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Sm3+,Sr2+共掺杂对CeO2基电解质性能影响的密度泛函理论+U计算

陈美娜 张蕾 高慧颖 宣言 任俊峰 林子敬

引用本文:
Citation:

Sm3+,Sr2+共掺杂对CeO2基电解质性能影响的密度泛函理论+U计算

陈美娜, 张蕾, 高慧颖, 宣言, 任俊峰, 林子敬

DFT+U calculation of Sm3+ and Sr2+ co-doping effect on performance of CeO2-based electrolyte

Chen Mei-Na, Zhang Lei, Gao Hui-Ying, Xuan Yan, Ren Jun-Feng, Lin Zi-Jing
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  • Sm3+,Sr2+共掺杂CeO2的离子电导率被证实可高达Sm3+掺杂CeO2离子电导率的近两倍,然而,共掺杂对CeO2电导率的作用机理尚不明确.本文利用第一性原理计算的密度泛函理论+U方法,对Sm3+和Sr2+共掺杂的CeO2进行了系统的研究,对比Sm3+或Sr2+单掺杂的CeO2体系,计算并分析了共掺杂体系的电子态密度、能带结构、氧空位形成能以及氧空位迁移能等微观属性.计算结果表明,Sm3+,Sr2+的共掺杂对CeO2基电解质性能的提高具有协同效应,二者的共掺杂不仅能协同抑制CeO2体系的电子电导率,还能在单掺杂CeO2的基础上进一步降低氧空位形成能,Sm3+的存在还有助于降低Sr2+对氧空位的俘获作用,而Sr2+的加入则能够在Sm3+掺杂CeO2的基础上进一步降低最低氧空位迁移能,爬坡式弹性能带方法计算表明共掺杂体系的氧空位迁移能最低可达0.314/0.295 eV,低于Sm3+掺杂CeO2的最低氧空位迁移能.研究揭示了Sm3+,Sr2+共掺杂对CeO2电导率的协同作用机理,对进一步研发其他高性能的共掺杂电解质材料具有重要的指导意义.
    Solid oxide fuel cells (SOFCs) have been attracting people's attention for their high energy conversion efficiency, good fuel compatibility, no precious metal catalysts, and pollution-free emissions. However, the high operating temperature (800-1200℃) of the traditional SOFC can reduce the long-term stability and cause the difficulties in either the selecting of material or the sealing of SOFC. Therefore, great efforts have been devoted to developing the intermediate temperature SOFC (IT-SOFC), which works at 600-800℃. In the IT-SOFC, the ionic conductivity of doped CeO2-based electrolyte has a significant advantage relative to that of the conventional yttria-stabilized zirconia (YSZ) electrolyte. For example, at 600℃, the ionic conductivity of Sm-doped CeO2 is 0.02 S/cm much higher than that of the traditional YSZ electrolyte (only 0.0032 S/cm). Therefore, the doped CeO2-based electrolyte is a very promising electrolyte for IT-SOFC.Recently, the co-doping of two different elements into CeO2 has become a hot research topic. The ionic conductivity of Sm3+ and Sr2+ co-doped CeO2 has proved to be nearly twice as high as that of Sm3+ doped CeO2 (SDC). However, the mechanism for the co-doping effect on the conductivity of CeO2 is not clear. In this paper, Sm3+ and Sr2+ co-doped CeO2 is systematically studied using the DFT+U method. The microscopic properties of the Sm3+ and Sr2+ co-doped CeO2 including electronic density of states, band structure, oxygen vacancy formation energy and oxygen vacancy migration energy and so on have been calculated and analyzed by comparing with those of the Sm3+ or Sr2+ single doped CeO2. The calculation results indicate that Sm3+ and Sr2+ co-doping has a synergistic effect on the performance improvement of CeO2-based electrolyte, which can not only suppress the electronic conductivity of doped CeO2 system, but also can reduce the oxygen vacancy formation energy on the basis of single doped CeO2. The existence of Sm3+ can help to reduce the trapping effect of Sr2+ on oxygen vacancies, meanwhile the addition of Sr2+ can further reduce the minimum oxygen vacancy migration energy on the basis of SDC. Calculations by the climbing image nudged elastic band (CINEB) method indicate that the oxygen vacancy migration energy of the co-doped system can reach as low as 0.314/0.295 eV, which is lower than the minimum oxygen vacancy migration energy of SDC. Our research reveals the synergistic mechanism for Sm3+ and Sr2+ co-doping effect on the conductivity of CeO2, which is of great instructive significance for the further research and development of other high-performance co-doped electrolyte materials in IT-SOFC.
      通信作者: 陈美娜, mnchen@sdnu.edu.cn
    • 基金项目: 国家自然科学基金(批准号:51602183)、山东省自然科学基金(批准号:ZR2014BP003)、中国博士后科学基金(批准号:2015M572074)和山东师范大学本科生科研基金项目(批准号:2017BKSKY35)资助的课题.
      Corresponding author: Chen Mei-Na, mnchen@sdnu.edu.cn
    • Funds: Project supported by National Natural Science Foundation of China (Grant No. 51602183), the Shandong Provincial Natural Science Foundation, China (Grant No. ZR2014BP003), the China Postdoctoral Science Foundation (Grant No. 2015M572074), and the Undergraduate Scientific Research Foundation of Shandong Normal University, China (Grant No. 2017BKSKY35).
    [1]

