Future Outlook

AEMs containing fluorenylidene biphenylene showed water retentive property and improved hydroxide conductivity and mechanical stability in humidified conditions. In addition, the polymer components of fluorene and alkylene groups have chemical stability in alkaline solution. However, these profiles have been inadequate yet for operating conditions.

In the future, alternative stable cationic groups are required, then, in order to improve performance, water management in less swelling is important. I recommend the following structure as AEM copolymer backbone components; bulky structure such as polycyclic aromatic compound for hydrophilic scaffolds, having crystallinity structure such as aliphatic or functionalized aliphatic groups for polymer main chain. These properties of QPA membrane seem promising for practical application in energy devices such as alkaline fuel cells and water electrolysis.

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List of Publications Journals

1. Anion Conductive Aromatic Polymers Containing Fluorenyl Groups: Effect of the Position and Number of Ammonium Groups.

M Shimada; S Shimada; J Miyake; M Uchida; K Miyatake J. Polym. Sci., Part A: Polym. Chem., 54, 935. (October 2016)

2. Anion Conductive Polymers Containing Aliphatic and Ammonium-functionalized Fluorene Groups.

M Shimada, R Akiyama, H Ono, J Miyake, and K Miyatake Chem. Lett.DOI:1 0.1246/cl.161073

3. Aromatic Copolymers Containing Ammonium-Functionalized Oligophenylene Moieties as Highly Anion Conductive Membranes.

N Yokota, M Shimada, H Ono, R Akiyama, E Nishino, K Asazawa, J Miyake, M Watanabe, and K Miyatake

Macromolecules 2014, 47, 8238−8246

4. Effect of Surface Ion Conductivity of Anion Exchange Membranes on Fuel Cell Performance.

M Hara, T Kimura, T Nakamura, M Shimada, H Ono, S Shimada, K Miyatake, M Uchida, J Inukai, and M Watanabe

Langmuir 2016, 32, 9557−9565

5. Anion-exchange Membranes Containing Fluorinated Poly(arylene ether)s: Properties and Application in Pt-free Hydrazine Fuel Cell.

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E Nishino, J Yamada, K Asazawa, S Yamaguchi, M Shimada, J Miyake, and K Miyatake

Chem. Lett., 2016, 45 (6) p.664–666

Patents

1. Anion exchange resin, electrolyte layer for fuel cell, binder for forming electrode catalyst layer, cell electrode catalyst layer, and fuel cell.

E Nishino, K Asazawa, K Miyatake, M Watanabe, N Yokota, M Shimada, and Y Yamamoto.

Japan Patent JP5972861B, PCT WO2014-050928A1.

2. Anion exchange resin, electrolyte layer for fuel cell, fuel cell, and method of manufacturing anion exchange resin.

E Nishino, K Asazawa, M Watanabe, K Miyatake, M Uchida, J Miyake, N Yokota, M Shimada.

Japan Patent JP2016-033199A.

3. Anion exchange resin, anion exchange membrane for fuel cell, binder for forming electrode catalyst layer, cell electrode catalyst layer, and fuel cell.

N Yokota, M Shimada, K Miyatake, M Watanabe, J Miyake, E Nishino, and K Asazawa.

Japan Patent JP2015-174956A, PCT WO2015-141450A1.

4. Anion exchange resin, anion exchange membrane for fuel cell, binder for forming electrode catalyst layer, cell electrode catalyst layer, and fuel cell.

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N Yokota, M Shimada, K Miyatake, M Watanabe, J Miyake, E Nishino, and K Asazawa.

Japan Patent JP2016-196664A, PCT WO2015-141450A1.

5. Anion exchange resin, anion exchange membrane for fuel cell, binder for forming electrode catalyst layer, cell electrode catalyst layer, and fuel cell.

M Shimada, N Yokota, K Miyatake, M Watanabe, J Miyake, H Ono, E Nishino, and K Asazawa.

Japan Patent JP5960763B, PCT WO2016-027902A1.

6. Cation exchange resin, cation exchange membrane, and fuel cell.

K Miyatake, M Uchida, J Miyake, T Mochizuki, H Ono, M Shimada, N Yokota, and N Yoshimura.

