- Email: [email protected]
Test factors affecting the performance of zinc–air battery
ARTICLE IN PRESS
JID: JECHEM
[m5G;September 25, 2019;14:50]
Journal of Energy Chemistry xxx (xxxx) xxx
Contents lists available at ScienceDirect
Journal of Energy Chemistry journal homepage: www.elsevier.com/locate/jechem
Test factors affecting the performance of zinc–air battery Dian Jiao a, Ziang Ma a, Jisi Li a, Yajing Han a,∗, Jing Mao a,∗, Tao Ling a,∗, Shizhang Qiao b
Q1
a Key Laboratory for Advanced Ceramics and Machining Technology of Ministry of Education, School of Materials Science and Engineering, Tianjin University, Tianjin 300072, China b School of Chemical Engineering, The University of Adelaide, Adelaide, SA 5005, Australia
a r t i c l e
i n f o
Article history: Received 14 August 2019 Revised 10 September 2019 Accepted 11 September 2019 Available online xxx Keywords: Zinc–air battery Power density Oxygen reduction reaction Non-noble metal catalysts
a b s t r a c t Zinc–air batteries provide a great potential for future large-scale energy storage. We assess the test factors that mainly affect the measured power density of the zinc–air battery. By fitting the polarization curves of the zinc–air batteries, we reveal the effect of testing parameters (electrode distance, electrolyte concentration, and oxygen flux) and preparation of catalysts ink on the activation, ohm, and concentration polarizations of the zinc–air battery. Finally, recommendations on evaluating the potentials of non-noblemetal electrocatalysts for applications in zinc–air batteries were given. © 2019 Published by Elsevier B.V. and Science Press on behalf of Science Press and Dalian Institute of Chemical Physics, Chinese Academy of Sciences
1
1. Introduction
2
With the rapid consumption of fossil fuels and environmental concerns, development of sustainable energy conversion and storage devices is of worldwide industrial and academic interests [1–7]. Recently, zinc–air battery has attracted intensive attentions due to its super-high theoretical energy density and reliable safety [8–10]. Although great advances have been made, this renewable energy technology is still limited by its relatively low power density compared with lithium-ion battery [11–14]. Similar as fuel cells, the efficiency of oxygen reduction reaction (ORR) at the air electrode is of significant importance to the performance of overall zinc–air battery [15–22]. During the last decade, tremendous efforts have been devoted to explore earth-abundant and cost-effective electrocatalysts as alternative to noble metal – platinum (Pt) for ORR [23–27]. These highly active catalysts have improved the peak power density of zinc–air battery – the most important performance indicator, to > 200 mW cm−2 [28,29]. In laboratories, rotating disk electrode (RDE) method is traditionally used to screen electrocatalysts for zinc–air batteries. However, in the reported literatures, we notice that excellent ORR activity of the catalysts do not necessarily lead to the high power density of the as-assembled zinc–air battery. That is, catalysts with inferior ORR intrinsic activity, however afforded high power density of zinc–air battery sometimes [16,28,30–34]. Whereas, cat-
3 4 5 6 7 8 9 10 11 12 13 14 15 16 17 18 19 20 21 22 23 24
∗
Corresponding authors. E-mail addresses: [email protected] (Y. Han), [email protected] (J. Mao), [email protected] (T. Ling).
alysts with superior ORR activity can exhibit low power density of zinc–air battery [35–38]. Therefore, elucidating the factors that exclude intrinsic ORR activity, which also affect the power density of zinc–air battery, is of crucial importance for practical applications. In this work, we aim to assess the possible test factors that influence the measured power densities of zinc–air batteries. Based on delicate fitting of the polarization curves, we show how the testing parameters (electrode distance, electrolyte concentration, and oxygen flux) and preparation of catalysts ink affect the power density of the zinc–air battery. Finally, we give our recommendations on evaluating the potentials of non-noble-metal electrocatalysts for applications in zinc–air batteries.
25
2. Experimental
37
2.1. Synthesis of oxide electrocatalysts
38
The synthesis of Ni-doped CoO catalysts for this study is via a simple cation exchange method [30,39–43]. Briefly, presynthesized ZnO template nanosheets were exchanged with cobalt chloride (CoCl2 ) and nickel chloride (NiCl2 ) at 525 °C for 30 min in a quartz tube with 50 s.c.c.m. nitrogen (N2 ) gas flow.
39
2.2. Preparation of electrocatalyst ink
44
Homogeneous catalyst ink was prepared by sonication (ScientzIID, Sientz) of 1 mg Ni-doped CoO catalysts or 1 mg Pt/C catalysts and 1 mg carbon material, 10 μL 5 wt% Nafion solution, and 10 μL isopropanol and 0–20 μL 5 wt% PTFE solution in 190 μL deionized water.
45
https://doi.org/10.1016/j.jechem.2019.09.008 2095-4956/© 2019 Published by Elsevier B.V. and Science Press on behalf of Science Press and Dalian Institute of Chemical Physics, Chinese Academy of Sciences
Please cite this article as: D. Jiao, Z. Ma and J. Li et al., Test factors affecting the performance of zinc–air battery, Journal of Energy Chemistry, https://doi.org/10.1016/j.jechem.2019.09.008
26 27 28 29 30 31 32 33 34 35 36
40 41 42 43
46 47 48 49
ARTICLE IN PRESS
JID: JECHEM 2
[m5G;September 25, 2019;14:50]
D. Jiao, Z. Ma and J. Li et al. / Journal of Energy Chemistry xxx (xxxx) xxx Table 1. The fitted parameters of zinc–air batteries with different electrode spacings.
Fig. 1. Schematic illustration of zinc–air battery.
50
2.3. Electrochemical characterizations
58
The intrinsic activity of the Ni-doped CoO catalysts in this study were tested on a Pine electrochemical workstation in a threeelectrode cell in 1 M KOH, using a saturated calomel electrode as the reference electrode and a Pt wire as the counter electrode. The prepared catalyst ink was dropped onto a glassy carbon RDE (0.196 cm2 ) to keep a specific Ni-doped CoO catalyst loading mass of 0.24 mg cm−2 . The polarization curves were recorded at 1600 rpm with a scan rate of 5 mV s−1 .
59
2.4. Zn–air battery assembly and testing
60
64
10 μL of the prepared catalyst ink was drop-casted onto a Teflon-treated carbon fiber paper (CFP) to achieve a catalyst mass loading of 0.24 mg cm−2 . The zinc–air battery was tested in a two-electrode configuration with the catalyst-loaded CFP as the air cathode, and a polished zinc plate as the anode (Fig. 1).
65
3. Results
66
3.1. Brief introduction on zinc–air battery
67
A zinc–air battery consists of an air electrode, a metal Zn electrode, and a membrane separator, as illustrated in Fig. 1. The reactions occurring at the cathode and anode of the zinc–air battery are as following:
51 52 53 54 55 56 57
61 62 63
68 69 70
Cathode: O2 + 4e– + 2H2 O→4OH– Anode: Zn + 4OH → Zn(OH)4 –
71 72
74 75 76 77 78 79 80
+ 2e
–
(2)
The polarization curve of a zinc–air battery can be described by following equation [44–46],
E = Etheoretical − 73
2–
(1)
RT ln αF
i i0
−
RT ln nF
iL iL − i
− iRi
(3)
where R, T and F represent gas constant, temperature and Faraday’s constant, respectively. i0 , iL and i represent exchange current density, limiting current density and the measured current density, respectively. α and n represent transfer coefficient, number of electrons involved, respectively. E and Etheoretical represent electrode potential and theoretical open circuit voltage of the battery, respectively. Ri represents the internal resistance of the zinc–air battery. iL In the polarization of zinc–air battery, αRTF ln( ii ), iRi and RT nF ln ( i −i ) 0
L
Electrode spacing (cm)
i0 (mA cm−2 )
Ri ( cm2 )
1 2 2.5
1.11 × 10−2 1.09 × 10−4 0.934 × 10−5
1.41 1.53 1.58
Power density (mW cm−2 ) 170 148 135
represent activation, ohm and concentration polarization, respectively. By fitting the polarization curve, the separate contributions of these three polarizations can be distinguished. It is noteworthy that the ohm polarization area is in the intermediate potential interval with a linear region, and the regions before and after this linear region are activation and concentration regions, respectively.
