Crystal Structure and Electronic Transport Properties of Chemically Modified Layered Cobalt Oxides

• Project/Area Number: 18360308
• Research Category: Grant-in-Aid for Scientific Research (B)
• Allocation Type: Single-year Grants
• Section: 一般
• Research Field: Inorganic materials/Physical properties
• Research Institution: Tohoku University
• Principal Investigator: MIYAZAKI Yuzuru Tohoku University, 大学院・工学研究科, 准教授 (40261606)
• Co-Investigator(Kenkyū-buntansha): KAJITANI Tsuyoshi 東北大学, 大学院・工学研究科, 教授 (80134039) ; YUBUTA Kunio 東北大学, 金属材料研究所, 助教 (00302208)
• Project Period (FY): 2006 – 2008
• Project Status: Completed (Fiscal Year 2008)
• Budget Amount: ¥17,660,000 (Direct Cost: ¥15,200,000、Indirect Cost: ¥2,460,000); Fiscal Year 2008: ¥2,990,000 (Direct Cost: ¥2,300,000、Indirect Cost: ¥690,000); Fiscal Year 2007: ¥7,670,000 (Direct Cost: ¥5,900,000、Indirect Cost: ¥1,770,000); Fiscal Year 2006: ¥7,000,000 (Direct Cost: ¥7,000,000)
• Keywords: コバルト酸化物 / イオン交換 / 結晶構造 / 輸送特性 / 電荷秩序 / 複合結晶 / 格子ミスフィット / 超空間群 / 規則配列 / ミスフィット

Research Abstract

ナトリウムコバルト酸化物およびイオン交換法によりナトリウムをカルシウム、ストロンチウムおよびバリウムで置換した層状コバルト酸化物を合成し、これらの陽イオン組成と結晶構造および輸送特性の関係を詳細に調べた。ナトリウム系では、特定の組成において、ナトリウムの規則配列を有する相が発見され、その規則配列が磁性や電気抵抗に影響を及ぼすことが確認された。またイオン交換をした系においても特定の組成で陽イオンの規則配列が見出され、これらの知見を積極的に活用することで、優れた熱電材料を設計するための指針が得られた。

Research Products

• [Journal Article] Synthesis, Crystal Structure and Physical Properties of Layered Cobalt Oxide Ca_xCoO_2(x-0.47) (2009)
  • Author(s): Y. Miyazaki, X.Y. Huang, T. Kajiwara, H. Yamane, T. Kajitani
  • Journal Title: J.Ceram.Soc.Jpn 117 Pages: 42-46
  • NAID: 110007026737
  • Peer Reviewed
• [Journal Article] On the excess oxygen in four-layered rock-salt-type units of modulated thermoelectric Bi-Sr-(Co, Rh)-O compounds (2009)
  • Author(s): K. Yubuta
  • Journal Title: Journal of Electronic Materials 38(印刷中)
  • Peer Reviewed
• [Journal Article] Structure and High-Temperature Thermodectric Properties of the n-TypeLayered Oxide Ca_<2-x>Bi_<x-δ>MnO_<4-γ> (2009)
  • Author(s): F. Kawashima
  • Journal Title: Journal of Electronic Materials 38(印刷中)
  • Peer Reviewed
• [Journal Article] Synthesis, Crystal Structure and Physical Properties of Layered Cobalt Oxide Ca_xCoO_2 (x〜0.47) (2009)
  • Author(s): Y. Miyazaki
  • Journal Title: Journal of the Ceramics Society of Japan 117 Pages: 42-46
  • NAID: 110007026737
  • Peer Reviewed
• [Journal Article] Disorder-order transitions in Na_xCoO_2(x-0.58) (2008)
  • Author(s): D. Igarashi, Y. Miyazaki, T. Kajitani, K. Yubuta
  • Journal Title: Phys.Rev.B 78
  • Peer Reviewed
• [Journal Article] Electronic structure of Ca_3Co_4O_9 studied by photoemission spectroscopy : Phase separation and charge localization (2008)
  • Author(s): Y. Wakisaka
  • Journal Title: Physical Review B 78
  • Peer Reviewed
• [Journal Article] Disorder-order transitions in Na_xCo0_2 (x〜0.58) (2008)
  • Author(s): D. Igarashi
  • Journal Title: Physical Review B 78
  • Peer Reviewed
• [Journal Article] High-Resolution Electron Microscopy Study of [(Ca, B)_2Co0_3]_<0.62>Co0_2 (2008)
  • Author(s): K. Yubuta
  • Journal Title: Journal of the Physical Society of Japan 77
  • Peer Reviewed
• [Journal Article] Discommensurate Structure in [(Ca_<0.90>Sr_<0.10>)_2CoO_3]_<0.61>]CoO_2 (2008)
