先端イオンビーム技術に立脚したエネルギー変換材料の表面解析

• Project/Area Number: 13F03770
• Research Category: Grant-in-Aid for JSPS Fellows
• Allocation Type: Single-year Grants
• Section: 外国
• Research Field: 構造・機能材料
• Research Institution: Kyushu University
• Principal Investigator: 石原 達己 九州大学, カーボンニュートラル・エネルギー国際研究所, 教授 (80184555)
• Co-Investigator(Kenkyū-buntansha): TELLEZ-LOZANO HELENA 九州大学, カーボンニュートラル・エネルギー国際研究所, 外国人特別研究員 ; TELLEZ-LOZANO Helena カーボンニュートラル, エネルギー国際研究所, 外国人特別研究員
• Project Period (FY): 2013-04-01 – 2016-03-31
• Project Status: Completed (Fiscal Year 2015)
• Budget Amount: ¥2,300,000 (Direct Cost: ¥2,300,000); Fiscal Year 2015: ¥400,000 (Direct Cost: ¥400,000); Fiscal Year 2014: ¥1,100,000 (Direct Cost: ¥1,100,000); Fiscal Year 2013: ¥800,000 (Direct Cost: ¥800,000)
• Keywords: 表面濃縮 / LaCoO3 / 低エネルギーイオン散乱 / 水蒸気電解 / 空気極 / 低エネルギーイオン錯乱

Outline of Annual Research Achievements

本研究では表面へのSrOなどのアルカリ土類酸化物の濃縮現象について検討を行ってきた。最終年度の今年度は、引き続きLaCoO3系ペロブスカイト酸化物やSrTiO3の表面へのSrOの濃縮を検討するとともに、アルカリ土類を含まない空気極触媒について検討を開始した。
従来の検討から、La0.6Sr0.4CoO3の表面濃縮について検討してきたが、今年度はPLD法で作製した薄膜の表面濃縮を検討し、濃縮して析出したSrOは水で洗浄すると除去できるが、焼鈍により比較的短い時間で析出するので、単純に除去するのみでは表面濃縮の課題は解決できないことが分かった。また、表面近傍のCoの役割についても検討し、表面の酸素欠陥を通して、反応に関与する機構を示した。
SrTiO3について表面がSrOで覆われた際に酸素を活性化できる機構を検討し、表面の酸素欠陥を通して酸素分子が活性化できることがわかった。また、酸素分子から酸素原子への電荷移動を生じることを示した。
本研究では量子計算との併用により、活性の低いアルカリ土類酸化物が表面濃縮した空気極触媒での優れた酸素還元活性が維持される機構の解明を進めるとともに、遷移金属の反応への寄与について、酸素欠陥の重要性の指摘を行った。また、アルカリ土類を含まない空気極として、Pr2Co(Cu)O4などを提案し、その活性の検討を開始した。

Research Progress Status

27年度が最終年度であるため、記入しない。

Strategy for Future Research Activity

27年度が最終年度であるため、記入しない。

Research Products

• [Journal Article] Segregated chemistry and structure on (001) and (100) surfaces of (La1-xSrx)2CoO4 override the crystal anisotropy in oxygen exchange kinetics (2015)
  • Author(s): Y. Chen, H. Tellez, M. Burriel, F. Yang, N. Tsvetkov, Z. Cai, D.W. McComb, J.A. Kilner, B. Yildiz
  • Journal Title: Chemistry of Materials Volume: 27 Issue: 15 Pages: 5436-5450
  • DOI: 10.1021/acs.chemmater.5b02292
  • Peer Reviewed / Int'l Joint Research
• [Journal Article] Oxygen exchange and transport in dual phase ceramic composite electrodes (2015)
  • Author(s): J. Druce, H. Tellez, T. Ishihara, J.A. Kilner
  • Journal Title: Faraday Discussions Volume: 182 Pages: 271-288
  • DOI: 10.1039/c5fd00028a
  • Peer Reviewed / Int'l Joint Research / Acknowledgement Compliant
• [Journal Article] Relating surface chemistry and oxygen surface exchange in LnBaCo2O5-δ air electrodes (2015)
  • Author(s): Helena Tellez, John Druce, John A Kilner and Tatsumi Ishihara
  • Journal Title: Faraday Discussions Volume: 印刷中 Pages: 145-157
  • DOI: 10.1039/c5fd00027k
  • Peer Reviewed
• [Journal Article] Fundamental electrochemistry: general discussion (2015)
  • Author(s): M. Mogensen, R. Gorte, J. Vohs, I. Metcalfe, S.D. Ebbesen, S. McIntosh, S. Barnett, S.P. Jiang, M. Li, T. Ishihara, R. Merkle, J.B. Hansen, J. Druce, H. Tellez, G. Lindbergh, V. Birss, X. Yue, J. Hartvigsen, C. Graves, J. Irvine, B. Yildiz, R. Kee, D. Cumming
  • Journal Title: Faraday Discussions Volume: 182 Pages: 177-212
  • DOI: 10.1039/c5fd90073e
