金属支撑固体氧化物燃料电池技术进展

doi:10.3969/j.issn.2097-0706.2022.08.001

摘要/Abstract

摘要：

可快速启动的金属支撑固体氧化物燃料电池（MS-SOFC）是助力实现“双碳”目标的变革性技术。MS-SOFC具有机械性能好、易于密封等优点,采用与陶瓷电解质热膨胀系数相近且成本低廉的铁素体不锈钢为电池提供结构支撑,有望大幅降低制造成本。金属连接体与金属支撑体是MS-SOFC的2个核心部件,常用的材料有铁素体不锈钢、Cr基合金以及Ni基合金。目前日本、德国、美国和我国均开发了面向SOFC应用的不锈钢体系,不锈钢涂层防护技术也取得了显著的进展,有效提高了材料的抗高温氧化与还原性质。为解决高温烧结制备MS-SOFC所产生的问题,主要采用热喷涂法与低温烧结法制备致密电解质。MS-SOFC使用金属支撑体与连接体,可以使用传统的焊接技术实现支撑体与连接体的有效连接,或通过粉末压制-烧结一体化多孔金属支撑体-连接体结构可以有效实现燃料侧燃料气体的密封。MS-SOFC长期运行性能衰减机理有金属材料的氧化、Cr挥发引起的阴极毒化、催化剂颗粒的粗化等。英国Ceres Power公司、美国通用电气公司（GE）、德国宇航中心（DLR）、德国于利希（FZJ）研究中心、奥地利Plansee公司等均取得了一定的成就,MS-SOFC已初步实现了商业化应用。

关键词: “双碳”目标, 金属支撑固体氧化物燃料电池, 铁素体不锈钢, 低温制备技术, 金属支撑电堆, 电解质, 钙钛矿

Abstract:

Metal-supported solid oxide fuel cell （MS-SOFC）, being able to start-up rapidly, are transformative technology to facilitate the realization of dual carbon target. With low-cost ferritic stainless steel as support whose thermal expansion coefficient（CTE） is similar to that of ceramic electrolyte, MS-SOFC is expected to be of a significantly lower manufacturing cost, good mechanical performance and sealing performance. Metal interconnect and metal support are two core components for a MS-SOFC, and their common materials are ferritic stainless steel, Cr-based alloy and Ni-based alloy. Japan, Germany, the United States and China have developed various stainless steels for SOFCs. And stainless-steel coating technologies have made significant progress which can improve the high temperature oxidation resistance of the materials. In view of the problem in the MS-SOFC prepared by high-temperature sintering method, thermal spraying method and low-temperature sintering method have taken its place. The metal support and interconnect of a MS-SOFC can be effectively connected by traditional welding method, and the fuel gas can be effectively sealed by taking porous metal support-connector structure which is formed in powder pressing and sintering processes. The reasons for the degradation of MS-SOFCs include oxidation of metal materials, cathodic toxicity caused by Cr volatilization, coarsening of catalyst particles,etc. Many companies, such as Ceres Power of the UK, General Electric（GE） of the US, German Aerospace Center（DLR）, German Forschungszentrum Jülich（FZJ） and Plansee of Austria, have made remarkable achievements in preliminary commercialization of MS-SOFC.

Key words: dual carbon target, metal supported solid oxide fuel cell, ferritic stainless steel, low temperature preparation technology, metal supported stacks, electrolyte, perovskite

中图分类号:

TK91

高圆, 李智, 李甲鸿, 高九涛, 李成新, 李长久. 金属支撑固体氧化物燃料电池技术进展[J]. 综合智慧能源, 2022, 44(8): 1-24.

GAO Yuan, LI Zhi, LI Jiahong, GAO Jiutao, LI Chengxin, LI Changjiu. Progress in technologies of metal-supported solid oxide fuel cells[J]. Integrated Intelligent Energy, 2022, 44(8): 1-24.

