Performance of Pr2(Ni,Cu)O4+δ electrodes in protonic ceramic electrochemical cells with unseparated and separated gas spaces

doi:10.1016/j.jmst.2021.03.056

Abstract

Abstract:

The Ln₂NiO_4+δ-based layered phases have attracted much attention as components for high-performance protonic ceramic fuel cells (PCFCs) and electrolysis cells (PCECs) enabling energy conversion with good efficiency and low pollution. The present paper aims at rationally engineering the Cu-doped Pr₂NiO_4+δ materials and analysing their electrode behaviour for reversible protonic ceramic cells operating in both PCFC and PCEC modes. Complex oxides of Pr₂Ni_1-_xCu_xO_4+δ (x = 0, 0.1, 0.2 and 0.3) were synthesised using the citrate-nitrate method. The obtained materials were characterised considering their crystalline structures, as well as thermal, thermomechanical and electrotransport properties. A special interest was focused on the quality of an electrode/electrolyte interface governing the electrochemical performance of the cells fabricated. It is shown that a copper doping of x = 0.2 has a positive impact on the thermomechanical compatibility of the Ba(Ce,Zr)O₃-based electrolytes, providing a better adhesion to these electrolytes at low-temperature sintering and resulting in a decrease of the polarisation resistance of the air electrodes. A reversible protonic ceramic cell demonstrates a power density of ~340 mW cm^-2 and a hydrogen output flux of ~3.8 ml cm^-2 min^-1 at 750 °С. The presented results propose modernised alkaline-earth-element-free and cobalt-free electrodes that can be successfully used in the electrochemical cells based on the-state-of-the-art proton-conducting electrolytes.

Key words: rSOC, Proton conductivity, Cathode, Cu-doping, Thermal expansion, Impedance spectroscopy

Artem P.Tarutin, Yulia G.Lyagaeva, Aleksey I.Vylkov, Maxim Yu.Gorshkov, Gennady K.Vdovin, Dmitry A.Medvedev. Performance of Pr₂(Ni,Cu)O_4+δ electrodes in protonic ceramic electrochemical cells with unseparated and separated gas spaces[J]. J. Mater. Sci. Technol., 2021, 93: 157-168.

Figures/Tables 13

Fig. 1. XRD patterns of the Pr2Ni1-xCuxO4+δ powders in the entire (a) and the narrow (b) angular ranges.

Fig. 2. Refined parameters of the cells (a) and calculated bond lengths between oxygen in different positions and cations in the nickel position in the Pr2Ni1-xCuxO4+δ materials.

Fig. 3. Temperature dependencies of sample weight in hydrogen-containing (a) and air (c) media, dependence of oxygen concentration in the samples at room temperature in air (b) and temperature dependence of oxygen concentration in the samples of the Pr2Ni1-xCuxO4+δ compositions in air (d).

Fig. 4. Dilatometry curves obtained at the cooling of the ceramic Pr2Ni1-xCuxO4+δ samples (a) and temperature dependencies of differential TEC values (b)

Fig. 5. Temperature (a) and concentration (b) dependencies of total conductivity for the Pr2Ni1-xCuxO4+δ materials in air. Inset: concentration dependencies of oxygen overstoichiometry at corresponding temperatures.

Fig. 6. EIS spectra for the symmetric cells with Pr2Ni1-xCuxO4+δ electrodes obtained after subtraction of ohmic resistance component at different temperatures: 500 °C (a), 550 °C (b), 600 °C (c), 650 °C (d), 700 °C (e) and 750 °C (f).

Fig. 7. Example of the EIS spectrum for the Pr2Ni0.8Cu0.2O4+δ sample at 600 °С (a) and examples of its processing by the methods of cross-section (b) and equivalent schemes (c), temperature dependencies of the overall Rp (d) and partial resistances for x = 0.2 (e)).