81
3.2. ORR catalysts for testing
87
Our previously reported highly active Ni-doped CoO catalysts [29] for cathodes in zinc–air batteries were applied in this study. As shown in Fig. 2(a) and (b), the Ni-doped CoO catalysts exhibit porous nanosheet morphology with face-centered cubic structure (Fig. 2(c)). Fig. 2(d) compares the ORR activity of Ni-doped CoO catalysts with the benchmark Pt/C catalysts in 1 M KOH. As shown, Ni-doped CoO affords half-wave potential (E1/2 ) of 0.77 VRHE , 90 mV inferior to that of Pt/C.
88
3.3. Evaluation of testing factors In zinc–air battery, the losses in activation, ohm and concentration polarization areas together determine the final performance [44,46]. The activation polarization is mainly related to the kinetics of electrocatalytic redox reactions in cathode. Ohm polarization is principally associated to the ionic resistance in the electrolyte and the electrical resistance of the electrode. Concentration polarization occurs when O2 is rapidly consumed at the cathode. In this work, the test factors that mainly influence these polarization losses were investigated and analyzed, including the electrode distance, the electrolyte concentration, the oxygen flux, and the preparation of the catalyst ink. 3.3.1. Electrode distance The ionic resistance of zinc–air battery can be affected by the distance between the air electrode and the zinc electrode. Fig. 3(a) shows the discharge polarization curves of the zinc–air batteries assembled with electrode distances of 1.0, 2.0 and 2.5 cm, and Fig. 3(b) illustrates the corresponding power densities. The fitted parameters of the polarization curves were shown in Table 1. As seen, Ri decreases with the decreasing of electrode spacing. Meanwhile, i0 increases with the decreasing of electrode spacing, which indicates that the exchange rate of oxidized ions and reduced ions at the electrode/solution interface is accelerated. These two factors result in the highest power density of the battery with 1 cm electrode distance among the three investigated devices (Fig. 3(b)). 3.3.2. Electrolyte concentration KOH solutions are widely employed as electrolytes in zinc–air batteries [13]. In this work, different concentration of KOH solution, which are 3, 6 and 12 M KOH, are compared. As shown in Fig. 4(a) and Table 2, the concentration of KOH affects the exchange current density – that is, i0 increases with the increasing of the electrolyte concentration. It is reasonable that the thicker KOH electrolyte, the more OH– taking part in ORR, thus promoting i0 . Moreover, different concentrations of KOH lead to variation of Ri values. The value of Ri for 6 M KOH is the lowest due to its highest ionic conductivity in the three investigated electrolytes. For the
Please cite this article as: D. Jiao, Z. Ma and J. Li et al., Test factors affecting the performance of zinc–air battery, Journal of Energy Chemistry, https://doi.org/10.1016/j.jechem.2019.09.008
82 83 84 85 86
89 90 91 92 93 94 95 96 97 98 99 100 101 102 103 104 105 106 107 108 109 110 111 112 113 114 115 116 117 118 119 120 121 122 123 124 125 126 127 128 129 130 131
JID: JECHEM
ARTICLE IN PRESS
[m5G;September 25, 2019;14:50]
D. Jiao, Z. Ma and J. Li et al. / Journal of Energy Chemistry xxx (xxxx) xxx
3
Fig. 2. Characterization of the Ni-doped CoO catalysts. (a) and (b) Low-magnification and high-magnification SEM images of Ni-doped CoO catalysts. (c) XRD spectrum of Ni-doped CoO catalysts. (d) RDE voltammograms of Ni-doped CoO and Pt/C in O2 saturated 1 M KOH at 1600 rpm.
Fig. 3. (a) and (b) Polarization curves and corresponding power density curves of zinc–air batteries with different electrode distances.
Please cite this article as: D. Jiao, Z. Ma and J. Li et al., Test factors affecting the performance of zinc–air battery, Journal of Energy Chemistry, https://doi.org/10.1016/j.jechem.2019.09.008
ARTICLE IN PRESS
JID: JECHEM 4
[m5G;September 25, 2019;14:50]
D. Jiao, Z. Ma and J. Li et al. / Journal of Energy Chemistry xxx (xxxx) xxx
Fig. 4. (a) and (b) Polarization curves and corresponding power density curves of zinc–air batteries with different KOH concentrations.
Table 2. The fitted parameters of zinc–air batteries with different KOH concentrations. Concentration of KOH (mol L− 1 )
i0 (mA cm−2 )
Ri ( cm2 )
3 6 12
0.833 × 10−4 1.11 × 10−2 1.21 × 10−2
1.55 1.41 1.65
Power density (mW cm−2 ) 149 173 156
Table 3. The fitted parameters of zinc–air batteries with the air electrodes passing through different magnitudes of oxygen flux.
132 133 134 135 136 137 138 139 140 141 142 143 144 145 146 147 148 149 150 151 152 153 154 155
Oxygen flux (mL min−1 )
i0 (mA cm−2 )
Ri ( cm2 )
20 40 60 80 100
1.09 × 10−2 1.10 × 10−2 1.10 × 10−2 1.11 × 10−2 1.11 × 10−2
1.140 1.141 1.143 1.140 1.142
Power density (mW cm−2 ) 150 172 201 210 227
KOH concentration > 6 M, the viscosity in the electrolyte is significantly increased, thus the transfer of ions in the electrolyte is greatly restrained. Besides, the overrich KOH electrolyte (> 6 M) hampers the diffusion of O2 in the gas (O2 )/solid (catalysts)/liquid (electrolyte) three-phase interface, thus decreases the current density in concentration polarization. Therefore, 6 M KOH nicely balances the ionic transportation and the O2 supply in the zinc–air battery, therefore results in the high power density of corresponding zinc–air battery (Fig. 4(b)). 3.3.3. Oxygen flux Because O2 gas is involved as the reactant in the air electrode of the zinc–air battery, the magnitude of the oxygen flow has a big impact on the polarization curve and corresponding power density, however hardly influences the ions transportation and the exchange current density (Table 3). The oxygen flux was progressively changed. As shown in Fig. 5 and Table 3, the larger the oxygen flux, the larger polarization current, and the higher power density. 3.3.4. Catalysts ink preparation Carbon materials: In electrode fabrication, electrocatalysts are generally supported on carbon materials to assure good dispersity and electrical conductivity [4,33,36,37,47–51]. In this study, carbon black and acetylene black were compared (Fig. 6 and Table 4). As summarized in Table 4, the value of i0 for the air electrode supported with carbon black is significantly larger than that supported
Table 4. The fitted parameters of zinc–air batteries with the air electrodes assembled with carbon black or acetylene black. Carbon material
i0 (mA cm−2 )
Ri ( cm2 )
Carbon black Acetylene black
1.18 × 10−2 4.44 × 10−4
0.84 0.93
Power density (mW cm−2 ) 238 174
Table 5. The fitted parameters of zinc–air batteries with the catalyst ink prepared with different amounts of PTFE. Adding volume of PTFE (μL)
i0 (mA cm−2 )
Ri ( cm2 )
5 10 15 20
1.12 × 10−2 1.14 × 10−2 1.13 × 10−2 1.13 × 10−2
0.944 0.961 0.975 0.992
Power density (mW cm−2 ) 314 301 291 283
with acetylene black. This origins from the larger surface area of the carbon black, which ensures that the electrocatalysts are well dispered and exposed during the electrocatalytic reactions. Moreover, the smaller Ri of the battery assembled with carbon black indicates better electrical conductivity of cabon black compared with acetylene black. Therefore, carbon black is more suitable to support electrocatalysts. Poly tetra fluoro ethylene (PTFE): Besides the above discussions, it is found from Figs. 3–6 that the performances of the zinc–air batteries are still limited by the concentration loss at the high current density range, indicating that the diffusion of oxygen gas in this polarization area is largely restricted. To solve this issue, PTFE was added into the catalyst ink to increase the hydrophobicity of the assembled air electrode. As shown in Fig. 7, with the introducing of PTFE, the discharge curves change into almost linear through ohm polarization area to concentration polarization area, significantly increasing the current density and corresponding power density. However, the continued increasing the amount of PTFE increases Ri , thus decreases the current density and corresponding power density (Fig. 7(b) and Table 5). 3.4. Comparison the performance of zinc–air batteries Nowadays, cost-effective and earth-abundant electrocatalysts can be fabricated with various morphologies [17,19,21,28,30,40]. The theoretical and experimental efforts [52] suggest that when the electrodes are immersed in electrolytes, gas pockets are formed in the nanostructured surface of the electrode. Meanwhile, the
Please cite this article as: D. Jiao, Z. Ma and J. Li et al., Test factors affecting the performance of zinc–air battery, Journal of Energy Chemistry, https://doi.org/10.1016/j.jechem.2019.09.008
156 157 158 159 160 161 162 163 164 165 166 167 168 169 170 171 172 173 174 175 176 177 178 179 180 181
JID: JECHEM
ARTICLE IN PRESS
[m5G;September 25, 2019;14:50]
D. Jiao, Z. Ma and J. Li et al. / Journal of Energy Chemistry xxx (xxxx) xxx
5
Fig. 5. (a) and (b) Polarization curves and corresponding power density curves of zinc–air batteries with the air electrodes passing through different magnitudes of oxygen flux.