  • Peer Reviewed / Int'l Joint Research
• [Journal Article] Materials development: general discussion (2015)
  • Author(s): R. Gorte, J. Vohs, T.L. Skafte, R. Kee, J. Varcoe, I. Metcalfe, S.D. Ebbesen, G. Kim, D. Dong, S.P. Jiang, M. Li, T. Ishihara, J.B. Hansen, B. Molero-Sanchez, S. McIntosh, H. Tellez, et al.
  • Journal Title: Faraday Discussions Volume: 182 Pages: 307-328
  • DOI: 10.1039/c5fd90074c
  • Peer Reviewed / Int'l Joint Research
• [Journal Article] Surface chemistry of La0.6Sr0.4CoO3－δ thin films and its impact on the oxygen surface exchange resistance (2015)
  • Author(s): G.M. Rupp, H. Tellez, J. Druce, A. Limbeck, T. Ishihara, J. Kilner, J. Fleig
  • Journal Title: Journal of Materials Chemistry A Volume: 3 Issue: 45 Pages: 22759-22769
  • DOI: 10.1039/c5ta05279c
  • Peer Reviewed / Int'l Joint Research / Acknowledgement Compliant
• [Journal Article] Oxygen Activation and Dissociation on Transition Metal Free Perovskite Surfaces (2015)
  • Author(s): A. Staykov, H. Tellez, T. Akbay, J. Druce, T. Ishihara, J. Kilner
  • Journal Title: Chemistry of Materials Volume: 27 Issue: 24 Pages: 8273-8281
  • DOI: 10.1021/acs.chemmater.5b03263
  • Peer Reviewed / Int'l Joint Research / Acknowledgement Compliant
• [Journal Article] Surface Segregation and Inter-Diffusion of Cations and Impurities in Microelectrodes for Solid Oxide Fuel Cells and Electrolyzers (2015)
  • Author(s): H. Tellez, J. Druce, Y. Shi, M. Kubicek, N.J. Simrick, J.L.M. Rupp, T. Ishihara, J.A. Kilner
  • Journal Title: ECS Transactions Volume: 66 Issue: 2 Pages: 69-77
  • DOI: 10.1149/06602.0069ecst
  • Peer Reviewed / Int'l Joint Research / Acknowledgement Compliant
• [Journal Article] Surface Composition of Layered Ruddlesden-Popper Lan+1NinO3n+1 (n = 1, 2 and 3) Epitaxial Films (2015)
  • Author(s): K.-T. Wu, H. Tellez, J. Druce, M. Burriel, T. Ishihara, J.A. Kilner, S.J. Skinner
  • Journal Title: ECS Transactions Volume: 66 Issue: 2 Pages: 89-93
  • DOI: 10.1149/06602.0089ecst
  • Peer Reviewed / Int'l Joint Research / Acknowledgement Compliant
• [Journal Article] Surface Segregation in Solid Oxide Electrode Materials Occurring at Intermediate Temperatures (2015)
  • Author(s): J. Druce, H. Tellez, T. Ishihara, J.A. Kilner
  • Journal Title: ECS Transactions Volume: 66 Issue: 2 Pages: 61-68
  • DOI: 10.1149/06602.0061ecst
  • Peer Reviewed / Int'l Joint Research / Acknowledgement Compliant
• [Journal Article] Surface Composition and Oxygen Transport Properties of LSCF: From Bulk Ceramics to Devices (2015)
  • Author(s): J. Druce, H. Tellez, T. Ishihara, J.A. Kilner
  • Journal Title: ECS Transactions Volume: 68 Issue: 1 Pages: 557-567
  • DOI: 10.1149/06801.0557ecst
  • Peer Reviewed / Int'l Joint Research / Acknowledgement Compliant
• [Journal Article] Low energy ion scattering: surface preparation and analysis of Cu(In,Ga)Se2 for photovoltaic applications (2015)
  • Author(s): Helena Tellez, John Druce, Allen Hall, Tatsumi Ishihara, John Kilner and Angus Rockett
  • Journal Title: Progress in Photovoltaics: Research and Applications Volume: 印刷中 Issue: 10 Pages: 1219-1227
