氨电氧化催化剂及其低温直接氨碱性膜燃料电池性能的研究进展

doi:10.11949/0438-1157.20220327

摘要/Abstract

摘要：

氨是一种无碳富氢的能源载体，体积能量密度高，易液化储存，是理想的储氢介质。以氨直接作为燃料，在低温碱性膜燃料电池中通过氨氧化反应实现化学能到电能的转化，是氨能源高效利用的理想路径之一。然而，低温氨氧化反应动力学缓慢、催化剂价格昂贵、易中毒等问题严重影响氨燃料电池性能，限制其大规模的商业化应用。因此，设计高效、廉价、稳定的催化剂是发展低温氨燃料电池技术的关键。本文首先综述了近些年研究者在氨氧化反应机理方面的探索，在深入理解反应体系的基础上，重点介绍了含贵金属和非贵金属催化剂设计制备及其在氨氧化反应中的进展，并总结了氨氧化催化剂在氨燃料电池中的性能。最后针对氨氧化催化剂目前存在的问题和未来的发展方向提出了建议，旨在为氨氧化催化剂的设计及低温氨燃料电池技术的发展提供研究思路。

关键词: 氨, 氨氧化反应, 低温氨燃料电池, 催化剂, 电催化

Abstract:

Ammonia is a carbon-free and hydrogen-rich energy carrier with high volumetric energy density and easy liquefaction storage. It is an ideal hydrogen storage medium. Transforming chemical energy in ammonia into electrical energy directly by ammonia oxidation reaction (AOR) in low-temperature alkaline exchange membrane fuel cells (AEMFCs) is an ideal way for efficient utilization of ammonia. However, the NH₃-AEMFCs are far away from the commercial application due to its low performance, which is limited by slow kinetics in AOR, high price of noble metals, catalyst poisoning and poor stability. It posts the significance of developing efficient, cheap and robust catalysts to achieve satisfied performance in low-temperature NH₃-AEMFCs. Herein, we firstly give a brief introduction of current status on understanding the fundamentals in AOR and then summarize the recent progress in the development of noble and non-noble metallic catalysts towards AOR. Based on the in-depth understanding of the reaction mechanism, the performance of NH₃-AEMFCs was further summarized and discussed. Finally, the R&D direction and prospect of catalyst design for AOR and NH₃-AEMFCs are proposed.

Key words: ammonia, ammonia oxidation reaction, low-temperature ammonia fuel cell, catalyst, electrocatalysis

中图分类号:

TQ 028.8

方辉煌, 程金星, 罗宇, 陈崇启, 周晨, 江莉龙. 氨电氧化催化剂及其低温直接氨碱性膜燃料电池性能的研究进展[J]. 化工学报, 2022, 73(9): 3802-3814.

Huihuang FANG, Jinxing CHENG, Yu LUO, Chongqi CHEN, Chen ZHOU, Lilong JIANG. Recent progress on ammonia oxidation catalysts at anode and their performances in low-temperature direct ammonia alkaline exchange membrane fuel cells[J]. CIESC Journal, 2022, 73(9): 3802-3814.

图/表 10

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反应中间物质	表征技术	文献
N^-₃参与AOR反应	SERS	[20]
N₂H₄、NO中间体；NO抑制了电化学反应	ATR-IR	[22]
低电位区(E(vs SCE)<-0.50 V)：N₂H₄、NH₂	FTIR	[23]
高电位区(E(vs SCE)>-0.10 V)：N₂O、NO^2-	FTIR	[23]
NO、NO₂、N₂H₄	ATR-FTIR	[28]
N₂、NO和N₂O	DEMS	[29]

反应中间物质	表征技术	文献
N^-₃参与AOR反应	SERS	[20]
N₂H₄、NO中间体；NO抑制了电化学反应	ATR-IR	[22]
低电位区(E(vs SCE)<-0.50 V)：N₂H₄、NH₂	FTIR	[23]
高电位区(E(vs SCE)>-0.10 V)：N₂O、NO^2-	FTIR	[23]
NO、NO₂、N₂H₄	ATR-FTIR	[28]
N₂、NO和N₂O	DEMS	[29]

