Utilization and synthesis of ammonia in proton-conducting solid oxide electrochemical devices

doi:10.19799/j.cnki.2095-4239.2021.0326

Abstract

Abstract:

Ammonia is an ideal energy storage material and hydrogen energy carrier. Its utilization and synthesis in proton-conducting solid oxide electrochemical devices can realize efficient and clean power generation and energy storage. In this paper, we review the advances in experimental and theoretical studies on the utilization and synthesis of ammonia in proton-conducting solid oxide electrochemical devices. In the aspect of experimental study, the development of electrolytes and ammonia electrode materials are comprehensively analyzed. While in the aspect of theoretical study, the research progress of thermodynamic-electrochemical models and density functional theory (DFT) are discussed emphatically. Since the proton conductivity of electrolyte materials and the catalytic activity of ammonia electrodes are the critical factors affecting the performance of electrochemical devices, the development of electrolyte materials with high proton conductivity and ammonia electrodes with high catalytic activity are still the main research topics. Thermodynamic-electrochemical models and DFT-based theoretical researches can provide guidance and ideas for the structural design of electrochemical device/optimization of operating conditions and development of ammonia electrode materials, respectively. However, theoretical studies of higher-level (three-dimensional) thermal-electrochemical models and the electrochemical activation mechanism of nitrogen on ammonia electrode materials still deserve further study. Finally, the future research directions of ammonia utilization and synthesis in electrochemical devices are also summarized.

Key words: solid oxide fuel cell, proton-conducting electrochemical reactor, ammonia, ammonia synthesis, ammonia electrode materials

CLC Number:

TQ 152

Wenchao LIAN, Libin LEI, Bo LIANG, Chao WANG, Lei WEI, Zhipeng TIAN, Jianping LIU, Huazheng YANG, Jiajian LIANG, Tao SHI. Utilization and synthesis of ammonia in proton-conducting solid oxide electrochemical devices[J]. Energy Storage Science and Technology, 2021, 10(6): 1998-2007.

Figures/Tables 5

Fig. 1

Fig. 2

Table 1

Fig. 3

Table 2

Representative experimental studies on electrochemical synthesis of ammonia in proton-conducting electrochemical reactors"

质子导体反应器(氢电极 \| 电解质 \| 氨电极)	工作温度/℃	$r N H 3$ / $[m o l / (s ? c m 2)]$	FE/%	年份，文献
Pd \| SCY \| Pd	570	$4.50 × 10 - 9$	78	1998，[34]
Ag-Pd \| LCZ \| Ag-Pd	520	$2.00 × 10 - 9$	—	2004，[37]
Ag-Pd \| CLC \| Ag-Pd	650	$7.5 × 10 - 9$	—	2005，[38]
Ag-Pd \| LSGM \| Ag-Pd	550	$2.37 × 10 - 9$	70	2007，[39]
Ag-Pd \| BCC \| Ag-Pd	500	$2.69 × 10 - 9$	50	2010，[40]
Ni-BCY15 \| BCY15 \| BSCF	530	$4.10 × 10 - 9$	60	2010，[41]
LSCF \| BZY20 \| LSCF	550	$8.50 × 10 - 11$	0.33	2015，[42]
Pt \| BCY \| LSTR-BCY	500	$3.80 × 10 - 12$	—	2016，[43]
Pt \| BCY \| LST-BCYR	500	$1.10 × 10 - 11$	2.1	2017，[44]
Ni-BCZYZ \| BCZYZ \| Fe-BCZYZ	450	$4.00 × 10 - 9$	2.5	2017，[45]
Ni-BZCY44 \| BZCY44 \| BSTR	500	$1.10 × 10 - 9$	5.9	2019，[46]
Ni-BZCY72 \| BZCY81 \| VN-Fe	600	$1.89 × 10 - 9$	14	2020，[36]