Fig. 8. Concentration dependencies of partial and total polarisation resistances and the corresponding capacitances for symmetrical cells based on BaCe0.7Zr0.1Y0.1Yb0.1O3-δ with Pr2Ni1-xCuxO4+δ electrodes. These data were obtained at 600 °C.

Fig. 9. Voltammetry characteristics of the electrochemical cell with the Pr2Ni0.8Cu0.2O4+δ air electrode in humid air 3% (a) and 20% (b) in the near-cathode area at different temperatures and open circuit voltage (OCV) values observed at these temperatures and humidity (insets in panels (a) and (b)), dependencies of the power density (c), hydrogen output flux (d) at the measurements in dry (filled markers) and humid (open markers) air and total resistance of the cell in dry (e) and humid (f) air.

Fig. 10. EIS spectra of the reversible cell with the Pr2Ni0.8Cu0.2O4+δ air electrode obtained at 550, 650 and 750 °С at pH2O=0.03 and 0.2 atm in the OCV regime (a), temperature dependencies of the total polarisation (left axis) and electrolyte conductivity (right axis) at different air humidity (b) and at different applied voltages (c); temperature dependencies of polarisation conductivity of different electrode processes in humid (open markers) and dry (filled markers) air atmospheres in the OCV regime (d).

Fig. 11. DRT-spectra of the reversible cell with the cathode of the Pr2Ni0.8Cu0.2O4+δ composition in dry (a) and humid (b) atmospheres in normal and standardised forms (c) at different voltages at 650 °С depending on the total polarisation and electrolyte conductivities (d) and conductivities of separate electrode processes calculated by the fit-DRT and EQC methods depending on the voltage (e) and the fitting example by a fit-DRT method at OCV in dry atmosphere. RMSE is the root mean square error, MSE is the mean square error.

Table 1. Comparison of the capacity characteristics, hydrogen output flux and rSOC resistances.

Electrolyte (Thickness)	Air electrode (Humidity)	T,°C	OCV,V	P_max,W cm^-2	JH2 at 1.3 V, ml cm^-2 min^-1	R_p at OCV,Ω cm²	R_total at OCV, Ω cm²	Refs.
BCZYYb (26 µm)	Pr₂Ni_0.8Cu_0.2O_4+δ (3%)	650 700	1.02 0.98	0.28 0.31	2.53 3.29	0.14 0.07	0.85 0.72	This work
BCZDy0.2 (25 µm)	PBN (3%)	650 700	1.03 0.99	0.36 0.39	2.80 3.73	0.21 0.12	0.70 0.59	[56]
BCZ0.3Y0.2 (25 µm)	Ca₃Co₄O_9+δ (3%)	650 700	0.98 0.96	0.22 0.29	2.90 4.02	0.21 0.12	0.76 0.61	[56]
BCZ0.1Y0.2 (16 µm)	LSN (3%)	650 700	0.99 0.98	~0.35 0.46	5.2 10.4	- 0.22	- 0.49	[57]
BCZY0.2 (800 µm)	LSN (3%)	650 700	1.00 0.98	0.33 0.46	5.62 9.77	0.62 0.27	0.88 0.48	[58]
BCZY0.2 (800 µm)	PSN (3%)	650 700	1.02 0.98	0.21 0.35	7.08 9.77	0.9 0.35	1.15 0.55	[58]
BCZIn0.3 (15 µm)	BaCe_0.5Zr_0.2In_0.3O_3-δ + NiO (3%)	650 700	0.94 0.91	0.11 0.15	2.86 4.10	1.85 0.90	2.92 1.7	[59]
BZY + BCY (20 µm)	LSM (10%)	650 700	0.97 0.96	0.08 0.14	1.73 3.06	2.01 0.97	2.73 1.57	[60]
BCZYYC2 (40 µm)	LSN- BCZYYC2 (3%)	650 700	0.98 1.00	0.81 1.22	23.02 21.03	0.14 0.04	0.29 0.15	[61]
BZ0.3CY0.2 (20 µm)	BZC-0.2 (30%) BZC-0.3 (30%) BZC-0.4 (30%) BZC-0.5 (30%)	700	0.93 0.94 0.95 0.96	0.10 0.15 0.26 0.18	1.78 2.45 3.74 3.13	0.85 0.55 0.20 0.52	1.86 1.30 0.77 1.16	[62]

