Development of ion conducting membrane and electrocatalyst based on hydroxide nanosheets for efficient enery conversion

• Project/Area Number: 18H03869
• Research Category: Grant-in-Aid for Scientific Research (A)
• Allocation Type: Single-year Grants
• Section: 一般
• Review Section: Medium-sized Section 28:Nano/micro science and related fields
• Research Institution: National Institute for Materials Science
• Principal Investigator: 馬 仁志 国立研究開発法人物質・材料研究機構, 国際ナノアーキテクトニクス研究拠点, グループリーダー (90391218)
• Co-Investigator(Kenkyū-buntansha): 坂井 伸行 国立研究開発法人物質・材料研究機構, 国際ナノアーキテクトニクス研究拠点, 主任研究員 (70431822)
• Project Period (FY): 2018-04-01 – 2022-03-31
• Project Status: Granted (Fiscal Year 2020)
• Budget Amount: ¥44,200,000 (Direct Cost: ¥34,000,000、Indirect Cost: ¥10,200,000); Fiscal Year 2021: ¥6,760,000 (Direct Cost: ¥5,200,000、Indirect Cost: ¥1,560,000); Fiscal Year 2020: ¥8,190,000 (Direct Cost: ¥6,300,000、Indirect Cost: ¥1,890,000); Fiscal Year 2019: ¥13,000,000 (Direct Cost: ¥10,000,000、Indirect Cost: ¥3,000,000); Fiscal Year 2018: ¥16,250,000 (Direct Cost: ¥12,500,000、Indirect Cost: ¥3,750,000)
• Keywords: 水酸化物 / ナノシート / イオン伝導 / 電極触媒 / 燃料電池 / 水電解

Outline of Annual Research Achievements

本年度において、主に単層ナノシートの精密合成およびOH-伝導メカニズムの解明を中心に研究を進めてきた。その中で、微細加工技術により絶縁基板に吸着した単一ナノシートの上に微小電極を形成したデバイスを用い、温度・湿度の制御に伴うイオン伝導度、活性化エネルギーなどの変化を系統的に解析することに成功した。理論計算と連携しながら、ナノシートの金属組成や水酸基、表面吸着水などが水酸化物イオンの伝導挙動に及ぼす影響を明らかにし、ナノシート表面における2次元的高速伝導経路を提案した。
同時に、遷移金属水酸化物ナノシートをベースとし、ORR及びOERに高い活性及び安定性を示す複合ナノ触媒の創製を推進してきた。特異な二層構造（Double-layer）を持つ遷移金属水酸化物ナノシートを合成する新しい戦略を確立した。電荷中性のブルーサイト型水酸化物（Co-Fe、Co-Ni-Fe）にFeのモル組成比を1/6に固定し、トポケミカル酸化インターカレーションにより、ブルーサイト層とイオンを有する帯電層が交互に積層したSecond-staging構造が得らた。陰イオン交換処理後、平均厚さ1.9 nmのDouble-layerナノシートの剥離に成功した。電極触媒特性測定により、二層構造Co-Ni-Fe水酸化物ナノシートが優れたOER触媒活性を示すことを明らかにした。また、２次元ナノシート同士のヘテロ集積化プロセスにおいて、水酸化物ナノシートと酸化グラフェン、MoS2、酸化ルテニウムなどの電導性ナノシートとのハイブリッド化を試み、そのヘテロ界面におけるイオン・電子移動反応を能動的制御することによって、電極反応の大幅な高効率化に大きな前進を得た。

Current Status of Research Progress

2: Research has progressed on the whole more than it was originally planned.

Reason

ナノシート1枚における究極的なイオン伝導挙動を評価できたことともに、理論計算と連携して、伝導メカニズムを根底から追及できるようになった。ナノシートの金属組成や表面水酸基ネットワークなどの構造特徴が水酸化物イオンの伝導に果たす役割を解明することによって、最終的に２次元伝導機構の確立と高い伝導率を持つイオン伝導膜の創製に繋げる成果が得られたと言える。
遷移金属組成のチューニングは電極触媒の性能向上に対してきわめて有効であることを実証できた。二つ以上の3d遷移金属元素の間のイオン・電子移動を高度制御して高性能ナノ触媒の開発につながる設計概念、方法論を確立しつつある。引き続き、金属イオンの電子の数や配位環境、酸化状態及び表面酸素との結合、ヘテロ金属イオンの間の電荷移動などの能動制御を重点的に行い、触媒性能のさらなる向上を目指す。
上述のように、ナノシートを用いたイオン伝導膜及び貴金属フリー触媒の創製に向けて順調に進展していると考える。