Fig. 6. (a) and (b) Polarization curves and corresponding power density curves of zinc–air batteries with the air electrodes assembled with carbon black or acetylene black.
Fig. 7. (a) and (b) Polarization curves and corresponding power density curves of zinc–air batteries with the catalyst ink prepared with different amounts of PTFE.
Please cite this article as: D. Jiao, Z. Ma and J. Li et al., Test factors affecting the performance of zinc–air battery, Journal of Energy Chemistry, https://doi.org/10.1016/j.jechem.2019.09.008
ARTICLE IN PRESS
JID: JECHEM 6
[m5G;September 25, 2019;14:50]
D. Jiao, Z. Ma and J. Li et al. / Journal of Energy Chemistry xxx (xxxx) xxx
Fig. 8. Comparison of polarization curves and corresponding power-density plots between optimized Ni-doped CoO and Pt/C catalysts.
199
micro structured surface provides gaseous channels for spreading of gas. Therefore, a combination of nano and micro structures is highly favorable to accelerate gas diffusion. In this study, Ni-doped CoO catalysts exhibit micro sized nanosheets with inside numerous nanosized pores. With the above optimized test parameters, the Ni-doped CoO catalysts based battery far exceeds the undefeatable Pt/C catalysts based device (Fig. 8). Therefore, for non-noble materials, taking their morphological advantage to reduce their concentration loss provides great opportunities for them to compete noble-metal catalysts. Taken together, the losses in activation, ohm and concentration polarization areas govern the final performance of zinc–air battery. To evaluate the potential of non-noble-metal electrocatalysts for applications in zinc–air batteries, besides intrinsic activity, their structural characteristics associated with gas diffusion should also be taken into consideration. For a given electrocatalyst, the test system, such as the electrode distance, the electrolyte concentration, and the oxygen flux, should be optimized.
200
4. Conclusions
201
211
We report the test factors that mainly affect the performance of zinc–air batteries. We show that the electrode distance, the electrolyte concentration, the oxygen flux, and the preparation of the catalyst ink strongly influence the activation, ohm and concentration polarizations. With the optimized test parameters, the performance of cost-effective and earth-abundant oxide electrocatalysts based zinc–air battery is far beyond that of the state-of-the-art Pt/C catalysts based battery. Our work establishes a trustable process to evaluate the application potentials of non-noble metal catalysts, which can aid in the development of highly active and lowcost catalysts for zinc–air batteries.
212
Acknowledgments
213 215
This work was supported by the National Science Fund for Excellent Young Scholars (51722103) and the National Natural Science Foundation of China (51571149 and 21576202).
216
References
182 183 184 185 186 187 188 189 190 191 192 193 194 195 196 197 198
202 203 204 205 206 207 208 209 210
214
217 218 219
[1] L. Peng, L.-F. Hu, X.-S. Fang, Adv. Funct. Mater. 24 (2014) 2591–2610. [2] J. Fu, Z.P. Cano, M.G. Park, A. Yu, M. Fowler, Z.-W. Chen, Adv. Mater. 29 (2017) 1604685.
[3] C.-Q. Sun, X.-S. Guo, J.-Y. Zhang, G.-L. Han, D.-Q. Gao, X.-P. Gao, J. Energy Chem. 38 (2019) 34–40. [4] C. Tang, B. Wang, H.-F. Wang, Q. Zhang, Adv. Mater. 29 (2017) 1703185. [5] D.-F. Yan, Y.-X. Li, J. Huo, R. Chen, L.-M. Dai, S.-Y. Wang, Adv. Mater. 29 (2017) 1606459. [6] J. Yang, X. Wang, B. Li, L. Ma, L. Shi, Y.-J. Xiong, H.-X. Xu, Adv. Funct. Mater. 27 (2017) 1606497. [7] X.-X. Han, X.-P. Li, J. White, C. Zhong, Y.-D. Deng, W.-B. Hu, T.-Y. Ma, Adv. Energy Mater. 8 (2018) 1801396. [8] Q.-C. Liu, L. Li, J.-J. Xu, Z.-W. Chang, D. Xu, Y.-B. Yin, X.-Y. Yang, T. Liu, Y.-S. Jiang, J.-M. Yan, X.-B. Zhang, Adv. Mater. 27 (2015) 8095–8101. [9] M. Xu, D.G. Ivey, Z. Xie, W. Qu, J. Power Sour. 283 (2015) 358–371. [10] P. Gu, M.-B. Zheng, Q.-X. Zhao, X. Xiao, H.-G. Xue, H. Pang, J. Mater. Chem. A 5 (2017) 7651–7666. [11] Y.-G. Li, J. Lu, ACS Energy Lett. 2 (2017) 1370–1377. [12] J.S. Lee, S.T. Kim, R.-G. Cao, N.S. Choi, M.-L. Liu, K.T. Lee, J. Cho, Adv. Energy Mater. 1 (2011) 34–50. [13] J. Pan, Y.-Y. Xu, H. Yang, Z.-H. Dong, H.-F. Liu, B.-Y. Xia, Adv. Sci. 5 (2018) 1700691. [14] Y.-G. Li, H.-J. Dai, Chem. Soc. Rev. 43 (2014) 5257–5275. [15] A.A. Mohamad, J. Power Sour. 159 (2006) 752–757. [16] L.L. Tian, J. Yang, M.-Y. Weng, R. Tan, J.-X. Zheng, H.-B. Chen, Q.-C. Zhuang, L.-M. Dai, F. Pan, ACS Appl. Mater. Interfaces 9 (2017) 7125–7130. [17] L. Kuai, E. Kan, W. Cao, M. Huttula, S. Ollikkala, T. Ahopelto, A.P. Honkanen, S. Huotari, W.