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h i g h l i g h t s
The peak power density of the 25 cm2 ZAFC can be as high as 454 mW cm2.
The EIS of ZAFCs were measured to study the performance of air cathode.
The degradation was due to the micropores clogging and catalysts losing.
Degradation mechanisms and mitigation strategies of air cathode were studied.
a r t i c l e i n f o a b s t r a c t
Article history: The zinc air fuel cell (ZAFC) is a promising candidate for electrical energy storage and electric vehicle
Received 5 May 2014 propulsion. However, its limited durability has become a major obstacle for its successful commercial-
Received in revised form ization. In this study, 2-cell stacks, 25 cm2 cells and three-electrode half-cells are constructed to
5 September 2014
experimentally investigate the degradation characteristics of the air cathode. The results of electro-
Accepted 6 October 2014
Available online 15 October 2014
chemical tests reveal that the peak power density for the 25 cm2 cell with a new air cathode is
454 mW cm2, which is twice as the value of the used air cathode. The electrochemical impedance
analysis shows that both the charge transfer resistance and the mass transfer resistance of the used air
Keywords:
Zinc air fuel cell
cathodes have increased, suggesting that the catalyst surface area and gas diffusion coefficient have
Air cathode decreased significantly. Additionally, the microstructure and morphology of the catalytic layer (CL) and
Degradation characteristics gas diffusion layer (GDL) are characterized by scanning electron microscopes (SEM). SEM results confirm
Electrochemical impedance analysis that the micropores in CL and GDL of the used air cathode are seriously clogged, and many catalyst
particles are lost. Therefore, the performance degradation is mainly due to the clogging of micropores
and loss of catalyst particles. Furthermore, hypotheses of degradation mechanism and mitigation stra-
tegies for GDL and CL are discussed briefly.
© 2014 Elsevier B.V. All rights reserved.
1. Introduction 2DS. However, both the worldwide demand for electricity and ve-
hicles are estimated to more than double by 2050 [2,3], producing a
To achieve greenhouse-gas emission targets for limiting global great challenge for this goal. All things considered, generating
warming to 2 C Scenario (2DS) [1], the energy-related CO2 emis- electricity from renewable sources and developing electric vehicles
sions must be reduced by more than 64% by 2050 (compared with (EVs) are necessary and promising solutions [4,5].
2009), and a continued falling must be maintained thereafter [2]. Solar and wind are not constant and reliable sources of power,
Two industrial sectors produced nearly two-thirds of global CO2 which will cause significant challenges for the electric grid opera-
emissions in 2010: 41% is accounted by electricity and heat gener- tors [6]. Electrical energy storage (EES) can smooth out the inter-
ation and 22% from transportation [3], therefore the reduction of mittency of renewable energy production and balance the supply
CO2 emissions from these two sectors are the key to achieving the and demand of electricity (electricity generation, distribution, and
usage requirement). Therefore, EES has been considered to be a key
enabler for the smart grid or future grid [6e8]. Several different
* Corresponding author. Tel./fax: þ86 10 62788558.
types of energy storage can be used for large-scale stationary ap-
E-mail address: pchpei@tsinghua.edu.cn (P. Pei). plications, including mechanical, electrical, chemical, and
http://dx.doi.org/10.1016/j.jpowsour.2014.10.030
0378-7753/© 2014 Elsevier B.V. All rights reserved.
Z. Ma et al. / Journal of Power Sources 274 (2015) 56e64 57
electrolyte could overflow via an overflow channel. The flow rates pressure drop; m, the viscosity of fluid; L, the length over which the
of the electrolyte that flowed through the anode chambers were pressure drop is taking place), the permeability of the air cathode
900 mL min1 and 96 mL min1 for 2-cell stack and 25 cm2 cell, can be determined by the pressure drop (DP) when air flows
respectively. The ambient air was fed by an electric fan. Meanwhile, through the GDL to the CL. The pressure drop (DP) when the air flux
the electrochemical characterization of the air cathodes was carried (Q/A) was 4 sccm cm2, 8 sccm cm2 and 12 sccm cm2 were
out in a three-electrode half-cell in 40 wt.% KOH with a Hg/HgO measured in the tests.
