固体氧化物电解池技术的应用前景与挑战

doi:10.3969/j.issn.1006-396X.2022.06.004

摘要/Abstract

摘要：

固体氧化物电解池(SOEC)技术基于固态电解质可实现电能、热能向化学能的高效、灵活转化，可与太阳能、风能和潮汐能等可再生能源衔接，利用所产生的过剩电能实现H₂的高效、清洁、大规模制备；可以耦合CO₂捕获过程，实现CO₂与H₂O共电解制备合成气；可与大型工业结合，利用产生的低附加值原料制备乙烯、氨气、甲醛等高附加值化学品。SOEC技术可以满足未来社会对大规模可再生能源转化及存储的需求，对加快全世界范围内非化石能源替代进程、加速实现我国“双碳”目标意义重大。主要讨论了SOEC技术所应用的电极和电解质材料、现阶段的应用场景及原理、面临的挑战，并对该技术的发展方向进行了展望。

关键词: 固体氧化物电解池技术, 合成气, 乙烯, 合成氨

Abstract:

Solid oxide electrolysis cell (SOEC) technology can realize the efficient and flexible conversion of electrical and thermal energy to chemical energy on the basis of solid electrolytes. It can be connected with renewable energy sources such as solar and wind power and tidal energy to utilize the excess electricity generated for efficient, clean, and large?scale production of hydrogen. When coupled with the CO₂ capture process, it enables the co?electrolysis of CO₂ and H₂O to produce syngas. In addition, it can be combined with large?scale industries to produce high?value?added chemicals such as ethylene, ammonia, and formaldehyde with low?value?added raw materials generated. SOEC technology can meet the needs of the future society for the large?scale renewable energy conversion and storage,which is of great significance for accelerating the substitution process of non?fossil energy worldwide and the realization of China's carbon peak and neutrality goals. This paper mainly discussed the electrode and electrolyte materials used in solid oxide electrolysis technology, the application scenarios and principles at the current stage, and the challenges faced. Moreover, it predicted the future development directions of the technology.

Key words: Solid oxide electrolysis cell technology, Syngas, Ethylene, Synthetic ammonia

中图分类号:

TQ151

勾匀婕, 李广东, 王振华, 孙克宁. 固体氧化物电解池技术的应用前景与挑战[J]. 石油化工高等学校学报, 2022, 35(6): 28-37.

Yunjie Gou, Guangdong Li, Zhenhua Wang, Kening Sun. Application Prospects and Challenges of Solid Oxide Electrolysis Cell Technology[J]. Journal of Petrochemical Universities, 2022, 35(6): 28-37.

图/表 6

图1 SOEC技术的应用示意图

Fig.1 Application diagram of SOEC technology

图2 电解水的工作原理图（a） O?SOEC （b） H?SOEC图2　

Fig.2 Working principle diagram of electrolytic water

图3 还原后LSTMN 的SEM 图、HRTEM 图及Ni 纳米颗粒粒径分布

Fig.3 The SEM and HRTEM of LSTMN restored and particle size distribution of Ni nanoparticles

图4 CH4辅助CO2?H2O共电解原理图和合成气生成的可逆电压

Fig.4 Schematic diagram of co?electrolysis with CO2?H2O assisted by methane and reversible potential generated by syngas

图5 C2H6电化学脱氢原理和不同阳极下的产物分布

Fig.5 Electrochemical dehydrogenation principle of C2H6 and product distribution with different anodes