  • DOI: 10.1002/pip.2535
  • Peer Reviewed
• [Journal Article] Accurate and Precise Measurement of Oxygen Isotopic Fractions and Diffusion Profiles by Selective Attenuation of Secondary Ions (SASI) (2015)
  • Author(s): Helena Tellez, John Druce, Jong-Eun Hong, Tatsumi Ishihara, and John A. Kilner
  • Journal Title: Analytical Chemistry Volume: 87 Issue: 5 Pages: 2907-2915
  • DOI: 10.1021/ac504409x
  • Peer Reviewed / Acknowledgement Compliant
• [Journal Article] New Perspectives in Surface Analysis of Energy Materials by combined Time-of-Flight Secondary Ion Mass Spectrometry (ToF-SIMS) and High Sensitivity Low-Energy Ion Scattering (HS-LEIS) (2014)
  • Author(s): Helena Téllez, Ainara Aguadero, Tatsumi Ishihara, John Kilner, et. al
  • Journal Title: J Anal. At. Spec Volume: accepted Issue: 8 Pages: 1361-1370
  • DOI: 10.1039/c3ja50292a
  • Peer Reviewed
• [Journal Article] Surface Termination and Subsurface Restructuring of Perovskite-Based Solid Oxide Electrode Materials (2014)
  • Author(s): John Druce, Helena Tellez, Monica Burriel, Matthew D. Sharp, Lydia J. Fawcett, Stuart N. Cook, David S. McPhail, Tatsumi Ishihara, Hidde H. Brongersma and John A. Kilner
  • Journal Title: Energy and Environmental Science Volume: 7 Pages: 3593-3599
  • Peer Reviewed
• [Journal Article] Surface chemistry evolution in LnBaCo2O5+δ double perovskites for oxygen electrodes (2014)
  • Author(s): Helena Tellez, John Druce, Young-Wan Ju, John Kilner, Tatsumi Ishihara
  • Journal Title: International Ｊournal of hydrogen energy Volume: 39 Issue: 35 Pages: 20856-20863
  • DOI: 10.1016/j.ijhydene.2014.06.102
  • Peer Reviewed / Acknowledgement Compliant
• [Journal Article] Surface segregation and poisoning in materials for low-temperature SOFCs (2014)
  • Author(s): 2.John Druce, Helena Tellez, Junji Hyodo
  • Journal Title: MRS Bulletin Volume: 39 Issue: 9 Pages: 810-815
  • DOI: 10.1557/mrs.2014.170
  • Peer Reviewed
• [Journal Article] Probing Active Surfaces in Solid Oxide Fuel Cells and Electrolysers by Low Energy Ion Scattering (LEIS) (2013)
  • Author(s): J. A. Kilner, T. Ishihara, J. Druce, H. Téllez
  • Journal Title: 燃料電池 Volume: 13 Pages: 40-46
  • NAID: 40019848839
• [Presentation] Probing surfaces and interfaces in electrochemical energy conversion devices by LEIS and ToF-SIMS (2015)
  • Author(s): Helena Tellez, John Druce, Tatsumi Ishihara, John Kilner
  • Organizer: 16th European Conference on Applications of Surface and Interface Analysis (ECASIA’15)
  • Place of Presentation: Granada, Spain
  • Year and Date: 2015-09-28
  • Int'l Joint Research / Invited
• [Presentation] Laterally Resolved Surface Analyses of Solid Oxide Electrodes by Complimentary Ion Beam Techniques (2015)
  • Author(s): John Druce, Helena Tellez, Tatsumi Ishihara, John Kilner
  • Organizer: 16th European Conference on Applications of Surface and Interface Analysis (ECASIA’15)
  • Place of Presentation: Granada, Spain
  • Year and Date: 2015-09-28
  • Int'l Joint Research
• [Presentation] Surface Composition and Oxygen Transport Properties of LSCF: From Bulk Ceramics to Devices (2015)