reference electrode and a nickel plate counter electrode. The air
cathode was pressed onto a copper plate which was acted as the 3. Results and discussion
current collect plate and had a round hole, 20 mm in diameter. Thus
the geometrical area of the air cathode was 3.14 cm2. 3.1. Electrochemical characterization of 2-cell stack
2.3. Electrochemical test and morphology examination Two 2-cell stacks were tested: one was assembled with two new
air cathodes, and the other was assembled with two used air
For the 2-cell stack and the 25 cm2 cell, the polarization char- cathodes. In the 2-cell stacks, the cell located close to the positive
acteristics of each cell were tested with an electronic load (Hoecherl electrode of the stack was numbered #1, and the other cell was
& Hackl GmbH ZLSV1502). A NI PXI-1033 data acquisition instru- numbered #2. The polarization characteristics of each cell in the 2-
ment was used to measure each cell voltage. To investigate the cell stacks are plotted in Fig. 2. The performances of cell #2 are
reasons for air cathode degradation over time, the electrochemical better than cell #1 in both of the stacks, and these differences may
impedance spectroscopy (EIS) measurements of ZAFCs were carried be caused by the non-uniform air distribution for different cells
out in the galvanostatic mode using a TrueData-EIS Impedance with non-optimized air supplying [21]. As shown in Table 1, the
Spectroscopy Analyzer. The impedance spectra were recorded by peak power density of cell #2 with a new air cathode is
sweeping frequencies over the range of 20 kHze100 mHz. 435 mW cm2, which is almost twice as the value of the cell with a
Note that the concentration of the hydroxide in the electrolyte used air cathode. This suggests an obvious degradation of the used
decreases with discharge Ah (Ampere Hour). The electrolyte con- air cathode. Meanwhile, it can be found that concentration polari-
ductivity would decrease and result in an increased cell resistance. zation occurs at relatively low current conditions in the cells with a
Measuring an EIS spectrum takes time, and the change of the used air cathode. This suggests that the degraded performance of
electrolyte concentration should be avoided throughout the mea- the cells for a used air cathode may be largely due to limited gas
surement. Each cell in the 2-cell stack had an active surface area of diffusion.
215 cm2, and the discharge current could be higher than 100 A. Fig. 3 presents the impedance spectra of the cell #1 in 2-cell
Thus, the EIS spectra of the 2-cell stacks were only measured at stacks with new and used cathodes. The high-frequency intercept
open circuit. For the 25 cm2 cell, which has a quite low discharge of the single impedance arc on the real axis, RU, represents the total
current, the change of electrolyte concentration was negligible as ohmic resistance of the cell, which can be expressed as the sum of
long as the amount of electrolyte was not too little. Therefore, the the contributions from contact resistances between components
EIS spectra of the 25 cm2 cells were measured at a discharge current and ohmic resistances of the cell components, such as the elec-
of 0 A, 1 A, 2 A and 3 A. The electrochemical characterizations of the trolyte, air cathode, zinc anode and polar plates. As seen in Fig. 3,
air cathodes were then studied in a three-electrode half-cell using a both the resistance values RU for the cell with a new air cathode and
CHI660D electrochemical workstation (CH Instruments Inc.). For a used air cathode are approximately 0.78 U cm2, which suggests
the chronopotentiometry with linear current scanning, the current that the two stacks were assembled in the same condition, such as
was linearly increased from 0 A to 0.24 A with a scan rate of assembly pressure, electrolyte flow condition and zinc pellets
2 mA s1. Impedance measurements were conducted at polarized filling state. However, the impedance spectra of the two are quite
conditions at 0 V, 0.1 V, 0.2 V and 0.3 V versus Hg/HgO by different. For the new air cathode, the impedance arc appears as a
sweeping frequencies over the range of 20 kHze10 mHz with a straight line with a slope of almost 1. The Nyquist spectrum of the
sinusoidal perturbation of 5 mV amplitude. The performance of the used cathode shows an additional semicircle in the high frequency
air cathode would degrade continuously when the fuel cells were (HF) range, and a big impedance loop is observed in low frequency
discharging. Since the EIS tests takes a long time, each air cathode range. The appearance of this HF semicircle is likely related to
was used only once to measure an EIS spectrum in the 25 cm2 cell electrode geometry changing [33].
