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Title: Oriented Multiwalled Organic-Co(OH) 2 Nanotubes for Energy Storage

Abstract

We report that in energy storage materials, large surface areas and oriented structures are key architecture design features for improving performance through enhanced electrolyte access and efficient electron conduction pathways. Layered hydroxides provide a tunable materials platform with opportunities for achieving such nanostructures via bottom-up syntheses. These nanostructures, however, can degrade in the presence of the alkaline electrolytes required for their redox-based energy storage. A layered Co(OH) 2–organic hybrid material that forms a hierarchical structure consisting of micrometer-long, 30 nm diameter tubes with concentric curved layers of Co(OH) 2 and 1-pyrenebutyric acid is reported. The nanotubular structure offers high surface area as well as macroscopic orientation perpendicular to the substrate for efficient electron transfer. Using a comparison with flat films of the same composition, it is demonstrated that the superior performance of the nanotubular films is the result of a large accessible surface area for redox activity. Finally, it is found that the organic molecules used to template nanotubular growth also impart stability to the hybrid when present in the alkaline environments necessary for redox function.

Authors:
 [1];  [1];  [2];  [1];  [1];  [1];  [3];  [4]; ORCiD logo [5]
  1. Northwestern Univ., Evanston, IL (United States)
  2. Northwestern Univ., Chicago, IL (United States)
  3. Univ. of California, Davis, CA (United States)
  4. Northwestern Univ., Chicago, IL (United States); Northwestern Univ., Evanston, IL (United States)
  5. Northwestern Univ., Evanston, IL (United States); Northwestern Univ., Chicago, IL (United States)
Publication Date:
Research Org.:
Energy Frontier Research Centers (EFRC) (United States). Center for Bio-Inspired Energy Science (CBES)
Sponsoring Org.:
USDOE Office of Science (SC), Basic Energy Sciences (BES) (SC-22)
OSTI Identifier:
1470148
Grant/Contract Number:  
SC0000989; FG02‐00ER45810
Resource Type:
Accepted Manuscript
Journal Name:
Advanced Functional Materials
Additional Journal Information:
Journal Volume: 28; Journal Issue: 3; Related Information: CBES partners with Northwestern University (lead); Harvard University; New York University; Pennsylvania State University; University of Michigan; University of Pittsburgh; Journal ID: ISSN 1616-301X
Publisher:
Wiley
Country of Publication:
United States
Language:
English
Subject:
25 ENERGY STORAGE; 36 MATERIALS SCIENCE; catalysis (homogeneous); solar (photovoltaic); bio-inspired; charge transport; mesostructured materials; materials and chemistry by design; synthesis (novel materials); synthesis (self-assembly); cobalt hydroxide; energy storage; hierarchical structures; hybrid materials

Citation Formats

Lau, Garrett C., Sather, Nicholas A., Sai, Hiroaki, Waring, Elizabeth M., Deiss-Yehiely, Elad, Barreda, Leonel, Beeman, Emily A., Palmer, Liam C., and Stupp, Samuel I. Oriented Multiwalled Organic-Co(OH)2 Nanotubes for Energy Storage. United States: N. p., 2017. Web. doi:10.1002/adfm.201702320.
Lau, Garrett C., Sather, Nicholas A., Sai, Hiroaki, Waring, Elizabeth M., Deiss-Yehiely, Elad, Barreda, Leonel, Beeman, Emily A., Palmer, Liam C., & Stupp, Samuel I. Oriented Multiwalled Organic-Co(OH)2 Nanotubes for Energy Storage. United States. doi:10.1002/adfm.201702320.
Lau, Garrett C., Sather, Nicholas A., Sai, Hiroaki, Waring, Elizabeth M., Deiss-Yehiely, Elad, Barreda, Leonel, Beeman, Emily A., Palmer, Liam C., and Stupp, Samuel I. Mon . "Oriented Multiwalled Organic-Co(OH)2 Nanotubes for Energy Storage". United States. doi:10.1002/adfm.201702320. https://www.osti.gov/servlets/purl/1470148.
@article{osti_1470148,
title = {Oriented Multiwalled Organic-Co(OH)2 Nanotubes for Energy Storage},
author = {Lau, Garrett C. and Sather, Nicholas A. and Sai, Hiroaki and Waring, Elizabeth M. and Deiss-Yehiely, Elad and Barreda, Leonel and Beeman, Emily A. and Palmer, Liam C. and Stupp, Samuel I.},
abstractNote = {We report that in energy storage materials, large surface areas and oriented structures are key architecture design features for improving performance through enhanced electrolyte access and efficient electron conduction pathways. Layered hydroxides provide a tunable materials platform with opportunities for achieving such nanostructures via bottom-up syntheses. These nanostructures, however, can degrade in the presence of the alkaline electrolytes required for their redox-based energy storage. A layered Co(OH)2–organic hybrid material that forms a hierarchical structure consisting of micrometer-long, 30 nm diameter tubes with concentric curved layers of Co(OH)2 and 1-pyrenebutyric acid is reported. The nanotubular structure offers high surface area as well as macroscopic orientation perpendicular to the substrate for efficient electron transfer. Using a comparison with flat films of the same composition, it is demonstrated that the superior performance of the nanotubular films is the result of a large accessible surface area for redox activity. Finally, it is found that the organic molecules used to template nanotubular growth also impart stability to the hybrid when present in the alkaline environments necessary for redox function.},
doi = {10.1002/adfm.201702320},
journal = {Advanced Functional Materials},
number = 3,
volume = 28,
place = {United States},
year = {2017},
month = {11}
}

