电化学还原二氧化碳电解器相关研究概述及展望

doi:10.19799/j.cnki.2095-4239.2020.0167

摘要/Abstract

摘要：

电化学还原二氧化碳技术可以解决可再生能源(如太阳能)供需不匹配的问题，将过剩的电能转化为具有高附加值的化学品储存，同时减少二氧化碳排放，缓解环境压力。早期研究多在H型电解池中进行，但是这与二氧化碳电化学还原技术的实际工业应用方式差别较大，且受到传质限制，面临电流密度较低的问题。本文主要聚焦于采用连续式二氧化碳电化学还原反应器的相关研究，介绍目前常用的几种反应器结构，对电解器各组成部分、运行条件、可能的优化方式如新型气体扩散电极结构等、电解器失效机理及可能的修复方法进行了探讨。同时认为，由于各研究中采用的电解器结构、组成及运行参数存在差异，电解器中参比电极的使用对于比较各研究中阴极催化剂性能十分有必要。最后，总结提出了二氧化碳电解器的几种改进方式：①催化剂层浆料制备工艺，黏结剂的选择；②优化气体扩散电极制备工艺，基底的选择；③高效稳定的聚合物电解质膜的开发；④运行操作参数优化。

关键词: 二氧化碳, 电化学还原, 电解反应器, 失效机理

Abstract:

The electrochemical reduction of carbon dioxide can deal with the mismatch between the demand and the supply of renewable energy, such as solar energy, converting excess electrical energy into chemical storage with a high added value while reducing carbon dioxide emissions, and alleviating environmental pressure. H-type electrolytic cells have mostly been adopted in early research, and this is far from the industrial application of the carbon dioxide electrochemical reduction technology. H-cells are susceptible to mass transfer limitations and often have low current density. This study no longer focuses on the research and development of cathode catalysts, but on studies using a continuous carbon dioxide electrochemical reduction reactor. We introduce herein several types of reactor structure commonly used in the current research and discuss the components, operating conditions, possible optimization methods (e.g., novel gas diffusion electrode structure), failure mechanism of the electrolyzer, and possible repair methods. A direct comparison of the performances of the cathode catalyst would be impossible due to the difference in structure, composition, and operating parameters of the electrolyzers used in each study; therefore, the reference electrode should be a necessary part of a CO₂ electrolyzer. The possible optimization methods of the carbon dioxide electrolyzer are as follows: ① preparation technology of the catalyst layer slurry and binder selection; ② preparation technology of the gas diffusion electrode and substrate selection; ③ development of a highly efficient and long-term stable polymer electrolyte membrane; and ④ optimization of the operating parameters.

Key words: carbon dioxide, electrochemical reduction, electrolytic reactor, failure mechanism

中图分类号:

O 646

古月圆, 韦聚才, 李金东, 王路阳, 吴旭. 电化学还原二氧化碳电解器相关研究概述及展望[J]. 储能科学与技术, 2020, 9(6): 1691-1701.

Yueyuan GU, Jucai WEI, Jindong LI, Luyang WANG, Xu WU. Overview and prospect of studies on electrochemical reduction of carbon dioxide electrolyzers[J]. Energy Storage Science and Technology, 2020, 9(6): 1691-1701.

图/表 7

图1

表1

部分连续式二氧化碳电解器运行参数及主要结论"