  • Author(s): John Druce, Helena Tellez, Tatsumi Ishihara and John A. Kilner
  • Organizer: 14th International Symposium on Solid Oxide Fuel Cells (SOFC-XIV)
  • Place of Presentation: Glasgow, UK
  • Year and Date: 2015-07-26
  • Int'l Joint Research
• [Presentation] Oxygen exchange and transport in dual phase ceramic composite electrodes (2015)
  • Author(s): John Druce, Helena Tellez, Tatsumi Ishihara, John A. Kilner
  • Organizer: 14th International Symposium on Solid Oxide Fuel Cells (SOFC-XIV)
  • Place of Presentation: Glasgow, UK
  • Year and Date: 2015-07-26
  • Int'l Joint Research
• [Presentation] Relating surface chemistry and oxygen evolution in LnBaCo2O5+δ air electrodes (2015)
  • Author(s): Helena Tellez, John Druce, John A. Kilner and Tatsumi Ishihara
  • Organizer: Faraday Discussions: Solid Oxide Electrolysis Fuels and Feedstocks from Water and Air
  • Place of Presentation: York, UK
  • Year and Date: 2015-07-13
  • Int'l Joint Research
• [Presentation] Probing fast grain boundary diffusion by ToF-SIMS depth profiling with Selective Attenuation of Specific Secondary Ions (SASI) (2015)
  • Author(s): Helena Tellez, John Druce, Tatsumi Ishihara, John Kilner
  • Organizer: 17th Scientific International Symposium on SIMS and related techniques based on Ion-Solid Interactions (SISS-17)
  • Place of Presentation: Seikei University, Tokyo
  • Year and Date: 2015-06-25
  • Int'l Joint Research
• [Presentation] Low Energy Ion Scattering Studies of Segregation in Materials for Electrochemical Energy Conversion Devices (2015)
  • Author(s): John Druce, Helena Tellez, Tatsumi Ishihara, John Kilner
  • Organizer: 17th Scientific International Symposium on SIMS and related techniques based on Ion-Solid Interactions (SISS-17)
  • Place of Presentation: Seikei University, Tokyo
  • Year and Date: 2015-06-25
  • Int'l Joint Research
• [Presentation] Surface and Near-Surface Characterisation of Electroceramic Materials for Solid Oxide Electrode Surfaces: from bulk ceramics to real devices (2015)
  • Author(s): John A. Kilner, Helena Tellez, John Druce, Tatsumi Ishihara
  • Organizer: 14th International Conference of the European Ceramic Society (ECerS XIV)
  • Place of Presentation: Toledo, Spain
  • Year and Date: 2015-06-21
  • Int'l Joint Research / Invited
• [Presentation] Oxygen Exchange and Transport in Mixed Conducting Dual Phase Composites (2015)
  • Author(s): John Druce, Helena Tellez, Tatsumi Ishihara and John A. Kilner
  • Organizer: 20th International Conference on Solid State Ionics (SSI-20)
  • Place of Presentation: Keystone, Colorado, USA
  • Year and Date: 2015-06-14
  • Int'l Joint Research
• [Presentation] Accurate Measurement of Fast Grain Boundary Ionic Diffusion by ToF-SIMS Depth Profiling with Selective Attenuation of Specific Secondary Ions (SASI) (2015)
  • Author(s): Helena Tellez, John Druce, Tatsumi Ishihara and John Kilner
  • Organizer: 20th International Conference on Solid State Ionics (SSI-20)
  • Place of Presentation: Keystone, Colorado, USA
  • Year and Date: 2015-06-14
  • Int'l Joint Research