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Works referenced in this record:

Molecular Manipulation of Microstructures: Biomaterials, Ceramics, and Semiconductors
journal, August 1997


A review of electrode materials for electrochemical supercapacitors
journal, January 2012

  • Wang, Guoping; Zhang, Lei; Zhang, Jiujun
  • Chemical Society Reviews, Vol. 41, Issue 2, p. 797-828
  • DOI: 10.1039/C1CS15060J

Pseudocapacitive oxide materials for high-rate electrochemical energy storage
journal, January 2014

  • Augustyn, Veronica; Simon, Patrice; Dunn, Bruce
  • Energy & Environmental Science, Vol. 7, Issue 5
  • DOI: 10.1039/c3ee44164d

Nano-architectured Co(OH)2 electrodes constructed using an easily-manipulated electrochemical protocol for high-performance energy storage applications
journal, January 2010

  • Chang, Jeng-Kuei; Wu, Chih-Ming; Sun, I-Wen
  • Journal of Materials Chemistry, Vol. 20, Issue 18
  • DOI: 10.1039/b925176f

Stabilized Octahedral Frameworks in Layered Double Hydroxides by Solid-Solution Mixing of Transition Metals
journal, December 2016

  • Lee, Ji Hoon; Lee, Hyeon Jeong; Lim, Soo Yeon
  • Advanced Functional Materials, Vol. 27, Issue 7
  • DOI: 10.1002/adfm.201605225

Materials for electrochemical capacitors
journal, November 2008

  • Simon, Patrice; Gogotsi, Yury
  • Nature Materials, Vol. 7, Issue 11
  • DOI: 10.1038/nmat2297

Behavior of Molybdenum Nitrides as Materials for Electrochemical Capacitors
journal, January 1998

  • Liu, T. -C.
  • Journal of The Electrochemical Society, Vol. 145, Issue 6
  • DOI: 10.1149/1.1838571

Intricate Hollow Structures: Controlled Synthesis and Applications in Energy Storage and Conversion
journal, February 2017


A kinetic study of the phase conversion of layered cobalt hydroxides
journal, January 2008

  • Du, Yi; Ok, Kang Min; O'Hare, Dermot
  • Journal of Materials Chemistry, Vol. 18, Issue 37
  • DOI: 10.1039/b809085h

Electrochemical synthesis of cobalt hydroxide films with tunable interlayer spacings
journal, January 2007

  • Yarger, Matthew S.; Steinmiller, Ellen M. P.; Choi, Kyoung-Shin
  • Chem. Commun., Issue 2
  • DOI: 10.1039/B609621B

High-rate electrochemical energy storage through Li+ intercalation pseudocapacitance
journal, April 2013

  • Augustyn, Veronica; Come, Jérémy; Lowe, Michael A.
  • Nature Materials, Vol. 12, Issue 6
  • DOI: 10.1038/nmat3601

Where Do Batteries End and Supercapacitors Begin?
journal, March 2014


Exaggerated capacitance using electrochemically active nickel foam as current collector in electrochemical measurement
journal, April 2011


General synthesis of inorganic single-walled nanotubes
journal, October 2015

  • Ni, Bing; Liu, Huiling; Wang, Peng-peng
  • Nature Communications, Vol. 6, Issue 1
  • DOI: 10.1038/ncomms9756

Semiconducting superlattices templated by molecular assemblies
journal, March 1996

  • Braun, Paul V.; Osenar, Paul; Stupp, Samuel I.
  • Nature, Vol. 380, Issue 6572
  • DOI: 10.1038/380325a0