tests and half-cell tests. The used air cathodes tested in the 25 cm2
cells were cut from the used air cathode, which had been tested in
2-cell stack. It is worth noticing that the air cathode, zinc pellets,
and KOH electrolyte were replaced with fresh ones before every
test.
To further quantify and identify the geometric structure changes
of the air cathode before and after fuel cell operation, the micro-
structure and morphology of the catalytic layer (CL) and gas
diffusion layer (GDL) were characterized by scanning electron mi-
croscopes (SEM) (Tescan MIRA 3 and JSM7401). Before the SEM
observation, the used air cathodes were soaked in deionized water
for 24 h and then dried at room temperature. Since the GDL was
insulated, the surfaces of GDL for the samples were Au-sputtered in
vacuum before the SEM examination.
Additionally, in order to characterize the changes of cathode
permeability over long-term operation, gas diffusion coefficients of
new and used air cathodes were measured. According to the Darcy
law (Q ¼ kA/mLDP; Q, the total discharge;k, the intrinsic perme- Fig. 2. Polarization characteristics of ZAFCs with the new air cathodes and used air
ability of the medium; A, the cross-sectional area; DP, the total cathodes.
Z. Ma et al. / Journal of Power Sources 274 (2015) 56e64 59
Table 1
Polarization characteristics of the zinc air fuel cell.
Fuel cell OCV (V) Peak power (mW cm2) EPa (V) iPb (mA cm2)
Fig. 3. Nyquist plots of EIS spectra for cell #1 in ZAFCs with a new air cathode and a
used air cathode. Fig. 6. Nyquist plots of EIS spectra for 25 cm2 ZAFC with a used air cathode.
60 Z. Ma et al. / Journal of Power Sources 274 (2015) 56e64
much smaller than that in the cell with a used cathode. Therefore, Table 2
these results imply that the HFL is related to air cathode geometry Calculated parameters of the equivalent circuit for 25 cm2 zinc air fuel cell.
rather than zinc anode. The medium frequency loop (MFL) becomes Fuel cell Re Ri Rk Rm
smaller as the current increases in the case of a new air cathode, as (U cm2)
seen in Fig. 5. As the overpotential increases with the increasing
25 cm2 cell with a new air cathode
current, and larger overpotential would enhance the kinetic driving
0A 0.535 0.177 0.243 0.093
force and decrease the charge transfer resistance [35e37], it can be 1A 0.532 0.158 0.153 0.076
concluded that the MFL is related to the kinetic behavior of the air 2A 0.535 0.143 0.098 0.073
cathode. However, there is no appreciable increase in the MFL for 3A 0.533 0.140 0.083 0.082
25 cm2 cell with a used air cathode
the cell with a used air cathode, which implies that the electro-
0A 0.556 1.134 0.469 0.455
catalytic activity of the used air cathode has degraded greatly. 1A 0.562 1.130 0.577 0.544
Furthermore, the low frequency loop (LFL) becomes larger with the 2A 0.567 1.115 0.765 1.201
increasing current for the cell with a used air cathode, as seen in 3A 0.568 1.105 0.903 3.234
Fig. 6. This behavior is indicative of mass transfer limitation,
because the mass transfer effect always becomes more significant
with the increasing current [35e37]. Interestingly, the LFL in the
cell with a new cathode does not vary much with increasing cur- also noteworthy that the Rk and Rm for the used air cathode are
rent. Therefore, it can be concluded that the LFL is related to the gas much larger than the new air cathode. The larger Rk implies that the
diffusion in GDL. The much smaller LFL in the cell with a new air catalyst surface area was smaller, or electrocatalytic activity was
cathode suggests that the gas diffusion coefficient of the new air lower, and the much larger Rm confirms that the gas diffusion co-
cathode is much higher. Therefore, these results may explain the efficient decreased seriously.
difference in the polarization behavior of the new air cathode and
used air cathode, and also prove that the degradation of the used air 3.3. Electrochemical characterization of air cathode in three-
cathode is mainly due to the decrease of electrocatalytic activity of electrode half-cell
CL and the gas diffusion coefficient of GDL.
