Progress in technologies of metal-supported solid oxide fuel cells

doi:10.3969/j.issn.2097-0706.2022.08.001

Abstract

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

CLC Number:

TK91

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.

Figures/Tables 33

Fig.1

Fig.2

Table 1

Parameters of MS-SOFC and AS-SOC

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

Table 1

Fig.3

Fig.4

Fig.5

Fig.6

Fig.7

Fig.8

Fig.9

Fig.10

Fig.11

Fig.12

Fig.13

Fig.14

Table 2

Performances of common materials of porous metal supports[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

Table 2

Fig.15

Fig.16

Table 3

Composition of ferrite stainless steels for SOFCs

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

Table 3

Table 4

Fig.17

Fig.18

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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