图6 以水和氮为原料的电化学合成氨原理图

Fig.6 Diagram of electrochemical synthesis of ammonia with H2O and N2

参考文献 60

1	Luo Y，Shi Y X，Li W Y，et al.Synchronous enhancement of H₂O/CO₂ co⁃electrolysis and methanation for efficient one⁃step power⁃to⁃methane［J］.Energy Convers Manage，2018，165（1）：127⁃136.
2	Ye L T，Xie K.High⁃temperature electrocatalysis and key materials in solid oxide electrolysis cells［J］.Journal of Energy Chemistry，2021，54：736⁃745.
3	Rabuni M F，VatcharasuwanA N，Li T，et al.High performance micro⁃monolithic reversible solid oxide electrochemical reactor［J］.Journal of Power Sources，2020，458：228026.
4	Yang X X，Sun K N，Ma M J，et al.Achieving strong chemical adsorption ability for efficient carbon dioxide electrolysis［J］.Applied Catalysis B：Environmental，2020，272：118968.
5	Li Y，Zhang Q，Mei Z W，et al.Recent advances and perspective on electrochemical ammonia synthesis under ambient conditions［J］.Small Methods，2021，5（11）：e2100460.
6	Zhang Y，Wang J C，Yu B，et al.A review of high temperature co⁃electrolysis of H₂O and CO₂ to produce sustainable fuels using solid oxide electrolysis cells（SOECs）：Advanced materials and technology［J］.Chemical Society Reviews，2017，46（5）：1427⁃1463.
7	Wang T P，Wang J J，Yu L B，et al.Effect of NiO/YSZ cathode support pore structure on CO₂ electrolysis via solid oxide electrolysis cells［J］.Journal of the European Ceramic Society，2018，38（15）：5051⁃5057.
8	Song Y F，Zhou Z W，Zhang X M，et al.Pure CO₂ electrolysis over an Ni/YSZ cathode in a solid oxide electrolysis cell［J］.Journal of Materials Chemistry A，2018，6（28）：13661⁃13667.
9	胡兴国，刘立敏，钱欣源，等.过渡金属Fe、Mn掺杂CeO₂浸渍改性高温固体氧化物电池Ni⁃YSZ电极的电化学性能研究［J］.陶瓷学报，2022，43（3）：401⁃411.
	Hu X G，Liu L M，Qian X Y，et al.Electrochemical properties of Fe/Mn doped CeO₂ impregnation modified Ni⁃YSZ electrode for high temperature solid oxide cells［J］.Journal of Ceramics，2022，43（3）：401⁃411.
10	Wang W，Qu J F，Julião P S B，et al.Recent advances in the development of anode materials for solid oxide fuel cells utilizing liquid oxygenated hydrocarbon fuels：A mini review［J］.Energy Technology，2019，7（1）：33⁃44.
11	Zhao K，Chen J，Li H B，et al.Effects of Co⁃substitution on the reactivity of double perovskite oxides LaSrFe_2- xCoxO₆ for the chemical⁃looping steam methane reforming［J］.Journal of the Energy Institute，2019，92（3）：594⁃603.
12	杨权森，王芳芳.A位缺陷对铁酸盐基阴极材料硫中毒特性影响［J］.石油化工高等学校学报，2021，34（6）：1⁃6.
	Yang Q S，Wang F F.Effect of A⁃site defect on sulfur poisoning behaivor of ferrite⁃based cathode materials［J］.Journal of Petrochemical Universities，2021，34（6）：1⁃6.
13	Wang S，Jiang H G，Gu Y H，et al.Mo⁃doped La_0.6Sr_0.4FeO_3-δ as an efficient fuel electrode for direct electrolysis of CO₂ in solid oxide electrolysis cells［J］.Electrochimica Acta，2020，337：135794.
14	Cao Z Q，Wang Z H，Li F J，et al.Insight into high electrochemical activity of reduced La_0.3Sr_0.7Fe_0.7Ti_0.3O₃ electrode for high temperature CO₂ electrolysis［J］.Electrochimica Acta，2020，332：135464.
15	Zhou Y J，Zhou Z W，Song Y F，et al.Enhancing CO₂ electrolysis performance with vanadium⁃doped perovskite cathode in solid oxide electrolysis cell［J］.Nano Energy，2018，50：43⁃51.
16	Zhu J X，Zhang W Q，Li Y F，et al.Enhancing CO₂ catalytic activation and direct electroreduction on in⁃situ exsolved Fe/MnOx nanoparticles from （Pr，Ba）₂Mn_2- yFeyO_5+δ layered perovskites for SOEC cathodes［J］.Applied Catalysis B：Environmental，2020，268：118389.
17	Chen L H，Xu J，Wang X，et al.Sr₂Fe_1.5+ xMo_0.5O_6-δ cathode with exsolved Fe nanoparticles for enhanced CO₂ electrolysis［J］.International Journal of Hydrogen Energy，2020，45（21）：11901⁃11907.
18	Lee S，Woo S H，Shin T H，et al.Pd and GDC Co⁃infiltrated LSCM cathode for high⁃temperature CO₂ electrolysis using solid oxide electrolysis cells［J］.Chemical Engineering Journal，2021，420：127706.
19	Wu P P，Tian Y T，Lü Z，et al.Electrochemical performance of La_0.65Sr_0.35MnO₃ oxygen electrode with alternately infiltrated Sm_0.5Sr_0.5CoO_3-δ and Sm_0.2Ce_0.8O_1.9 nanoparticles for reversible solid oxide cells［J］.International Journal of Hydrogen Energy，2022，47（2）：747⁃760.