To simulate the experimental data and evaluate the associated In order to make a clear comparison, the electrochemical char-
parameters, an equivalent circuit model for zinc air fuel cell is acterizations of the new air cathodes and the used air cathodes
proposed based on the above discussions, as shown in Fig. 7. This were investigated in a three-electrode half-cell. Fig. 8 gives the
model includes an external ohmic resistance, Re, which is the sum results of the chronopotentiometry with linear current scanning of
of uncompensated electrolyte resistance (between the working and air cathodes. This result was consistent with the 2-cell stack and
the reference electrodes), electronic resistance of cell components, 25 cm2 cell tests, suggesting that the used air cathode had degraded
and any contact resistances. The internal ohmic resistance, Ri, is the significantly.
sum of the electrolyte resistance within the electrode, the elec- Figs. 9 and 10 present the EIS spectra of half-cell with new air
tronic resistance of the electrode material, and the contact resis- cathodes and used air cathodes. There are two impedance loops in
tance between the electrode components. The faradaic impedance, the Nyquist plot of the new cathode, but a knot is observed, possibly
Zf, is further divided into a kinetic resistance, Rk, and a mass- caused by serious overlapping of the two loops. And the imaginary
transfer impedance, Zm. In this model, Zm is represented by a par- part of the high frequency impedance is positive, as shown in Fig. 9.
allel combination of overall mass-transport resistance, Rm, and While for the Nyquist plot of the used cathodes, as clearly seen in
capacitance, Cm [38]. The double-layer capacitance is distributed, Fig. 10, there is clear distinction between the loops and the imag-
according to the difference in the magnitude of the time constant, inary part of the high frequency impedance is negative. There is no
between the ohmic and faradaic processes and represented by Cd1 appreciable increase in the HF loop with the increasing over-
and Cd2, respectively. A quantitative analysis was performed to potential for both of the two cathodes, which indicates that this
estimate ohmic, kinetic, and mass-transfer resistances and double- portion of the impedance is related to the air cathode geometry
layer capacitance by fitting the impedance spectra with the model. [33,39]. In contrast, the diameters of the low frequency loop (LFL)
The values of the equivalent-circuit components are shown in for both air cathodes decrease with the increasing overpotential.
Table 2.
For the 25 cm2 cell with a new air cathode, the Re and Rm remain
almost constant, and the Ri and Rk decrease with the increasing
discharge current. However, the values of Rk and Rm increase
significantly for the 25 cm2 cell in the case of used air cathode. It is
Fig. 7. Schematic representation of the equivalent circuit for the EIS of the zinc air fuel
cell. Fig. 8. Polarization characteristics of the new air cathode and used air cathode.
Z. Ma et al. / Journal of Power Sources 274 (2015) 56e64 61
Table 3
Calculated parameters of the equivalent circuit for three-electrode half-cell (vs. Hg/
HgO).
Half-cell Re Ri Rk
(U cm2)
Fig. 9. Nyquist plots of EIS spectra for the new air cathodes.