Fig. 12. Microstructure analysis of the reversible proton-conducting cell performed in the mode of backscattered electrons at different magnifications (a) and EDS map at the electrode and electrolyte contact (b). The designations: 1 - supporting fuel electrode layer; 2 - functional fuel electrode layer; 3 - electrolyte layer; 4 - Pr2Ni0.8Cu0.2O4+δ air electrode layer.

References 62

[1]	A. Chapman, K. Itaoka, K. Hirose, F.T. Davidson, K. Nagasawa, A.C. Lloyd, M.C. Lewis, Int. J Hydrogen Energy, 44(2019), pp. 6371-6382.
[2]	M.A. Pellow, C.J.M. Emmott, C.J. Barnhart, S.M. Benson, Energy Environ. Sci., 8(2015), pp. 1938-1952.
[3]	C. Duan, R. Kee, H. Zhu, N. Sullivan, L. Zhu, L. Bian, R. O'Hayre, Nat. Energy, 4(2019), pp. 230-240.
[4]	W. Wang, D. Medvedev, Z. Shao, Adv. Funct. Mater., 28(2018), Article 1802592.
[5]	L. Bi, S. Boulfrad, E. Traversa, Chem. Soc. Rev., 43(2014), pp. 8255-8270.
[6]	L. Lei, J. Zhang, Z. Yuan, J. Liu, M. Ni, F. Chen, Adv. Funct. Mater., 29(2019), Article 1903805.
[7]	C. Duan, J. Tong, M. Shang, S. Nikodemski, M. Sanders, S. Ricote, A. Almansoori, R. O'Hayre, Science, 349(2015), pp. 1321-1326.
[8]	M. Ni, M.K.H. Leung, D.Y.C. Leung, Int. J. Hydrog. Energy, 33(2008), pp. 4040-4047.
[9]	L. Bi, E. Fabbri, Z. Sun, E. Traversa, J. Electrochem. Soc., 158(2011), pp. B797-B803.
[10]	S.S. Hashim, F. Liang, W. Zhou, J. Sunarso, ChemElectroChem, 6(2019), pp. 3549-3569.
[11]	A. Jun, J. Kim, J. Shin, G. Kim, ChemElectroChem, 3(2016), pp. 511-530.
[12]	H. Ullmann, N. Trofimenko, F. Tietz, D. Stover, A. Ahmad-Khanlou, Solid State Ionics, 138(2000), pp. 79-90.
[13]	N. Nasani, D. Ramasamy, S. Mikhalev, A.V. Kovalevsky, D.P. Fagg, J. Power Sources, 278(2015), pp. 582-589.
[14]	E. Pikalova, A. Kolchugin, N. Bogdanovich, D. Medvedev, J. Lyagaeva, L. Vedmid, S.Plaksin M.Ananyev, A. Farlenkov, Int. J. Hydrog. Energy, 45(2020), pp. 13612-13624.
[15]	V. Vibhu, I.C. Vinke, R.A. Eichel, L.G.J. Haart, J. Power Sources, 482(2021), Article 228909.
[16]	A.P. Tarutin, J.G. Lyagaeva, D.A. Medvedev, L. Bi, A.A. Yaremchenko, J. Mater. Chem. A, 9(2021), pp. 154-195.
[17]	X. Xu, Y. Pan, Y. Zhong, R. Ranc, Z. Shao, Mater. Horiz., 7(2020), pp. 2519-2565.
[18]	N. Danilov, J. Lyagaeva, G. Vdovin, E. Pikalova, D. Medvedev, Energy Convers. Manag., 172(2018), pp. 129-137.
[19]	E.Y. Pikalova, V.A. Sadykov, E.A. Filonov, N.F. Eremeev, E.M. Sadovskaya, S.M. Pikalov, N.M. Bogdanovich, J.G. Lyagaeva, A.A. Kolchugin, L.B. Vedmid, A.V. Ishchenko, V.B. Goncharov, Solid State Ionics, 335(2019), pp. 53-60.