Phase Transformation Guided Single-Layer β-Co(OH) 2 Nanosheets for Pseudocapacitive Electrodes
journal, March 2014

  • Wang, Lei; Lin, Chong; Zhang, Fengxing
  • ACS Nano, Vol. 8, Issue 4
  • DOI: 10.1021/nn500386u

Nanomaterials for energy conversion and storage
journal, January 2013

  • Zhang, Qifeng; Uchaker, Evan; Candelaria, Stephanie L.
  • Chemical Society Reviews, Vol. 42, Issue 7
  • DOI: 10.1039/c3cs00009e

Potentiostatically deposited nanostructured α-Co(OH)2: A high performance electrode material for redox-capacitors
journal, September 2007


Low Cost Facile Synthesis of Large-Area Cobalt Hydroxide Nanorods with Remarkable Pseudocapacitance
journal, April 2015

  • Deng, Ming-Jay; Song, Cheng-Zhao; Wang, Chien-Chia
  • ACS Applied Materials & Interfaces, Vol. 7, Issue 17
  • DOI: 10.1021/acsami.5b01163

Ordered mesoporous molecular sieves synthesized by a liquid-crystal template mechanism
journal, October 1992

  • Kresge, C. T.; Leonowicz, M. E.; Roth, W. J.
  • Nature, Vol. 359, Issue 6397, p. 710-712
  • DOI: 10.1038/359710a0

Orienting Periodic Organic−Inorganic Nanoscale Domains Through One-Step Electrodeposition
journal, December 2010

  • Herman, David J.; Goldberger, Joshua E.; Chao, Stephen
  • ACS Nano, Vol. 5, Issue 1
  • DOI: 10.1021/nn102697r

Enhanced Pseudocapacitance of Ionic Liquid/Cobalt Hydroxide Nanohybrids
journal, February 2013

  • Choi, Bong Gill; Yang, MinHo; Jung, Sung Chul
  • ACS Nano, Vol. 7, Issue 3
  • DOI: 10.1021/nn305750s

Oxidation mechanism of cobalt hydroxide to cobalt oxyhydroxide
journal, January 1999

  • Pralong, V.; Delahaye-Vidal, A.; Beaudoin, B.
  • Journal of Materials Chemistry, Vol. 9, Issue 4
  • DOI: 10.1039/a807689h

Organically Modified Aluminosilicate Mesostructures from Block Copolymer Phases
journal, December 1997


Rapidly falling costs of battery packs for electric vehicles
journal, March 2015


Fabrication and electrochemical characterization of cobalt-based layered double hydroxide nanosheet thin-film electrodes
journal, October 2008


Surfactant-assisted electrochemical deposition of α-cobalt hydroxide for supercapacitors
journal, January 2011


Lamellar diblock copolymer grain boundary morphology. 1. Twist boundary characterization
journal, August 1993

  • Gido, Samuel P.; Gunther, Janelle; Thomas, Edwin L.
  • Macromolecules, Vol. 26, Issue 17
  • DOI: 10.1021/ma00069a016

Amorphous Cobalt Hydroxide with Superior Pseudocapacitive Performance
journal, December 2013

  • Li, H. B.; Yu, M. H.; Lu, X. H.
  • ACS Applied Materials & Interfaces, Vol. 6, Issue 2
  • DOI: 10.1021/am404769z

Interconversion of Brucite-like and Hydrotalcite-like Phases in Cobalt Hydroxide Compounds
journal, January 1999

  • Xu, Z. P.; Zeng, H. C.
  • Chemistry of Materials, Vol. 11, Issue 1
  • DOI: 10.1021/cm980420b

Ultrahigh Energy Density Realized by a Single-Layer β-Co(OH) 2 All-Solid-State Asymmetric Supercapacitor
journal, September 2014

  • Gao, Shan; Sun, Yongfu; Lei, Fengcai
  • Angewandte Chemie International Edition, Vol. 53, Issue 47
  • DOI: 10.1002/anie.201407836

Electrodeposition of ordered mesoporous cobalt hydroxide film from lyotropic liquid crystal media for electrochemical capacitors
journal, January 2008

  • Zhou, Wen-jia; Zhang, Jin; Xue, Tong
  • Journal of Materials Chemistry, Vol. 18, Issue 8
  • DOI: 10.1039/b715070a

Advanced Graphene-Based Binder-Free Electrodes for High-Performance Energy Storage
journal, August 2015


Nanostructure Templating in Inorganic Solids with Organic Lyotropic Liquid Crystals
journal, August 1999

