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Electrochimica Acta
journal homepage: www.elsevier.com/locate/electacta
a r t i c l e
i n f o
Article history:
Received 15 April 2012
Received in revised form 23 July 2012
Accepted 2 October 2012
Available online 5 November 2012
Keywords:
Ammonia electrolysis
Hydrogen production
Alkaline electrolytes
Polyacrylic acid
Gel electrolytes
a b s t r a c t
An alkaline polymer gel electrolyte was synthesized using potassium salt of cross-linked polyacrylic
acid (PAA-K) and tested for its efficacy as an alternative to aqueous potassium hydroxide for ammonia
electrolysis. Upon using PAA-K, the onset potential for the anodic ammonia electro-oxidation reaction
increased, while that for the hydrogen evolution reaction decreased. This resulted in a larger operating
potential window for ammonia electrolysis while simultaneously improving the efficiency of hydrogen
production. The conversion of ammonia improved from 15.882 0.002% to 25.000 0.004%, while the
current efficiency for the consumption of ammonia increased from 92 1% to 97 2% by using PAA-K. The
use of PAA-K also prevented the crossover of the hydrogen produced to the anode side, unlike aqueous
KOH.
2012 Elsevier Ltd. All rights reserved.
1. Introduction
[19,20].
Corresponding author. Tel.: +1 740 593 9670; fax: +1 740 593 0873.
E-mail address: botte@ohio.edu (G.G. Botte).
0013-4686/$ see front matter 2012 Elsevier Ltd. All rights reserved.
http://dx.doi.org/10.1016/j.electacta.2012.10.023
E 0 = 0.77 VvsSHE
(1)
E 0 = 0.82 VvsSHE
(2)
E 0 = 0.059 V
(3)
Polymer
Copolymer and
additives
1
2
3
4
5
6
7
8
9
10
11
PVA + KOH
PVA + KOH
PVA + KOH
PVA + KOH
PVA + KOH
PVA + Li Salt
PEO + KOH
PEO + KOH
PEO + LiClO4
PAA + KOH
PAA + KOH
PC + Al2 O3
ZrO2
PECH
PEO
PECH
PECH
MBA
8.54 104
1 104
2.67 101
1 103 to 1 102
1 107 to 1 102
9.25 105
5.1 103 to 1 102
1 103
1 105
6 101
2.88 101
773
774
Fig. 1. Exploded view of cell assembly used for evaluating the gel electrolyte. (A)
Setup used for cyclic voltammetry experiments. (B) Setup used for diffusion studies
and galvanostatic experiments.
(4)
(Nc,i Nc,f )
At
(5)
where J is the diffusion flux (mol cm2 s1 ), Nc,i is the initial moles
of ammonia at the cathode, Nc,f is the final moles of ammonia at
the cathode (mol), A is the cross sectional area (cm2 ), and t is the
time (s). Upon performing a shell mole balance in the spacer compartment and using Ficks law of diffusion the diffusion flux can be
written as follows:
J = D
(C)
X
(6)
775
776
Table 2
Comparison of diffusion flux and diffusion coefficient of ammonia in aqueous 5 M KOH with PAA-K electrolytes measured at OCV.
Electrolyte
Compartment
Aqueous 5 M KOH
a
PAA (7%)
a
Anode
Cathode
Anode
Cathode
Volume of feed
(ml) (0.1)
9.0
9.0
6.0
6.0
NH3 concentration
(ppm) (1)
Before
After
17,000
0
17,100
0
9100
8700
14,500
1250
Diffusion coefficient
(105 cm2 s1 )
(0.3347)
0.0046
0.0051
0.0015
0.0007
6.335 0.197
1.9024
0.910 0.028
0.2733
In all the cases a polypropylene separator from Celgard (25 m porous product no. 3401) was present in the compartment of the cell, as illustrated in Fig. 1(A).
Fig. 2. Cyclic voltammograms comparing the electro-oxidation of ammonia on PtIr electrodeposited on titanium gauze substrate with aqueous 5 M KOH and PAA-K. The
normalized current density for CVs in the absence of ammonia (dotted lines) has been multiplied by a factor of 16 for visual clarity. The results show that, upon using PAA-K
the onset potential as well as the peak potential for OH ion electrosorption and ammonia electro-oxidation shift to more positive potentials. The charge for AER, using the
PAA-K electrolyte, decreased by a factor of 3.5 when compared to the aqueous electrolyte.