[20]	A.P. Tarutin, J.G. Lyagaeva, A.S. Farlenkov, A.I. Vylkov, D.M. Medvedev, Ceram. Int., 45(2019), pp. 16105-16112.
[21]	J. Hou, Z. Zhu, J. Qian, W. Liu, J. Power Sources, 264 (214)(2021), pp. 67-75.
[22]	J.R. Tolchard, T. Grande, Solid State Ionics, 178(2007), pp. 593-599.
[23]	S.J. Kim, K.J. Kim, A.M. Dayaghi, G.M. Choi, Int. J. Hydrog. Energy, 41(2016), pp. 14498-14506.
[24]	M. Wei, W. Che, H. Li, Z. Wang, F. Yan, Y. Liu, J. Liu, App. Surf. Sci., 484(2019), pp. 551-559.
[25]	H. An, D. Shin, H.I. Ji, H. An, D. Shin, H.I. Ji, J. Korean Ceram. Soc., 55(2018), pp. 358-363.
[26]	G. Taillades, J. Dailly, M. Taillades-Jacquin, F. Mauvy, A. Essouhmi, M. Marrony, J. Rozière, Fuel Cells, 10(2010), pp. 166-173.
[27]	J. Dailly, F. Mauvy, M. Marrony, M. Pouchard, J.C. Grenier, J. Solid State Electrochem., 15(2011), pp. 245-251.
[28]	G. Li, H. Jin, Y. Cui, L. Gui, B. He, L. Zhao, J. Power Sources, 341(2017), pp. 192-198.
[29]	A. Tarutin, A. Kasyanova, J. Lyagaeva, G. Vdovin, D. Medvedev, J. Energy Chem., 40(2020), pp. 65-74.
[30]	A. Tarutin, N. Danilov, J. Lyagaeva, D. Medvedev, App. Sci., 10 (2020), p.2481.
[31]	D. Mesguich, J.-M. Bassat, C. Aymonier, A. Brull, L. Dessemond, E. Djurado, Electrochimica Acta, 87(2013), pp. 330-335.
[32]	X.Q. Liu, C.L. Song, Y.J. Wu, X.M. Chen, Ceram. Int., 37(2011), pp. 2423-2427.
[33]	T. Chen, Y. Zhou, C. Yuan, M. Liu, X. Meng, Z. Zhan, C. Xia, S. Wang, J. Power Sources, 269(2014), pp. 812-817.
[34]	Q. Zhou, T. Zhang, C. Zhao, L. Qu, Y. He, T. Wei, X. Tong, Mater. Res. Bull., 131(2020), Article 110986.
[35]	https://zirconiaproject.wordpress.com/devices/zirconia-318/.
[36]	T.H. Wan, DRTTOOLS website(2015), URL https://sites.google.com/site/drttools.URL
[37]	M. Jammali, R.B. Hassen, J. Rohlicek, Powder Diffr, 27(2012), pp. 184-188.
[38]	H. Chaker, T. Roisnel, M. Ceretti, R.B. Hassen, Powder Diffr, 25(2010), pp. 241-246.
[39]	S.R. Taylor, Geochim. Cosmochim. Acta, 28(1964), pp. 1273-1285.
[40]	T. Ogier, C. Prestipino, S. Figueroa, F. Mauvy, J. Mougin, J.C. Greniera, A. Demourgues, J.M. Bassat, Chem. Phys. Lett., 727(2019), pp. 116-120.
[41]	F. Gervais, R.P. Lobo, C. Allançon, N. Pellerin, J.M. Bassat, J.P. Loup, P. Odier, Solid State Commun, 88(1993), pp. 245-249.
[42]	E. Niwa, K. Wakai, T. Hori, K. Yashiro, J. Mizusaki, T. Hashimoto, Thermochim. Acta, 575(2014), pp. 129-134.