setup	membrane	current collector	catalysts		reference electrode	feeding	electrolyte composition		main results	Ref.
setup	membrane	current collector	cathode	anode	reference electrode	feeding	cathode	anode	main results	Ref.
(a)	Nafion^? 117	Al	Ag 10mg/1.5 cm²	Pt 10mg/1.5 cm²	Home-made Ag/Ag⁺	CO₂ 2.5 sccm solution 0.5 mL/min	18% EMIM BF₄	100 mM H₂SO₄	1.5～2.5 V, CO FE>96% for at least 7 hours	[32]
(d)	none	Al	Ag 0.75 mg/cm²	Pt/C 4.25 mg/cm²	External Ag/AgCl	CO₂ 7 sccm solution 0.5mL/min	1 mol/L KCl		-1.56 V vs Ag/AgCl Air-brushed , CO FE (95±5)%; hand-painted, CO FE (83±14)%	[27]
(d)	none	Al and graphite	Ag 0.9 mg/cm²	Pt 1.0 mg/cm²	none	CO₂ diluted by N₂ 7 sccm solution 0.4 mL/min	1 mol/L KCl		3 V, 10%～100% v/v CO₂, CO FE>80%	[43]
(b)	BPM	gold-coated graphite	Ag BiO_x	NiFeO_x	none	-	0.5 mol/L KHCO₃saturated with CO₂	0.1 mol/L KOH	50 mA/cm², CO FE>60%	[35]
(d)	none	Stainless steel	Ag (2±0.1) mg/cm²	IrO₂ (2±0.1) mg/cm²	Ag/AgCl (inlet)	CO₂ 17 sccm solution 0.5 mL/min	3 mol/L KOH		2.75 V, 342.8 mA/cm² CO (101.2%)	[44]
(a)	AEM	-	Ag	IrO₂	none	CO₂ 10 sccm	50% EMIMCI	0.5 mol/L H₂SO₄	50 mA/cm², CO FE 97.08% pH adjusted to 6.6, 25 mA/cm², CO FE 99.1%	[7]
(d)	none	Al	Ag 0.75 mg/cm²	Pt/C 4.25 mg/cm²	External Ag/AgCl	CO₂ 7 sccm solution 0.5mL/min	1 mol/L KCl		-1.62 V vs Ag/AgCl (cell potential 3V), CO FE ～98%, partial current density ～90mA/cm²	[31]
(d)	none	Al	CN/MWCNT 2.39 mg/cm²	Pt/C 4.25 mg/cm²	External Ag/AgCl	CO₂ 7 sccm solution 0.5mL/min	1 mol/L KCl		-1.68 V vs Ag/AgCl (cell potential 3V), CO FE ～93%, partial current density ～86 mA/cm²	[31]
(c)	CEM	Ti	Ag or Cu (5mg/cm²)	IrO₂ (2mg/cm²)	Ag/AgCl	CO₂ 4.5 sccm	0.5 mol/L K₂SO₄		Cu, -0.8 V vs. RHE, CO FE ～75% Ag, -0.8 V vs. RHE, CO FE ～80%	[13]
(d)	none	Al	MWNT/PyPBI/Au 0.34 mg/cm²	Pt /C 4.25 mg/cm²	Ag/AgCl (outlet)	CO₂ 7 sccm solution 0.5 mL/min	1 mol/L KCl		-1.4 V vs Ag/AgCl, CO FE 92%	[30]
(d)	none	stainless steel	MWNT/PyPBI/Au (1±0.1) mg/cm²	IrO₂ (4.25±0.25) mg/cm²	Ag/AgCl (inlet)	CO₂ 17 sccm solution 0.5mL/min	2 mol/L KOH		-0.22 V vs RHE (cell potential-1.7 V) CO FE 98.3%	[29]
(b)	CEM	titanium	Cu	IrO₂	none	both 100 sccm	CO₂	humidified N₂（25、50、75%）	relative humidity 72.5%, 30 ^oC, 6 V Hydrocarbons FE 0.12%; relative humidity 73.7 %, 70 ^oC, 2.4 V hydrocarbons FE 0.11%	[11]
(a)	AEM	Stainless steel	Cu 1.0 mg/cm²	IrO₂ 1.0 mg/cm²	Ag/AgCl (outlet)	CO₂ 7 sccm; solution 0.5 mL/min（-2～-3.5 V）0.1 mL/min (-1.6～-2 V)	1 mol/L KOH	1 mol/L KOH	-0.58 V vs. RHE, C₂H₄ and C₂H₅OH FE 46%, partial current density ～200 mA/cm²	[48]
(c)	Nafion^?117	-	Cu₂O 1 mg/cm²	Ti	Ag/AgCl	CO₂ 10～40 mL/min solution 1～3 mL/min	0.5 mol/L KHCO₃	0.5 mol/L KHCO₃	10 mA/cm²CH₃OH FE 42.3%, r_T=83.2 μmol/(m²·s^-1)	[56]
(c)	Nafion^?117	-	Cu₂O/ZnO 1mg/cm²	Ti	Ag/AgCl	CO₂ 10～40 mL/min solution 1～3 mL/min	0.5 mol/L KHCO₃	0.5 mol/L KHCO₃	10 mA/cm²CH₃OH FE 27.5%, r_T=50.8 μmol/(m²·s^-1)	[56]