  • Author(s): K. Yubuta
  • Journal Title: Journal of the Physical Society of Japan 77
  • NAID: 110006781582
  • Peer Reviewed
• [Journal Article] Domain Structure of Misfit-layered Compounds in Bi-Ca-Co-O (2008)
  • Author(s): K. Yubuta
  • Journal Title: Journal of Flux Growth 3 Pages: 18-23
  • Peer Reviewed
• [Journal Article] Crystal Structure of Sr_<0.35>CoO_2Compound Studied by High-Resolution Electron Microscopy (2007)
  • Author(s): K. Yubuta, Y. Hasegawa, Y. Miyazaki, T. Kajitani
  • Journal Title: Jpn.J.Appl.Phys. 46 Pages: 712-715
  • NAID: 10018545510
  • Peer Reviewed
• [Journal Article] Superspace Group Approach to the Crystal Structure of Na_<0.5>CoO_2 (2007)
  • Author(s): D. Igarashi, Y. Miyazaki, K. Yubuta, T. Kajitani
  • Journal Title: Jpn.J.Appl.Phys. 46 Pages: 304-310
  • NAID: 10018705183
  • Peer Reviewed
• [Journal Article] Modulated structure of misfit-layered compound Bi_<2.12>Ba_<2.00>Rh_<1.95>O_x (2007)
  • Author(s): K. Yubuta
  • Journal Title: Philosophical Magazine 87 Pages: 2641-2646
  • Peer Reviewed
• [Journal Article] High-resolution microscopy study of misfit-layered Bi-based cobaltites (2007)
  • Author(s): K. Yubuta
  • Journal Title: Philosophical Magazine 87 Pages: 2663-2669
  • Peer Reviewed
• [Journal Article] High temperature thermoelectric properties of Ca_<1-x>Bi_xMn_<1-y>V_yO_<3-δ>(0〓x=y〓0.08) (2007)
  • Author(s): X. Y. Huang
  • Journal Title: Solid State Communications 145 Pages: 132-136
  • Peer Reviewed
• [Journal Article] Superspace Group Approach to the Crystal Structure of Na_<0.5>CoO_2 (2007)
  • Author(s): Dai Igarashi
  • Journal Title: Japanese Journal of Applied Physics 46・1 Pages: 304-310
• [Journal Article] Crystal Structure of Sr_<0.35>CoO_2 Compound Studied by High-Resolution Electron Microscopy (2007)
  • Author(s): Kunio Yubuta
  • Journal Title: Japanese Journal of Applied Physics 46・2 Pages: 712-715
  • NAID: 10018545510
• [Journal Article] Static and Dynamic Characteristics of Thermoelectric Ceramics (2007)
  • Author(s): Tsuyoshi Kajitani
  • Journal Title: Key Engineering Materials 336-338 Pages: 826-830
• [Journal Article] 層状コバルト酸化物の結晶構造と熱電特性 (2006)
  • Author(s): 宮崎譲、舟橋良次
  • Journal Title: セラミックス 41 Pages: 178-182
  • NAID: 10020525417
  • Peer Reviewed
• [Presentation] Mo置換したぺロブスカイト型CaMn_<1-x>MoxO_3の高温熱電特性 (2009)
  • Author(s): 川島史也
  • Organizer: 第56回応用物理学関係連合講演会
  • Place of Presentation: つくば
  • Year and Date: 2009-03-31
• [Presentation] [(Ca, Bi)_2CoO_3]_<0.62>CoO_2の高分解能電子顕微鏡観察 (2009)
  • Author(s): 湯蓋邦夫
  • Organizer: 第56回応用物理学関係連合講演会
  • Place of Presentation: つくば
  • Year and Date: 2009-03-31
• [Presentation] Aperiodic compounds as potential thermoelectric materials (Invited) (2009)
  • Author(s): Y. Miyazaki
  • Organizer: 33^<rd> Int'l Conf.and Expo.on Advanced Ceramics and Composites
  • Place of Presentation: Daytona Beach,FL,USA
  • Year and Date: 2009-01-22
• [Presentation] Aperiodic compounds as potential thermoelectric materials (2009)
  • Author(s): Y. Miyazaki
  • Organizer: 33^<rd> International Conference and Exposition on Advanced Ceramics and Composites
  • Place of Presentation: Daytona Beach(USA)
  • Year and Date: 2009-01-22
• [Presentation] Crystal Structure of K_xRhO_2 Single Crystal (2008)