催化剂	电解液溶液	扫描速率/ (mV·s^-1)	起始电位 (vs RHE)/V	峰值电流密度	文献
PtIr/CNT (Pt∶Ir=4∶1)	0.1 mol·L^-1 NH₃ + 0.1 mol·L^-1 KOH	50	0.38	230 mA·cm^-2 ECSA	[68]
PtIr/N-rGO (Pt∶Ir=1∶3)	0.1 mol·L^-1 NH₃ + 1 mol·L^-1 KOH	10	约0.37	71 A·g^-1	[55]
PtRh/C (Pt∶Rh=9∶1)	0.1 mol·L^-1 NH₃ + 1 mol·L^-1 KOH	20	-0.44^①	93.8 A·g^-1	[90]
Pt/SiO₂-CNT	0.1 mol·L^-1 NH₃+ 1 mol·L^-1 KOH	5	0.484	77.3 A·g^-1	[13]
PtIr/C	0.1 mol·L^-1 NH₃ + 1 mol·L^-1 KOH	5	0.43	25.1 A·g^-1	[13]
Pt₅Ir₅/SiO₂-CNT	0.1 mol·L^-1 NH₃ + 1 mol·L^-1 KOH	5	0.369	66.3 A·g^-1	[13]
PtIr/ SiO₂-CNT (Pt∶Ir=9∶1)	0.1 mol·L^-1 NH₃ + 1 mol·L^-1 KOH	5	0.42	90.6 A·g^-1	[13]
PtIrNi₁/SiO₂-CNT (Pt∶Ir=9∶1)	0.1 mol·L^-1 NH₃ + 1 mol·L^-1 KOH	5	0.399	124 A·g^-1	[13]
PtZn	0.1 mol·L^-1 NH₃ + 0.5 mol·L^-1 KOH	100	0.42	0.60 mA·cm^-2 ECSA	[72]
PtIrZn (Pt∶Ir=8∶2)	0.1 mol·L^-1 NH₃ + 0.5 mol·L^-1 KOH	100	0.30	0.56 mA·cm^-2 ECSA	[72]
CuPtRu (Pt∶Ru=7∶1)	1 mol·L^-1 KOH saturated with NH₃	20	0.49	180 A·g^-1	[76]
PtIrZn₂/CeO₂-ZIF-8	0.1 mol·L^-1 NH₃ + 1 mol·L^-1 KOH	5	0.35	31.8 A·g^-1	[73]
PtIrZn₂/SiO₂-CNT-COOH	0.1 mol·L^-1 NH₃ + 1 mol·L^-1 KOH	5	0.35	61.4 A·g^-1	[73]
PtIr/SiO₂-CNT-COOH	0.1 mol·L^-1 NH₃ + 1 mol·L^-1 KOH	5	0.33	64.6 A·g^-1	[73]
PtIrCu HCOND	0.1 mol·L^-1 NH₃ + 1 mol·L^-1 KOH	5	0.35	122.9 A·g^-1	[75]
PtNi	0.1 mol·L^-1 NH₃ + 1 mol·L^-1 KOH	10	0.69	75 A·g^-1	[91]
PtAu/C (Pt∶Au=7∶3)	0.1 mol·L^-1 NH₃ + 1 mol·L^-1 KOH	20	0.51	90 A·g^-1	[92]
PtNi	0.1 mol·L^-1 NH₃ + 1 mol·L^-1 KOH	10	约0.5	75.32 A·g^-1	[91]
Pt/C	0.1 mol·L^-1 NH₃ + 1 mol·L^-1 KOH	50	约0.52^②	39.9 A·g^-1	[93]
PtNi/C	0.1 mol·L^-1 NH₃ + 1 mol·L^-1 KOH	50	约0.55^②	76.4 A·g^-1	[93]
PtNiO/C	0.1 mol·L^-1 NH₃ + 1 mol·L^-1 KOH	50	约0.55^②	86.9 A·g^-1	[93]
Ni₉₈Pd₂	0.5 mol·L^-1 NaNO₃ + 0.2 mol·L^-1 NH₄NO₃	50	1.3^①	150 A·g^-1	[83]
NiCu/C	55 m mol·L^-1 NH₄Cl + 0.5 mol·L^-1 NaOH	25	0.47^②	52 mA·cm^-2	[94]
NiCu/C	0.5 mol·L^-1 NH₃ + 1 mol·L^-1 KOH	50	0.4^①	110.4 mA·cm^-2	[95]
NiCu/C	55 m mol·L^-1 NH₄Cl + 0.5 mol·L^-1 NaOH	25	0.43^①	105 mA·cm^-2	[85]
Ni(OH)₂/C	55 m mol·L^-1 NH₄Cl + 0.5 mol·L^-1 NaOH	25	0.43^①	15 mA·cm^-2	[85]
NiCr/C	55 m mol·L^-1 NH₄Cl + 0.5 mol·L^-1 NaOH	25	0.40^①	10 mA·cm^-2	[85]
NiMn/C	55 m mol·L^-1 NH₄Cl + 0.5 mol·L^-1 NaOH	25	0.40^①	20 mA·cm^-2	[85]
NiCo/C	55 m mol·L^-1 NH₄Cl + 0.5 mol·L^-1 NaOH	25	0.35^①	10 mA·cm^-2	[85]
NiZn/C	55 m mol·L^-1 NH₄Cl + 0.5 mol·L^-1 NaOH	25	0.45^①	2 mA·cm^-2	[85]
Ni(OH)₂ on NiOOH	0.1 mol·L^-1 NaSO₄ + 0.003 mol·L^-1 NH₃	10	0.6^①	2.7 mA·cm^-2	[84]
①vs Hg/HgO。 ②vs Ag/AgCl。