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    Maheshwari A, Wiemhfer H D 2015 Ceram. Int. 41 9122

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    Baqu L, Caneiro A, Moreno M S, Serquis A 2008 Electrochem. Commun. 10 1905

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    Shi F, Song X P 2010 Int. J. Hydrogen Energ. 35 10620

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    Tao Z T, Ding H P, Chen X H, Hou G H, Zhang Q F, Tang M, Gu W 2016 J. Alloy. Compd. 663 750

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    Peng R R, Xia C R, Fu Q X, Meng G Y, Peng D K 2002 Mater. Lett. 56 1043

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    Shi F, Xiao H T 2013 Int. J. Hydrogen Energ. 38 2318

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    Chen L J, Tang Y H, Cui L X, Ouyang C Y, Shi S Q 2013 J. Power Sources 234 69

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    Cui L X, Tang Y H, Zhang H, Hector Jr L G, Ouyang C Y, Shi S Q, Li H, Chen L 2012 Chem. Chem. Phys. 14 1923

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    Shi S Q, Ke X Z, Ouyang C Y, Zhang H, Ding H C, Tang Y H, Zhou W W, Li P J, Lei M S, Tang W H 2009 J. Power Sources 194 830

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    Shi S Q, Tang Y H, Ouyang C Y, Cui L X, Xin X G, Li P J, Zhou W W, Zhang H, Lei M S, Chen L Q 2010 J. Phys. Chem. Solids 71 788

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    Li P J, Zhou W W, Tang Y H, Zhang H, Shi S Q 2010 Acta Phys. Sin. 59 3426 (in Chinese)[李沛娟, 周薇薇, 唐元昊, 张华, 施思齐 2010 物理学报 59 3426]

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    Zha S W, Xia C R, Meng G Y 2003 J. Power Sources 115 44

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    Nilsson J O, Vekilova O Y, Hellman O, Klarbring J, Simak S I, Skorodumova N V 2016 Phys. Rev. B 93 024102

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    Guo C, Wei S X, Zhou S N, Zhang T, Wang Z J, Ng S P, Lu X P, Wu C M L, Guo W Y 2017 ACS Appl. Mater. Inter. 9 26107

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    Tang Y H, Zhang H, Guan C M, Shen J Q, Shi S Q, Tang W H 2012 Sci. Sin.-Phys. Mech. Astron. 42 914 (in Chinese)[唐元昊, 张华, 管春梅, 沈静琴, 施思齐, 唐为华 2012 中国科学:物理学 力学 天文学 42 914]

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    Fu Z M, Sun Q, Ma D W, Zhang N, An Y P, Yang Z X 2017 Appl. Phys. Lett. 111 023903

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    [22]

    Tang Y H, Zhang H, Cui L X, Ouyang C Y, Shi S Q, Tang W H, Li H, Lee J S, Chen L Q 2010 Phys. Rev. B 82 125104

    [23]

    Xiong Y P, Yamaji K, Horita T, Sakai N, Yokokawa H 2004 J. Electrochem. Soc. 151 A407

    [24]

    Yoshida H, Inagaki T, Miura K, Inaba M, Ogumi Z 2003 Solid State Ionics 160 109

    [25]