  • Author(s): D. Igarashi
  • Organizer: The IUMRS International Conference in Asia 2008
  • Place of Presentation: 名古屋
  • Year and Date: 2008-12-11
• [Presentation] Na_xCoO_2におけるNa規則配列転移温度と組成の関係 (2008)
  • Author(s): 五十嵐大, 宮崎譲
  • Organizer: 応用物理学会東北支部第63回学術講演会
  • Place of Presentation: 仙台
  • Year and Date: 2008-12-04
• [Presentation] 層状酸化物Ca_2Mn_<1-x>Mo_xO_4の合成と熱電特性 (2008)
  • Author(s): 川島史也
  • Organizer: 応用物理学会東北支部第63回学術講演会
  • Place of Presentation: 仙台
  • Year and Date: 2008-12-04
• [Presentation] Effects of Na atom ordering on the physical properties in Na_<0.58>CoO_2 (2008)
  • Author(s): D. Igarashi, Y. Miyazaki
  • Organizer: 27^<th> Int'l Conf.on Thermoelectrics(ICT2008)
  • Place of Presentation: Corvallis,OR,USA
  • Year and Date: 2008-08-05
• [Presentation] Discommensuration of doped Co-121 (2008)
  • Author(s): T. Kaiitani
  • Organizer: International Conference on Thermoelectrics (ICT 2008)
  • Place of Presentation: Oregon (USA)
  • Year and Date: 2008-08-05
• [Presentation] High temperature thermoelectric properties of layered oxide Ca_<2-x>Bi_xMnO_4 (2008)
  • Author(s): F. Kawashima
  • Organizer: International Conference on Thermoelectrics (ICT 2008)
  • Place of Presentation: Oregon (USA)
  • Year and Date: 2008-08-05
• [Presentation] Effects of Na atom ordering on the physical properties in Na_<0.58>CoO_2 (2008)
  • Author(s): D. Igarashi
  • Organizer: International Conference on Thermoelectrics (ICT 2008)
  • Place of Presentation: Oregon (USA)
  • Year and Date: 2008-08-05
• [Presentation] Excess oxygen in Rock-Salt-type layers of misfit-layered Bi-based oxides (2008)
  • Author(s): K. Yubuta
  • Organizer: International Conference on Thermoelectrios (ICT 2008)
  • Place of Presentation: Oregon (USA)
  • Year and Date: 2008-08-05
• [Presentation] Aperiodic Cuprates and Cobaltates(Invited) (2008)
  • Author(s): Y. Miyazaki
  • Organizer: Solid State Chemistry : Past & Future
  • Place of Presentation: Birmingham,UK
  • Year and Date: 2008-04-18
• [Presentation] Aneriodic Cunrates and Cobaltates (2008)
  • Author(s): Y. Miyazaki
  • Organizer: Solid State Chemistry : Past & Future
  • Place of Presentation: Birmingham (UK)
  • Year and Date: 2008-04-18
• [Presentation] Elecronic structure and thermoelectric properties of delafossite-type oxide CuFeO_2 (2008)
  • Author(s): T. Nozaki
  • Organizer: Solid State Chemistry : Past & Future
  • Place of Presentation: Birmingham (UK)
  • Year and Date: 2008-04-18
• [Presentation] Preparation, crystal structure and physical properties of α'-Na_xCoO_2 (2008)
  • Author(s): Y. Miyazaki
  • Organizer: Zing Solid State Chemistry Conference
  • Place of Presentation: Cancun,Mexico
  • Year and Date: 2008-03-12
• [Presentation] Preparation, Crystal Structure and Physical Properties of α'‐Na_XCoO_2 (2008)
  • Author(s): Y. Miyazaki
  • Organizer: Zing Solid State Chemistry
  • Place of Presentation: Grand Oasis Resort Cancun,メキシコ
  • Year and Date: 2008-03-12
• [Presentation] Chemical tuning of the misfit-layered cobaltate [Ca_2CoO_3]_pCoO_2(Invited) (2008)
  • Author(s): Y. Miyazaki
  • Organizer: 32^<nd> Int'l Conf.and Expo.on Advanced Ceramics and Composites
  • Place of Presentation: Daytona Beach,FL,USA