Table 2

References 57

1	李璐伶, 樊栓狮, 陈秋雄, 等. 储氢技术研究现状及展望[J]. 储能科学与技术, 2018, 7(4): 586-594.
	LI L L, FAN S S, CHEN Q X, et al. Hydrogen storage technology: Current status and prospects[J]. Energy Storage Science and Technology, 2018, 7(4): 586-594.
2	SIDDIQUI O, DINCER I. A review and comparative assessment of direct ammonia fuel cells[J]. Thermal Science and Engineering Progress, 2018, 5: 568-578.
3	董旭, 杜志鸿, 张旸, 等. 固体氧化物燃料电池高催化活性阴极材料SrFeFxO_3-x_-δ[J]. 储能科学与技术, 2020, 9(2): 415-424.
	DONG X, DU Z H, ZHANG Y, et al. SrFeFxO_3-x_-δ cathode with high catalytic activity for solid oxide fuel cells[J]. Energy Storage Science and Technology, 2020, 9(2): 415-424.
4	NI M, LEUNG M K H, LEUNG D Y C. Ammonia-fed solid oxide fuel cells for power generation-A review[J]. International Journal of Energy Research, 2009, 33(11): 943-959.
5	MINIC D. Hydrogen energy-challenges and perspectives[M]. London: InTech, 2012.
6	王月姑, 周梅, 王兆林, 等. 以氨燃料为介质的全生命周期储能效率估算[J]. 储能科学与技术, 2018, 7(2): 301-308.
	WANG Y G, ZHOU M, WANG Z L, et al. Life-cycle energy efficiency estimation of large-scale ammonia fuel energy storage system[J]. Energy Storage Science and Technology, 2018, 7(2): 301-308.
7	MCFARLAN A, PELLETIER L, MAFFEI N. An intermediate-temperature ammonia fuel cell using Gd-doped Barium cerate electrolyte[J]. Journal of the Electrochemical Society, 2004, 151(6): A930.
8	PELLETIER L, MCFARLAN A, MAFFEI N. Ammonia fuel cell using doped Barium cerate proton conducting solid electrolytes[J]. Journal of Power Sources, 2005, 145(2): 262-265.
9	MAFFEI N, PELLETIER L, CHARLAND J P, et al. An ammonia fuel cell using a mixed ionic and electronic conducting electrolyte[J]. Journal of Power Sources, 2006, 162(1): 165-167.
10	MA Q L, PENG R R, LIN Y J, et al. A high-performance ammonia-fueled solid oxide fuel cell[J]. Journal of Power Sources, 2006, 161(1): 95-98.
11	XIE K, MA Q L, LIN B, et al. An ammonia fuelled SOFC with a BaCe_0.9Nd_0.1O_3-δ thin electrolyte prepared with a suspension spray[J]. Journal of Power Sources, 2007, 170(1): 38-41.
12	MAFFEI N, PELLETIER L, MCFARLAN A. A high performance direct ammonia fuel cell using a mixed ionic and electronic conducting anode[J]. Journal of Power Sources, 2008, 175(1): 221-225.
13	ZHANG L M, YANG W S. Direct ammonia solid oxide fuel cell based on thin proton-conducting electrolyte[J]. Journal of Power Sources, 2008, 179(1): 92-95.
14	LIN Y, RAN R, GUO Y M, et al. Proton-conducting fuel cells operating on hydrogen, ammonia and hydrazine at intermediate temperatures[J]. International Journal of Hydrogen Energy, 2010, 35(7): 2637-2642.
15	YANG J, MOLOUK A F, OKANISHI T, et al. Electrochemical and catalytic properties of Ni/BaCe_0.75Y_0.25O_3-δ anode for direct ammonia-fueled solid oxide fuel cells[J]. ACS Applied Materials & Interfaces, 2015, 7(13): 7406-7412.
16	MIYAZAKI K, OKANISHI T, MUROYAMA H, et al. Development of Ni-Ba(Zr, Y)O₃ cermet anodes for direct ammonia-fueled solid oxide fuel cells[J]. Journal of Power Sources, 2017, 365: 148-154.
17	MIYAZAKI K, MUROYAMA H, MATSUI T, et al. Impact of the ammonia decomposition reaction over an anode on direct ammonia-fueled protonic ceramic fuel cells[J]. Sustainable Energy & Fuels, 2020, 4(10): 5238-5246.
18	HE F, GAO Q N, LIU Z Q, et al. Proton-conducting fuel cells: A new Pd doped proton conducting perovskite oxide with multiple functionalities for efficient and stable power generation from ammonia at reduced temperatures[J]. Advanced Energy Materials, 2021, 11(19): 2170075.
19	BHIDE S V, VIRKAR A V. Stability of BaCeO₃-Based proton conductors in water-containing atmospheres[J]. Journal of the Electrochemical Society, 1999, 146(6): 2038-2044.
20	LEI L B, ZHANG J H, YUAN Z H, et al. Progress report on proton conducting solid oxide electrolysis cells[J]. Advanced Functional Materials, 2019, 29(37): doi:10.10021adfm.201903805.