3.4. Microstructure and morphology of CL and GDL and air
permeability
The size of the LFL, which is expected for kinetic impedance of ORR
[39], decreases with the increasing overpotential. The LFLs in Representative SEM images of CL and GDL are given in Figs. 11
Nyquist plots at 0 V and 0.1 V present the start of an incomplete and 12, which show marked differences between these two air
semicircle with a large diameter, which is related to the small value cathodes. As illustrated in Fig. 11A and C, there are many macro-
of exchange current density for ORR. Therefore, the larger LFL for pores and crevices at the CL surface of the new air cathode, while
used air cathodes suggests that electrocatalytic activity has these pores and crevices have been clogged seriously for the used
degraded seriously. Furthermore, the high-frequency intercepts of air cathode. The clogging may result from the KOH and potassium
the used cathodes are smaller. This may be explained by the lower zincate (K2ZnO2) precipitation in the residual electrolyte after the
ohmic resistance between the current collector layer (CCL) and cell was dismantled and soaked in deionized water. Fortunately, the
copper plate, since the thickness of the catalytic layer in the used air solid KOH and K2ZnO2 would be dissolved into the flowing alkaline
cathodes was decreased due to catalyst particles loss. electrolyte in the cell's operation. As shown in Fig. 11B and D, the CL
Similar to the ZAFC, the EIS data of the half-cell can also be of the used air cathode presents a more compact and less porous
simulated by the equivalent circuit model shown in Fig. 7 to eval- structure, and the roughness has decreased significantly compared
uate the associated parameters. However, the mass limitations with the new one, and the height of the salient portions and the
caused by shortage of air was not observed in the three-electrode depth of the pores decreases. Part of the problem may result from
half-cell, so the faradaic impedance, Zf, in the equivalent circuit the loss of surface catalyst particles in the cell's operation and in the
model can be simplified to a kinetic resistance, Rk. The values of the process of dismantling, which would lead to a decrease of catalyst
equivalent-circuit components are shown in Table 3. The Ri and Rk surface area. Similarly, the microstructure and morphology of the
decrease with the increasing overpotential. Smaller Re for the GDL has also changed greatly, as shown in Fig. 12. There are a large
three-electrode half-cell with a used air cathode suggests that the number of micropores in the new cathode's GDL (Fig. 12A and B),
thickness of the catalytic layer has decreased. Moreover, the Re of but most of them have been clogged in the used air cathode
the three-electrode half-cell is larger than that of the 25 cm2 cell, (Fig. 12C and D). The clogging of the micropores in the air cathode
which is due to the fact that the CL in the edge-clad regions of the results in a higher gas diffusion resistance.
air cathodes used in the 25 cm2 cells were cleared to minimize the Air permeability of the new air cathode and used air cathode
ohmic resistance. The much larger Rk for the used air cathode were quietly different. Fig. 13 shows the pressure drop (DP) when
suggests the catalyst surface area was smaller or electrocatalytic compressed air flowed through the air cathodes. For a certain air
activity was lower. The Ri of the used air cathodes increased flux, the pressure drop (DP) of the used air cathode was almost
dramatically, and this may be a result of the change of air cathode three times higher than that of the new air cathode, indicating that
geometry. the intrinsic permeability (k) of the used air cathode has decreased
by 70%. This was likely due to the clogging of pores, and it was
consistent with the increase of diffusion resistances in EIS tests as
discussed above.
Fig. 11. SEM pictures of the catalytic layer of air cathode: A and B show the new air cathode, C and D show the used air cathode.
especially at the electrolyte inlet and outlet. Second, during the by phase transition between KOH solution and crystal will cause
standby condition, the KOH electrolyte would precipitate in the uneven mechanical stress for different components, and resulting
porous of CL. Thus, after numerous precipitate/dissolve cycles be- in interfacial delaminations and damages. Third, carbon would be
tween fuel cell operation and parking periods, a shear force induced oxidized by O2, especially at high potentials and high temperatures
Fig. 12. SEM pictures of the gas diffusion layer of air cathode: A and B show the new air cathode, C and D show the used air cathode.
Z. Ma et al. / Journal of Power Sources 274 (2015) 56e64 63
changes of the porous geometry. All these effects will lead not only
to blocking of the diffusion paths but also to destruction of the
layers mechanically, resulting in apparent gas diffusion coefficient
decrease in the GDL during long-term operation.
