working on these related projects:

Electrokinetic Remediation View project

High performance direct coal fuel cell View project

All content following this page was uploaded by Jie Xiao on 17 June 2020.

The user has requested enhancement of the downloaded file.

FULL PAPER
www.entechnol.de

A Microtubular Direct Carbon Solid Oxide Fuel Cell

Operated on the Biochar Derived from Pepper Straw
Fangyong Yu,* Yishang Wang, Yujiao Xie, Weimin Zhang, Jinjin Zhang, Xiuxia Meng,
Jie Xiao, and Naitao Yang*

cost.[2] DCFCs can be classified into molten

Direct carbon solid oxide fuel cell (DC-SOFC) is a promising energy conversion hydroxide,[3] molten carbonate,[4] and oxygen
system, which can directly convert the chemical energy of biomass into electrical ion conducting solid oxide DCFC[5] in terms
energy with high efficiency and low pollution. Herein, a microtubular DC-SOFC of the diverse electrolytes used. Generally, a
DCFC needs to operate at a relatively high
fueled with the biochar derived from pepper straw for electrical power generation
temperature due to the high activation
is reported. The DC-SOFC operated on pepper straw char gives a maximum energy of carbon oxidation. For the safety
power density of 217 mW cm
2, comparable with 252 mW cm
2 for that with view, the solid oxide electrolyte, which is the
hydrogen fuel at 850  C. Moreover, the lifetime of the DC-SOFC reaches 21 h at a only one in solid state, offers many advan-
discharge current of 100 mA with the fuel utilization of 44.4%. The pepper straw tages over the liquid electrolyte in a DCFC.
char is characterized physically by scanning electron microscopy, energy- Accordingly, the direct carbon solid oxide
fuel cell (DC-SOFC) with all-solid-state struc-
dispersive spectrometer, X-ray diffraction, Raman spectroscopy, thermogravi-
ture has received widespread attention.[6]
metric analysis, and differential scanning calorimetry. The results demonstrate As early as 1988, Nakagawa and Ishida[7]
that the pepper straw char contains natural catalysts in itself and their contri- first proposed the mechanism of DC-SOFC
bution on the electrochemical performance of the microtubular DC-SOFC is on the basis of the experimental results,
analyzed in detail. which consisted of electrochemical reac-
tion of carbon monoxide (1) and carbon
gasification reaction named as the reverse
Boudouard reaction (2).

1. Introduction CO þ O2
¼ CO2 þ 2e
(1)

With the increasing concern on the global climate change caused by
the overconsumption of fossil fuels, there has emerged an urgent
need to explore alternative clean energy resources or utilization
strategies for reducing carbon dioxide emission.[1] However,
because the fossil fuels, especially coal, will still be the major energy
source in the foreseeable future, it is extremely critical to develop
novel technologies which can efficiently convert the intrinsic chem-
ical energy to electricity with low emission. Therefore, among the
various energy convert systems, direct carbon fuel cell (DCFC) has
regained increasing attention due to its high conversion efficiency
and concentrated CO2 product which can be sequestrated with low
Dr. F. Yu, Y. Wang, Dr. Y. Xie, Prof. W. Zhang, Dr. J. Zhang, Prof. X. Meng,
Prof. N. Yang
School of Chemistry and Chemical Engineering
Shandong University of Technology
Zibo 255049, P. R. China
E-mail: yfy316@sdut.edu.cn; naitao@sdut.edu.cn
Dr. J. Xiao
Key Laboratory of Advanced Battery Materials of Yunnan Province
Faculty of Metallurgical and Energy Engineering
Kunming University of Science and Technology
Kunming 650093, P. R. China
The ORCID identification number(s) for the author(s) of this article
can be found under https://doi.org/10.1002/ente.201901077.
DOI: 10.1002/ente.201901077
CO2 þ C ¼ 2CO (2)
According to the operation mechanism, which has been veri-
fied by Xie et al.,[8] the power of DC-SOFC is derived from the
electrochemical oxidation of carbon monoxide. The produced
CO2 from reaction (1) diffuses into solid carbon fuel and reacts
with it to yield more CO from the reaction (2), followed by
diffusing to the electrode to perform the electrochemical oxida-
tion reaction again. In this process, the electricity will be gener-
ated continuously from a DC-SOFC as the carbon fuel being
consumed, as shown in Figure 1. In addition to possessing all
the advantages of DCFCs, DC-SOFC has its unique advantages
in the utilization of fossil fuels, such as higher energy conversion
efficiency and good operation stability, and no feeding gas or
liquid medium involved.
However, there are still several barriers remaining to be over-
come for the performance improvement and widespread applica-
tion of DC-SOFCs. Currently, many types of biomass derived from
crop residues, such as corn cob char,[9] leaf char,[10] wheat straw,[11]
bagasse,[12] pomelo peel char,[13] and walnut shells,[14] have been
adopted as carbon fuels to improve the cell performance due to the
naturally existing catalysts of the reverse Boudouard reaction.
Cai et al.[11] developed an electrolyte-supported solid oxide fuel
cell (SOFC), which yielded a maximum power density of
197 mW cm
2 at 800  C using wheat straw as fuel. An et al.[13]
found that pomelo peel char is a promising solid carbon fuel