  • Braun, Paul V.; Osenar, Paul; Tohver, Valeria
  • Journal of the American Chemical Society, Vol. 121, Issue 32
  • DOI: 10.1021/ja9833725

Hybrid nanostructured materials for high-performance electrochemical capacitors
journal, March 2013


Large-Scale Uniform α-Co(OH) 2 Long Nanowire Arrays Grown on Graphite as Pseudocapacitor Electrodes
journal, December 2010

  • Jiang, Jian; Liu, Jinping; Ding, Ruimin
  • ACS Applied Materials & Interfaces, Vol. 3, Issue 1
  • DOI: 10.1021/am1009887

A synergistic assembly of nanoscale lamellar photoconductor hybrids
journal, December 2008

  • Sofos, Marina; Goldberger, Joshua; Stone, David A.
  • Nature Materials, Vol. 8, Issue 1, p. 68-75
  • DOI: 10.1038/nmat2336

Nitrogen-doped ordered mesoporous carbon single crystals: aqueous organic–organic self-assembly and superior supercapacitor performance
journal, January 2015

  • Shen, Guozhu; Sun, Xiaoran; Zhang, Hongwei
  • Journal of Materials Chemistry A, Vol. 3, Issue 47
  • DOI: 10.1039/C5TA06129F

Pseudocapacitive Contributions to Electrochemical Energy Storage in TiO2 (Anatase) Nanoparticles
journal, October 2007

  • Wang, John; Polleux, Julien; Lim, James
  • The Journal of Physical Chemistry C, Vol. 111, Issue 40, p. 14925-14931
  • DOI: 10.1021/jp074464w

Low-crystalline iron oxide hydroxide nanoparticle anode for high-performance supercapacitors
journal, March 2017

  • Owusu, Kwadwo Asare; Qu, Longbing; Li, Jiantao
  • Nature Communications, Vol. 8, Issue 1
  • DOI: 10.1038/ncomms14264

Rationalizing Molecular Design in the Electrodeposition of Anisotropic Lamellar Nanostructures
journal, October 2013

  • Bruns, Carson J.; Herman, David J.; Minuzzo, Julian B.
  • Chemistry of Materials, Vol. 25, Issue 21
  • DOI: 10.1021/cm402505p

Multidimensional materials and device architectures for future hybrid energy storage
journal, September 2016

  • Lukatskaya, Maria R.; Dunn, Bruce; Gogotsi, Yury
  • Nature Communications, Vol. 7, Issue 1
  • DOI: 10.1038/ncomms12647

Selective and Controlled Synthesis of α- and β-Cobalt Hydroxides in Highly Developed Hexagonal Platelets
journal, October 2005

  • Liu, Zhaoping; Ma, Renzhi; Osada, Minoru
  • Journal of the American Chemical Society, Vol. 127, Issue 40
  • DOI: 10.1021/ja0523338

Cheap and scalable synthesis of α-Fe2O3 multi-shelled hollow spheres as high-performance anode materials for lithium ion batteries
journal, January 2013

  • Zhou, Liang; Xu, Hongyi; Zhang, Hongwei
  • Chemical Communications, Vol. 49, Issue 77
  • DOI: 10.1039/c3cc43867h

Layered α-Co(OH) 2 Nanocones as Electrode Materials for Pseudocapacitors: Understanding the Effect of Interlayer Space on Electrochemical Activity
journal, December 2012

  • Wang, Lei; Dong, Zhi Hui; Wang, Zheng Gong
  • Advanced Functional Materials, Vol. 23, Issue 21
  • DOI: 10.1002/adfm.201202786

High-Yield Preparation, Versatile Structural Modification, and Properties of Layered Cobalt Hydroxide Nanocones
journal, April 2014

  • Liu, Xiaohe; Ma, Renzhi; Bando, Yoshio
  • Advanced Functional Materials, Vol. 24, Issue 27
  • DOI: 10.1002/adfm.201400193

Molecular-Scale Hybridization of Clay Monolayers and Conducting Polymer for Thin-Film Supercapacitors
journal, March 2015

  • Zhao, Jingwen; Xu, Simin; Tschulik, Kristina
  • Advanced Functional Materials, Vol. 25, Issue 18
  • DOI: 10.1002/adfm.201500408

High-Performing Monometallic Cobalt Layered Double Hydroxide Supercapacitor with Defined Local Structure
journal, May 2014

  • Vialat, Pierre; Mousty, Christine; Taviot-Gueho, Christine
  • Advanced Functional Materials, Vol. 24, Issue 30
  • DOI: 10.1002/adfm.201400310