20	Chen G，Zhou W，Guan D Q，et al.Two orders of magnitude enhancement in oxygen evolution reactivity on amorphous Ba_0.5Sr_0.5Co_0.8Fe_0.2O_3-δ nanofilms with tunable oxidation state［J］.Science Advances，2017，3：1603206.
21	Choi S，Davenport T C，Haile S M.Protonic ceramic electrochemical cells for hydrogen production and electricity generation：Exceptional reversibility，stability，and demonstrated faradaic efficiency［J］.Energy & Environmental Science，2019，12（1）：206⁃215.
22	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）：1903805.
23	Li G D，Gou Y J，Ren R Z，et al.Fluorinated Pr₂NiO_4+δ as high⁃performance air electrode for tubular reversible protonic ceramic cells［J］.Journal of Power Sources，2021，508：230343.
24	Xu K，Zhang H，Xu Y S，et al.An efficient steam‐induced heterostructured air electrode for protonic ceramic electrochemical cells［J］.Advanced Functional Materials，2022，32（23）：2110998.
25	Li G D，Gou Y J，Cheng X J，et al.Enhanced electrochemical performance of the Fe⁃based layered perovskite oxygen electrode for reversible solid oxide cells［J］.ACS Applied Materials & Interfaces，2021，13（29）：34282⁃34291.
26	Ebbesen S D，Jensen S H，Hauch A，et al.High temperature electrolysis in alkaline cells，solid proton conducting cells，and solid oxide cells［J］.Chemical Reviews，2014，114（21）：10697⁃10734.
27	Zhang L H，Xu C M，Sun W，et al.Constructing perovskite/alkaline⁃earth metal composite heterostructure by infiltration to revitalize CO₂ electrolysis［J］.Separation and Purification Technology，2022，298：121475.
28	Xu S S，Li S S，Yao W T，et al.Direct electrolysis of CO₂ using an oxygen⁃ion conducting solid oxide electrolyzer based on La_0.75Sr_0.25Cr_0.5Mn_0.5O_3-δ electrode［J］.Journal of Power Sources，2013，230：115⁃121.
29	Song Y F，Zhang X M，Xie K，et al.High⁃temperature CO₂ electrolysis in solid oxide electrolysis cells：Developments，challenges，and prospects［J］.Advanced Materials，2019，31（50）：1902033.
30	Ma M J，Yang X X，Xu C M，et al.Constructing highly active alloy⁃perovskite interfaces for efficient electrochemical CO₂ reduction reaction［J］.Separation and Purification Technology，2022，296：121411.
31	Ye L T，Zhang M Y，Huang P，et al.Enhancing CO₂ electrolysis through synergistic control of non⁃stoichiometry and doping to tune cathode surface structures［J］.Nature Communications，2017，8：14785.
32	Chen D，Niakolas D K，Papaefthimoou V，et al.How the surface state of nickel/gadolinium⁃doped ceria cathodes influences the electrochemical performance in direct CO₂ electrolysis［J］.Journal of Catalysis，2021，404：518⁃528.
33	Lo Faro M，Trocino S，Zignani S C，et al.Production of syngas by solid oxide electrolysis：A case study［J］.International Journal of Hydrogen Energy，2017，42（46）：27859⁃27865.
34	Zheng M H，Wang S，Yang Y，et al.Barium carbonate as a synergistic catalyst for the H₂O/CO₂ reduction reaction at Ni–yttria stabilized zirconia cathodes for solid oxide electrolysis cells［J］.Journal of Materials Chemistry A，2018，6（6）：2721⁃2829.
35	Yu S B，Lee S H，Mehran M T，et al.Syngas production in high performing tubular solid oxide cells by using high⁃temperature H₂O/CO₂ co⁃electrolysis［J］.Chemical Engineering Journal，2018，335：41⁃51.
36	Irvinbe J T S，Neagu D，Vervraeken M C，et al.Evolution of the electrochemical interface in high⁃temperature fuel cells and electrolysers［J］.Nature Energy，2016，1：15014.
37	Wang Y，Liu T，Fang S M，et al.Syngas production on a symmetrical solid oxide H₂O/CO₂ co⁃electrolysis cell with Sr₂Fe_1.5Mo_0.5O_6–δ⁃Sm_0.2Ce_0.8O_1.9 electrodes［J］.Journal of Power Sources，2016，305：240⁃248.
38	Gan J J，Hou N J，Yao T T，et al.A high performing perovskite cathode with in situ exsolved Co nanoparticles for H₂O and CO₂ solid oxide electrolysis cell［J］.Catalysis Today，2021，364：89⁃96.
39	Wang Y，Liu T，Lei L B，et al.Methane assisted solid oxide co⁃electrolysis process for syngas production［J］.Journal of Power Sources，2017，344：119⁃127.