• [Presentation] Surface Chemistry of La0.6Sr0.4CoO3-δ Thin Films and Its Impact on the Oxygen Surface Exchange Resistance (2015)
  • Author(s): Ghislain M. Rupp, Helena Tellez, John Druce, Andreas Limbeck, Tatsumi Ishihara, John Kilner and Juergen Fleig
  • Organizer: 20th International Conference on Solid State Ionics (SSI-20)
  • Place of Presentation: Keystone, Colorado, USA
  • Year and Date: 2015-06-14
  • Int'l Joint Research
• [Presentation] Cation Surface Segregation and Composition Depth Profile Variations in Thin Films Of SOFC Cathode Materials Analysed by Low Energy Ion Scattering (2015)
  • Author(s): Jose Santiso, Helena Tellez-Lozano, Araceli Gutierrez-Llorente, James Zapata, Roberto Moreno, Jaume Roqueta, Nuria Bagues, Anna Magraso, Jose M. Caicedo, John Druce, John A. Kilner and Tatsumi Ishihara
  • Organizer: 20th International Conference on Solid State Ionics (SSI-20)
  • Place of Presentation: Keystone, Colorado, USA
  • Year and Date: 2015-06-14
  • Int'l Joint Research
• [Presentation] Surface Analysis of SOFC Cathode Degradation Using Low Energy Ion Scattering and In-Operando Atmospheres (2015)
  • Author(s): Mathew Niania, Samuel Cooper, Helena Tellez, John Druce, Stephen Skinner, Tatsumi Ishihara and John Kilner
  • Organizer: 20th International Conference on Solid State Ionics (SSI-20)
  • Place of Presentation: Keystone, Colorado, USA
  • Year and Date: 2015-06-14
  • Int'l Joint Research
• [Presentation] Oxygen diffusion/exchange processes in two-dimensional Ln2NiO4+δ (Ln=La, Pr, and Nd) single crystals: IEDP/LEIS measurements (2015)
  • Author(s): Jean-Marc Bassat, Helena Tellez, Monica Burriel, Remi Castaing, W. Paulus, P. Veber, Tatsumi Ishihara, John Kilner
  • Organizer: 20th International Conference on Solid State Ionics (SSI-20)
  • Place of Presentation: Keystone, Colorado, USA
  • Year and Date: 2015-06-14
  • Int'l Joint Research
• [Presentation] Surface Composition of Layered Ruddlesden-Popper Lan+1NinO3n+1 (n = 1, 2 and 3) Epitaxial Films (2015)
  • Author(s): Kuan-Ting Wu, Helena Tellez, John Druce, Monica Burriel, Tatsumi Ishihara, John Kilner and Stephen Skinner
  • Organizer: 227th ECS Meeting, Symposium I05: Solid-Gas Electrochemical Interfaces (SGEI 1)
  • Place of Presentation: Chicago, Illinois, USA
  • Year and Date: 2015-05-24
  • Int'l Joint Research
• [Presentation] Surface Segregation in Solid Oxide Electrode Materials Occurring at Intermediate Temperatures (2015)
  • Author(s): John Druce, Helena Tellez, Tatsumi Ishihara and John Kilner
  • Organizer: 227th ECS Meeting, Symposium I05: Solid-Gas Electrochemical Interfaces (SGEI 1)
  • Place of Presentation: Chicago, Illinois, USA
  • Year and Date: 2015-05-24
  • Int'l Joint Research
• [Presentation] Surface Segregation and Inter-Diffusion of Cations and Impurities in Microelectrodes for Solid Oxide Fuel Cells and Electrolysers (2015)
  • Author(s): Helena Tellez, John Druce, Yanuo Shi, Markus Kubicek, Neil Simrick, Jennifer Rupp, Tatsumi Ishihara, John Kilner
  • Organizer: 227th ECS Meeting, Symposium I05: Solid-Gas Electrochemical Interfaces (SGEI 1)
