English

Regulating the High Entropy Component of Double Perovskite for High-Temperature Oxygen Evolution Reaction

• Weicheng Feng ^{1, 2, †,} ,
• Jingcheng Yu ^{1, 2, †,} ,
• Yilan Yang ^3, ,
• Yige Guo ^{1, 2,} ,
• Geng Zou ^{1, 2,} ,
• Xiaoju Liu ^4, ,
• Zhou Chen ^5, ,
• Kun Dong ^6, ,
• Yuefeng Song ^{1, ,} ,
• Guoxiong Wang ^{1, ,} ,
• Xinhe Bao ^1,

• 1.

  State Key Laboratory of Catalysis, Dalian National Laboratory for Clean Energy, Dalian Institute of Chemical Physics, Chinese Academy of Sciences, Dalian 116023, Liaoning Province, China

• 2.

  College of Energy, University of Chinese Academy of Sciences, Beijing 100049, China

• 3.

  School of Environmental and Chemical Engineering, Dalian Jiaotong University, Dalian 116028, Liaoning Province, China

• 4.

  School of Chemistry and Chemical Engineering, Yulin University, Yulin 719100, Shannxi Province, China

• 5.

  College of Materials, Xiamen University, Xiamen 361005, Fujian Province, China

• 6.

  Beijing Key Laboratory of Ionic Liquids Clean Process, State Key Laboratory of Multiphase Complex Systems, Institute of Process Engineering, Chinese Academy of Sciences, Beijing 100190, China

Corresponding author: Email: songyf2014@dicp.ac.cn (Y.S.); Email: wanggx@dicp.ac.cn (G.W.); Tel.: +86-411-84379976 (G.W.)

• Received Date: 05 June 2023
  Accepted Date: 31 July 2023
  Revised Date: 31 July 2023
  Available Online: 15 June 2024
• Fund Project:

  the National Key R & D Program of China 

  the National Natural Science Foundation of China 

  the National Natural Science Foundation of China 

  the National Natural Science Foundation of China 

  the National Natural Science Foundation of China 

  the National Natural Science Foundation of China 

  the DNL Cooperation Fund, CAS 

  the Joint Fund of the Yulin University and the Dalian National Laboratory for Clean Energy 

  the CAS Youth Innovation Promotion 

Abstract: Solid oxide electrolysis cells (SOECs) could convert CO₂ to CO powered by clean electricity with low overpotential, high Faradaic efficiency, and high current density. Since the performance of SOEC is affected by sluggish oxygen evolution reaction (OER) kinetics at the anodes, the modification of anode materials is crucial for the further application of SOEC. Perovskites with high configurational entropy exhibit high catalytic activity in many reactions, but are rarely reported in SOECs. Herein, two kinds of high entropy perovskites (HEPs), with formulas of (Pr_0.2La_0.2Sm_0.2Nd_0.2Gd_0.2)BaCo₂O_6−δ (A-HEP) and Pr(Ba_0.2Sr_0.2Ca_0.2Na_0.2K_0.2) Co₂O_6−δ (A′-HEP), are synthesized by doping different rare earth metal, and alkaline metal or alkaline earth metal ions into A-site and A′-site of the double perovskites. Rietveld refinement of X-ray diffraction patterns and elemental maps of scanning electron microscope images confirm the successful synthesis of the two samples. The tetragonal double perovskite structure of A-HEP and the transformation to orthorhombic structure of A′-HEP due to the difference in average atomic radii and oxidation states of the doped ions are also detected. Co 2p X-ray photoelectron spectroscopy (XPS) and O K-edge X-ray absorption spectroscopy reveal that the average oxidation state of Co is lifted from +3.23 in Aʹ-HEP to +3.39 in A-HEP, and the hybridization of Co 2p and O 1s orbitals is also enhanced in A-HEP, which increase the electron transfer pathway and reduce the transfer barrier. Therefore, the electrical conductivity of A-HEP at 800 ℃ is higher than that of Aʹ-HEP. Moreover, the increased absorption oxygen species concentration of A-HEP in O 1s XPS and O₂-temperature programmed desorption results indicates more surface oxygen vacancies, thus increasing active sites for the anodic OER. Consequently, the anodic polarization resistances related to oxygen transportation, electron transfer and surface reaction processes are decreased remarkably in A-HEP, resulting in a high current density of 1.76 A∙cm⁻² at 800 ℃ and a stability of 200 h. This work presents a new method for designing high-performance HEPs as SOEC anode materials.