Energy Technol. 2020, 8, 1901077 1901077 (1 of 8) © 2019 WILEY-VCH Verlag GmbH & Co. KGaA, Weinheim
www.advancedsciencenews.com
Figure 1. Schematic illustration of operation mechanism of the DC-SOFC.
for DC-SOFCs, and the single cell achieved a maximum power
density of 309 mW cm
2 at 850  C with the fuel utilization of
47.25%. Pepper, as one main crop, is widely cultivated in the
world, and thus huge amount of pepper straws are produced each
year. However, the pepper straws are far from achieving efficient
use. Most of them are directly burned with high pollution and low
efficiency. In fact, pepper straw is a potential biomass resource that
contains a variety of metal catalysts of the reverse Boudouard
reaction. If they can be utilized effectively through the DC-SOFC
system, the fields including environmental protection, energy con-
version, and waste recycling will be greatly benefited.
For another, it is well known that the solid carbon is being
consumed continuously during the cell operation, and then its
surface for the reaction is shrinking with operating time.
Once the residual carbon cannot provide sufficient reaction area
for the reverse Boudouard reaction to produce sufficient CO for
the electrochemical oxidation reaction, the DC-SOFC perfor-
mance drops rapidly.[15] Nevertheless, most of the cell structure
are button-type or tubular single cell according to previously
reported literature and that only a small amount of solid carbon
can be loaded, leading to a poor output and short lifetime of the
DC-SOFC. To increase the carbon storage and thus improve the
cell performance, the tubular segmented-in-series SOFC stack
has been designed and developed as a portable power supply
system. Liu and co-workers[16] reported an anode-supported
cone-shaped DC-SOFC stack with 5 wt% Fe-loaded activated
carbon loaded inside. The three-cell stack shows the peak power
density of 465 mW cm
2 and volumetric power density of
710 mW cm
2 at 850  C. Wang et al.[17] developed a tubular
electrolyte-supported segmented-in-series DC-SOFC stack, and
the three-cell-stack performance was compared when the carbon
fuel was loaded inside or outside the stack. It showed that the
electrochemical performance of the stack with carbon fuel out-
side, which was so spacious that much more carbon fuel can
be loaded, was significantly higher than that with carbon fuel
inside. However, the fabrication process of the stack is more
complex, time-consuming, and high cost. Therefore, it urgently
needs to explore more novel and efficient strategies to achieve a
superior DC-SOFC performance. Recently, microtubular solid
oxide fuel cell (MT-SOFC) has attracted increasing interests
Energy Technol. 2020, 8, 1901077 1901077 (2 of 8)
www.entechnol.de
due to their high power output, good tolerance to thermocycling,
fast start-up operation, and good portable characteristics.[18] In
contrast to the traditional tubular and planar SOFCs, the MT-
SOFC can be expertly prepared through the facile extrusion pro-
cess, slip casting, and phase inversion technique with higher
yield and lower cost.[19] Especially, for the MT-SOFC fueled with
solid carbon, the carbon fuel can be loaded outside so that much
more solid carbon can be integrated with the cell. In this case, the
electrochemical performance of such MT-SOFC can be effec-
tively improved. Given all these advantages, however, there
has been no detailed investigation of the feasibility of the
MT-SOFC operated on solid carbon fuel so far.
In this study, we demonstrate a high-performance MT-SOFC
fueled with the biochar derived from pepper straw for electrical
power generation. The electrolyte-supported SOFC is fabricated
by the phase inversion technique and characterized in terms
of electrical power output and energy conversion efficiency.
The effects of the composition and microstructure of pepper
straw on the electrochemical performance of the microtubular
DC-SOFC are analyzed and demonstrated in detail. The results
provide a novel and green pathway for efficient utilization of
pepper straw char, and it will be helpful for the development
of high-performance MT-SOFCs using local biomass as fuel.
2. Results and Discussion
2.1. Characterization of the Biochar
Figure 2 shows the scanning electron microscopy (SEM) image
and energy-dispersive X-ray spectroscopy (EDS) analysis of the
pepper straw char. The morphology of the biochar shows that
there are few micropores on the particle of the biochar. It can
also be seen from the EDS result that the dominant elements
are carbon, oxygen, calcium, potassium, and magnesium on
the pepper straw char. Typically, the carbon content in the bio-
char is 61.59 wt%, whereas that of oxygen, calcium, potassium,
and magnesium are 17.55, 11.73, 5.47, and 3.66 wt%, respec-
tively. The result demonstrates that the as-mentioned metal
elements might mainly exist in the form of metal oxides or
carbonates. It is worth noting that calcium, potassium, and
magnesium elements are the excellent catalysts for the reverse