-H. Wang, B.-Y. Geng, Nano Energy 43 (2018) 81–90. [18] S.S. Shinde, C.H. Lee, J.-Y. Yu, D.H. Kim, S.U. Lee, J.H. Lee, ACS Nano 12 (2018) 596–608. [19] Z.-M. Cui, G.-T. Fu, Y.-T. Li, J.B. Goodenough, Angew. Chem. Int. Ed. 56 (2017) 9901–9905. [20] Z.-L. Wang, D. Xu, J.-J. Xu, X.-B. Zhang, Chem. Soc. Rev. 43 (2014) 7746–7786. [21] Z.-M. Cui, Y.-T. Li, G.-T. Fu, X. Li, J.B. Goodenough, Adv. Mater. 29 (2017) 1702385. [22] M.-H. Yu, Z.-K. Wang, C. Hou, Z.-L. Wang, C.-L. Liang, C.-Y. Zhao, Y.-X. Tong, X.-H. Lu, S.-H. Yang, Adv. Mater. 29 (2017) 1602868. [23] D. Banham, S.-Y. Ye, K. Pei, J.i. Ozaki, T. Kishimoto, Y. Imashiro, J. Power Sour. 285 (2015) 334–348. [24] H.-W. Liang, Z.-Y. Wu, L.-F. Chen, C. Li, S.-H. Yu, Nano Energy 11 (2015) 366– 376. [25] W.-J. Jiang, L. Gu, L. Li, Y. Zhang, X. Zhang, L.-J. Zhang, J.-Q. Wang, J.-S. Hu, Z.-D. Wei, L.-J. Wan, J. Am. Chem. Soc. 138 (2016) 3570–3578. [26] F. Jaouen, E. Proietti, M. Lefèvre, R. Chenitz, J.P. Dodelet, G. Wu, H.T. Chung, C.M. Johnston, P. Zelenay, Energy Environ. Sci. 4 (2011) 114–130. [27] Y.-Z. Sun, M. Yang, J.-Q. Pan, P.-Y. Wang, W. Li, P.-Y. Wan, Electrochim. Acta. 197 (2016) 68–76. [28] Y.-G. Li, M. Gong, Y.-Y. Liang, J. Feng, J.E. Kim, H.-L. Wang, G.-S. Hong, B. Zhang, H.-J. Dai, Nat. Commun. 4 (2013) 1805. [29] G. Nam, J. Park, M. Choi, P. Oh, S. Park, M.G. Kim, N. Park, J. Cho, J.S. Lee, ACS Nano 9 (2015) 6493–6501. [30] Y.-J. Li, L. Cui, P.-F. Da, K.-W. Qiu, W.-J. Qin, W.-B. Hu, X.-W. Du, K. Davey, T. Ling, S.-Z. Qiao, Adv. Mater. 30 (2018) 1804653. [31] M.-D. Zhang, Q.-B. Dai, H.-G. Zheng, M.-D. Chen, L.-M. Dai, Adv. Mater. 30 (2018) 1705431. [32] H.-F. Wang, C. Tang, B. Wang, B.-Q. Li, Q. Zhang, Adv. Mater. 29 (2017) 1702327. [33] F.-L. Meng, H.-X. Zhong, D. Bao, J.-M. Yan, X.-B. Zhang, J. Am. Chem. Soc. 138 (2016) 10226–10231. [34] Q. Liu, Y.-B. Wang, L. Dai, J.-N. Yao, Adv. Mater. 28 (2016) 30 0 0–30 06.
Please cite this article as: D. Jiao, Z. Ma and J. Li et al., Test factors affecting the performance of zinc–air battery, Journal of Energy Chemistry, https://doi.org/10.1016/j.jechem.2019.09.008
220 221 222 223 224 225 226 227 228 229 230 231 232 233 234 235 236 237 238 239 240 241 242 243 244 245 246 247 248 249 250 251 252 253 254 255 256 257 258 259 260 261 262 263 264 265 266 267 268 269 270 271 272 273
JID: JECHEM
ARTICLE IN PRESS
[m5G;September 25, 2019;14:50]
D. Jiao, Z. Ma and J. Li et al. / Journal of Energy Chemistry xxx (xxxx) xxx
274 275 276 277 278 279 280 281 282 283 284 285 286 287 288 289
[35] X. Liu, M. Park, M.G. Kim, S. Gupta, X.-J. Wang, G. Wu, J. Cho, Nano Energy 20 (2016) 315–325. [36] P.-T. Liu, D.-Q. Gao, W. Xiao, L. Ma, K. Sun, P.-X. Xi, D.-S. Xue, J. Wang, Adv. Funct. Mater. 28 (2018) 1706928. [37] C.-Y. Su, H. Cheng, W. Li, Z.-Q. Liu, N. Li, Z.-F. Hou, F.-Q. Bai, H.-X. Zhang, T.-Y. Ma, Adv. Energy Mater. 7 (2017) 1602420. [38] B.-Q. Li, C.-X. Zhao, S.-M. Chen, J.-N. Liu, X. Chen., L. Song, Q. Zhang, Adv. Mater. 31 (2019) 1900592. [39] T. Ling, P.-F. Da, X.-L. Zheng, B.-H. Ge, Z.-P. Hu, M.-Y. Wu, X.-W. Du, W.-B. Hu, M. Jaroniec, S.-Z. Qiao, Sci. Adv. 4 (2018) 6261. [40] T. Ling, D.-Y. Yan, Y. Jiao, H. Wang, Y. Zheng, X. Zheng, J. Mao, X.-W. Du, Z. Hu, M. Jaroniec, S.-Z. Qiao, Nat. Commun. 7 (2016) 12876. [41] T. Ling, D.-Y. Yan, H. Wang, Y. Jiao, Z. Hu, Y. Zheng, L. Zheng, J. Mao, H. Liu, X.-W. Du, M. Jaroniec, S.-Z. Qiao, Nat. Commun. 8 (2017) 1509. [42] T. Ling, T. Zhang, B.-H. Ge, L.-L. Han, L.-R. Zheng, F. Lin, Z.-R. Xu, W.-B. Hu, X.-W. Du, K. Davey, S.-Z. Qiao, Adv. Mater. 31 (2019) 1807771. [43] C. Meng, T. Ling, T.-Y. Ma, H. Wang, Z.-P. Hu, Y. Zhou, J. Mao, X.-W. Du, M. Jaroniec, S.-Z. Qiao, Adv. Mater. 29 (2017) 1604607.
7
[44] M. Winter, R.J. Brodd, Chem. Rev. 104 (2004) 4245–4269. [45] A. Kirubakaran, S. Jain, R.K. Nema, Renew. Sustain. Energy Rev. 13 (2009) 2430–2440. [46] F. Barbir, PEM Fuel Cells: Theory and Practice, second ed., Academic Press, New York, 2012. [47] Z.-Q. Liu, H. Cheng, N. Li, T.-Y. Ma, Y.-Z. Su, Adv. Mater. 28 (2016) 3777–3784. [48] C.Y. Su, H. Cheng, W. Li, Z.-Q. Liu, N. Li, Z.-F. Hou, F.-Q. Bai, H.-X. Zhang, T.-Y. Ma, Adv. Energy Mater. 7 (2017) 1602420. [49] H.-F. Wang, C. Tang, B. Wang, B.-Q. Li, X.-Y. Cui, Q. Zhang, Energy Storage Mater. 15 (2018) 124–130. [50] B.-Q. Li, S.-Y. Zhang, B. Wang, Z.-J. Xia, C. Tang, Q. Zhang, Energy Environ. Sci. 11 (2018) 1723–1729. [51] B.-Q. Li, S.-Y. Zhang, X. Chen, C.-Y. Chen, Z.-J. Xia, Q. Zhang, Adv. Funct. Mater. 29 (2019) 1901301. [52] W.-W. Xu, Z.-Y. Lu, X.-M. Sun, L. Jiang, X. Duan, Acc. Chem. Res. 51 (2018) 1590–1598.