21	KATAHIRA K, KOHCHI Y, SHIMURA T, et al. Protonic conduction in Zr-substituted BaCeO₃[J]. Solid State Ionics, 2000, 138(1/2): 91-98.
22	HE F, TENG Z Y, YANG G M, et al. Manipulating cation nonstoichiometry towards developing better electrolyte for self-humidified dual-ion solid oxide fuel cells[J]. Journal of Power Sources, 2020, 460: doi:10.1016/jpousour.2020.228105.
23	QIU R M, LIAN W C, OU Y Z, et al. Multifactor theoretical analysis of current leakage in proton-conducting solid oxide fuel cells[J]. Journal of Power Sources, 2021, 505:doi:10.1016/j.jpowsour.2021.230038.
24	RARÓG-PILECKA W, SZMIGIEL D, KOWALCZYK Z, et al. Ammonia decomposition over the carbon-based ruthenium catalyst promoted with Barium or cesium[J]. Journal of Catalysis, 2003, 218(2): 465-469.
25	BELL T E, TORRENTE-MURCIANO L. H₂ production via ammonia decomposition using non-noble metal catalysts: A review[J]. Topics in Catalysis, 2016, 59(15/16): 1438-1457.
26	YANG J, MOLOUK A F S, OKANISHI T, et al. A stability study of Ni/yttria-stabilized zirconia anode for direct ammonia solid oxide fuel cells[J]. ACS Applied Materials & Interfaces, 2015, 7(51): 28701-28707.
27	NI M, LEUNG D Y C, LEUNG M K H. Thermodynamic analysis of ammonia fed solid oxide fuel cells: Comparison between proton-conducting electrolyte and oxygen ion-conducting electrolyte[J]. Journal of Power Sources, 2008, 183(2): 682-686.
28	ISHAK F, DINCER I, ZAMFIRESCU C. Thermodynamic analysis of ammonia-fed solid oxide fuel cells[J]. Journal of Power Sources, 2012, 202: 157-165.
29	NI M, LEUNG D Y C, LEUNG M K H. Electrochemical modeling of ammonia-fed solid oxide fuel cells based on proton conducting electrolyte[J]. Journal of Power Sources, 2008, 183(2): 687-692.
30	KALINCI Y, DINCER I. Analysis and performance assessment of NH₃ and H₂ fed SOFC with proton-conducting electrolyte[J]. International Journal of Hydrogen Energy, 2018, 43(11): 5795-5807.
31	NI M, LEUNG D Y C, LEUNG M K H. An improved electrochemical model for the NH₃ fed proton conducting solid oxide fuel cells at intermediate temperatures[J]. Journal of Power Sources, 2008, 185(1): 233-240.
32	NI M. 2D CFD modeling of ammonia fueled solid oxide fuel cells with proton conducting electrolyte[C]//Proceedings of ASME 2010 8th International Conference on Fuel Cell Science, Engineering and Technology, June 14-16, 2010, Brooklyn, New York, USA. 2010: 25-33.
33	GUNDUZ S, DEKA D J, OZKAN U S. A review of the current trends in high-temperature electrocatalytic ammonia production using solid electrolytes[J]. Journal of Catalysis, 2020, 387: 207-216.
34	MARNELLOS G, STOUKIDES M. Ammonia synthesis at atmospheric pressure[J]. Science, 1998, 282(5386): 98-100.
35	SKODRA A, STOUKIDES M. Electrocatalytic synthesis of ammonia from steam and nitrogen at atmospheric pressure[J]. Solid State Ionics, 2009, 180(23/24/25): 1332-1336.
36	KYRIAKOU V, GARAGOUNIS I, VOURROS A, et al. An electrochemical Haber-Bosch process[J]. Joule, 2020, 4(1): 142-158.
37	XIE Y H, WANG J D, LIU R Q, et al. Preparation of La_1.9Ca_0.1Zr₂O_6.95 with pyrochlore structure and its application in synthesis of ammonia at atmospheric pressure[J]. Solid State Ionics, 2004, 168(1/2): 117-121.
38	刘瑞泉, 谢亚红, 李志杰, 等. 质子导体(Ce_0.8La_0.2)_1-xCaxO_2-δ在合成氨中的应用[J]. 物理化学学报, 2005, 21(9): 967-970.
	LIU R Q, XIE Y H, LI Z J, et al. Application of proton conductors(Ce_0.8La_0.2)_1-xCaxO_2-δ in synthesis of ammonia[J]. Acta Physico-Chimica Sinica, 2005, 21(9): 967-970.
39	ZHANG F, YANG Q, PAN B, et al. Proton conduction in La_0.9Sr_0.1Ga_0.8Mg_0.2O_3-α ceramic prepared via microemulsion method and its application in ammonia synthesis at atmospheric pressure[J]. Materials Letters, 2007, 61(19/20): 4144-4148.