777
Fig. 3. Cyclic voltammograms comparing the electro-oxidation of ammonia on PtIr electrodeposited on CFP substrate with aqueous 5 M KOH and PAA-K. The normalized
current density for CVs in the absence of ammonia (dotted lines) has been multiplied by a factor of 8 for visual clarity. The charge for AER, using the PAA-K electrolyte,
decreased by a factor of 2.6 when compared to the aqueous electrolyte.
could cause the activity to decrease further and pH at the electrode surface to increase, in turn causing the potentials to shift in
the cathodic direction. However, a more detailed study needs to be
performed in order to completely understand the contributions of
the change in pH and activity of water for the less cathodic onset
potential for HER in the presence of PAA-K. In addition, from the CV
results, it can be observed that the presence of ammonia for both
aqueous 5 M KOH and PAA-K does not have any significant effect
on the HER.
3.3.3. Galvanostatic studies
Fig. 5 shows the comparison of cell voltages for the galvanostatic step experiments for ammonia electrolysis with PAA-K to
5 M aqueous KOH with ammonia performed in a two electrode
Fig. 4. Cyclic voltammograms comparing the cathodic reduction of water on PtIr electroplated on CFP substrate with aqueous 5 M KOH and PAA-K. It can be seen that the
onset of HER with PAA-K starts at a less negative potential when compared with aqueous 5 M KOH electrolyte.
778
Fig. 5. Comparison of the galvanostatic-step test results for ammonia electrolysis using aqueous 5 M KOH with PAA-K electrolytes. The dashed lines (- - -) represent the
applied specific current density, while the solid lines () represent the voltage response of the cell. It can be seen from the cell voltage for the AEC using PAA-K electrolyte
that the power consumption is slightly higher than the 5 M KOH electrolyte at 5 mA cm2 g1 .
Fig. 6. Comparison of voltage response of the AEC for constant current tests at 125 mA (6.5 mA cm2 g1 ) with aqueous and PAA-K. The inset shows the comparison of the
OCV as a function of time for the aqueous and PAA-K systems. The results indicate that the cell voltage for PAA-K electrolyte is higher than its aqueous counterpart by 100 mV
initially and keeps increasing continuously.
is lower than its aqueous counter part by 250 mV. Ammonia was
electrolyzed using PAA-K and aqueous 5 M KOH electrolyte for one
hour at 0.0625 mA cm2 g1 . Initially the cell voltage for the PAA-K
was 0.76 V, higher by 100 mV when compared with aqueous 5 M
KOH. The final voltage recorded for ammonia electrolysis with
PAA-K was 0.98 V, which is higher than the aqueous electrolyte by
236 mV. The electrodes, after being used with PAA-K, were retested
with aqueous 5 M KOH by applying a current of 125 mA, in order to
check for any deterioration. It was found that the voltage response
was similar to the response that was obtained before testing
with PAA-K, implying that the electrodes were not deteriorated.
Therefore, the continuous increase in the cell voltage could be
attributed to different reasons: the disruption in the conductivity
Conversion (%) =
(Ca,i Ca,f )
100
Ca,i
(7)
779
(Ca,i Ca,f )
V
At
(8)
92%
97%
90%
Power consumed (W h g1 ) =
3.65
4.07
3.72
6.06
6.44
5.95
15.882
25.000
15.497
(9)
Nexpt
100
Ntheo
(10)
where NH3,current is the current efficiency based on ammonia consumption, Nexpt is the experimental moles of ammonia consumed
given by (Ca,i Ca,f )VM, and Ntheo is the moles of ammonia consumed based on Faradays law.
The conversion, power consumption for ammonia electrolysis,
and current efficiency are summarized in Table 3. The gases generated at the anode and cathode were collected during each constant
current experiment and then analyzed. Based on the results presented in Table 3, it can be understood that the conversion for
ammonia, the rate of ammonia consumed, and current efficiency
are higher with the gel electrolyte. However, previous CV results
explain that the ammonia electrolysis had been retarded when
PAA-K was used as the electrolyte in lieu of aqueous 5 M KOH.
Nevertheless, the electrodes when used with PAA-K, encounter
catalytic poisoning at a higher potential when compared with the
PAA-K electrolyte leading to the higher conversion and efficiency.