Please cite this article as: D. Jiao, Z. Ma and J. Li et al., Test factors affecting the performance of zinc–air battery, Journal of Energy Chemistry, https://doi.org/10.1016/j.jechem.2019.09.008
290 291 292 293 294 295 296 297 298 299 300 301 302 303 304
JID: JECHEM
[m5G;September 25, 2019;14:50]
Journal of Energy Chemistry xxx (xxxx) xxx
Contents lists available at ScienceDirect
Journal of Energy Chemistry journal homepage: www.elsevier.com/locate/jechem
Test factors affecting the performance of zinc–air battery Dian Jiao a, Ziang Ma a, Jisi Li a, Yajing Han a,∗, Jing Mao a,∗, Tao Ling a,∗, Shizhang Qiao b
Q1
a Key Laboratory for Advanced Ceramics and Machining Technology of Ministry of Education, School of Materials Science and Engineering, Tianjin University, Tianjin 300072, China b School of Chemical Engineering, The University of Adelaide, Adelaide, SA 5005, Australia
a r t i c l e
i n f o
Article history: Received 14 August 2019 Revised 10 September 2019 Accepted 11 September 2019 Available online xxx Keywords: Zinc–air battery Power density Oxygen reduction reaction Non-noble metal catalysts
a b s t r a c t Zinc–air batteries provide a great potential for future large-scale energy storage. We assess the test factors that mainly affect the measured power density of the zinc–air battery. By fitting the polarization curves of the zinc–air batteries, we reveal the effect of testing parameters (electrode distance, electrolyte concentration, and oxygen flux) and preparation of catalysts ink on the activation, ohm, and concentration polarizations of the zinc–air battery. Finally, recommendations on evaluating the potentials of non-noblemetal electrocatalysts for applications in zinc–air batteries were given. © 2019 Published by Elsevier B.V. and Science Press on behalf of Science Press and Dalian Institute of Chemical Physics, Chinese Academy of Sciences
1
1. Introduction
2
With the rapid consumption of fossil fuels and environmental concerns, development of sustainable energy conversion and storage devices is of worldwide industrial and academic interests [1–7]. Recently, zinc–air battery has attracted intensive attentions due to its super-high theoretical energy density and reliable safety [8–10]. Although great advances have been made, this renewable energy technology is still limited by its relatively low power density compared with lithium-ion battery [11–14]. Similar as fuel cells, the efficiency of oxygen reduction reaction (ORR) at the air electrode is of significant importance to the performance of overall zinc–air battery [15–22]. During the last decade, tremendous efforts have been devoted to explore earth-abundant and cost-effective electrocatalysts as alternative to noble metal – platinum (Pt) for ORR [23–27]. These highly active catalysts have improved the peak power density of zinc–air battery – the most important performance indicator, to > 200 mW cm−2 [28,29]. In laboratories, rotating disk electrode (RDE) method is traditionally used to screen electrocatalysts for zinc–air batteries. However, in the reported literatures, we notice that excellent ORR activity of the catalysts do not necessarily lead to the high power density of the as-assembled zinc–air battery. That is, catalysts with inferior ORR intrinsic activity, however afforded high power density of zinc–air battery sometimes [16,28,30–34]. Whereas, cat-
3 4 5 6 7 8 9 10 11 12 13 14 15 16 17 18 19 20 21 22 23 24
∗
Corresponding authors. E-mail addresses: [email protected] (Y. Han), [email protected] (J. Mao), [email protected] (T. Ling).
alysts with superior ORR activity can exhibit low power density of zinc–air battery [35–38]. Therefore, elucidating the factors that exclude intrinsic ORR activity, which also affect the power density of zinc–air battery, is of crucial importance for practical applications. In this work, we aim to assess the possible test factors that influence the measured power densities of zinc–air batteries. Based on delicate fitting of the polarization curves, we show how the testing parameters (electrode distance, electrolyte concentration, and oxygen flux) and preparation of catalysts ink affect the power density of the zinc–air battery. Finally, we give our recommendations on evaluating the potentials of non-noble-metal electrocatalysts for applications in zinc–air batteries.
25
2. Experimental
37
2.1. Synthesis of oxide electrocatalysts
38
The synthesis of Ni-doped CoO catalysts for this study is via a simple cation exchange method [30,39–43]. Briefly, presynthesized ZnO template nanosheets were exchanged with cobalt chloride (CoCl2 ) and nickel chloride (NiCl2 ) at 525 °C for 30 min in a quartz tube with 50 s.c.c.m. nitrogen (N2 ) gas flow.
39
2.2. Preparation of electrocatalyst ink
44
Homogeneous catalyst ink was prepared by sonication (ScientzIID, Sientz) of 1 mg Ni-doped CoO catalysts or 1 mg Pt/C catalysts and 1 mg carbon material, 10 μL 5 wt% Nafion solution, and 10 μL isopropanol and 0–20 μL 5 wt% PTFE solution in 190 μL deionized water.
45
https://doi.org/10.1016/j.jechem.2019.09.008 2095-4956/© 2019 Published by Elsevier B.V. and Science Press on behalf of Science Press and Dalian Institute of Chemical Physics, Chinese Academy of Sciences
Please cite this article as: D. Jiao, Z. Ma and J. Li et al., Test factors affecting the performance of zinc–air battery, Journal of Energy Chemistry, https://doi.org/10.1016/j.jechem.2019.09.008
26 27 28 29 30 31 32 33 34 35 36
40 41 42 43
46 47 48 49
ARTICLE IN PRESS
JID: JECHEM 2
[m5G;September 25, 2019;14:50]
D. Jiao, Z. Ma and J. Li et al. / Journal of Energy Chemistry xxx (xxxx) xxx Table 1. The fitted parameters of zinc–air batteries with different electrode spacings.
Fig. 1. Schematic illustration of zinc–air battery.
50
2.3. Electrochemical characterizations
58
The intrinsic activity of the Ni-doped CoO catalysts in this study were tested on a Pine electrochemical workstation in a threeelectrode cell in 1 M KOH, using a saturated calomel electrode as the reference electrode and a Pt wire as the counter electrode. The prepared catalyst ink was dropped onto a glassy carbon RDE (0.196 cm2 ) to keep a specific Ni-doped CoO catalyst loading mass of 0.24 mg cm−2 . The polarization curves were recorded at 1600 rpm with a scan rate of 5 mV s−1 .
59
2.4. Zn–air battery assembly and testing
60
64
10 μL of the prepared catalyst ink was drop-casted onto a Teflon-treated carbon fiber paper (CFP) to achieve a catalyst mass loading of 0.24 mg cm−2 . The zinc–air battery was tested in a two-electrode configuration with the catalyst-loaded CFP as the air cathode, and a polished zinc plate as the anode (Fig. 1).
65
3. Results
66
3.1. Brief introduction on zinc–air battery
67
A zinc–air battery consists of an air electrode, a metal Zn electrode, and a membrane separator, as illustrated in Fig. 1. The reactions occurring at the cathode and anode of the zinc–air battery are as following:
51 52 53 54 55 56 57
61 62 63
68 69 70
Cathode: O2 + 4e– + 2H2 O→4OH– Anode: Zn + 4OH → Zn(OH)4 –
71 72
74 75 76 77 78 79 80
+ 2e
–
(2)
The polarization curve of a zinc–air battery can be described by following equation [44–46],
E = Etheoretical − 73
2–
(1)
RT ln αF
i i0
−
RT ln nF
iL iL − i
− iRi
(3)
where R, T and F represent gas constant, temperature and Faraday’s constant, respectively. i0 , iL and i represent exchange current density, limiting current density and the measured current density, respectively. α and n represent transfer coefficient, number of electrons involved, respectively. E and Etheoretical represent electrode potential and theoretical open circuit voltage of the battery, respectively. Ri represents the internal resistance of the zinc–air battery. iL In the polarization of zinc–air battery, αRTF ln( ii ), iRi and RT nF ln ( i −i ) 0
L
Electrode spacing (cm)
i0 (mA cm−2 )
Ri ( cm2 )
1 2 2.5
1.11 × 10−2 1.09 × 10−4 0.934 × 10−5
1.41 1.53 1.58
Power density (mW cm−2 ) 170 148 135
represent activation, ohm and concentration polarization, respectively. By fitting the polarization curve, the separate contributions of these three polarizations can be distinguished. It is noteworthy that the ohm polarization area is in the intermediate potential interval with a linear region, and the regions before and after this linear region are activation and concentration regions, respectively.