40	LIU J W, LI Y D, WANG W B, et al. Proton conduction at intermediate temperature and its application in ammonia synthesis at atmospheric pressure of BaCe_1-x Cax O_3-α[J]. Journal of Materials Science, 2010, 45(21): 5860-5864.
41	WANG W B, CAO X B, GAO W J, et al. Ammonia synthesis at atmospheric pressure using a reactor with thin solid electrolyte BaCe_0.85Y_0.15O_3-α membrane[J]. Journal of Membrane Science, 2010, 360(1/2): 397-403.
42	YUN D S, JOO J H, YU J H, et al. Electrochemical ammonia synthesis from steam and nitrogen using proton conducting yttrium doped Barium zirconate electrolyte with silver, platinum, and lanthanum strontium cobalt ferrite electrocatalyst[J]. Journal of Power Sources, 2015, 284: 245-251.
43	KOSAKA F, NODA N, NAKAMURA T, et al. In situ formation of Ru nanoparticles on La_1-xSrxTiO₃-based mixed conducting electrodes and their application in electrochemical synthesis of ammonia using a proton-conducting solid electrolyte[J]. Journal of Materials Science, 2017, 52(5): 2825-2835.
44	KOSAKA F, NAKAMURA T, OTOMO J. Electrochemical ammonia synthesis using mixed protonic-electronic conducting cathodes with exsolved Ru-nanoparticles in proton conducting electrolysis cells[J]. Journal of the Electrochemical Society, 2017, 164(13): F1323-F1330.
45	KLINSRISUK S, IRVINE J T S. Electrocatalytic ammonia synthesis via a proton conducting oxide cell with BaCe_0.5Zr_0.3Y_0.16Zn_0.04O_3-δ electrolyte membrane[J]. Catalysis Today, 2017, 286: 41-50.
46	KIM H, CHUNG Y S, KIM T, et al. Ru-doped Barium strontium titanates of the cathode for the electrochemical synthesis of ammonia[J]. Solid State Ionics, 2019, 339:doi:10.1016/j.ssi.2019.115010.
47	MA G L, ZHANG F, ZHU J L, et al. Proton conduction in La_0.9Sr_0.1Ga_0.8Mg_0.2O_3-α[J]. Chemistry of Materials, 2006, 18(25): 6006-6011.
48	SHIMURA T, FUJIMOTO S, IWAHARA H. Proton conduction in non-perovskite-type oxides at elevated temperatures[J]. Solid State Ionics, 2001, 143(1): 117-123.
49	LIU R Q, XIE Y H, WANG J D, et al. Synthesis of ammonia at atmospheric pressure with Ce_0.8M0.2O_2-δ (M = La, Y, Gd, Sm) and their proton conduction at intermediate temperature[J]. Solid State Ionics, 2006, 177(1/2): 73-76.
50	GIDDEY S, BADWAL S P S, KULKARNI A. Review of electrochemical ammonia production technologies and materials[J]. International Journal of Hydrogen Energy, 2013, 38(34): 14576-14594.
51	GUO Y X, LIU B X, YANG Q, et al. Preparation via microemulsion method and proton conduction at intermediate-temperature of BaCe_1-xYxO_3-α[J]. Electrochemistry Communications, 2009, 11(1): 153-156.
52	AMAR I A, LAN R, TAO S W. Synthesis of ammonia directly from wet nitrogen using a redox stable La_0.75Sr_0.25Cr_0.5Fe_0.5O_3–δ-Ce_0.8Gd_0.18Ca_0.02O_2–δ composite cathode[J]. RSC Adv, 2015, 5(49): 38977-38983.
53	LING Y H, YU J, LIN B, et al. A cobalt-free Sm_0.5Sr_0.5Fe_0.8Cu_0.2O_3-δ-Ce_0.8Sm_0.2O_2-δ composite cathode for proton-conducting solid oxide fuel cells[J]. Journal of Power Sources, 2011, 196(5): 2631-2634.
54	SAADATJOU N, JAFARI A, SAHEBDELFAR S. Ruthenium nanocatalysts for ammonia synthesis: A review[J]. Chemical Engineering Communications, 2015, 202(4): 420-448.
55	PANAGOS E, VOUDOURIS I, STOUKIDES M. Modelling of equilibrium limited hydrogenation reactions carried out in H+ conducting solid oxide membrane reactors[J]. Chemical Engineering Science, 1996, 51(11): 3175-3180.
56	GARAGOUNIS I, KYRIAKOU V, STOUKIDES M. Electrochemical promotion of catalytic reactions: Thermodynamic analysis and calculation of the limits in Faradaic Efficiency[J]. Solid State Ionics, 2013, 231: 58-62.
57	KYRIAKOU V, GARAGOUNIS I, VASILEIOU E, et al. Progress in the electrochemical synthesis of ammonia[J]. Catalysis Today, 2017, 286: 2-13.