Boudouard reaction, which may be helpful for the enhancement
of the cell performance.[20]
X-ray diffraction measurements were performed on the pep-
per straw char to determine the phase composition. As shown in
Figure 3a, two broaden peaks are around 2θ values of 25 and
43 , which reflect the typical peaks of (002) and (100) crystal faces
of graphite and amorphous carbon. It is common knowledge
that broader diffraction peaks correspond to smaller crystal size,
demonstrating that the carbon in the biochar is with small grain
size. The other major phases of the biochar are some simple
oxides and carbonate, such as CaCO3 (JCPDS 05-0586),
K2CO3 (JCPDS 16-0820), and MgO (JCPDS 45-0946), which is
in good agreement with the EDS analysis results. Raman spectra
is recorded to unravel the graphitic structure of the pepper straw
char, as shown in Figure 3b. A G band at approximately
1598 cm
1 corresponds to the first-order scattering of the E2g
mode which is attributed to the relative motion of sp2 carbon
© 2019 WILEY-VCH Verlag GmbH & Co. KGaA, Weinheim
www.advancedsciencenews.com
Figure 2. a) SEM image and b–h) EDS analysis of the pepper straw char.
atoms in the graphitic lattice.[21] Moreover, a D band at approxi-
mately 1326 cm
1 is associated with the structural imperfections
created by the vibrations of carbon atoms in the disordered
carbon.[22] It has been demonstrated that the peak intensity ratio
of the D band to G band (ID/IG) is strongly correlated with the
disorder of carbons of the sample. Most notably, the amorphous
carbon is more active to the Boudouard reaction compared with
graphite. Consequently, the calculated ID/IG value of the pepper
Energy Technol. 2020, 8, 1901077 1901077 (3 of 8)
www.entechnol.de
straw char is 0.98, which is close to the result of 0.94 in the
previous literature,[23] suggesting that the pepper straw can be
considered as a good fuel for the microtubular DC-SOFCs.
Thermogravimetric analysis (TGA) and differential scanning
calorimetry (DSC) are applied to evaluate the thermal decompo-
sition and oxidation reactivity behavior of the pepper straw char
from 30 to 900  C in air atmosphere. As shown in Figure 4,
a slight weight loss of 2.8 wt% is observed before 100  C due
© 2019 WILEY-VCH Verlag GmbH & Co. KGaA, Weinheim
www.advancedsciencenews.com
Figure 3. a) X-ray diffraction and b) Raman spectra of the pepper straw char.
Figure 4. The TGA and DSC curves of the pepper straw char in air
atmosphere.
to the vaporization of moisture and release of volatiles, indicating
that the char reabsorbed some moisture from the atmosphere
after thermal pyrolysis at 800  C.[24] After a stable period, there
is an abrupt weight loss of 83.0 wt% at the temperature range
from 300 to 590  C, along with a big exothermic peak in the
DSC curve. It originates from the oxidation of the effective car-
bon, which is an ideal fuel for DC-SOFCs. With further increase
of the temperature, a very small weight loss caused by the decom-
position of some carbonates occurred over 600  C with a rela-
tively smooth platform of the DSC curve. During the whole
process, the residual ash of the biochar is 8.9 wt%, which is
mainly composed of metal oxides.
2.2. Characterization of the MT-SOFCs
Figure 5 shows the SEM micrographs of the as-prepared MT-
SOFC. It can be seen that the yttria-stabilized zirconia (YSZ) elec-
trolyte displays a symmetric structure with thin dense layer in the
middle and porous surfaces on both sides, which is attributed
to the different precipitation rates between the outside and inside
electrolyte.[25] The dense electrolyte layer, with the sponge-like
structure, may greatly reduce the ohmic loss during MT-SOFC
operation. In addition, the finger-like porous layer structure may
Energy Technol. 2020, 8, 1901077 1901077 (4 of 8)
www.entechnol.de
Figure 5. Image of a) the electrolyte-supported MT-SOFC, b) cross-
sectional fracture surface micrograph of the MT-SOFC, microstructure
of the c) anode and d) cathode.
provide high surface area for electrode deposition. Nonetheless,
the YSZ electrolyte shows the high density with a thickness of
280 μm, which can be confirmed by the cell performance in
Figure 6. The microstructure of the cathode layer, which is
homogenously coated on the YSZ electrolyte surface, is shown
in Figure 5c. Moreover, the cathode is also porous and uniformly
distributed with a thickness of 60 μm. Figure 5d is the cross-
sectional micrographs of the anode, which provides unique
porous to transport the fuel and the thickness is 30 μm.
In an attempt to evaluate the quality of the as-prepared MT-
SOFCs, the hydrogen-fueled MT-SOFCs were first tested with
ambient air as the oxidant. Figure 6 shows the electrochemical
performance of the MT-SOFC operated on H2 at a temperature
range of 750–850  C. It can be seen that the open-circuit voltage
(OCV) is 1.16 V, which is slightly higher than the theoretical val-
ues calculated from the Nernst equation at 850  C. This could be
© 2019 WILEY-VCH Verlag GmbH & Co. KGaA, Weinheim
www.advancedsciencenews.com www.entechnol.de