81
3.2. ORR catalysts for testing
87
Our previously reported highly active Ni-doped CoO catalysts [29] for cathodes in zinc–air batteries were applied in this study. As shown in Fig. 2(a) and (b), the Ni-doped CoO catalysts exhibit porous nanosheet morphology with face-centered cubic structure (Fig. 2(c)). Fig. 2(d) compares the ORR activity of Ni-doped CoO catalysts with the benchmark Pt/C catalysts in 1 M KOH. As shown, Ni-doped CoO affords half-wave potential (E1/2 ) of 0.77 VRHE , 90 mV inferior to that of Pt/C.
88
3.3. Evaluation of testing factors In zinc–air battery, the losses in activation, ohm and concentration polarization areas together determine the final performance [44,46]. The activation polarization is mainly related to the kinetics of electrocatalytic redox reactions in cathode. Ohm polarization is principally associated to the ionic resistance in the electrolyte and the electrical resistance of the electrode. Concentration polarization occurs when O2 is rapidly consumed at the cathode. In this work, the test factors that mainly influence these polarization losses were investigated and analyzed, including the electrode distance, the electrolyte concentration, the oxygen flux, and the preparation of the catalyst ink. 3.3.1. Electrode distance The ionic resistance of zinc–air battery can be affected by the distance between the air electrode and the zinc electrode. Fig. 3(a) shows the discharge polarization curves of the zinc–air batteries assembled with electrode distances of 1.0, 2.0 and 2.5 cm, and Fig. 3(b) illustrates the corresponding power densities. The fitted parameters of the polarization curves were shown in Table 1. As seen, Ri decreases with the decreasing of electrode spacing. Meanwhile, i0 increases with the decreasing of electrode spacing, which indicates that the exchange rate of oxidized ions and reduced ions at the electrode/solution interface is accelerated. These two factors result in the highest power density of the battery with 1 cm electrode distance among the three investigated devices (Fig. 3(b)). 3.3.2. Electrolyte concentration KOH solutions are widely employed as electrolytes in zinc–air batteries [13]. In this work, different concentration of KOH solution, which are 3, 6 and 12 M KOH, are compared. As shown in Fig. 4(a) and Table 2, the concentration of KOH affects the exchange current density – that is, i0 increases with the increasing of the electrolyte concentration. It is reasonable that the thicker KOH electrolyte, the more OH– taking part in ORR, thus promoting i0 . Moreover, different concentrations of KOH lead to variation of Ri values. The value of Ri for 6 M KOH is the lowest due to its highest ionic conductivity in the three investigated electrolytes. For the
Please cite this article as: D. Jiao, Z. Ma and J. Li et al., Test factors affecting the performance of zinc–air battery, Journal of Energy Chemistry, https://doi.org/10.1016/j.jechem.2019.09.008
82 83 84 85 86
89 90 91 92 93 94 95 96 97 98 99 100 101 102 103 104 105 106 107 108 109 110 111 112 113 114 115 116 117 118 119 120 121 122 123 124 125 126 127 128 129 130 131
JID: JECHEM
ARTICLE IN PRESS
[m5G;September 25, 2019;14:50]
D. Jiao, Z. Ma and J. Li et al. / Journal of Energy Chemistry xxx (xxxx) xxx
3
Fig. 2. Characterization of the Ni-doped CoO catalysts. (a) and (b) Low-magnification and high-magnification SEM images of Ni-doped CoO catalysts. (c) XRD spectrum of Ni-doped CoO catalysts. (d) RDE voltammograms of Ni-doped CoO and Pt/C in O2 saturated 1 M KOH at 1600 rpm.
Fig. 3. (a) and (b) Polarization curves and corresponding power density curves of zinc–air batteries with different electrode distances.
Please cite this article as: D. Jiao, Z. Ma and J. Li et al., Test factors affecting the performance of zinc–air battery, Journal of Energy Chemistry, https://doi.org/10.1016/j.jechem.2019.09.008
ARTICLE IN PRESS
JID: JECHEM 4
[m5G;September 25, 2019;14:50]
D. Jiao, Z. Ma and J. Li et al. / Journal of Energy Chemistry xxx (xxxx) xxx
Fig. 4. (a) and (b) Polarization curves and corresponding power density curves of zinc–air batteries with different KOH concentrations.
Table 2. The fitted parameters of zinc–air batteries with different KOH concentrations. Concentration of KOH (mol L− 1 )
i0 (mA cm−2 )
Ri ( cm2 )
3 6 12
0.833 × 10−4 1.11 × 10−2 1.21 × 10−2
1.55 1.41 1.65
Power density (mW cm−2 ) 149 173 156
Table 3. The fitted parameters of zinc–air batteries with the air electrodes passing through different magnitudes of oxygen flux.
132 133 134 135 136 137 138 139 140 141 142 143 144 145 146 147 148 149 150 151 152 153 154 155
Oxygen flux (mL min−1 )
i0 (mA cm−2 )
Ri ( cm2 )
20 40 60 80 100
1.09 × 10−2 1.10 × 10−2 1.10 × 10−2 1.11 × 10−2 1.11 × 10−2
1.140 1.141 1.143 1.140 1.142
Power density (mW cm−2 ) 150 172 201 210 227
KOH concentration > 6 M, the viscosity in the electrolyte is significantly increased, thus the transfer of ions in the electrolyte is greatly restrained. Besides, the overrich KOH electrolyte (> 6 M) hampers the diffusion of O2 in the gas (O2 )/solid (catalysts)/liquid (electrolyte) three-phase interface, thus decreases the current density in concentration polarization. Therefore, 6 M KOH nicely balances the ionic transportation and the O2 supply in the zinc–air battery, therefore results in the high power density of corresponding zinc–air battery (Fig. 4(b)). 3.3.3. Oxygen flux Because O2 gas is involved as the reactant in the air electrode of the zinc–air battery, the magnitude of the oxygen flow has a big impact on the polarization curve and corresponding power density, however hardly influences the ions transportation and the exchange current density (Table 3). The oxygen flux was progressively changed. As shown in Fig. 5 and Table 3, the larger the oxygen flux, the larger polarization current, and the higher power density. 3.3.4. Catalysts ink preparation Carbon materials: In electrode fabrication, electrocatalysts are generally supported on carbon materials to assure good dispersity and electrical conductivity [4,33,36,37,47–51]. In this study, carbon black and acetylene black were compared (Fig. 6 and Table 4). As summarized in Table 4, the value of i0 for the air electrode supported with carbon black is significantly larger than that supported
Table 4. The fitted parameters of zinc–air batteries with the air electrodes assembled with carbon black or acetylene black. Carbon material
i0 (mA cm−2 )
Ri ( cm2 )
Carbon black Acetylene black
1.18 × 10−2 4.44 × 10−4
0.84 0.93
Power density (mW cm−2 ) 238 174
Table 5. The fitted parameters of zinc–air batteries with the catalyst ink prepared with different amounts of PTFE. Adding volume of PTFE (μL)
i0 (mA cm−2 )
Ri ( cm2 )
5 10 15 20
1.12 × 10−2 1.14 × 10−2 1.13 × 10−2 1.13 × 10−2
0.944 0.961 0.975 0.992
Power density (mW cm−2 ) 314 301 291 283
with acetylene black. This origins from the larger surface area of the carbon black, which ensures that the electrocatalysts are well dispered and exposed during the electrocatalytic reactions. Moreover, the smaller Ri of the battery assembled with carbon black indicates better electrical conductivity of cabon black compared with acetylene black. Therefore, carbon black is more suitable to support electrocatalysts. Poly tetra fluoro ethylene (PTFE): Besides the above discussions, it is found from Figs. 3–6 that the performances of the zinc–air batteries are still limited by the concentration loss at the high current density range, indicating that the diffusion of oxygen gas in this polarization area is largely restricted. To solve this issue, PTFE was added into the catalyst ink to increase the hydrophobicity of the assembled air electrode. As shown in Fig. 7, with the introducing of PTFE, the discharge curves change into almost linear through ohm polarization area to concentration polarization area, significantly increasing the current density and corresponding power density. However, the continued increasing the amount of PTFE increases Ri , thus decreases the current density and corresponding power density (Fig. 7(b) and Table 5). 3.4. Comparison the performance of zinc–air batteries Nowadays, cost-effective and earth-abundant electrocatalysts can be fabricated with various morphologies [17,19,21,28,30,40]. The theoretical and experimental efforts [52] suggest that when the electrodes are immersed in electrolytes, gas pockets are formed in the nanostructured surface of the electrode. Meanwhile, the
Please cite this article as: D. Jiao, Z. Ma and J. Li et al., Test factors affecting the performance of zinc–air battery, Journal of Energy Chemistry, https://doi.org/10.1016/j.jechem.2019.09.008
156 157 158 159 160 161 162 163 164 165 166 167 168 169 170 171 172 173 174 175 176 177 178 179 180 181
JID: JECHEM
ARTICLE IN PRESS
[m5G;September 25, 2019;14:50]
D. Jiao, Z. Ma and J. Li et al. / Journal of Energy Chemistry xxx (xxxx) xxx
5
Fig. 5. (a) and (b) Polarization curves and corresponding power density curves of zinc–air batteries with the air electrodes passing through different magnitudes of oxygen flux.