燃料电池(氨电极 \| 电解质 \| 空气电极)	电解质厚度/μm	工作温度/℃	最大功率密度/(mW/cm²)	年份，文献
Pt \| BCGO \| Pt	1300	700	25	2004，[7]
Pt \| BCGP \| Pt	1300	700	35	2005，[8]
Pt \| BCE \| Pt	1000	700	32	2006，[9]
Ni-BCGO \| BCGO \| LSCO	50	650	184	2006，[10]
Ni-BCGO \| BCGO \| LSCO	50	700	355	2006，[10]
Ni-BCNO \| BCNO \| LSCO	20	700	315	2007，[11]
Ni-BCE \| BCGP \| Pt	1000	500	15	2008，[12]
Ni-BCE \| BCGP \| Pt	1000	600	28	2008，[12]
Ni-CGO \| BCGO \| BSCFO-CGO	30	600	147	2008，[13]
Ni-CGO \| BCGO \| BSCFO-CGO	30	650	200	2008，[13]
Ni-BZCY17 \| BZCY17 \| BSCF	35	450	25	2010，[14]
Ni-BZCY17 \| BZCY17 \| BSCF	35	700	325	2010，[14]
Ni-BCY25 \| BCY10 \| SSC	1000	600	165	2015，[15]
Ni-BCY25 \| BCY10 \| SSC	1000	650	210	2015，[15]
Ni-BZY20 \| BZY20 \| Pt	60～90	600	70	2017，[16]
Ni-BZY20 \| BZY20 \| Pt	60～90	700	130	2017，[16]
Ni-BZCY44 \| BCY20 \| BCY20-LSCF	50～60	600	130	2020，[17]
Ni-BZCY44 \| BCY20 \| BCY20-LSCF	50～60	700	180	2020，[17]
Ni-BZCYYbPd \| BZCYYbPd \| BCFZY	17	600	500	2021，[18]
Ni-BZCYYbPd \| BZCYYbPd \| BCFZY	17	650	724	2021，[18]