图/表 33

图1

图2

表1

MS-SOFC与AS-SOFC参数对比

项目	Ceres Power	Elcogen	SOLID Power	CCTC
国家	英国	芬兰	意大利	中国
电堆结构	金属支撑平板式	阳极支撑平板式	阳极支撑平板式	阳极支撑平板式
电堆图片
典型应用	SteelGen	Convion C50	BuleGen BG15	BlueGen
制造厂家	Ceres Power	Convion	SOLID Power SpA	CFCL
产品照片
产品功率（电功率/热功率）/kW	0.70/—	58.00/32.00	1.50/0.81	1.50/0.61
发电效率/%	47	55	57	60
整体效率/%	87	85	88	85
启动时间	15 $∼$ 50 min	$>$ 5 h	约24 h	约25 h

表1

图3

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图9

图10

图11

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图13

图14

表2

常用的多孔金属支撑体材料性能[3]

合金	晶体结构	α（×10^-6）/K^-1	抗氧化性	机械强度	加工性	成本
Cr基	BCC	11.0 $∼$ 12.5	好	高	难	很高
铁素体不锈钢	BCC	11.5 $∼$ 14.0	好	低	较难	低
奥氏体不锈钢	FCC	18.0 $∼$ 20.0	好	较高	易	低
Fe基超合金	FCC	15.0 $∼$ 20.0	好	高	易	较低
Ni基超合金	FCC	14.0 $∼$ 19.0	好	高	易	高
纯Ni	FCC	16.0 $∼$ 17.0	差	低	易	高
Ni-Fe	FCC	13.0 $∼$ 14.0	差	低	易	较高

表2

图15

图16

表3

SOFC不锈钢体系成分

公司及牌号	w(Fe)/%	w(Cr)/%	w(C)/%	w(Nb)/%	w(Ti)/%	w(Mn)/%	w(Si)/%	w(Cu)/%	w(Al)/%	w(W)/%	w(RE)/%	α
VDM Metals Crofer22 APU	Bal.	20.0 $∼$ 24.0	<0.03		0.03 $∼$ 0.20	0.3 $∼$ 0.8	<0.5	0 $∼$ 0.5	0 $∼$ 0.5	—	La:0.04 $∼$ 0.20	11.9
VDM Metals Crofer22 H	Bal.	20.0 $∼$ 24.0	<0.03	0.5	0.02 $∼$ 0.20	<0.8	0.1 $∼$ 0.6	<0.5	<0.1	1.0 $∼$ 3.0	La:0.04 $∼$ 0.20	11.8
Hitachi Metals ZGM232L	Bal.	22.0	0.02	—	—	0.5	0.1	—	0.1	—	La:0.07; Zr:0.25
Hitachi Metals ZGM232G10	Bal.	24.0	0.02	—	—	0.3	0.1	1.0	0.1	2.0	La:0.07; Zr:0.25	12.4
西安交通大学 NYBR25	Bal.	24.0 $∼$ 26.0	<0.02	0.5	0.14	0.5	<0.2	0.3 $∼$ 0.5	—	0.3 $∼$ 0.5	Re:0.50

表3

表4

图17

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元素		尖晶石	电导率/(S·cm^-1)	α(×10^-6)/K^-1
Mg	Al	MgAl₂O₄	1.00×10^-5	9.0
	Cr	MgCr₂O₄	0.02	7.2
	Mn	MgMn₂O₄	0.97	8.7
	Fe	MgFe₂O₄	0.08	12.3
Mn	Al	MnAl₂O₄	0.01	7.9
	Cr	Mn_1.2Cr_1.8O₄	0.02	6.8
	Mn	Mn₃O₄	0.10	8.8
	Fe	MnFe₂O₄	8.00	12.5
	Co	MgCo₂O₄	60.00	9.7
Co	Al	CoAl₂O₄	1.00×10^-4	8.7
	Cr	CoCr₂O₄	7.40	7.5
	Mn	CoMn₂O₄	6.40	7.0
	Fe	CoFe₂O₄	0.93	12.1
	Co	Co₂O₄	6.70	9.3
Ni	Al	NiAl₂O₄	1.00×10^-3	8.1
	Cr	NiCr₂O₄	0.73	7.3
	Mn	NiMn₂O₄	1.40	8.5
	Fe	NiFe₂O₄	0.26	10.8
Cu	Al	CuAl₂O₄	0.05	—
	Cr	CuCr₂O₄	0.40	—
	Mn	Cu_1.3Mn_1.7O₄	225.00（750 ℃）	12.2
	Fe	CuFe₂O₄	9.10	11.2
Zn	Al	ZnAl₂O₄	1.00×10^-5	8.7
	Cr	ZnCr₂O₄	0.01	7.1
	Mn	ZnMn₂O₄	—	—
	Fe	ZnFe₂O₄	0.07	7.0