Strategy for Future Research Activity

イオン伝導膜に応用するため、LDHナノシートの分散液を用いたマイクロスケールの薄膜やフィルムの調製を本格的に始める。水酸化物ナノシートをビニルアルコールなどのモノマーとの混合、重合させることにより、高分子骨格を有する複合ゾル・ゲルを調製し、無機ナノシート・有機樹脂複合膜の作製を引き続き試作する。複合膜内のナノシートの含有量調整およびナノシートと有機樹脂との間の相互作用を最適化することにより、優れた機械的性質・力学的特性を持つ厚さ数μm～数十μmの大面積（cmサイズ）イオン伝導膜の加工手法や作製プロセスを確立する。薄膜面内および膜面垂直の二方向に対してそれぞれイオン伝導特性を系統的に評価し、主要な伝導経路である膜面垂直方向において高いイオン伝導度の達成を目指す。
引き続き、層状複水酸化物の金属組成チューニングおよび配位環境の制御を重点的に行い、異なる金属組成や電荷密度を持つ新型層状複水酸化物の合成に挑戦する。合成した水酸化物ナノシートとグラフェン、MoS2ならびにMXeneなど２次元物質同士との超格子材料を構築し、電極触媒として貴金属代替可能なレベルの高性能を実現する。特に、超格子内部のヘテロ接合界面における電荷移動・分極は、隣接するナノシートの間に強い相互作用をもたらすため、電極反応中の電子移動および反応中間体の電子構造の調節に着目して、触媒特性評価とメカニズムの解明を進める。理論モデルを用いて、ヘテロ表面・界面に存在する電子・イオンの挙動をシミュレーションすることにより、ORR及びOER触媒反応素過程の推定と最適反応条件を理論的に導きだす。
このように開発したイオン伝導膜および電極触媒を膜ー電極集合体とし、燃料電池や水電解セルに組み立てて、発電試験を行うことを視野に入れて、全固体アルカリ燃料電池をはじめとするエネルギー変換の基盤技術の創出に繋げていく。