Japan Patent application No.JP2015-134000, PCT application No.JP2016-069364.

7. Anion exchange resin, method of manufacturing anion exchange resin, anion exchange membrane for fuel cell, binder for forming electrode catalyst layer, cell electrode catalyst layer, and fuel cell.

K Miyatake, J Miyake, H Ono, M Shimada, N Yokota, N Yoshimura, E Nishino, and K Asazawa.

Japan Patent application No.JP2015-186152, PCT application No.JP2016-077610.

8. Anion exchange resin, anion exchange membrane for fuel cell, binder for forming electrode catalyst layer, cell electrode catalyst layer, and fuel cell.

K Miyatake, J Miyake, H Ono, M Shimada, N Yokota, N Yoshimura, K Asazawa, and E Nishino. PREPARING

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Meeting Abstracts

1. Proc. 62th Annual Meeting of the Society of Polymer Science, Japan, May 29-31, 2013, Kyoto, Japan

Anion Conductive Aromatic Polymer Electrolyte Membranes Containing Fluorenyl Moiety

M. Shimada, E. Nishino, K. Asazawa, H. Tanaka, J. Miyake, M. Watanabe, K. Miyake 2. Fuel Cells 2014 Science & Technology, 2014 (Amsterdam, Netherlands) April. 3-4th.

Synthesis and Properties of Aromatic Block Copolymers Containing Ammonium- functionalized Fluorenyl Groups as Anion Exchange Membranes.

M. Shimada, J. Miyake, M. Watanabe, and K. Miyatake

3. International Workshop on Green Energy Conversion 2014 (Kiyosato, Japan) Aug.

25-27th.

Synthesis and properties of aromatic block copolymers containing ammonium-functionalized fluorenyl groups as anion exchange membranes

M. Shimada, E. Nishino, K. Asazawa, J. Miyake, M. Watanabe, and K. Miyatake 4. International Workshop on Green Energy Conversion 2016 (Koumi, Japan) Aug. 30^th

– Sep. 1^th.

Synthesis and Properties of New Alkylene Containing Polymer Backbone for Anion Conductive Polymer

M Shimada, R Akiyama, H Ono, J Miyake, and K Miyatake

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Acknowledgement

This present thesis is the summary of studies at Fuel Cell Nanomaterials Center, Clean Energy Research Center, and Interdisciplinary Graduate School of Medicine and Engineering in University of Yamanashi from 2012 to 2017.

I would like to express my sincere appreciation and deepest gratitude to Professor Kenji Miyatake of University of Yamanashi for this academic supervisor of this work, for his continuous guidance, considerate support, invaluable suggestion, and warm encouragement throughout my life here.

I also would like to express my gratitude to Professor Hiroyuki Uchida, Professor Masahiro Watanabe, Professor Akihiro Iiyama for their constructive advice and continuous encouragement.

Sincere appreciation is expressed to members of advisory committee Professor Junji Inukai for his helpful suggestions and detailed advice, Professor Hiroshi Irie for his interesting advice and discussion, Professor Makoto Uchida for his cordial advice and strong encouragement.

I would like to appreciate to Professor Yoshimi Kubo of National Institute of Materials Science for fundamental comment and suggestion, Professor Kim Hasuck of Daegu Gyeongbuk Institute of Science and Technology (DGIST) for fruitful advice and discussion.

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I would like to express my sincerely great appreciation to Professor Steven Holdcroft of Simon Fraser University for his kind support and invaluable suggestion.

I would like to appreciate to former Professor Shigehito Deki and former Visiting Professor Keiji Kunimatsu, for valuable discussion and advice.

I would like to thank Professor Donald Alexander Tryk, Professor Tomio Omata, Professor Kazutoshi Higashiyama, Professor Manuel Eduardo Brito, Professor Toshio Miyao, Professor Takao Tsuneda, Professor Katsuyoshi Kakinuma, Visiting Professor Takeo Kamino, Visiting Professor Atsushi Ohma, Associate Professor Shinji Nohara, Associate Professor Mitsuru Wakisaka, Associate Professor Hiroshi Yano, Assistant Professor Hanako Nishino and former Assistant Professor Youngchul Park of University of Yamanashi for useful support and advice.