    Zhang D S, Qian Y L, Shi L Y, Mai H L, Gao R H, Zhang J P, Yu W J, Cao W G 2012 Catal. Commun. 26 164

    [26]

    Zhang T S, Hing P, Huang H T, Kilner J 2002 J. Mater. Sci. 37 997

    [27]

    Singh P, Hegde M 2010 Cryst. Growth Des. 10 2995

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    Nakayama M, Martin M 2009 Phys. Chem. Chem. Phys. 11 3241

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    Yahiro H, Eguchi K, Arai H 1989 Solid State Ionics 36 71

    [30]

    Ou D R, Mori T, Ye F, Zou J, Auchterlonie G, Drennan J 2008 Phys. Rev. B 77 024108

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    Kashyap D, Patro P K, Lenka R K, Mahata T, Sinha P K 2014 Ceram. Int. 40 11869

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    Jaiswal N, Upadhyay S, Kumar D, Parkash O 2014 Int. J. Hydrogen Energ. 39 543

    [33]

    Yamamura H, Katoh E, Ichikawa M, Kakinuma K, Mori T, Haneda H 2000 Electrochemistry 68 455

    [34]

    Ji Y, Liu J, He T M, Wang J X, Su W H 2005 J. Alloy. Compd. 389 317

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    Banerjee S, Devi P S, Topwal D, Mandal S, Menon K 2007 Adv. Funct. Mater. 17 2847

    [36]

    Cioateră N, Parvulescu V, Rolle A, Vannier R 2009 Solid State Ionics 180 681

    [37]

    Kasse R M, Nino J C 2013 J. Alloy. Compd. 575 399

    [38]

    Yoshida H, Deguchi H, Miura K, Horiuchi M, Inagaki T 2001 Solid State Ionics 140 191

    [39]

    Burbano M, Nadin S, Marrocchelli D, Salanne M, Watson G W 2014 Phys. Chem. Chem. Phys. 16 8320

    [40]

    Andersson D A, Simak S I, Skorodumova N V, Abrikosov I A, Johansson B 2006 Proc. Natl. Acad. Sci. USA 103 3518

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    Alaydrus M, Sakaue M, Aspera S M, Wungu T D, Linh T P, Kasai H, Ishihara T, Mohri T 2013 J. Phys.:Condens. Mater. 25 225401

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    Kresse G, Furthmller J 1996 Phys. Rev. B 54 11169

    [43]

    Blchl P E 1994 Phys. Rev. B 50 17953

    [44]

    Perdew J P, Burke K, Ernzerhof M 1996 Phys. Rev. Lett. 77 3865

    [45]

    Nolan M, Grigoleit S, Sayle D C, Parker S C, Watson G W 2005 Surf. Sci. 576 217

    [46]

    Feng J, Xiao B, Wan C, Qu Z, Huang Z, Chen J, Zhou R, Pan W 2011 Acta Mater. 59 1742

    [47]

    Henkelman G, Uberuaga B P, Jnsson H 2000 J. Chem. Phys. 113 9901

    [48]

    Gerward L, Olsen J S, Petit L, Vaitheeswaran G, Kanchana V, Svane A 2005 J. Alloy. Compd. 400 56

    [49]

    Lucid A K, Keating P R, Allen J P, Watson G W 2016 J. Phys. Chem. C 120 23430

  • [1]

    Steele B 2000 Solid State Ionics 129 95

    [2]

    Maheshwari A, Wiemhfer H D 2015 Ceram. Int. 41 9122

    [3]

    Shi F 2010 Int. J. Hydrogen Energ. 35 10556

    [4]

    Baqu L, Caneiro A, Moreno M S, Serquis A 2008 Electrochem. Commun. 10 1905

    [5]

    Shi F, Song X P 2010 Int. J. Hydrogen Energ. 35 10620

    [6]

    Tao Z T, Ding H P, Chen X H, Hou G H, Zhang Q F, Tang M, Gu W 2016 J. Alloy. Compd. 663 750

    [7]

    Peng R R, Xia C R, Fu Q X, Meng G Y, Peng D K 2002 Mater. Lett. 56 1043

    [8]

    Shi F, Xiao H T 2013 Int. J. Hydrogen Energ. 38 2318

    [9]

    Chen L J, Tang Y H, Cui L X, Ouyang C Y, Shi S Q 2013 J. Power Sources 234 69

    [10]