Key words:
• Solid oxide electrolysis cell
•  /  High entropy perovskite
•  /  Oxygen evolution reaction
•  /  Oxygen vacancy
•  /  Electron transfer

• 1. [1]

     Hauch, A.; Kungas, R.; Blennow, P.; Hansen, A. B.; Hansen, J. B.; Mathiesen, B. V.; Mogensen, M. B. Science 2020, 370, eaba6118. doi: 10.1126/science.aba6118

  2. [2]

     Zheng, Y.; Wang, J. C.; Yu, B.; Zhang, W. Q.; Chen, J.; Qiao, J. L.; Zhang, J. J. Chem. Soc. Rev. 2017, 46, 1427. doi: 10.1039/C6CS00403B

  3. [3]

     Ebbesen, S.; Jensen, S.; Hauch, A.; Mogensen, M. Chem. Rev. 2014, 114, 10697. doi: 10.1021/cr5000865

  4. [4]

     Song, Y. F.; Zhang, X. M.; Xie, K.; Wang, G. X.; Bao, X. H. Adv. Mater. 2019, 31, e1902033. doi: 10.1002/adma.201902033

  5. [5]

     Hwang, J.; Rao, R. R.; Giordano, L.; Katayama, Y.; Yu, Y.; Shao-Horn, Y. Science 2017, 358, 751. doi: 10.1126/science.aam7092

  6. [6]

     Choi, J.; Park, S.; Han, H.; Kim, M.; Park, M.; Han, J.; Kim, W. B. J. Mater. Chem. A 2021, 9, 8740. doi: 10.1039/d0ta11328j

  7. [7]

     Ai, N.; He, S.; Li, N.; Zhang, Q.; Rickard, W. D. A.; Chen, K. F.; Zhang, T.; Jiang, S. P. J. Power Sources 2018, 384, 125. doi: 10.1016/j.jpowsour.2018.02.082

  8. [8]

     Shao, Z. P.; Haile, S. M. Nature 2004, 431, 170. doi: 10.1038/nature02863

  9. [9]

     Jiang, S. P. Solid State Ionics 2002, 146, 1. doi: 10.1016/S0167-2738(01)00997-3

  10. [10]

      Chen, K. F.; Ai, N.; Jiang, S. P. Int. J. Hydrogen Energy 2014, 39, 0349. doi: 10.1016/j.ijhydene.2014.05.013

  11. [11]

      Woodward, P. M.; Suard, E.; Karen, P. J. Am. Chem. Soc. 2003, 125, 8889. doi: 10.1021/ja034813+

  12. [12]

      Woodward, P. M.; Karen, P. Inorg. Chem. 2003, 42, 1121. doi: 10.1021/ic026022z

  13. [13]

      King, G.; Woodward, P. M. J. Mater. Chem. 2010, 20, 5785. doi: 10.1039/B926757C

  14. [14]

      Karen, P.; Woodward, P. M.; Lindén, J.; Vogt, T.; Studer, A.; Fischer, P. Phys. Rev. B 2001, 64, 214405. doi: 10.1103/PhysRevB.64.214405

  15. [15]

      Karen, P.; M. Woodward, P. J. Mater. Chem. 1999, 9, 789. doi: 10.1039/A809302D

  16. [16]

      Zhukov, V. P.; Chulkov, E. V.; Politov, B. V.; Suntsov, A. Y.; Kozhevnikov, V. L. Phys. Chem. Chem. Phys. 2021, 23, 2313. doi: 10.1039/D0CP05497F

  17. [17]

      Taskin, A. A.; Lavrov, A. N.; Ando, Y. Prog. Solid State Chem. 2007, 35, 481. doi: 10.1016/j.progsolidstchem.2007.01.014

  18. [18]

      Taskin, A. A.; Lavrov, A. N.; Ando, Y. Appl. Phys. Lett. 2005, 86, 091910. doi: 10.1063/1.1864244

  19. [19]

      Shin, T. H.; Myung, J.-H.; Verbraeken, M.; Kim, G.; Irvine, J. T. S. Faraday Discuss. 2015, 182, 227. doi: 10.1039/C5FD00025D

  20. [20]

      Seymour, I. D.; Tarancón, A.; Chroneos, A.; Parfitt, D.; Kilner, J. A.; Grimes, R. W. Solid State Ionics 2012, 216, 41. doi: 10.1016/j.ssi.2011.09.002

  21. [21]

      Kim, G.; Wang, S.; Jacobson, A. J.; Reimus, L.; Brodersen, P.; Mims, C. A. J. Mater. Chem. 2007, 17, 2500. doi: 10.1039/B618345J

  22. [22]

      Dong, F.; Ni, M.; Chen, Y.; Chen, D.; Tadé, M. O.; Shao, Z. J. Mater. Chem. A 2014, 2, 20520. doi: 10.1039/C4TA04372C

  23. [23]