催化剂	电解液溶液	扫描速率/ (mV·s^-1)	起始电位 (vs RHE)/V	峰值电流密度	文献
PtIr/CNT (Pt∶Ir=4∶1)	0.1 mol·L^-1 NH₃ + 0.1 mol·L^-1 KOH	50	0.38	230 mA·cm^-2 ECSA	[68]
PtIr/N-rGO (Pt∶Ir=1∶3)	0.1 mol·L^-1 NH₃ + 1 mol·L^-1 KOH	10	约0.37	71 A·g^-1	[55]
PtRh/C (Pt∶Rh=9∶1)	0.1 mol·L^-1 NH₃ + 1 mol·L^-1 KOH	20	-0.44^①	93.8 A·g^-1	[90]
Pt/SiO₂-CNT	0.1 mol·L^-1 NH₃+ 1 mol·L^-1 KOH	5	0.484	77.3 A·g^-1	[13]
PtIr/C	0.1 mol·L^-1 NH₃ + 1 mol·L^-1 KOH	5	0.43	25.1 A·g^-1	[13]
Pt₅Ir₅/SiO₂-CNT	0.1 mol·L^-1 NH₃ + 1 mol·L^-1 KOH	5	0.369	66.3 A·g^-1	[13]
PtIr/ SiO₂-CNT (Pt∶Ir=9∶1)	0.1 mol·L^-1 NH₃ + 1 mol·L^-1 KOH	5	0.42	90.6 A·g^-1	[13]
PtIrNi₁/SiO₂-CNT (Pt∶Ir=9∶1)	0.1 mol·L^-1 NH₃ + 1 mol·L^-1 KOH	5	0.399	124 A·g^-1	[13]
PtZn	0.1 mol·L^-1 NH₃ + 0.5 mol·L^-1 KOH	100	0.42	0.60 mA·cm^-2 ECSA	[72]
PtIrZn (Pt∶Ir=8∶2)	0.1 mol·L^-1 NH₃ + 0.5 mol·L^-1 KOH	100	0.30	0.56 mA·cm^-2 ECSA	[72]
CuPtRu (Pt∶Ru=7∶1)	1 mol·L^-1 KOH saturated with NH₃	20	0.49	180 A·g^-1	[76]
PtIrZn₂/CeO₂-ZIF-8	0.1 mol·L^-1 NH₃ + 1 mol·L^-1 KOH	5	0.35	31.8 A·g^-1	[73]
PtIrZn₂/SiO₂-CNT-COOH	0.1 mol·L^-1 NH₃ + 1 mol·L^-1 KOH	5	0.35	61.4 A·g^-1	[73]
PtIr/SiO₂-CNT-COOH	0.1 mol·L^-1 NH₃ + 1 mol·L^-1 KOH	5	0.33	64.6 A·g^-1	[73]
PtIrCu HCOND	0.1 mol·L^-1 NH₃ + 1 mol·L^-1 KOH	5	0.35	122.9 A·g^-1	[75]
PtNi	0.1 mol·L^-1 NH₃ + 1 mol·L^-1 KOH	10	0.69	75 A·g^-1	[91]
PtAu/C (Pt∶Au=7∶3)	0.1 mol·L^-1 NH₃ + 1 mol·L^-1 KOH	20	0.51	90 A·g^-1	[92]
PtNi	0.1 mol·L^-1 NH₃ + 1 mol·L^-1 KOH	10	约0.5	75.32 A·g^-1	[91]
Pt/C	0.1 mol·L^-1 NH₃ + 1 mol·L^-1 KOH	50	约0.52^②	39.9 A·g^-1	[93]
PtNi/C	0.1 mol·L^-1 NH₃ + 1 mol·L^-1 KOH	50	约0.55^②	76.4 A·g^-1	[93]
PtNiO/C	0.1 mol·L^-1 NH₃ + 1 mol·L^-1 KOH	50	约0.55^②	86.9 A·g^-1	[93]
Ni₉₈Pd₂	0.5 mol·L^-1 NaNO₃ + 0.2 mol·L^-1 NH₄NO₃	50	1.3^①	150 A·g^-1	[83]
NiCu/C	55 m mol·L^-1 NH₄Cl + 0.5 mol·L^-1 NaOH	25	0.47^②	52 mA·cm^-2	[94]
NiCu/C	0.5 mol·L^-1 NH₃ + 1 mol·L^-1 KOH	50	0.4^①	110.4 mA·cm^-2	[95]
NiCu/C	55 m mol·L^-1 NH₄Cl + 0.5 mol·L^-1 NaOH	25	0.43^①	105 mA·cm^-2	[85]
Ni(OH)₂/C	55 m mol·L^-1 NH₄Cl + 0.5 mol·L^-1 NaOH	25	0.43^①	15 mA·cm^-2	[85]
NiCr/C	55 m mol·L^-1 NH₄Cl + 0.5 mol·L^-1 NaOH	25	0.40^①	10 mA·cm^-2	[85]
NiMn/C	55 m mol·L^-1 NH₄Cl + 0.5 mol·L^-1 NaOH	25	0.40^①	20 mA·cm^-2	[85]
NiCo/C	55 m mol·L^-1 NH₄Cl + 0.5 mol·L^-1 NaOH	25	0.35^①	10 mA·cm^-2	[85]
NiZn/C	55 m mol·L^-1 NH₄Cl + 0.5 mol·L^-1 NaOH	25	0.45^①	2 mA·cm^-2	[85]
Ni(OH)₂ on NiOOH	0.1 mol·L^-1 NaSO₄ + 0.003 mol·L^-1 NH₃	10	0.6^①	2.7 mA·cm^-2	[84]
①vs Hg/HgO。 ②vs Ag/AgCl。