    Cui L X, Tang Y H, Zhang H, Hector Jr L G, Ouyang C Y, Shi S Q, Li H, Chen L 2012 Chem. Chem. Phys. 14 1923

    [11]

    Shi S Q, Ke X Z, Ouyang C Y, Zhang H, Ding H C, Tang Y H, Zhou W W, Li P J, Lei M S, Tang W H 2009 J. Power Sources 194 830

    [12]

    Shi S Q, Tang Y H, Ouyang C Y, Cui L X, Xin X G, Li P J, Zhou W W, Zhang H, Lei M S, Chen L Q 2010 J. Phys. Chem. Solids 71 788

    [13]

    Tang Y H, Zhang H, Cui L X, Ouyang C Y, Shi S Q, Tang W H, Li H, Chen L Q 2012 J. Power Sources 197 28

    [14]

    Li P J, Zhou W W, Tang Y H, Zhang H, Shi S Q 2010 Acta Phys. Sin. 59 3426 (in Chinese)[李沛娟, 周薇薇, 唐元昊, 张华, 施思齐 2010 物理学报 59 3426]

    [15]

    Bowman W J, Zhu J, Sharma R, Crozier P A 2015 Solid State Ionics 272 9

    [16]

    Zha S W, Xia C R, Meng G Y 2003 J. Power Sources 115 44

    [17]

    Nilsson J O, Vekilova O Y, Hellman O, Klarbring J, Simak S I, Skorodumova N V 2016 Phys. Rev. B 93 024102

    [18]

    Guo C, Wei S X, Zhou S N, Zhang T, Wang Z J, Ng S P, Lu X P, Wu C M L, Guo W Y 2017 ACS Appl. Mater. Inter. 9 26107

    [19]

    Tang Y H, Zhang H, Guan C M, Shen J Q, Shi S Q, Tang W H 2012 Sci. Sin.-Phys. Mech. Astron. 42 914 (in Chinese)[唐元昊, 张华, 管春梅, 沈静琴, 施思齐, 唐为华 2012 中国科学:物理学 力学 天文学 42 914]

    [20]

    Fu Z M, Sun Q, Ma D W, Zhang N, An Y P, Yang Z X 2017 Appl. Phys. Lett. 111 023903

    [21]

    Mogensen M, Sammes N M, Tompsett G A 2000 Solid State Ionics 129 63

    [22]

    Tang Y H, Zhang H, Cui L X, Ouyang C Y, Shi S Q, Tang W H, Li H, Lee J S, Chen L Q 2010 Phys. Rev. B 82 125104

    [23]

    Xiong Y P, Yamaji K, Horita T, Sakai N, Yokokawa H 2004 J. Electrochem. Soc. 151 A407

    [24]

    Yoshida H, Inagaki T, Miura K, Inaba M, Ogumi Z 2003 Solid State Ionics 160 109

    [25]

    Zhang D S, Qian Y L, Shi L Y, Mai H L, Gao R H, Zhang J P, Yu W J, Cao W G 2012 Catal. Commun. 26 164

    [26]

    Zhang T S, Hing P, Huang H T, Kilner J 2002 J. Mater. Sci. 37 997

    [27]

    Singh P, Hegde M 2010 Cryst. Growth Des. 10 2995

    [28]

    Nakayama M, Martin M 2009 Phys. Chem. Chem. Phys. 11 3241

    [29]

    Yahiro H, Eguchi K, Arai H 1989 Solid State Ionics 36 71

    [30]

    Ou D R, Mori T, Ye F, Zou J, Auchterlonie G, Drennan J 2008 Phys. Rev. B 77 024108

    [31]

    Kashyap D, Patro P K, Lenka R K, Mahata T, Sinha P K 2014 Ceram. Int. 40 11869

    [32]

    Jaiswal N, Upadhyay S, Kumar D, Parkash O 2014 Int. J. Hydrogen Energ. 39 543

    [33]

    Yamamura H, Katoh E, Ichikawa M, Kakinuma K, Mori T, Haneda H 2000 Electrochemistry 68 455

    [34]

    Ji Y, Liu J, He T M, Wang J X, Su W H 2005 J. Alloy. Compd. 389 317

    [35]

    Banerjee S, Devi P S, Topwal D, Mandal S, Menon K 2007 Adv. Funct. Mater. 17 2847