[1]	Changyang LIU, Liuzhen BIAN, Jianquan GAO, Jihua PENG, Jun PENG, Shengli AN. Electrochemical performance of La_0.7Sr_0.3Fe_0.9Ni_0.1O_3-_δ symmetric electrode for solid oxide fuel cell with CO as fuel [J]. Energy Storage Science and Technology, 2022, 11(7): 2059-2065.
[2]	XIE Chenglu, HUANG Xiankun, KANG Lixia, LIU Yongzhong. Electrocatalytic performances of Ru nanoparticles supported on carbon nanotubes by colloidal solution for synthetic ammonia [J]. Energy Storage Science and Technology, 2022, 11(6): 1947-1956.
[3]	Hui TIAN, Dong HUA, Maoli MAN, Chunzhe LIU, Guojun LI, Xiongwen ZHANG. Experimental study on carbon deposition characteristics of planar solid oxide fuel cell [J]. Energy Storage Science and Technology, 2022, 11(5): 1314-1321.
[4]	Chunlin YU, Xudong CHEN, Toshio MIYAGAWA, Hui SUN, Xingwang ZHANG, Lige TONG. Precursor with special structure for improving the performance of the ternary cathode material of Li-ion batteries [J]. Energy Storage Science and Technology, 2022, 11(3): 1000-1007.
[5]	Pingping LI, Shanshan CHEN, Lulu ZHAO, Mingliang SHI, Yan HUANG, Chufu LI. Test design of integrated gasification solid oxide fuel cell （IG-SOFC） grid-connection technology [J]. Energy Storage Science and Technology, 2021, 10(6): 2039-2045.
[6]	Tingting HAN, Yuxi WU, Ziheng XIE, Xiuxia MENG, Jinjin ZHANG, Yujiao XIE, Fangyong YU, Naitao YANG. Recent advances in carbon deposition mechanism and performance improvement of Ni-based anode for solid oxide fuel cells [J]. Energy Storage Science and Technology, 2021, 10(6): 1931-1942.
[7]	Shouli WEI, Xichao LI, Xiuliang CHANG, Bing CHEN, Zhuo XU, Tao ZHANG, Lili ZHENG, Zuoqiang DAI. Review of development of bipolar plate materials for solid oxide fuel cell [J]. Energy Storage Science and Technology, 2021, 10(6): 1943-1951.
[8]	Yuxi WU, Tingting HAN, Ziheng XIE, Lin LI, Yanwen SONG, Jiacang LIANG, Jinjin ZHANG, Fangyong YU, Naitao YANG. Recent progress in direct carbon solid oxide fuel cells： Carbon fuels and reverse Boudouard reaction catalysts [J]. Energy Storage Science and Technology, 2021, 10(6): 1977-1986.
[9]	Lina ZHENG, Wenzhong WANG, Kaijie JIA, Shaofeng QIU, Haoyuan ZHU, Fangyong YU, Xiuxia MENG, Jinjin ZHANG, Naitao YANG. Three-dimensional printing technologies in the field of solid oxide fuel cells [J]. Energy Storage Science and Technology, 2021, 10(6): 1952-1962.
[10]	Xuqing YANG, Zhenzhu YU, Xiaohu YANG, Zhan LIU. Combined heating and power system coupled with compressed air energy storage and absorption heat pump cycle [J]. Energy Storage Science and Technology, 2021, 10(1): 362-369.
[11]	DONG Xu, DU Zhihong, ZHANG Yang, LI Keyun, ZHAO Hailei. SrFeF _x O_3- _x _- _δ cathode with high catalytic activity for solid oxide fuel cells [J]. Energy Storage Science and Technology, 2020, 9(2): 415-424.
[12]	WANG Yuegu, ZHOU Mei, WANG Zhaolin, ZHENG Songsheng . Life-cycle energy efficiency estimation of large-scale ammonia fuel energy storage system [J]. Energy Storage Science and Technology, 2018, 7(2): 301-308.
[13]	LV Zewei, HAN Minfang. Design of solar cogeneration system of hydrogen and power with solid oxide cells#br# [J]. Energy Storage Science and Technology, 2017, 6(2): 275-279.