膜	燃料	阳极催化剂	阴极催化剂	温度/℃	峰值功率密度/ (mW·cm^-2)	文献
AEM (PAP-TP)	3 mol·L^-1 NH₃ 3 mol·L^-1 KOH	PtIr/C 2 mg PGM·cm^-2	Acta 4020 1 mg·cm^-2	80	135	[11]
AEM (PAP-TP)	7 mol·L^-1 NH₃ 1.25 mol·L^-1 KOH	PtIr/C 2 mg PGM·cm^-2	Acta 4020 1 mg·cm^-2	95	390 (0.2 MPa)	[98]
AEM (PAP-TP)	7 mol·L^-1 NH₃ 1.25 mol·L^-1 KOH	PtIr/C 2 mg PGM·cm^-2	Pd/C 0.4 mg·cm^-2	95	304 (0.2 MPa)	[98]
AEM	NH₃	Pt/C 2 mg Pt·cm^-2	PGM-free	100	420	[101]
HEM (AHA)	0.2 mol·L^-1 NH₃ 1 mol·L^-1 KOH	Pt/C 0.6 mg Pt·cm^-2	Pt/C 0.6 mg Pt·cm^-2	80	0.22	[102]
HEM (CPPO-PVA)	NH₃	Cr-Ni/C 10 mg·cm^-2	MnO₂/C 20 mg·cm^-2	25	11	[100]
HEM (Resin-PVA)	35% NH₃	Cr-Ni/C 10 mg·cm^-2	MnO₂/C 20 mg·cm^-2	25	9	[100]
HEM (AMI-7001)	NH₃	Pt/C 0.45 mg Pt·cm^-2	Pt/C 0.45 mg Pt·cm^-2	65	0.26	[103]
HEM (AMI-7001)	1 mol·L^-1 NH₃	Pt/C 0.45 mg Pt·cm^-2	Pt/C 0.45 mg Pt·cm^-2	25	0.71	[103]
Mg-Al-CO₃^2- LDH	5 mol·L^-1 MH₃ 1 mol·L^-1 KOH	PtRu 3.3 mg·cm^-2	Pt/C	80	4.5	[104]
FAA AEM	35% NH₃ 1 mol·L^-1 KOH	NiCu/C 2.5 mg·cm^-2	SrCo_0.8Cu_0.1 Nb_0.1O_3-_δ 18.67 mg·cm^-2	25	0.25	[105]
PAP-TP	NH₃ + N₂	PtIr 2 mg PGM·cm^-2	Fe-N-C 3 mg·cm^-2	95	75	[99]
Tokuyama membrance	16 mol·L^-1 NH₃	Pt₁Ir₁₀ 2 mg PGM·cm^-2	Ag 2 mg·cm^-2	120	180	[99]
Tokuyama membrance	12 mol·L^-1 NH₃ 2.5 mol·L^-1 KOH	Pt₁Ir₁₀ 2 mg PGM·cm^-2	Ag 2 mg·cm^-2	100	280	[99]
AEM (A201)	NH₃	Pt/C 0.5 mg Pt·cm^-2	Pt/C 0.5 mg Pt·cm^-2	50	4.76	[106]
AEM (A201)	NH₃	PtRu/C 0.5 mg Pt·cm^-2	Pt/C 0.5 mg Pt·cm^-2	50	3.07	[106]
AEM (A201)	NH₃	SnO₂-Pt/C 0.4 mg Pt·cm^-2	Pt/C 0.4 mg Pt·cm^-2	50	4.15	[62]