In order to enhance the lifetime of air cathode, carbon dioxide
and air particles must be removed from the feed air. One possible
way is scrubbing of the air by chemical absorption including soda
lime, LiOH, Ca(OH)2, to lower the CO2 concentration to a tolerable
level [43,44]. A high efficiency particulate air filter can also be used
to eliminate the particle matters (PM). Additionally, if the air
cathode has been clogged seriously by particle matters, compressed
air (the gauge pressure is about 50 mbar) can be supplied inter-
mittently to flush the air cathode, and the clogging particle matters
can be pushed through the cathode and carried out by electrolyte.
Therefore, the porosity can be regenerated to a certain extent. With
respect to the degradation of PTFE, making the distribution of the
Fig. 13. Pressure drop (DP) between the two sides of air cathode. micropores in GDL more uniformly can alleviate the negative in-
fluence of the porous geometry changing.
4.1.1. Gas diffusion layer The National Basic Research Program of China (973 Program)
Direct reasons for GDL degradation include: (1) electrolyte (2012CB215500), the National Natural Science Foundation of China
leakage and carbonate precipitation, (2) particle matters clogging, (No. 21376138), 863 Programs (2012AA110601, 2012AA053402) are
and (3) degradation of PTFE. In typical operation, the electrolyte gratefully acknowledged for funding this work.
and gas fill pores inside the active layer side by side, and no elec-
trolyte goes inside the GDL because of its high hydrophobicity. References
However, the electrolyte would leak throughout the GDL for some
€fer, Energy Policy
[1] W. Krewitt, S. Simon, W. Graus, S. Teske, A. Zervos, O. Scha
reasons, for example electrocapillary migration. Irreversible car-
35 (2007) 4969e4980.
bonate precipitation will occur inside the electrolyte-filled pores of [2] World Energy Outlook 2012, International Energy Agency, Paris, 2012.
GDL as the feed air contains carbon dioxide (CO2). Moreover, there [3] Energy Technology Perspectives 2012, International Energy Agency, Paris,
are lots of particle matters (PM) in the feed air, such as PM2.5, 2012.
[4] E.K. Hart, M.Z. Jacobson, Energy Environ. Sci. 5 (2012) 6592e6601.
which would also clog the macropores in GDL. Last but not least, [5] E.V. Global, Outlook: Understanding the Electric Vehicle Landscape to 2020,
the PTFE may be degraded by caustic electrolyte, resulting in International Energy Agency, Paris, 2013.
64 Z. Ma et al. / Journal of Power Sources 274 (2015) 56e64
[6] C.J. Barnhart, M. Dale, A.R. Brandt, S.M. Benson, Energy Environ. Sci. 6 (2013) [26] R. Cao, J.-S. Lee, M. Liu, J. Cho, Adv. Energy Mater. 2 (2012) 816e829.
2804e2810. [27] X.G. Zhang, Corrosion and Electrochemistry of Zinc, Plenum Publisher, 1996.
[7] J. Rugolo, M.J. Aziz, Energy Environ. Sci. 5 (2012) 715e7160. [28] D. Linden, D.B. Reddy, Handbook of Batteries, third ed., McGraw Hill, New
[8] B. Müller, W. Arlt, P. Wasserscheid, Energy Environ. Sci. 4 (2011) 4322e4331. York, NY, 2002.
[9] M.C. Toroker, E.A. Carter, J. Mater. Chem. A 1 (2013) 2474e2484. [29] C.W. Lee, K. Sathiyanarayanan, S.W. Eom, H.S. Kim, M.S. Yun, J. Power Sources
[10] T.J. Kucharski, Y. Tian, S. Akbulatov, R. Boulatov, Energy Environ. Sci. 4 (2011) 160 (2006) 161e164.
4449e4472. [30] X.G. Zhang, ECS Trans. 16 (2009) 47e59.
[11] Z. Yang, J. Zhang, M.C.W. Kintner-Meyer, X. Lu, D. Choi, J.P. Lemmon, J. Liu, [31] M.A. Rahman, X. Wang, C. Wen, J. Electrochem. Soc. 160 (2013) 1759e1771.