[43]	T. Ogier, C. Prestipino, S. Figueroa, F. Mauvy, J. Mougin, J.C. Grenier, J.M. Bassat, Chem. Phys. Lett., 727(2019), pp. 116-120.
[44]	Y. Zuo, S. Carter-Searjeant, M. Green, L. Mills, S.H. Mannan, Adv. Power. Technol., 31(2020), pp. 4135-4144.
[45]	J. Dailly, S. Fourcade, A. Largeteau, F. Mauvy, J.C. Grenier, M. Marrony, Electrochim. Acta, 55(2010), pp. 5847-5853.
[46]	A. Grimaud, F. Mauvy, J.M. Bassat, S. Fourcade, M. Marrony, J.C. Grenier, J. Mater. Chem., 22(2012), pp. 16017-16025.
[47]	A. Grimaud, F. Mauvy, J.M. Bassat, S. Fourcade, L. Rocheron, M. Marrony, J.C. Grenier, J. Electrochem. Soc., 159(2012), pp. B683-B694.
[48]	P. Batocchi, F. Mauvy, S. Fourcade, M. Parco, Electrochim. Acta, 145(2014), pp. 1-10.
[49]	A.P. Tarutin, G.K. Vdovin, D.A. Medvedev, A.A. Yaremchenko, Electrochim. Acta, 337(2020), Article 135808.
[50]	S.-Y. Jeon, M.-B. Choi, H.-N. Im, J.-H. Hwang, S.-J. Song, J. Phys. Chem. Solids, 73(2012), pp. 656-660.
[51]	E.G. Kalinina, E. Yu. Pikalova, A.A. Kolchugin, Russ. J. Electrochem., 54(2018), pp. 723-732.
[52]	E. Pikalova, A. Kolchugin, N. Bogdanovich, D. Medvedev, J. Lyagaeva, L. Vedmid, A. Farlenkov, Int. J. Hydrog. Energy, 45(2020), pp. 13612-13624.
[53]	A. Tarutin, J. Lyagaeva, A. Farlenkov, S. Plaksin, G. Vdovin, A. Demin, D. Medvedev, Materials, 12 (2019), p.118.
[54]	M. Dippon, S.M. Babiniec, H. Ding, S. Ricote, N.P. Sullivan, Solid State Ionics, 286(2016), pp. 117-121.
[55]	W.G. Coors, A. Manerbino, J. Membr. Sci., 376(2011), pp. 50-55.
[56]	E. Pikalova, A. Kolchugin, M. Koroleva, G. Vdovin, A. Farlenkov, D. Medvedev, J. Power Sources, 438(2019), Article 226996.
[57]	S. Yang, Y. Lu, Q. Wang, C. Sun, X. Ye, Z. Wen, Int. J. Hydrog. Energy, 43(2018), pp. 20050-20058.
[58]	S. Yang, Y. Wen, J. Zhang, Y. Lu, X. Ye, Z. Wen, Electrochim. Acta, 267(2018), pp. 269-277.
[59]	S. Yang, Y. Wen, S. Zhang, S. Gu, Z. Wen, X. Ye, Int. J. Hydrog. Energy, 42(2017), pp. 28549-28558.
[60]	Y. Wen, S. Yang, S. Gu, X. Ye, Z. Wen, Solid State Ionics, 308(2017), pp. 167-172.
[61]	C. Sun, S. Yang, Y. Lu, J. Wen, X. Ye, Z. Wen, J. Power Sources, 449(2020), Article 227498.
[62]	Y. Rao, S. Zhong, F. He, Z. Wang, R. Peng, Y. Lu, Int. J. Hydrog. Energy, 37(2012), pp. 12522-12527.

Performance of Pr₂(Ni,Cu)O_4+δ electrodes in protonic ceramic electrochemical cells with unseparated and separated gas spaces

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