Figure 6. a) Output performance and b) electrochemical impedance spectra of the as-prepared MT-SOFC fueled with H2.

ascribed to the excessive oxygen partial pressure in the cathode,
where the air is not nature circulation but precisely controlled by
the flowmeter with 50 mL min
1. Furthermore, the peak power
densities of the MT-SOFC are 109, 187, and 252 mW cm
2 at
750, 800, and 850  C, respectively. Figure 6b displays the typical
impedance spectra of the MT-SOFC. The ohmic resistance of the
MT-SOFC is 0.55 Ω cm2, whereas the total resistance reaches the
lowest value of 1.61 Ω cm2 at 850  C. In addition, the equivalent
circuit with the configuration of Ro(RhQ h)(RlQ l) was provided
and fitted well to the obtained impedance spectra.[26] Here, Ro,
Rh, and R1 represent the ohmic resistance, high-frequency resis-
tance, and low-frequency resistance, respectively; Q h and Q l are
the corresponding constant phase elements of the high- and
low-frequency arc. On the basis of the results, it can be concluded
that the as-prepared MT-SOFC is superior quality for further
research.
2.3. Electrochemical Performance of the DC-SOFCs
Figure 7 shows the electrochemical performance of the microtu-
bular DC-SOFC fueled with pepper straw char at 750–850  C. It
is noteworthy that repeated testing has been performed at least
three times to ensure the reliability and accuracy of the data. It is
observed that OCV of the microcell is 0.99 V, which is close to the
theoretical value of 1.06 V at 850  C,[8] indicating a fine sealability
of the system. In addition, a peak power density of 217 mW cm
2
is obtained by the microtubular DC-SOFC at 850  C, which is
comparable with that using hydrogen in this work. The electro-
chemical impedance spectra of the DC-SOFC measured under
OCV is shown in Figure 7b. As is well-known, the electrolyte
dominates the overall ohmic resistance of an electrolyte-
supported SOFC.[27] The ohmic resistance of the DC-SOFC is
0.53 Ω cm2 at 850  C, which is primarily consistent with that
of operating on hydrogen (0.55 Ω cm2). Yet, the total resistance
of the DC-SOFC (1.78 Ω cm2) is slightly higher than that of the
hydrogen due to the bulk particles and low oxidation reactivity of
the solid carbon fuel.
Figure 8 shows the operation stability of the microtubular DC-
SOFC fueled with pepper straw char at a constant current of
100 mA. Apparently, the single cell gives a high initial voltage
of 0.65 V and a relatively stable discharging platform from begin-
ning to end. The discharging time lasts for 21 h, corresponding
to a released electric quantity of 7560 C. Considering the overall
reaction as a four-electron reaction (C þ 2O2
¼ CO2 þ 4e), the
pepper straw char consumed in the system is 0.24 g.
Accordingly, the fuel utilization of the microtubular DC-SOFC
is 44.4% calculated from Faraday’s law with 0.54 g char as

Figure 7. a) Output performances and b) electrochemical impedance spectra of the microtubular DC-SOFC at various temperatures.