      Akande, S. O.; Boulfrad, S.; Schwingenschlö gl, U. J. Mater. Chem. A 2016, 4, 3560. doi: 10.1039/C5TA06858D

  24. [24]

      Rost, C. M.; Sachet, E.; Borman, T.; Moballegh, A.; Dickey, E. C.; Hou, D.; Jones, J. L.; Curtarolo, S.; Maria, J.-P. Nat. Commun. 2015, 6, 8485. doi: 10.1038/ncomms9485

  25. [25]

      Wright, A. J.; Wang, Q. Y.; Huang, C. Y.; Nieto, A.; Chen, R. K.; Luo, J. J. Eur. Ceram. Soc. 2020, 40, 2120. doi: 10.1016/j.jeurceramsoc.2020.01.015

  26. [26]

      Jiang, S. Y.; Sun, D.; Zhang, Y. Q.; Wang, S. B.; Zhao, C. Z. J. Mater. Sci. 2017, 52, 3199. doi: 10.1007/s10853-016-0609-x

  27. [27]

      Xu, H. D.; Zhang, Z. H.; Liu, J. X.; Do-Thanh, C.-L.; Chen, H.; Xu, S. H.; Lin, Q. J.; Jiao, Y.; Wang, J. L.; Wang, Y.; et al. Nat. Commun. 2020, 11, 3908. doi: 10.1038/s41467-020-17738-9

  28. [28]

      Chen, H.; Fu, J.; Zhang, P. F.; Peng, H. G.; Abney, C. W.; Jie, K. C.; Liu, X. M.; Chi, M. F.; Dai, S. J. Mater. Chem. A 2018, 6, 11129. doi: 10.1039/C8TA01772G

  29. [29]

      Sarkar, A.; Wang, Q.; Schiele, A.; Chellali, M. R.; Bhattacharya, S. S.; Wang, D.; Brezesinski, T.; Hahn, H.; Velasco, L.; Breitung, B. Adv. Mater. 2019, 31, e1806236. doi: 10.1002/adma.201806236

  30. [30]

      Shi, Y. C.; Ni, N.; Ding, Q.; Zhao, X. F. J. Mater. Chem. A 2022, 10, 2256. doi: 10.1039/d1ta07275g

  31. [31]

      Yang, Q.; Wang, G. Q.; Wu, H. D.; Beshiwork, B. A.; Tian, D.; Zhu, S. Y.; Yang, Y.; Lu, X. Y.; Ding, Y. Z.; Ling, Y. H.; et al. J. Alloy. Compd. 2021, 872, 159633. doi: 10.1016/j.jallcom.2021.159633

  32. [32]

      He, F.; Zhou, Y.; Hu, T.; Xu, Y.; Hou, M.; Zhu, F.; Liu, D.; Zhang, H.; Xu, K.; Liu, M.; Chen, Y. Adv. Mater. 2023, 35, e2209469. doi: 10.1002/adma.202209469

  33. [33]

      Garcı́a-Muñoz, J. L.; Frontera, C.; Llobet, A.; Carrillo, A. E.; Caneiro, A.; Aranda, M. A. G.; Ritter, C.; Dooryee, E. Phys. B 2004, 350, e277. doi: 10.1016/j.physb.2004.03.069

  34. [34]

      Brinks, H. W.; Fjellvåg, H.; Kjekshus, A.; Hauback, B. C. J. Solid State Chem. 1999, 147, 464. doi: 10.1006/jssc.1999.8384

  35. [35]

      Guo, D.; Zhang, M.; Chen, Z.; Liu, X.-X. RSC Adv. 2018, 8, 33374. doi: 10.1039/C8RA07032F

  36. [36]

      Xin, W.-L.; Lu, K.-K.; Zhu, D.-R.; Zeng, H.-B.; Zhang, X.-J.; Marks, R.-S.; Shan, D. Electrochim. Acta 2019, 307, 375. doi: 10.1016/j.electacta.2019.03.196

  37. [37]

      Zhao, K.; Shen, Y.; Huang, Z.; He, F.; Wei, G. Q.; Zheng, A. Q.; Li, H. B.; Zhao, Z. L. J. Energy Chem. 2017, 26, 501. doi: 10.1016/j.jechem.2016.11.016

  38. [38]

      Sunarso, J.; Hashim, S. S.; Zhu, N.; Zhou, W. Prog. Energy Combust. Sci. 2017, 61, 57. doi: 10.1016/j.pecs.2017.03.003

  39. [39]

      Suntivich, J.; Hong, W. T.; Lee, Y.-L.; Rondinelli, J. M.; Yang, W.; Goodenough, J. B.; Dabrowski, B.; Freeland, J. W.; Shao-Horn, Y. J. Phys. Chem. C 2014, 118, 1856. doi: 10.1021/jp410644j