Sincere gratitude is expressed to Assistant Professor Junpei Miyake for his contentious guidance, meaningful advice and warm encouragement.

I would like to appreciate former Associate Professor Masanori Hara of TOYOTA Techinological Institute for his helpful support and kind advice.

I would like to sincerely appreciate to Dr. Ryo Akiyama of TechnoPro, Inc for continuous support and so many helpful advice.

I would like to thank Ms. Toshiko Gomyo of University of Yamanashi for kind assistance of TEM measurement.

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I would like to express gratitude to Dr. Takefumi Mikami of Yamanashi prefectural Industrial Technology Center for his suggestive advice and valuable discussion.

I am grateful to Dr. Koichiro Asazawa, Ms. Eriko Nishino, Mr. Yui Kuwabara and Mr.

Aoi Takano of Daihatsu Motor Co., Ltd. for their active discussion and beneficial suggestion.

I am grateful to Mr. Shigefumi Shimada of Daihatsu Motor Co., Ltd. for his help in fuel cell performance, gas permeability test.

I extend my appreciation to Ms. Kaori ichinose, Ms. Nozomi Toyoda and all staffs of Clean Energy Research Center, Fuel Cell Nanomaterials Center and Special Doctoral Program for Green Energy Conversion Science and Technology for continuous support and kind consideration.

I would like to thank Dr. Jumpei Saito, Dr. Takuya Shimura, Dr. Satoki Hirakata, Dr.

Takuya Omata, Mr. Takahiro Miyahara, Mr. Keita Fukasawa, Mr. Daigo Hirayama, Ms.

Mayu Sakai, Mr. Masaya Hara, Ms. Shin Wang, Mr. Shoya Morishima, Mr. Masahiro Haraguchi, Mr. Masataka Kurihara, Mr. Takuya Nakamura, for kind and great help.

I sincerely appreciate to Dr. Takayuki Hoshi, Dr. Masaru Sakamoto, Dr. Takashi Mochizuki, Dr. Yuji Chino, Dr. Morio Chiwata, Mr. Hideaki Ono, Mr. Yaojian Zhang, Mr.

Kazuhiro Takanohashi, Mr. Yuya Yamashita, Mr. Kento Takahashi, Mr. Kazuki Shimura, Mr. Yoshiyuki Ogihara, Mr. Ahmed Mohamed Ahmed Mahmoud, Ms. Ahn Jinju, Mr.

Ryosuke Nishikawa, Mr. Takashi Kobayashi, Mr. Ryunosuke Taki, Ms. Febrina Tri Hartanti, Mr. Ryo Shimizu, Mr. Taro Kimura, Mr. Ibuki Hosaka, Mr. Yuma Shimizu, Ms.

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Mizuki Ozawa, Ms. Reika Oida, Mr. Kanji Otsuji and Mr. Toshiki Tanaka for thoughtful help, valuable discussion and continuous inspiration.

I would like to express my gratitude to Mr. Yasuo Yamamoto, CEO and Mr. Nobuhisa Watanabe of TAKAHATA PRECISION JAPAN, CO., LTD. for giving me a great opportunity to study.

I deeply thank former boss Mr. Yuichi Kiribayashi, former boss Mr. Nobui Morikita, Mr. Shoji Toshima of TAKAHATA PRECISION JAPAN, CO., LTD., Mr. Izumi Shimura of TAKAHATA PRECISION TENNESSEE, INC., Mr. Masao Furuya of TAKAHATA PRECISION (THAILAND) LTD., Mr. Aiji Mochizuki of TAKAHATA PRECISION (SHENZHEN) CO., LTD. for their continuous concern and warm encouragement.

Sincere acknowledgement is expressed to Dr. Naoki Yokota, Dr. Katsuya Nagase, Mr.

Akmal Khairi bin Muhazar, Ms. Natsumi Yoshimura of TAKAHATA PRECISION JAPAN, CO., LTD. for their kind cooperation and warm understanding.

Special thanks are due to my teachers, colleagues and friends for their heart-warming support and encouragement.

Finally I would like to express my gratefulness to my parents, my brother and his wife and my grandmother for their kind cooperation.

Manai Shimada March 2017