Energy Technol. 2020, 8, 1901077 1901077 (5 of 8) © 2019 WILEY-VCH Verlag GmbH & Co. KGaA, Weinheim
www.advancedsciencenews.com
Figure 8. Discharge curve of the DC-SOFC operated on the pepper straw
char at 850  C.
feedstock, which is obviously higher than that with other biomass
fuels.[9,11,12] The result has once again proven that the pepper
straw containing natural catalysts is an ideal fuel for the
DC-SOFCs.
3. Conclusions
In summary, the biochar derived from pepper straw has been
proved to be a superior energy source for microtubular DC-
SOFCs due to the naturally existing metal catalysts in fuel itself.
The microtubular DC-SOFC powered with the pepper straw char
shows the peak power density of 217 mW cm
2, which is com-
parable with that operated with hydrogen of 252 mW cm
2 at
850  C. Moreover, the discharge time of the DC-SOFC lasts
for 21 h under the constant current of 100 mA with a stable dis-
charging voltage and platform, and the fuel utilization reaches up
to 44.4%. Based on the research findings, the current work is
valuable for developing microtubular DC-SOFC into a safe,
effective, and environment-friendly distributed power generation
system for electrical power generation using local biomass as
fuel.
4. Experimental Section
Preparation and Characterization of Carbon Fuels: Carbon fuels were pre-
pared according to the following procedures that are similar to the previous
work.[12] One-year-old pepper straws were collected as agriculture byproduct
from local farmland in Linyi city, Shandong province of China (35 5 0 N,
118 35 0 E). The raw pepper straws were broken into pieces with the length
of 2 cm, and dried in an oven at 100  C for 24 h to remove the internal
water furthest. Then, the dry pieces were placed into a quartz tube, followed
by a heat treatment at 800  C in N2 atmosphere for 1 h. After cooling down
to room temperature, the as-prepared chars were pulverized into powder
with an electric grinder and then sieved using a 200 mesh sieve.
The microstructure and morphology of the biochar were investigated via
SEM (Carl Zeiss AG-Merlin, Germany) equipped with an EDS. The phase
composition and crystal structure of the carbon fuel were analyzed by X-ray
diffraction with a Rigaku D/max-IIIA diffractometer (Cu Kα radiation, oper-
ated at 35 kV, 30 mA, λ ¼ 1.54184 Å) at 293 K. The selected 2θ was ranged
from 10 to 90 with the scanning rate of 10 min
1. The TGA and
Energy Technol. 2020, 8, 1901077 1901077 (6 of 8)
www.entechnol.de
differential scanning calorimetric measurements of the biochar were per-
formed simultaneously on a thermogravimetric analyzer (STA449F3,
Netzsch, Germany). The data were collected in the air atmosphere from
30 to 900  C with a heating rate of 10  C min
1. The Raman spectra
of the biochar were measured by a confocal LabRAM HR Evolution spec-
trometer (Horiba Join Yvon, FR) with an Argon laser wavelength of
514.5 nm.
Fabrication of MT-SOFCs: In this work, electrolyte-supported microtu-
bular SOFCs were fabricated for the fuel cells testing. To improve the ionic
conductivity, the YSZ (Ningbo SOFCMAN Energy Technology Co., Ltd,
China) doped with 1 wt% Al2O3 (Xinfumeng Co., Ltd, China) was used
as the electrolyte material.[28] First, the YSZ and Al2O3 powders were mixed
with ethanol and ball milled using zirconia balls as milling media for
2 h. Subsequently, the mixture was thoroughly dried under an infrared
lamp followed by grinding in an agate mortar to obtain the Al2O3-YSZ pow-
der. Then, the electrolyte was prepared by the phase-inversion technique.