Chem. Rev. 111 (2011) 3577e3613. [32] J.-S. Lee, S.T. Kim, R. Cao, N.-S. Choi, M. Liu, K.T. Lee, J. Cho, Adv. Energy Mater.
[12] G.L. Soloveichik, Annu. Rev. Chem. Biomol. Eng. 2 (2011) 503e527. 1 (2011) 34e50.
[13] Q. Li, R. Cao, J. Cho, G. Wu, Adv. Energy Mater. 4 (2014) 1301415. [33] F. Zhang, D. Pant, B.E. Logan, Biosens. Bioelectron. 30 (2011) 49e55.
[14] J.W.D. Ng, Y. Gorlin, T. Hatsukade, T.F. Jaramillo, Adv. Energy Mater. 3 (2013) [34] A. Fischer, J. Jindra, H. Wendt, J. Appl. Electrochem. 28 (1988) 277e282.
1545e1550. [35] E. Barsoukov, J.R. Macdonald, Impedance Spectroscopy Theory, Experiment,
[15] F. Cheng, J. Chen, Chem. Soc. Rev. 41 (2012) 2172e2192. and Applications, John Wiley & Sons, Inc., Hoboken, NJ, 2005.
[16] H. Kim, G. Jeong, Y.-U. Kim, J.-H. Kim, C.-M. Park, H.-J. Sohn, Chem. Soc. Rev. 42 [36] X. Yuan, H. Wang, J.C. Sun, J. Zhang, Int. J. Hydrogen Energy 32 (2007)
(2013) 9011e9034. 4365e4380.
[17] J. Goldstein, I. Brown, B. Koretz, J. Power Sources 80 (1999) 171e179. [37] X. Yuan, J.C. Sun, M. Blanco, H. Wang, J. Zhang, D.P. Wilkinson, J. Power
[18] P. Sapkota, H. Kim, J. Ind. Eng. Chem. 15 (2009) 445e450. Sources 161 (2006) 920e928.
[19] V. Neburchilov, H. Wang, J.J. Martin, W. Qu, J. Power Sources 195 (2010) [38] R. Holze, W. Vielstich, J. Electrochem. Soc. 131 (1984) 2298e2303.
1271e1291. [39] H. Huang, W. Zhang, M. Li, Y. Gan, J. Chen, Y. Kuang, J. Colloid Interface Sci. 284
[20] S.I. Smedley, X.G. Zhang, J. Power Sources 165 (2007) 897e904. (2005) 593e599.
[21] P. Pei, Z. Ma, K. Wang, X. Wang, M. Song, H. Xu, J. Power Sources 249 (2014) [40] S. Zhang, X.-Z. Yuan, J.N. Cheng Hin, H. Wang, K.A. Friedrich, M. Schulze,
13e20. J. Power Sources 194 (2009) 588e600.
[22] J. F. Cooper, D. Fleming, D. Hargrove, R. Koopman, K. Peterman, SAE papers [41] P.H. Benhangi, A. Alfantazi, E. Gyenge, Electrochim. Acta 123 (2014) 42e50.
951948. [42] M. Cifrain, K.V. Kordesch, J. Power Sources 127 (2004) 234e242.
[23] G. Du, X. Liu, Y. Zong, T.S.A. Hor, A. Yu, Z. Liu, Nanoscale 5 (2013) 4657e4661. [43] J.-F. Drillet, F. Holzer, T. Kallis, S. Müller, V.M. Schmidt, Phys. Chem. Chem.
[24] S. Yang, X. Feng, X. Wang, K. Müllen, Angew. Chem. Int. Ed. 50 (2011) Phys. 3 (2001) 368e371.
5339e5343. [44] H.-H. Cheng, C.-S. Tan, J. Power Sources 162 (2006) 1431e1436.
[25] M. Prabu, K. Ketpang, S. Shanmugam, Nanoscale 6 (2014) 3173e3181.