Fig. 6. (a) and (b) Polarization curves and corresponding power density curves of zinc–air batteries with the air electrodes assembled with carbon black or acetylene black.
Fig. 7. (a) and (b) Polarization curves and corresponding power density curves of zinc–air batteries with the catalyst ink prepared with different amounts of PTFE.
Please cite this article as: D. Jiao, Z. Ma and J. Li et al., Test factors affecting the performance of zinc–air battery, Journal of Energy Chemistry, https://doi.org/10.1016/j.jechem.2019.09.008
ARTICLE IN PRESS
JID: JECHEM 6
[m5G;September 25, 2019;14:50]
D. Jiao, Z. Ma and J. Li et al. / Journal of Energy Chemistry xxx (xxxx) xxx
Fig. 8. Comparison of polarization curves and corresponding power-density plots between optimized Ni-doped CoO and Pt/C catalysts.
199
micro structured surface provides gaseous channels for spreading of gas. Therefore, a combination of nano and micro structures is highly favorable to accelerate gas diffusion. In this study, Ni-doped CoO catalysts exhibit micro sized nanosheets with inside numerous nanosized pores. With the above optimized test parameters, the Ni-doped CoO catalysts based battery far exceeds the undefeatable Pt/C catalysts based device (Fig. 8). Therefore, for non-noble materials, taking their morphological advantage to reduce their concentration loss provides great opportunities for them to compete noble-metal catalysts. Taken together, the losses in activation, ohm and concentration polarization areas govern the final performance of zinc–air battery. To evaluate the potential of non-noble-metal electrocatalysts for applications in zinc–air batteries, besides intrinsic activity, their structural characteristics associated with gas diffusion should also be taken into consideration. For a given electrocatalyst, the test system, such as the electrode distance, the electrolyte concentration, and the oxygen flux, should be optimized.
200
4. Conclusions
201
211
We report the test factors that mainly affect the performance of zinc–air batteries. We show that the electrode distance, the electrolyte concentration, the oxygen flux, and the preparation of the catalyst ink strongly influence the activation, ohm and concentration polarizations. With the optimized test parameters, the performance of cost-effective and earth-abundant oxide electrocatalysts based zinc–air battery is far beyond that of the state-of-the-art Pt/C catalysts based battery. Our work establishes a trustable process to evaluate the application potentials of non-noble metal catalysts, which can aid in the development of highly active and lowcost catalysts for zinc–air batteries.
212
Acknowledgments
213 215
This work was supported by the National Science Fund for Excellent Young Scholars (51722103) and the National Natural Science Foundation of China (51571149 and 21576202).
216
References
182 183 184 185 186 187 188 189 190 191 192 193 194 195 196 197 198
202 203 204 205 206 207 208 209 210
214
217 218 219
[1] L. Peng, L.-F. Hu, X.-S. Fang, Adv. Funct. Mater. 24 (2014) 2591–2610. [2] J. Fu, Z.P. Cano, M.G. Park, A. Yu, M. Fowler, Z.-W. Chen, Adv. Mater. 29 (2017) 1604685.
[3] C.-Q. Sun, X.-S. Guo, J.-Y. Zhang, G.-L. Han, D.-Q. Gao, X.-P. Gao, J. Energy Chem. 38 (2019) 34–40. [4] C. Tang, B. Wang, H.-F. Wang, Q. Zhang, Adv. Mater. 29 (2017) 1703185. [5] D.-F. Yan, Y.-X. Li, J. Huo, R. Chen, L.-M. Dai, S.-Y. Wang, Adv. Mater. 29 (2017) 1606459. [6] J. Yang, X. Wang, B. Li, L. Ma, L. Shi, Y.-J. Xiong, H.-X. Xu, Adv. Funct. Mater. 27 (2017) 1606497. [7] X.-X. Han, X.-P. Li, J. White, C. Zhong, Y.-D. Deng, W.-B. Hu, T.-Y. Ma, Adv. Energy Mater. 8 (2018) 1801396. [8] Q.-C. Liu, L. Li, J.-J. Xu, Z.-W. Chang, D. Xu, Y.-B. Yin, X.-Y. Yang, T. Liu, Y.-S. Jiang, J.-M. Yan, X.-B. Zhang, Adv. Mater. 27 (2015) 8095–8101. [9] M. Xu, D.G. Ivey, Z. Xie, W. Qu, J. Power Sour. 283 (2015) 358–371. [10] P. Gu, M.-B. Zheng, Q.-X. Zhao, X. Xiao, H.-G. Xue, H. Pang, J. Mater. Chem. A 5 (2017) 7651–7666. [11] Y.-G. Li, J. Lu, ACS Energy Lett. 2 (2017) 1370–1377. [12] J.S. Lee, S.T. Kim, R.-G. Cao, N.S. Choi, M.-L. Liu, K.T. Lee, J. Cho, Adv. Energy Mater. 1 (2011) 34–50. [13] J. Pan, Y.-Y. Xu, H. Yang, Z.-H. Dong, H.-F. Liu, B.-Y. Xia, Adv. Sci. 5 (2018) 1700691. [14] Y.-G. Li, H.-J. Dai, Chem. Soc. Rev. 43 (2014) 5257–5275. [15] A.A. Mohamad, J. Power Sour. 159 (2006) 752–757. [16] L.L. Tian, J. Yang, M.-Y. Weng, R. Tan, J.-X. Zheng, H.-B. Chen, Q.-C. Zhuang, L.-M. Dai, F. Pan, ACS Appl. Mater. Interfaces 9 (2017) 7125–7130. [17] L. Kuai, E. Kan, W. Cao, M. Huttula, S. Ollikkala, T. Ahopelto, A.P. Honkanen, S. Huotari, W.-H. Wang, B.-Y. Geng, Nano Energy 43 (2018) 81–90. [18] S.S. Shinde, C.H. Lee, J.