40	Kyriakou V，Neagu D，Zafeiropoulos G，et al.Symmetrical exsolution of Rh nanoparticles in solid oxide cells for efficient syngas production from greenhouse gases［J］.ACS Catalysis，2019，10（2）：1278⁃1288.
41	耿志强，毕帅，王尊，等.基于改进NSGA⁃Ⅱ算法的乙烯裂解炉操作优化［J］.化工学报，2020，71（3）：1088⁃1094.
	Geng Z Q，Bi S，Wang Z，et al.Operation optimization of ethylene cracking furnace based on improved NSGA⁃Ⅱ algorithm［J］.CIESC Journal，2020，71（3）：1088⁃1094.
42	Song Y F，Lin L，Feng W C，et al.Interfacial enhancement by gamma⁃Al₂O₃ of electrochemical oxidative dehydrogenation of ethane to ethylene in solid oxide electrolysis cells［J］.Angewandte Chemie International Edition，2019，58（45）：16043⁃16046.
43	Schwach P，Pan X L，Bao X H.Direct conversion of methane to value⁃added chemicals over heterogeneous catalysts： challenges and prospects［J］.Chemical Reviews，2017，117（13）：8497⁃8520.
44	Zhu C L，Hou S S，Hu X L，et al.Electrochemical conversion of methane to ethylene in a solid oxide electrolyzer［J］.Nature Communications，2019，10（1）：1173.
45	Ye L T，Shang Z B，Xie K.Selective oxidative coupling of methane to ethylene in a solid oxide electrolyser based on porous single⁃crystalline CeO₂ monoliths［J］.Angewandte Chemie International Edition，2022，61（32）：e202207211.
46	Zhang X R，Ye L T，Li H，et al.Electrochemical dehydrogenation of ethane to ethylene in a solid oxide electrolyzer［J］.ACS Catalysis，2020，10（5）：3505⁃3513.
47	刘恒源，王海辉，徐建鸿.电催化氮还原合成氨电化学系统研究进展［J］.化工学报，2022，73（1）：32⁃45.
	Liu H Y，Wang H H，Xu J H.dvances in electrochemical systems for ammonia synthesis by electrocatalytic reduction of nitrogen［J］.CIESC Journal，2022，73（1）：32⁃45.
48	Lan R，Alkhazmi K A，Amar I A，et al.Synthesis of ammonia directly from wet air using Sm_0.6Ba_0.4Fe_0.8Cu_0.2O_3-δ as the catalyst［J］.Faraday Discuss，2015，182：353⁃363.
49	Marnellos G，Stoukides M.Ammonia synthesis at atmospheric pressure［J］.Science，1998，282（5386）：98⁃100.
50	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.
51	Yoo C Y，Park J H，Kim K，et al.Role of protons in electrochemical ammonia synthesis using solid⁃state electrolytes［J］.ACS Sustainable Chemistry & Engineering，2017，5（9）：7972⁃7978.
52	Amar I A，Lan R，Hmphreys J，et al.Electrochemical synthesis of ammonia from wet nitrogen via a dual⁃chamber reactor using La_0.6Sr_0.4Co_0.2Fe_0.8O_3-δ⁃Ce_0.8Gd_0.18Ca_0.02O_2-δ composite cathode［J］.Catalysis Today，2017，286：51⁃56.
53	练文超，雷励斌，梁波，等.质子导体固体氧化物电化学装置中氨的利用与合成［J］.储能科学与技术，2021，10（6）：1998⁃2007.
	Lian W C，Lei L B，Liang B，et al.Utilization and synthesis of ammonia in proton⁃conducting solid oxide electrochemical devices［J］.Energy Storage Science and Technology，2021，10（6）：1998⁃2007.
54	Zhang H F，Wang L G，Van Herle J，et al.Techno⁃economic optimization of CO₂⁃to⁃methanol with solid⁃oxide electrolyzer［J］.Energies，2019，12（19）：3742.
55	Schemme S，Breuer J L，Köller M，et al.H₂⁃based synthetic fuels：A techno⁃economic comparison of alcohol，ether and hydrocarbon production［J］.International Journal of Hydrogen Energy，2020，45（8）：5395⁃5414.
56	Morejudo S H，Zanón R，Escolástico S，et al. Direct conversion ofmethane to aromatics in a catalytic co⁃ionic membrane reactor［J］.Science，2016，353（6299）：563⁃565.
57	Hjalmarsson P，Sun X F，Liu Y L， et al.Durability of high performance Ni⁃yttria stabilized zirconia supported solid oxide electrolysis cells at high current density［J］.Journal of Power Sources，2014，262：316⁃322.
58	Alenazey F，Alyousef Y，Almisned O，et al.Production of synthesis gas （H₂ and CO） by high⁃temperature Co⁃electrolysis of H₂O and CO₂［J］.International Journal of Hydrogen Energy，2015，40（32）：10274⁃10280.
59	Chen M，Hogh J V T，Nielsen J U，et al.High temperature Co⁃electrolysis of steam and CO₂ in an SOC stack：Performance and durability［J］.Fuel Cells，2013，13（4）：638⁃645.
60	Rao M，Sun X F，Hagen A.Durability of solid oxide electrolysis stack under dynamic load cycling for syngas production［J］.Journal of Power Sources，2020，451：227781.

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