    [36]

    Cioateră N, Parvulescu V, Rolle A, Vannier R 2009 Solid State Ionics 180 681

    [37]

    Kasse R M, Nino J C 2013 J. Alloy. Compd. 575 399

    [38]

    Yoshida H, Deguchi H, Miura K, Horiuchi M, Inagaki T 2001 Solid State Ionics 140 191

    [39]

    Burbano M, Nadin S, Marrocchelli D, Salanne M, Watson G W 2014 Phys. Chem. Chem. Phys. 16 8320

    [40]

    Andersson D A, Simak S I, Skorodumova N V, Abrikosov I A, Johansson B 2006 Proc. Natl. Acad. Sci. USA 103 3518

    [41]

    Alaydrus M, Sakaue M, Aspera S M, Wungu T D, Linh T P, Kasai H, Ishihara T, Mohri T 2013 J. Phys.:Condens. Mater. 25 225401

    [42]

    Kresse G, Furthmller J 1996 Phys. Rev. B 54 11169

    [43]

    Blchl P E 1994 Phys. Rev. B 50 17953

    [44]

    Perdew J P, Burke K, Ernzerhof M 1996 Phys. Rev. Lett. 77 3865

    [45]

    Nolan M, Grigoleit S, Sayle D C, Parker S C, Watson G W 2005 Surf. Sci. 576 217

    [46]

    Feng J, Xiao B, Wan C, Qu Z, Huang Z, Chen J, Zhou R, Pan W 2011 Acta Mater. 59 1742

    [47]

    Henkelman G, Uberuaga B P, Jnsson H 2000 J. Chem. Phys. 113 9901

    [48]

    Gerward L, Olsen J S, Petit L, Vaitheeswaran G, Kanchana V, Svane A 2005 J. Alloy. Compd. 400 56

    [49]

    Lucid A K, Keating P R, Allen J P, Watson G W 2016 J. Phys. Chem. C 120 23430

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    [20] 徐任信, 陈 文, 周 静. 聚合物电导率对0-3型压电复合材料极化性能的影响. 物理学报, 2006, 55(8): 4292-4297. doi: 10.7498/aps.55.4292
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出版历程
  • 收稿日期:  2017-12-26
  • 修回日期:  2018-02-02
  • 刊出日期:  2019-04-20

Sm3+,Sr2+共掺杂对CeO2基电解质性能影响的密度泛函理论+U计算

  • 1. 山东师范大学物理与电子科学学院, 济南 250358;
  • 2. 中国科学技术大学物理系, 合肥 230026
  • 通信作者: 陈美娜, mnchen@sdnu.edu.cn
    基金项目: 国家自然科学基金(批准号:51602183)、山东省自然科学基金(批准号:ZR2014BP003)、中国博士后科学基金(批准号:2015M572074)和山东师范大学本科生科研基金项目(批准号:2017BKSKY35)资助的课题.

摘要: Sm3+,Sr2+共掺杂CeO2的离子电导率被证实可高达Sm3+掺杂CeO2离子电导率的近两倍,然而,共掺杂对CeO2电导率的作用机理尚不明确.本文利用第一性原理计算的密度泛函理论+U方法,对Sm3+和Sr2+共掺杂的CeO2进行了系统的研究,对比Sm3+或Sr2+单掺杂的CeO2体系,计算并分析了共掺杂体系的电子态密度、能带结构、氧空位形成能以及氧空位迁移能等微观属性.计算结果表明,Sm3+,Sr2+的共掺杂对CeO2基电解质性能的提高具有协同效应,二者的共掺杂不仅能协同抑制CeO2体系的电子电导率,还能在单掺杂CeO2的基础上进一步降低氧空位形成能,Sm3+的存在还有助于降低Sr2+对氧空位的俘获作用,而Sr2+的加入则能够在Sm3+掺杂CeO2的基础上进一步降低最低氧空位迁移能,爬坡式弹性能带方法计算表明共掺杂体系的氧空位迁移能最低可达0.314/0.295 eV,低于Sm3+掺杂CeO2的最低氧空位迁移能.研究揭示了Sm3+,Sr2+共掺杂对CeO2电导率的协同作用机理,对进一步研发其他高性能的共掺杂电解质材料具有重要的指导意义.

English Abstract

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