The volume of the gases generated at the cathode, the results
of the GC analysis, and efficiencies are reported in Table 4. From
the gas collection and gas chromatography results the current and
energy efficiencies for hydrogen generation were calculated as follows:
H2 ,current (%) =
Before
After
After
(corrected for diffusion)
I Et
(Ca,i Ca,f )VM
Conversion for 1 h
(%)
(0.014)
NH3 concentration (ppm) (1)
Volume of feed
(ml)
(0.1)
System
Table 3
Ammonia concentration at the anode compartment before and after constant current electrolysis at PtIr (loading 1.25 mg cm2 ) for one hour at 0.125 A (conversion, rate of ammonia removal, power required, and current
efficiency for ammonia electrolysis were all calculated after correction for ammonia loss through diffusion).
VH2 PH2
MH2 ,theo
100
1.55
I Et/(V
H2 H2 )
100
(11)
(12)
where H2 ,current is the current efficiency, H2 ,energy is the energy
efficiency based on hydrogen produced. VH2 is the volume of hydrogen collected and H2 is the density of hydrogen at standard,
temperature and pressure, and MH2 ,theo is the theoretical mass of
hydrogen produced based on Faradays law.
It can be seen that the amount of hydrogen generated at the cathode, when aqueous 5 M KOH was used as the electrolyte, is less than
the volume of hydrogen that could be expected based on the conversion of ammonia. It can also be seen that traces of nitrogen are
present in the gases collected at the cathode side. The only possible
explanation for the nitrogen being detected at the cathode side is
that the nitrogen generated at the anode may have crossed over to
the cathode compartment of the electrolytic cell. Similarly, part of
the hydrogen that was generated at the cathode could have diffused
to the anodic compartment of the electrolytic cell thereby causing
the volume of the hydrogen to be lower. On the other hand, when
PAA-K was used as the electrolyte the volume of hydrogen collected
was the closest to the volume of hydrogen expected from Faradays
law calculation. The absence of nitrogen in the gas chromatography results for the gases generated at the cathode side reflects the
absence of nitrogen crossover to the cathode.
780
Table 4
Gas analysis and efficiency calculations for the production of hydrogen during the constant current electrolysis of ammonia on PtIr (loading 1.25 mg cm2 ) CFP electrodes
at 0.125 A.
System
46
50
48
Nitrogen
98.37
100.00
99.59
1.84
0.00
1.41
4. Conclusions
A systematic study to compare the performance of PAA-K electrolytes with KOH on the electrolysis of ammonia was carried
out. It was found that the diffusivity of ammonia in PAA-K electrolyte/polypropylene separator (0.27 105 cm2 s1 ) decreased
by a factor of 10 when compared with aqueous 5 M KOH electrolyte/polypropylene separator, thereby reducing the amount of
ammonia crossing over to the cathode side of the ammonia electrolytic cell.
Cyclic voltammetry results for the ammonia electro-oxidation
reaction with PAA-K revealed that the carbon fiber paper substrates offer a surface area large enough to maintain a good sorption
of ammonia and OH ions in the active catalyst for electrolyzing
ammonia. The use of PAA-K as an electrolyte increased the onset
potential for ammonia electro-oxidation to more anodic potentials
while simultaneously reducing its reaction rate.
The onset potential for the hydrogen evolution reaction in the
presence of PAA-K is reduced to less cathodic potentials, consequently increasing the rate of hydrogen production before anode
electrocatalysts poisoning occurs. Thereby, it allows for a wider
potential window for operation of the ammonia electrolytic cell.
Galvanostatic studies showed that the use of PAA-K caused an
increase in the conversion of ammonia from 15.882 0.002% to
25.000 0.004%, while the current efficiency for ammonia removal
increased from 92 1% to 97 2%.
Further, the use of PAA-K prevented the diffusion of gases generated from one compartment to another compartment of the
ammonia electrolytic cell. In order for PAA-K to be used in lieu of the
aqueous KOH electrolyte for ammonia electrolysis, further research
is required to improve the mechanical strength of the polymer.
Acknowledgments
The authors would like to thank the financial support of
the Center for Electrochemical Engineering Research (CEER) at
Ohio University and the Department of Defense through the U.S.
Army Construction Engineering Research Laboratory (W9132T-0910001). The content of the information does not reflect the position
or the policy of the U.S. government. The authors would like to
thank Dr. Dan Wang and Dr. Howard Dewald for their guidance
and support.
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