  • Year and Date: 2008-01-31
• [Presentation] Chemical Tuning of the Misfit‐layered Cobaltate[Ca_2CoO_3]_pCoO_2 (2008)
  • Author(s): Y. Miyazaki
  • Organizer: 32nd International Conference & Exposition on Advanced Ceramics & Composites
  • Place of Presentation: Hilton Daytona Beach Resort & Ocean Center,米国
  • Year and Date: 2008-01-31
• [Presentation] The Effect of the Misfit Parameter on the Physical Properties of Misfit‐Layered Cobalt Oxides (2007)
  • Author(s): H. Abe
  • Organizer: 7th Pacific Rim Conference on Ceramic and Glass Technology
  • Place of Presentation: Shanghai International Con‐vention Center,中国
  • Year and Date: 2007-11-12
• [Presentation] Na_<0.58.CoO_2の中間規則相 (2007)
  • Author(s): 五十嵐大, 宮崎譲
  • Organizer: 日本物理学会第62回年次大会
  • Place of Presentation: 札幌
  • Year and Date: 2007-09-21
• [Presentation] Na_<0.58>CoO_2の中間規則相 (2007)
  • Author(s): 五十嵐大
  • Organizer: 日本物理学会第62回年次大会
  • Place of Presentation: 北海道大学
  • Year and Date: 2007-09-21
• [Presentation] 高配向層状コバルト酸化物の作製とその高温熱電特性 (2007)
  • Author(s): 生出 嘉
  • Organizer: 第68回応用物理学会学術講演会
  • Place of Presentation: 北海道工業大学
  • Year and Date: 2007-09-07
• [Presentation] The thermoelectric properties of α'-Na_xCoO_2 (2007)
  • Author(s): X.Y. Huang, Y. Miyazaki, T. Kajitani
  • Organizer: 26^<th> Int'l Conf.on Thermoelectrics(ICT2007)
  • Place of Presentation: Jeju,South Korea
  • Year and Date: 2007-06-05
• [Presentation] Triclinic Crystal Structure of[(Bi_<1-x>Co_x)_2(Sr_<1-y>Bi_y)_2 O_<4+δ>]_p[CoO_2]_2 with p=1.05 and δ=0.7 (2007)
  • Author(s): T. Kajitani
  • Organizer: 26th International Conference on Thermoelectrics
  • Place of Presentation: Shineville Luxury Resort Jeju,韓国
  • Year and Date: 2007-06-05
• [Presentation] The thermoelectric properties of α'‐Na_xCoO_2 (2007)
  • Author(s): X. Y. Huang
  • Organizer: 26th International Conference on Thermoelectrics
  • Place of Presentation: Shineville Luxury Resort Jeju,韓国
  • Year and Date: 2007-06-05
• [Presentation] High-resolution transmission electron microscopy study of[(Ca_<0.90>Sr_<0.10>)_2CoO_3]_<0.61>[CoO_2]single crystal (2007)
  • Author(s): K. Yubuta
  • Organizer: 26th International Conference on Thermoelectrics
  • Place of Presentation: Shineville Luxury Resort Jeju,韓国
  • Year and Date: 2007-06-04
• [Presentation] Preparation and high‐temperature thermoelectric properties of textured cobaltite ceramics (2007)
  • Author(s): Y. Oide
  • Organizer: 26th International Conference on Thermoelectrics
  • Place of Presentation: Shineville Luxury Resort Jeju,韓国
  • Year and Date: 2007-06-04
• [Presentation] Crystal structure of Na_<0.5>CoO_2 : Nearly a commensurate misfit-layered cobalt oxide (2006)
  • Author(s): D. Igarashi, Y. Miyazaki
  • Organizer: 25^<th> Int'l Conf.on Thermoelectrics(ICT2006)
  • Place of Presentation: Wien,Austria
  • Year and Date: 2006-08-08
• [Book] 熱電変換技術ハンドブック (2008)
  • Author(s): 宮崎譲
  • Publisher: (株)エヌ・ティー・エス
• [Book] 熱電変換技術ハンドブック (2008)
  • Author(s): 宮崎譲
  • Publisher: 株式会社エヌ・ティー・エス
• [Patent(Industrial Property Rights)] カルシウム・コバルト層状酸化物単結晶からなる熱電材料の製造方法 (2006)
  • Inventor(s): 黄向陽, 梶谷剛, 宮崎譲, 湯蓋邦夫
  • Industrial Property Rights Holder: 科学技術振興機構
  • Industrial Property Number: 2006-197490
  • Filing Date: 2006-07-19