  • Place of Presentation: Chicago, Illinois, USA
  • Year and Date: 2015-05-24
  • Int'l Joint Research
• [Presentation] Cation depth profile evolution upon annealing times in thin epitaxial films of oxide perovskite materials explored by LEIS (2015)
  • Author(s): J. Santiso, H. Tellez, A. Gutierrez, J. Zapata, R. Moreno, J. Roqueta, J. Druce, T. Ishihara
  • Organizer: 2015 Spring Meeting European MRS
  • Place of Presentation: Lille, France
  • Year and Date: 2015-05-11
  • Int'l Joint Research
• [Presentation] Fast Kinetics of Surface Reconstruction and Its Implications for Oxygen Surface Exchange in Mixed Conducting Solid Oxide Electrodes (2014)
  • Author(s): Helena Tellez, John Druce, John Kilner, Tatsumi Ishihara
  • Organizer: 2014 E-MRS Fall Meeting & Exhibit
  • Place of Presentation: Sheraton Boston Hotel, Boston, USA
  • Year and Date: 2014-11-30 – 2014-12-05
• [Presentation] Characterisation of Photovoltaic CdS-CIGS Heterojunctions by Low Energy Ion Scattering (LEIS) Spectroscopy (2014)
  • Author(s): Helena Tellez, John Druce, Allen Hall, Tatsumi Ishihara, John Kilner, Angus Rockett
  • Organizer: 2014 E-MRS Fall Meeting & Exhibit
  • Place of Presentation: Sheraton Boston Hotel, Boston, USA
  • Year and Date: 2014-11-30 – 2014-12-05
• [Presentation] Relating Oxygen Transport Propertiesto Surface and Near-Surface Chemistryin Perovskite-based Solid Oxide Electrode Materials (2014)
  • Author(s): Tellez Helena, Druce John, 伊田進太郎, 石原達己, Kilner John
  • Organizer: 2014年電気化学秋季大会
  • Place of Presentation: 北海道大学高等教育推進機構（札幌市）
  • Year and Date: 2014-09-27 – 2014-09-28
• [Presentation] Blocking of electro-active surfaces in mixed ionic-electronic conductors studied by Low-Energy Ion Scattering (LEIS) (2014)
  • Author(s): H. Tellez, J. Druce, Y-W. Ju, M. Burriel, R. Castaing, J-M. Bassat, J.A. Kilner and T. Ishihara
  • Organizer: The 15th IUMRS-International Conference in Asia (IUMRS-ICA2014)
  • Place of Presentation: 福岡大学（福岡市）
  • Year and Date: 2014-08-24 – 2014-08-30
• [Presentation] Decrease of the electrochemically active surface in mixed ionic-electronic conductors (MIECs) by impurity segregation (2014)
  • Author(s): Helena Tellez, John Druce, Young-Wan Ju, Tatsumi Ishihara, John Kilner
  • Organizer: 11th EUROPEAN SOFC & SOE FORUM 2014
  • Place of Presentation: Kultur-und Kongresszentrum Luzern, Lucerne, Switzerland
  • Year and Date: 2014-07-01 – 2014-07-04
• [Presentation] Evidence for the formation of higher order Ruddlesden-Popper phases in thin film air electrodes by HS-LEIS (2014)
  • Author(s): Helena Tellez, Kuan-Ting Wu, Monica Burriel, Yan Chen, Bilge Yildiz, John Kilner, Stephen Skinner, Tatsumi Ishihara
  • Organizer: E-MRS 2014 Spring Meeting
  • Place of Presentation: Congress Center, Lille, France
  • Year and Date: 2014-05-26 – 2014-05-30
• [Presentation] Surface chemistry evolution in LnBaCo_2O_<5+□> double perovskites for oxygen electrodes (2014)
  • Author(s): Helena Téllez, John Druce, John Kilner, Tatsumi Ishihara.
  • Organizer: International Conference on Hydrogen Production
  • Place of Presentation: 九州大学(福岡)