(b)	PBI	carbon paper	Cu-CNF 0.5 mg/cm²	IrO₂ 0.5 mg/cm²	-	CO₂ 0.5 NmL/min N₂ 6 NmL/min	CO₂	N₂ 1 mol/L H₃PO₄saturator	110 ℃, -0.8 mA/cm², acetaldehyde FE 85%, r>24 nmol/(h·cm^-2); 110 ℃, -1.6 mA/cm², acetaldehyde FE 70%, r>55nmol/(h·cm^-2)	[12]
(b)	Nafion115 AAEM	-	1 mg/cm² Cu/CNTs Pt/C Pd/C	Pt/C	none	both 20 mL/min	humidified CO₂ (100%)	humidified H₂(100%)	40 ℃, 3V, CO, r=8.88 μmol/(h·cm^-2), r=0.75 μmol/(h·cm^-2), r=7.59 μmol/(h·cm^-2)	[10]
(c)	Nafion^?117	-	Sn 1.5 mg/cm²	DSA	Ag/AgCl	CO₂ 0.57 mL/(min·cm^-2)	0.45 mol/L KHCO₃ + 0.5 mol/L KCl	1 mol/L KOH	40 mA/cm², cell potential 3.21 V, Formate FE 70.5%	[57]
(b)	BPM	-	Sn	Ir-MMO	none	solution 10 mL/min	pressured CO₂ 0.5mol/L KHCO₃	pressured N₂ 1mol/L KOH	3.5 V, 40 bar, ～30 mA/cm², HCOOH FE ～90% 4 V, 50 bar, ～100 mA/cm², HCOOH FE ～65%	[51]
(b)	CEM	-	Sn	Ir-MMO	none	solution 10 mL/min	pressured CO₂ 1mol/L KHCO₃	pressured N₂ 0.5mol/L H₂SO₄	3.5 V, 40 bar, ～50 mA/cm², HCOOH FE ～90% 3.5 V, 50 bar, ～60 mA/cm², HCOOH FE ～80%	[51]
(d)	none	graphite	Ru–Pd/C 2 mg/cm²	Pt/C 2 mg/cm²	Ag/AgCl (outlet)	CO₂ 5sccm solution 0.5 mL/min	0.5 mol/L KHCO₃		3.25 V, HCOOH FE～ 16%, EE～ 7%	[45]
(d)	none	graphite	Sn 5 mg/cm²	Pt/C 2 mg/cm²	Ag/AgCl (outlet)	CO₂ 5sccm solution 0.5 mL/min	0.5 mol/L KCl+1mol/L HCl (pH=4)		3V, ～100 mA/cm² HCOOH FE 89%, EE 45%	[45]
(b)	Nafion117	-	1mg/cm² Pt/C Pt-Ru/C	Pt/C 1mg/cm²	DHE	Both 50 sccm	N₂or CO₂ (fully humidified)	H₂ (fully humidified)	80 ℃ ,0.06 V vs. DHE CH₃OH FE 35% CH₃OH FE 75%	[8]
(b)	Nafion^?115	titanium	PtRu/C metal 0.5 mg/cm²	IrRuO_x 0.4 mg/cm²	none	CO₂ 50 mL/min solution 4 mL/min	humidified CO₂	H₂O	40 ℃, 1.25V, CH₃OH r=0.9 μmol/(g·h^-1) 95 ℃, 1.25V, CH₃OH r=56 μmol/(g·h^-1)	[58]
(b)	Nafion 115	gold-plated graphite (anode)	Indium	Pt/C	none	-	1mol/L NaHCO₃	10%（w/v）NaOH	40 mA/cm², HCOOH FE ～77%	[59]
(b)	AEM	gold-plated graphite (anode)	Indium	Pt/C	none	-	1mol/L NaHCO₃	1 mol/L NaHCO₃	40 mA/cm², HCOOH FE 80%	[59]
(b)	Nafion117	-	Pb	DSA	Ag/AgCl	CO₂ 200 mL/min solution 1.44 mL /(min·cm^-2)	0.45 mol/L KHCO₃ + 0.5 mol/L KCl	1 mol/L KOH	10.5 mA/cm², HCOOH FE 57%	[33]
(b)	Nafion	-	N-doped graphene 0.3～0.5 mg/cm²	Pt 0.3 mg/cm²	DHE	CO₂ 45 sccm H₂ 50 sccm	CO₂	H₂	-0.58 V vs RHE, ～1.8 mA/cm², CO FE ～85% for at least 5 h	[60]
(b)	AEM	Ti	Ni-NG 0.5 mg/cm²	IrO₂ 0.5 mg/cm²	none	CO₂ 50 sccm solution 2 mL/min	humidified CO₂	0.1 mol/L KHCO₃	2.78V, ～ 50 mA/cm², CO FE >90%, for at least 8 h, 3.81 mmol/h	[61]
(b)	PSMIM AEM	Ti	Ni-NG 1.25 mg/cm²	IrO₂ 1.25 mg/cm²	none	CO₂ 50 or 500 sccm solution 2 or 10 mL/min for different area	humidified CO₂	0.1 mol/L KHCO₃	2×2 cm², 2.46V, ～80 mA/cm², CO FE～100% for 20h10×10 cm², 2.8V, ～8A, CO FE >90% for 6h, r=3.34 L/h	[47]

表1

图2

图3

图4

图5

图6

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