Research Products

• [Journal Article] Alternate Restacking of 2D CoNi Hydroxide and Graphene Oxide Nanosheets for Energetic Oxygen Evolution (2019)
  • Author(s): Jia Lulu、Wan Hao、Liu Xiaohe、Chen Gen、Zhang Ning、Li Junhui、Zhou Wei、Cao Yijun、Ma Renzhi、Qiu Guanzhou
  • Journal Title: ChemSusChem Volume: 12 Pages: 5274-5281
  • DOI: 10.1002/cssc.201902641
  • Peer Reviewed / Int'l Joint Research
• [Journal Article] Hybrid Nanostructures of Bimetallic NiCo Nitride/N-Doped Reduced Graphene Oxide as Efficient Bifunctional Electrocatalysts for Rechargeable Zn-Air Batteries (2019)
  • Author(s): He Yuanqing、Liu Xiaohe、Yan Ailing、Wan Hao、Chen Gen、Pan Jiangling、Zhang Ning、Qiu Tingsheng、Ma Renzhi、Qiu Guanzhou
  • Journal Title: ACS Sustainable Chemistry & Engineering Volume: 7 Pages: 19612-19620
  • DOI: 10.1021/acssuschemeng.9b04703
  • Peer Reviewed / Int'l Joint Research
• [Journal Article] Superionic conduction along ordered hydroxyl networks in molecular-thin nanosheets (2019)
  • Author(s): Sun Pengzhan、Chen Fashen、Zhou Wei、Liu Xiaohe、Ma Renzhi、Sasaki Takayoshi
  • Journal Title: Materials Horizons Volume: 6 Pages: 2087-2093
  • DOI: 10.1039/c9mh00549h
  • Peer Reviewed / Int'l Joint Research
• [Journal Article] Constructing Conductive Interfaces between Nickel Oxide Nanocrystals and Polymer Carbon Nitride for Efficient Electrocatalytic Oxygen Evolution Reaction (2019)
  • Author(s): Liao Chengan、Yang Baopeng、Zhang Ning、Liu Min、Chen Guoxin、Jiang Xiaoming、Chen Gen、Yang Junliang、Liu Xiaohe、Chan Ting‐Shan、Lu Ying‐Jui、Ma Renzhi、Zhou Wei
  • Journal Title: Advanced Functional Materials Volume: 29 Pages: 1904020-1904020
  • DOI: 10.1002/adfm.201904020
  • Peer Reviewed / Int'l Joint Research
• [Journal Article] Interface Modulation of Two-Dimensional Superlattices for Efficient Overall Water Splitting (2019)
  • Author(s): Xiong Pan、Zhang Xiuyun、Wan Hao、Wang Shijian、Zhao Yufei、Zhang Jinqiang、Zhou Dong、Gao Weicheng、Ma Renzhi、Sasaki Takayoshi、Wang Guoxiu
  • Journal Title: Nano Letters Volume: 19 Pages: 4518-4526
  • DOI: 10.1021/acs.nanolett.9b01329
  • Peer Reviewed / Int'l Joint Research
• [Journal Article] Activity enhancement of layered cobalt hydroxide nanocones by tuning interlayer spacing and phosphidation for electrocatalytic water oxidation in neutral solutions (2019)
  • Author(s): Qin Ruinan、Wan Hao、Liu Xiaohe、Chen Gen、Zhang Ning、Ma Renzhi、Qiu Guanzhou
  • Journal Title: Inorganic Chemistry Frontiers Volume: 6 Pages: 1744-1752
  • DOI: 10.1039/c9qi00453j
  • Peer Reviewed / Int'l Joint Research
• [Journal Article] Recent advances in developing high-performance nanostructured electrocatalysts based on 3d transition metal elements (2019)
  • Author(s): Wan Hao、Liu Xiaohe、Wang Haidong、Ma Renzhi、Sasaki Takayoshi
  • Journal Title: Nanoscale Horizons Volume: 4 Pages: 789-808
  • DOI: 10.1039/c8nh00461g
  • Peer Reviewed / Int'l Joint Research
• [Journal Article] Large-area graphene-nanomesh/carbon-nanotube hybrid membranes for ionic and molecular nanofiltration (2019)
  • Author(s): Yang Yanbing、Yang Xiangdong、Liang Ling、Gao Yuyan、Cheng Huanyu、Li Xinming、Zou Mingchu、Ma Renzhi、Yuan Quan、Duan Xiangfeng
  • Journal Title: Science Volume: 364 Pages: 1057-1062
  • DOI: 10.1126/science.aau5321
  • Peer Reviewed / Int'l Joint Research
• [Journal Article] Post-synthesis isomorphous substitution of layered Co-Mn hydroxide nanocones with graphene oxide as high-performance supercapacitor electrodes (2019)
  • Author(s): Zhang Dan、Wang Hao、Chen Gen、Wan Hao、Zhang Ning、Liu Xiaohe、Ma Renzhi
  • Journal Title: Nanoscale Volume: 11 Pages: 6165-6173
  • DOI: 10.1039/c8nr10473e
  • Peer Reviewed / Int'l Joint Research
• [Journal Article] Cobalt iron phosphide nanoparticles embedded within a carbon matrix as highly efficient electrocatalysts for the oxygen evolution reaction (2019)
  • Author(s): Han Jiang、Chen Gen、Liu Xiaohe、Zhang Ning、Liang Shuquan、Ma Renzhi、Qiu Guanzhou