Briefly, the Al2O3-YSZ powder, polyethersulfone (Dare Chemicals, China),
and 1-methyl-2-pyrrolidone (Komiou Chemical Reagent Development
Center, China) with a certain mass ratio of 9:1:4 were dispersed in distilled
water and stirred for 72 h to form a precursor solution. After degassing for
1 h in the spinning reservoir, the mixture was extruded by a spinneret with
the orifice (outer diameter/inside diameter ¼ 2.0/1.0 mm) under a
nitrogen pressure of 0.2 MPa using deionized water and tap water as
the internal and external coagulants, respectively. Afterward, the prepared
hollow fiber precursors were soaked in the deionized water for 24 h to
complete the solidification process. Finally, the dense electrolyte micro-
tubes were obtained by sintering the precursors at 1400  C for 4 h in
air atmosphere.
The cathode consists of two parts including transition layer and func-
tional layer. The suspension of the transition layer was prepared by ball
milling the YSZ and La0.8Sr0.2MnO3
x (LSM, Ningbo Institute of Material
Technology and Engineering, Chinese Academy of Sciences) powders with
dioctyl phthalate, polyethylene glycol, triethanolamine, and polyviyl butyral
(PVB)-ethanol solution (10 wt% in concentration) in ethanol solvent for
3 h (Table 1). Then, the suspension was deposited on the inner surface
of the YSZ microtube which was repeated for two times. The same process
was used for preparing the functional layer of a pure LSM. After that, cosin-
tering of the cathode was performed at 1100  C for 2 h in air. A composite
anode paste containing 0.6 g Ce0.8Gd0.2O1.9 (GDC, Ningbo Institute of
Material Technology and Engineering, Chinese Academy of Sciences),
1.75 g sliver paste (DAD-87, Shanghai Research Institute of Synthetic
Resins, China), and 3 g PVB-terpineol solution (10 wt%) were prepared
by mixing and grinding in an agate mortar for 3 h.[29] After that, the homo-
geneous Ag-GDC paste was painted onto the outer surface of the YSZ
microtube by brush painting and then dried in an oven at 120  C. This
process was repeated four times until a required thickness was achieved.
Finally, a sintering process was conducted at 880  C for 4 h to construct
the complete single cells. The anode area (effective area) was controlled at
0.28 cm2 of all the microcells.
Cell Assembling and Characterization: Each single microcell was con-
nected to two quartz tubes on both ends by using sliver paste as the seal-
ant. Sliver wires were attached to inside and outside of the microcell as
Table 1. Composition of the cathode slurry.
Parameters Transition layer [g] Functional layer [g]
LSM 14 g 20 g
Yttria-stabilized zirconia 6g –
Ethanol 47 g 47 g
Dioctyl phthalate 0.76 g 0.76 g
Polyethylene glycol 0.75 g 0.75 g
Triethanolamine 0.57 g 0.57 g
PVB-ethanol (10 wt%) 10 g 10 g
© 2019 WILEY-VCH Verlag GmbH & Co. KGaA, Weinheim
www.advancedsciencenews.com
Figure 9. Schematic illustration of a) a single MT-SOFC and b) testing
setup of a microtubular DC-SOFC.
current leading wires, as shown in Figure 9a. In the fuel cell measure-
ments, a tubular furnace was used to control the high temperature for
SOFC operation, and the ambient air (50 mL min
1) was used as the oxi-
dant. A hydrogen SOFC (50 mL min
1) was first tested to evaluate the
quality of the as-prepared microcells from 750 to 850  C. For each DC-
SOFC, 0.54 g of pepper straw char was filled into the glass container which
serves as the anode chamber. Some ceramic cotton was stuffed to fix the