  40. [40]

      Miao, X.; Wu, L.; Lin, Y.; Yuan, X.; Zhao, J.; Yan, W.; Zhou, S.; Shi, L. Chem. Commun. 2019, 55, 1442. doi: 10.1039/c8cc08817a

  41. [41]

      Luo, Q. X.; Lin, D.; Zhan, W. Q.; Zhang, W. Q.; Tang, L. L.; Luo, J. J.; Gao, Z.; Jiang, P.; Wang, M.; Hao, L. Y.; et al. ACS Appl. Energy Mater. 2020, 3, 7149. doi: 10.1021/acsaem.0c01192

  42. [42]

      Grimaud, A.; Diaz-Morales, O.; Han, B.; Hong, W. T.; Lee, Y. L.; Giordano, L.; Stoerzinger, K. A.; Koper, M. T. M.; Shao-Horn, Y. Nat. Chem. 2017, 9, 457. doi: 10.1038/nchem.2695

  43. [43]

      Xi, X.; Liu, J. W.; Luo, W. Z.; Fan, Y.; Zhang, J. J.; Luo, J. L.; Fu, X. Z. Adv. Energy Mater. 2021, 11, 2102845. doi: 10.1002/aenm.202102845

  44. [44]

      Li, J. W.; Fu, Z. M.; Wei, B.; Su, C. X.; Yue, X.; Lü, Z. J. Mater. Chem. A 2020, 8, 18778. doi: 10.1039/d0ta04857g

  45. [45]

      Guan, F.; Zhang, X. M.; Song, Y. F.; Zhou, Y. J.; Bao, X. H. Chin. J. Catal. 2018, 39, 1484. doi: 10.1016/S1872-2067(18)63118-3

  46. [46]

      Zhang, X. M.; Song, Y. F.; Guan, F.; Zhou, Y. J.; Lv, H. F.; Wang, G. X.; Bao, X. H. J. Catal. 2018, 359, 8. doi: 10.1016/j.jcat.2017.12.027

  47. [47]

      Li, Q.; Wu, J. B.; Wu, T.; Jin, H. R.; Zhang, N.; Li, J.; Liang, W. X.; Liu, M. L.; Huang, L.; Zhou, J. Adv. Funct. Mater. 2021, 31, 2102002. doi: 10.1002/adfm.202102002

  48. [48]

      Song, Y. F.; Zhou, Z. W.; Zhang, X. M.; Zhou, Y. J.; Gong, H. M.; Lv, H. F.; Liu, Q. X.; Wang, G. X.; Bao, X. H. Angew. Chem. Int. Ed. 2019, 58, 4617. doi: 10.1002/anie.201814612

  49. [49]

      Wang, W. H.; Yang, Y.; Huan, D. M.; Wang, L. K.; Shi, N.; Xie, Y.; Xia, C. R.; Peng, R. R.; Lu, Y. L. J. Mater. Chem. A 2019, 7, 12538. doi: 10.1039/c9ta03099a

  50. [50]

      Ciucci, F.; Chen, C. Electrochim. Acta 2015, 167, 439. doi: 10.1016/j.electacta.2015.03.123

  51. [51]

      Saccoccio, M.; Wan, T. H.; Chen, C.; Ciucci, F. Electrochim. Acta 2014, 147, 470. doi: 10.1016/j.electacta.2014.09.058

  52. [52]

      Li, Y. H.; Li, Y.; Wan, Y. H.; Xie, Y.; Zhu, J. F.; Pan, H. B.; Zheng, X. S.; Xia, C. R. Adv. Energy Mater. 2019, 9, 1803156. doi: 10.1002/aenm.201803156

  53. [53]

      Lv, H. F.; Lin, L.; Zhang, X. M.; Song, Y. F.; Matsumoto, H.; Zeng, C. B.; Ta, N.; Liu, W.; Gao, D. F.; Wang, G. X.; et al. Adv. Mater. 2020, 32, e1906193. doi: 10.1002/adma.201906193

  54. [54]

      Song, Y. F.; Zhang, X. M.; Zhou, Y. J.; Lv, H. F.; Liu, Q. X.; Feng, W. F.; Wang, G. X.; Bao, X. H. J. Energy Chem. 2019, 35, 181. doi: 10.1016/j.jechem.2019.03.013

  55. [55]

      Zhang, X. M.; Song, Y. F.; Guan, F.; Zhou, Y. J.; Lv, H. F.; Liu, Q. X.; Wang, G. X.; Bao, X. H. J. Power Sources 2018, 400, 104. doi: 10.1016/j.jpowsour.2018.08.017

•