  • Journal Title: Chemical Communications Volume: 55 Pages: 9212-9215
  • DOI: 10.1039/c9cc03117k
  • Peer Reviewed / Int'l Joint Research
• [Journal Article] Heterostructured NiFe oxide/phosphide nanoflakes for efficient water oxidation (2019)
  • Author(s): Yan Ailing、Wan Hao、Chen Gen、Zhang Ning、Ma Wei、Liu Xiaohe、Cao Yijun、Ma Renzhi
  • Journal Title: Dalton Transactions Volume: 48 Pages: 8442-8448
  • DOI: 10.1039/c9dt01275c
  • Peer Reviewed / Int'l Joint Research
• [Journal Article] 2D free‐standing nitrogen‐doped Ni‐Ni3S2@carbon nanoplates derived from metal-organic frameworks for enhanced oxygen evolution reaction (2019)
  • Author(s): Lin Yifan、Chen Gen、Wan Hao、Chen Fashen、Liu Xiaohe、Ma Renzhi
  • Journal Title: Small Volume: 15 Pages: 1900348-1900348
  • DOI: 10.1002/smll.201900348
  • Peer Reviewed / Int'l Joint Research
• [Journal Article] Progress and perspective on two-dimensional unilamellar metal oxide nanosheets and tailored nanostructures from them for electrochemical energy storage (2019)
  • Author(s): Xiong Pan、Ma Renzhi、Wang Guoxiu、Sasaki Takayoshi
  • Journal Title: Energy Storage Materials Volume: 19 Pages: 281-298
  • DOI: 10.1016/j.ensm.2018.12.011
  • Peer Reviewed / Int'l Joint Research
• [Journal Article] Recent progress in functionalized layered double hydroxides and their application in efficient electrocatalytic water oxidation (2019)
  • Author(s): Deng Xiaolong、Huang Jinzhao、Wan Hao、Chen Fashen、Lin Yifan、Xu Xijin、Ma Renzhi、Sasaki Takayoshi
  • Journal Title: Journal of Energy Chemistry Volume: 32 Pages: 93-104
  • DOI: 10.1016/j.jechem.2018.07.007
  • Peer Reviewed / Int'l Joint Research
• [Journal Article] In situ growth of metallic Ag0 intercalated CoAl layered double hydroxides as efficient electrocatalysts for the oxygen reduction reaction in alkaline solutions (2019)
  • Author(s): Deng Xiaolong、Huang Jinzhao、Chen Fashen、Wan Hao、Lin Yifan、Xu Xijin、Ma Renzhi、Sasaki Takayoshi
  • Journal Title: Dalton Transactions Volume: 48 Pages: 1084-1094
  • DOI: 10.1039/c8dt04610g
  • Peer Reviewed / Int'l Joint Research
• [Journal Article] Unilamellar Metallic MoS2/Graphene Superlattice for Efficient Sodium Storage and Hydrogen Evolution (2018)
  • Author(s): Xiong Pan、Ma Renzhi、Sakai Nobuyuki、Nurdiwijayanto Leanddas、Sasaki Takayoshi
  • Journal Title: ACS Energy Letters Volume: 3 Pages: 997-1005
  • DOI: 10.1021/acsenergylett.8b00110
  • Peer Reviewed
• [Journal Article] Liquid phase exfoliation of MoS2 assisted by formamide solvothermal treatment and enhanced electrocatalytic activity based on (H3Mo12O40P/MoS2)n multilayer structure (2018)
  • Author(s): Jinzhao Huang, Xiaolong Deng, Hao Wan, Fashen Chen, Yifan Lin, Xijin Xu, Renzhi Ma, Takayoshi Sasaki
  • Journal Title: ACS Sustainable Chemistry & Engineering Volume: 6 Pages: 5227-5237
  • DOI: 10.1021/acssuschemeng.7b04873
  • Peer Reviewed / Int'l Joint Research
• [Journal Article] Two-dimensional porous cuprous oxide nanoplatelets derived from metal-organic frameworks (MOFs) for efficient photocatalytic dye degradation under visible light (2018)
  • Author(s): Lin Yifan、Wan Hao、Chen Fashen、Liu Xiaohe、Ma Renzhi、Sasaki Takayoshi
  • Journal Title: Dalton Transactions Volume: 47 Pages: 7694-7700
  • DOI: 10.1039/c8dt01117f
  • Peer Reviewed / Int'l Joint Research
• [Journal Article] Rare Cobalt-Based Phosphate Nanoribbons with Unique 5-Coordination for Electrocatalytic Water Oxidation (2018)
  • Author(s): Wan Hao、Ma Renzhi、Liu Xiaohe、Pan Jiangling、Wang Haidong、Liang Shuquan、Qiu Guanzhou、Sasaki Takayoshi
  • Journal Title: ACS Energy Letters Volume: 3 Pages: 1254-1260
  • DOI: 10.1021/acsenergylett.8b00621
  • Peer Reviewed / Int'l Joint Research
• [Journal Article] Cobalt-doped Ni-Mn layered double hydroxide nanoplates as high-performance electrocatalyst for oxygen evolution reaction (2018)
  • Author(s): Wang Yi、Liu Xiaohe、Zhang Ning、Qiu Guanzhou、Ma Renzhi
  • Journal Title: Applied Clay Science Volume: 165 Pages: 277-283