solid carbon, and some Teflon tape and vacuum sealing resin were coated
on the gap between quart tubes and SOFCs reactor to prevent leakage
(Figure 9b).
The microstructure and morphology of MT-SOFCs were also character-
ized by a SEM. The electrochemical performance of all the cells was mea-
sured by a four-probe method using an IM6ex electrochemical workstation
(Zahnere Elektric GmbH, Kronach, Germany). The current–voltage curve
testing was implemented by linear sweep voltammetry over a voltage
range of 0–1.2 V with scanning in increments of 5 mV s
1. For the electro-
chemical impedance measurements, the selected frequency range was
from 0.1 to 106 Hz with voltage amplitude of 10 mV at various tempera-
tures. Equivalent circuit and data fitting for electrochemical impedance
analysis were completed using the ZView software (Scribner
Associates, Southern Pines, NC, USA). Finally, the operational stability
of microtubular DC-SOFCs was measured under the constant current
of 100 mA.
Acknowledgements
This work was supported by the National Natural Science Foundation of
China (grant nos. 21908133, 21808128, and 51904136) and Natural
Science Foundation of Shandong Province (grant nos. ZR2018BB062
and 2019GGX103016).
Conflict of Interest
The authors declare no conflict of interest.
Keywords
Boudouard reaction, direct carbon, microtubular, pepper straws, solid
oxide fuel cells
Energy Technol. 2020, 8, 1901077 1901077 (7 of 8)
www.entechnol.de
Received: September 11, 2019
Revised: October 20, 2019
Published online: November 14, 2019
[1] a) L. Bi, S. P. Shafi, E. H. Da’as, E. Traversa, Small 2018, 14, 1801231;
b) X. Xu, H. Q. Wang, J. M. Ma, W. Y. Liu, X. F. Wang, M. Fronzi, L. Bi,
J. Mater. Chem. A 2019, 7, 18792; c) T. Hibino, K. Kobayashi, P. L. Lv,
M. Nagao, S. Teranishi, Bull. Chem. Soc. Jpn. 2017, 90, 1017;
d) T. Hibino, K. Kobayashi, P. L. Lv, M. Nagao, S. Teranishi,
T. Mori, J. Electrochem. Soc. 2017, 164, F557.
[2] a) S. Giddey, S. P. S. Badwal, A. Kulkarni, C. Munnings, Prog. Energy
Combust. 2012, 38, 360; b) T. M. Gür, Chem. Rev. 2013, 113, 6179;
c) C. R. Jiang, J. J. Ma, G. Corre, S. L. Jaina, J. T. S. Irvine, Chem. Soc.
Rev. 2017, 46, 2889.
[3] a) S. Zecevic, E. M. Patton, P. Parhami, Chem. Eng. Commun. 2005,
192, 1655; b) A. Kacprzak, R. Kobylecki, Z. Bis, J. Power Sources 2013,
239, 409.
[4] a) C. Li, H. Yi, D. Lee, J. Power Sources 2016, 309, 99; b) S. Y. Ahn,
S. Y. Eom, Y. H. Rhie, Y. M. Sung, C. E. Moon, G. M. Choi, D. J. Kim,
Appl. Energy 2013, 105, 207.
[5] a) A. Jayakumar, R. Kungas, S. Roy, A. Javadekar, D. J. Buttrey,
J. M. Vohs, Energy Environ. Sci. 2011, 4, 4133; b) A. C. Rady,
S. Giddey, A. Kulkarni, S. P. S. Badwal, S. Bhattacharya,
B. P. Ladewig, Appl. Energy 2014, 120, 56; c) C. Q. Wang, Z. Lü,
C. X. Su, J. W. Li, Z. Q. Cao, X. B. Zhu, Y. Y. Wu, H. Li, Int. J.
Hydrogen Energy 2019, 44, 1174.
[6] a) B. Yang, R. Ran, Y. Zhong, C. Su, M. O. Tadé, Z. P. Shao, Angew.
Chem. Int. Ed. 2015, 127, 3793; b) J. Liu, M. Y. Zhou, Y. P. Zhang,
P. P. Liu, Z. J. Liu, Y. M. Xie, W. Z. Cai, F. Y. Yu, Q. Zhou,
X. Q. Wang, M. Ni, M. L. Liu, Energy Fuel 2018, 32, 4107;
c) W. Wang, Z. J. Liu, Y. P. Zhang, P. P. Liu, Q. Y. Qiu,
M. Y. Zhou, M. L. Liu, J. Liu, J. Alloys Compd. 2019, 794, 294;
d) W. Z. Cai, P. P. Liu, B. Chen, H. R. Xu, Z. J. Liu, Q. Zhou,
F. Y. Yu, M. L. Liu, M. N. Chen, J. Liu, M. Ni, Int. J. Hydrogen
Energy 2019, 44, 1867.
[7] N. Nakagawa, M. Ishida, Ind. Eng. Chem. Res. 1988, 27, 1181.
[8] Y. M. Xie, Y. B. Tang, J. Liu, J. Solid State Electron. 2013, 17, 121.