-Y. Yu, D.H. Kim, S.U. Lee, J.H. Lee, ACS Nano 12 (2018) 596–608. [19] Z.-M. Cui, G.-T. Fu, Y.-T. Li, J.B. Goodenough, Angew. Chem. Int. Ed. 56 (2017) 9901–9905. [20] Z.-L. Wang, D. Xu, J.-J. Xu, X.-B. Zhang, Chem. Soc. Rev. 43 (2014) 7746–7786. [21] Z.-M. Cui, Y.-T. Li, G.-T. Fu, X. Li, J.B. Goodenough, Adv. Mater. 29 (2017) 1702385. [22] M.-H. Yu, Z.-K. Wang, C. Hou, Z.-L. Wang, C.-L. Liang, C.-Y. Zhao, Y.-X. Tong, X.-H. Lu, S.-H. Yang, Adv. Mater. 29 (2017) 1602868. [23] D. Banham, S.-Y. Ye, K. Pei, J.i. Ozaki, T. Kishimoto, Y. Imashiro, J. Power Sour. 285 (2015) 334–348. [24] H.-W. Liang, Z.-Y. Wu, L.-F. Chen, C. Li, S.-H. Yu, Nano Energy 11 (2015) 366– 376. [25] W.-J. Jiang, L. Gu, L. Li, Y. Zhang, X. Zhang, L.-J. Zhang, J.-Q. Wang, J.-S. Hu, Z.-D. Wei, L.-J. Wan, J. Am. Chem. Soc. 138 (2016) 3570–3578. [26] F. Jaouen, E. Proietti, M. Lefèvre, R. Chenitz, J.P. Dodelet, G. Wu, H.T. Chung, C.M. Johnston, P. Zelenay, Energy Environ. Sci. 4 (2011) 114–130. [27] Y.-Z. Sun, M. Yang, J.-Q. Pan, P.-Y. Wang, W. Li, P.-Y. Wan, Electrochim. Acta. 197 (2016) 68–76. [28] Y.-G. Li, M. Gong, Y.-Y. Liang, J. Feng, J.E. Kim, H.-L. Wang, G.-S. Hong, B. Zhang, H.-J. Dai, Nat. Commun. 4 (2013) 1805. [29] G. Nam, J. Park, M. Choi, P. Oh, S. Park, M.G. Kim, N. Park, J. Cho, J.S. Lee, ACS Nano 9 (2015) 6493–6501. [30] Y.-J. Li, L. Cui, P.-F. Da, K.-W. Qiu, W.-J. Qin, W.-B. Hu, X.-W. Du, K. Davey, T. Ling, S.-Z. Qiao, Adv. Mater. 30 (2018) 1804653. [31] M.-D. Zhang, Q.-B. Dai, H.-G. Zheng, M.-D. Chen, L.-M. Dai, Adv. Mater. 30 (2018) 1705431. [32] H.-F. Wang, C. Tang, B. Wang, B.-Q. Li, Q. Zhang, Adv. Mater. 29 (2017) 1702327. [33] F.-L. Meng, H.-X. Zhong, D. Bao, J.-M. Yan, X.-B. Zhang, J. Am. Chem. Soc. 138 (2016) 10226–10231. [34] Q. Liu, Y.-B. Wang, L. Dai, J.-N. Yao, Adv. Mater. 28 (2016) 30 0 0–30 06.
Please cite this article as: D. Jiao, Z. Ma and J. Li et al., Test factors affecting the performance of zinc–air battery, Journal of Energy Chemistry, https://doi.org/10.1016/j.jechem.2019.09.008
220 221 222 223 224 225 226 227 228 229 230 231 232 233 234 235 236 237 238 239 240 241 242 243 244 245 246 247 248 249 250 251 252 253 254 255 256 257 258 259 260 261 262 263 264 265 266 267 268 269 270 271 272 273
JID: JECHEM
ARTICLE IN PRESS
[m5G;September 25, 2019;14:50]
D. Jiao, Z. Ma and J. Li et al. / Journal of Energy Chemistry xxx (xxxx) xxx
274 275 276 277 278 279 280 281 282 283 284 285 286 287 288 289
[35] X. Liu, M. Park, M.G. Kim, S. Gupta, X.-J. Wang, G. Wu, J. Cho, Nano Energy 20 (2016) 315–325. [36] P.-T. Liu, D.-Q. Gao, W. Xiao, L. Ma, K. Sun, P.-X. Xi, D.-S. Xue, J. Wang, Adv. Funct. Mater. 28 (2018) 1706928. [37] C.-Y. Su, H. Cheng, W. Li, Z.-Q. Liu, N. Li, Z.-F. Hou, F.-Q. Bai, H.-X. Zhang, T.-Y. Ma, Adv. Energy Mater. 7 (2017) 1602420. [38] B.-Q. Li, C.-X. Zhao, S.-M. Chen, J.-N. Liu, X. Chen., L. Song, Q. Zhang, Adv. Mater. 31 (2019) 1900592. [39] T. Ling, P.-F. Da, X.-L. Zheng, B.-H. Ge, Z.-P. Hu, M.-Y. Wu, X.-W. Du, W.-B. Hu, M. Jaroniec, S.-Z. Qiao, Sci. Adv. 4 (2018) 6261. [40] T. Ling, D.-Y. Yan, Y. Jiao, H. Wang, Y. Zheng, X. Zheng, J. Mao, X.-W. Du, Z. Hu, M. Jaroniec, S.-Z. Qiao, Nat. Commun. 7 (2016) 12876. [41] T. Ling, D.-Y. Yan, H. Wang, Y. Jiao, Z. Hu, Y. Zheng, L. Zheng, J. Mao, H. Liu, X.-W. Du, M. Jaroniec, S.-Z. Qiao, Nat. Commun. 8 (2017) 1509. [42] T. Ling, T. Zhang, B.-H. Ge, L.-L. Han, L.-R. Zheng, F. Lin, Z.-R. Xu, W.-B. Hu, X.-W. Du, K. Davey, S.-Z. Qiao, Adv. Mater. 31 (2019) 1807771. [43] C. Meng, T. Ling, T.-Y. Ma, H. Wang, Z.-P. Hu, Y. Zhou, J. Mao, X.-W. Du, M. Jaroniec, S.-Z. Qiao, Adv. Mater. 29 (2017) 1604607.
7
[44] M. Winter, R.J. Brodd, Chem. Rev. 104 (2004) 4245–4269. [45] A. Kirubakaran, S. Jain, R.K. Nema, Renew. Sustain. Energy Rev. 13 (2009) 2430–2440. [46] F. Barbir, PEM Fuel Cells: Theory and Practice, second ed., Academic Press, New York, 2012. [47] Z.-Q. Liu, H. Cheng, N. Li, T.-Y. Ma, Y.-Z. Su, Adv. Mater. 28 (2016) 3777–3784. [48] C.Y. Su, H. Cheng, W. Li, Z.-Q. Liu, N. Li, Z.-F. Hou, F.-Q. Bai, H.-X. Zhang, T.-Y. Ma, Adv. Energy Mater. 7 (2017) 1602420. [49] H.-F. Wang, C. Tang, B. Wang, B.-Q. Li, X.-Y. Cui, Q. Zhang, Energy Storage Mater. 15 (2018) 124–130. [50] B.-Q. Li, S.-Y. Zhang, B. Wang, Z.-J. Xia, C. Tang, Q. Zhang, Energy Environ. Sci. 11 (2018) 1723–1729. [51] B.-Q. Li, S.-Y. Zhang, X. Chen, C.-Y. Chen, Z.-J. Xia, Q. Zhang, Adv. Funct. Mater. 29 (2019) 1901301. [52] W.-W. Xu, Z.-Y. Lu, X.-M. Sun, L. Jiang, X. Duan, Acc. Chem. Res. 51 (2018) 1590–1598.
Please cite this article as: D. Jiao, Z. Ma and J. Li et al., Test factors affecting the performance of zinc–air battery, Journal of Energy Chemistry, https://doi.org/10.1016/j.jechem.2019.09.008
290 291 292 293 294 295 296 297 298 299 300 301 302 303 304