  • DOI: 10.1016/j.clay.2018.07.036
  • Peer Reviewed / Int'l Joint Research
• [Journal Article] Synthesis and Substitution Chemistry of Redox-Active Manganese/Cobalt Oxide Nanosheets (2018)
  • Author(s): Sakai Nobuyuki、Fukuda Katsutoshi、Ma Renzhi、Sasaki Takayoshi
  • Journal Title: Chemistry of Materials Volume: 30 Pages: 1517-1523
  • DOI: 10.1021/acs.chemmater.7b04068
  • Peer Reviewed
• [Presentation] 2D Functional Nanosheets: Soft Chemical Synthesis, Hetero-assembly and Emergent Properties (2019)
  • Author(s): Ma Renzhi, Sasaki Takayoshi
  • Organizer: The 13th Pacific Rim Conference of Ceramic Societies (PACRIM13)
  • Int'l Joint Research / Invited
• [Presentation] Ion Conducting and Electrocatalytic Properties of LDH Nanosheets (2019)
  • Author(s): Sun Pengzhan, Chen Fashen, Ma Wei, Zhou Wei, Ma Renzhi, Sasaki Takayoshi
  • Organizer: The 13th Pacific Rim Conference of Ceramic Societies (PACRIM13)
  • Int'l Joint Research / Invited
• [Presentation] Exploration of 2D Nanosheets and Hetero-structured Composites with Emergent properties. (2019)
  • Author(s): Ma Renzhi, Sasaki Takayoshi
  • Organizer: The 4th International Symposium on Creation of Life Innovation Materials for Interdisciplinary and International Research Development
  • Int'l Joint Research / Invited
• [Presentation] Exploration of Single-layer Nanosheets and Hybrids for Emergent Functions (2019)
  • Author(s): Ma Renzhi, Sasaki Takayoshi
  • Organizer: The 8th Asian Conference on Colloid and Interface Science (ACCIS 2019)
• [Presentation] Exploration of 2D nanosheets for energy-related applications (2019)
  • Author(s): Ma Renzhi, Sasaki Takayoshi
  • Organizer: 5th International Symposium of Advanced Inorganic Materials
• [Presentation] Anion Conductors and Electrocatalysts based on 2D Nanosheets (2019)
  • Author(s): Ma Renzhi, Sasaki Takayoshi
  • Organizer: 2019 International Conference on Electrochemical Energy
• [Presentation] Exploration of 2D hydroxide nanosheets and their hetero-assemblies with emergent properties (2019)
  • Author(s): Ma Renzhi, Sasaki Takayoshi
  • Organizer: The 2nd International Symposium on Chemistry of Nanomaterials
• [Presentation] Exploration of Single-layer Nanosheets and Their Assemblies with Emergent Properties (2019)
  • Author(s): Ma Renzhi, Sasaki Takayoshi
  • Organizer: １＆２DM Conference & Exhibition
• [Presentation] Superlattice of CoNiFe LDH/Ruthenium Oxide Nanosheets as Efficient Electrocatalysts for Oxygen Evolution Reaction (2019)
  • Author(s): Lu Xueyi, Sakai Nobuyuki, Tang Daiming, Li Xinming, Taniguchi Takaaki, Ma Renzhi, Sasaki Takayoshi
  • Organizer: The 2nd International Symposium on Chemistry of Nanomaterials
  • Int'l Joint Research
• [Presentation] Superior Anionic Transport in 2D Hydroxide Nanosheets (2019)
  • Author(s): Sun Pengzhan, Chen Fashen, Zhou Wei, Ma Renzhi, Sasaki Takayoshi
  • Organizer: 日本化学会第99春季年会
• [Presentation] Superlattice Structured CoNiFe Layered Double Hydroxides/Ruthenium Oxide Nanosheets as Efficient Electrocatalysts for Oxygen Evolution Reaction (2019)
  • Author(s): Lu Xueyi, Sakai Nobuyuki, Tang Daiming, Li Xinming, Taniguchi Takaaki, Ma Renzhi, Sasaki Takayoshi
  • Organizer: 日本化学会第99春季年会
• [Presentation] Exploration of Single-layer Nanosheets and Their Assemblies with Emergent Properties (2019)
  • Author(s): Ma Renzhi, Sun Pengzhan, Ma Wei, Sasaki Takayoshi
  • Organizer: １＆２DM Conference & Exhibition
  • Int'l Joint Research / Invited
• [Presentation] Single-layer Nanosheets and their Assembly for Emergent Functions (2018)
  • Author(s): Ma Renzhi
  • Organizer: Asian Conference on Nanoscience and Nanotechnology 2018
  • Int'l Joint Research / Invited
• [Presentation] Solution-Based Lattice Engineering with 2D Oxide and Hydroxide Nanosheets (2018)
  • Author(s): Sasaki Takayoshi, Ebina Yasuo, Sakai Nobuo, Ma Renzhi, Osada Minoru
  • Organizer: 19th International Symposium on the Reactivity of Solids
  • Int'l Joint Research / Invited