[9] Q. Zhou, W. Z. Cai, Y. P. Zhang, J. Liu, L. L. Yuan, F. Y. Yu,
X. Q. Wang, M. L. Liu, Biomass Bioenergy 2016, 91, 250.
[10] W. Z. Cai, Q. Zhou, Y. M. Xie, J. Liu, G. H. Long, S. Cheng, M. L. Liu,
Appl. Energy 2016, 179, 1232.
[11] W. Z. Cai, J. Liu, P. P. Liu, Z. J. Liu, H. R. Xu, B. Chen, Y. Z. Li, Q. Zhou,
M. L. Liu, M. Ni, Int. J. Energy Res. 2019, 43, 2468.
[12] Q. Y. Qiu, M. Y. Zhou, W. Z. Cai, Q. Zhou, Y. P. Zhang, W. Wang,
Biomass Bioenergy 2019, 121, 56.
[13] W. T. An, X. J. Sun, Y. Jiao, P. S. B. Julião, W. Wang, S. B. Wang,
S. D. Li, S. M. Shuang, Int. J. Energy Res. 2019, 43, 2514.
[14] M. Dudek, B. Adamczyk, M. Sitarz, M. Sliwa, R. Lachb,
M. Skrzypkiewiczd, A. Raźniaka, M. Ziąbkab, J. Zuwałae,
P. Grzywacza, Biomass Bioenergy 2018, 119, 144.
[15] F. Y. Yu, Y. P. Zhang, L. Yu, W. Z. Cai, L. L. Yuan, J. Liu, M. L. Liu,
Int. J. Hydrogen Energy 2016, 41, 9048.
[16] Y. H. Bai, Y. Liu, Y. B. Tang, Y. M. Xie, J. Liu, Int. J. Hydrogen Energy
2011, 36, 9189.
[17] X. Q. Wang, J. Liu, Y. M. Xie, W. Z. Cai, Y. P. Zhang, Q. Zhou, F. Y. Yu,
M. L. Liu, Acta Phys. Chim. Sin. 2017, 33, 1614.
[18] a) N. Hedayat, D. Panthi, Y. H. Du, Ceram. Int. 2019, 45, 579;
b) H. Y. Zeng, S. Q. Gong, Y. X. Shi, Y. Q. Wang, N. S. Cai,
Energy 2019, 179, 154; c) X. X. Meng, N. T. Yang, X. Gong,
Y. M. Yin, Z. F. Ma, X. Y. Tan, Z. P. Shao, S. M. Liu, J. Mater.
Chem. A 2015, 3, 1017; d) C. Ren, S. W. Wang, T. Liu, Y. Lin,
F. L. Chen, J. Power Sources 2015, 290, 1.
© 2019 WILEY-VCH Verlag GmbH & Co. KGaA, Weinheim
www.advancedsciencenews.com
[19] a) S. M. Jamil, M. H. D. Othman, M. A. Rahman, J. Jaafar, A. F. Ismail,
K. Li, J. Eur. Ceram. Soc. 2015, 35, 1; b) N. T. Yang, X. Y. Tan, Z. F. Ma,
A. Thursfield, J. Am. Ceram. Soc. 2009, 92, 2544.
[20] a) W. Z. Cai, J. Liu, F. Y. Yu, Q. Zhou, Y. P. Zhang, X. Q. Wang,
M. L. Liu, Int. J. Hydrogen Energy 2017, 42, 21167; b) H. Wu,
J. Xiao, X. Y. Zeng, X. Liu, J. Yang, Y. L. Zou, S. D. F. Liu,
P. Dong, Y. J. Zhang, J. Liu, Appl. Energy 2019, 248, 679;
c) A. C. Rady, S. Giddey, A. Kulkarni, S. P. S. Badwal,
S. Bhattacharya, Electrochim. Acta 2014, 143, 278.
[21] A. M. Rao, E. Richter, S. Bandow, B. Chase, P. C. Eklund, K. A. Williams,
S. Fang, K. R. Subbaswamy, M. Menon, A. Thess, R. E. Smalley,
G. Dresselhaus, M. S. Dresselhaus, Science 1997, 275, 187.
[22] M. Balabajew, H. Reinhardt, N. Bock, M. Duchardt, S. Kachel,
N. Hampp, B. Roling, Electrochim. Acta 2016, 211, 679.
[23] H. S. Zhang, W. Xiao, W. J. Zhou, S. Y. Chen, Y. H. Zhang,
Nanomaterials 2019, 9, 553.
Energy Technol. 2020, 8, 1901077 1901077 (8 of 8)
View publication stats
www.entechnol.de
[24] A. C. Rady, S. Giddey, A. Kulkarni, S. P. S. Badwal, S. Bhattacharya,
B. P. Ladewig, Appl. Energy 2014, 120, 56.
[25] C. C. Wei, K. Li, Ind. Eng. Chem. Res. 2008, 47, 1506.
[26] a) H. Q. Tang, F. Y. Yu, Y. S. Wang, Y. J. Xie, X. X. Meng, H. B. Sun,
N. T. Yang, X. Y. Tan, Energy Technol. 2019, 7, 1800885; b) L. Y. Wei,
J. J. Zhang, F. Y. Yu, W. M. Zhang, X. X. Meng, N. T. Yang, S. M. Liu,
Int. J. Hydrogen Energy 2019, 44, 6182.
[27] M. J. Verkerk, A. J. A. Winnubst, A. J. Burggraaf, J. Mater. Sci. 1982, 17,
3113.
[28] a) F. Y. Yu, J. Xiao, L. B. Lei, W. Z. Cai, Y. P. Zhang, J. Liu, M. L. Liu,
Solid State Ionics 2016, 289, 28; b) J. Xiao, Q. L. Han, F. Y. Yu,
Y. J. Zhang, H. Wu, X. Li, X. Y. Zeng, P. Dong, Y. J. Zhang, J. Liu,
J. Alloys Compd. 2018, 731, 1080.
[29] Y. P. Zhang, F. Y. Yu, X. Q. Wang, Q. Zhou, J. Liu, M. L. Liu, J. Power
Sources 2017, 366, 56.
© 2019 WILEY-VCH Verlag GmbH & Co. KGaA, Weinheim