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Title: Bamboo–Like Nitrogen–Doped Carbon Nanotube Forests as Durable Metal–Free Catalysts for Self–Powered Flexible Li–CO 2 Batteries

Abstract

The Li-CO 2 battery is a promising energy storage device for wearable electronics due to its long discharge plateau, high energy density, and environmental friendliness. Furthermore, its utilization is largely hindered by poor cyclability and mechanical rigidity due to the lack of a flexible and durable catalyst electrode. Herein, flexible fiber-shaped Li-CO 2 batteries with ultralong cycle-life, high rate capability, and large specific capacity are fabricated, employing bamboo-like N-doped carbon nanotube fiber (B-NCNT) as flexible, durable metal-free catalysts for both CO 2 reduction and evolution reactions. Benefiting from high N-doping with abundant pyridinic groups, rich defects, and active sites of the periodic bamboo-like nodes, the fabricated Li-CO 2 battery shows outstanding electrochemical performance with high full-discharge capacity of 23328 mAh g -1, high rate capability with a low potential gap up to 1.96 V at a current density of 1000 mA g -1, stability over 360 cycles, and good flexibility. Meanwhile, the bifunctional B-NCNT is used as the counter electrode for a fiber-shaped dye-sensitized solar cell to fabricate a self-powered fiber-shaped Li-CO 2 battery with overall photochemical-electric energy conversion efficiency of up to 4.6%. Along with a stable voltage output, this design demonstrates great adaptability and application potentiality in wearablemore » electronics with a breath monitor as an example.« less

Authors:
 [1];  [1];  [1];  [2];  [3];  [4];  [1];  [1];  [5];  [1];  [5]; ORCiD logo [3];  [1]
  1. China Academy of Engineering Physics, Sichuan (People's Republic of China). Inst. of Chemical Materials
  2. Argonne National Lab. (ANL), Lemont, IL (United States). Chemical Sciences and Engineering Div.; Univ. of Waterloo, Waterloo, ON (Canada). Dept. of Chemical Engineering Waterloo Inst. of Nanotechnology
  3. Argonne National Lab. (ANL), Lemont, IL (United States). Chemical Sciences and Engineering Div.
  4. Argonne National Lab. (ANL), Lemont, IL (United States). Chemical Sciences and Engineering Div.; Peking Univ. Shenzhen Graduate School Shenzhen 518055 (China). School of Advanced Materials
  5. Nanjing Univ., Nanjing (People's Republic of China). Center of Energy Storage Materials & Technology College of Engineering and Applied Sciences Jiangsu Key Laboratory of Artificial Functional Materials National Laboratory of Solid State Microstructures and Collaborative Innovation Center of Advanced Microstructures
Publication Date:
Research Org.:
Argonne National Lab. (ANL), Argonne, IL (United States)
Sponsoring Org.:
USDOE Office of Energy Efficiency and Renewable Energy (EERE)
OSTI Identifier:
1574295
Alternate Identifier(s):
OSTI ID: 1548797
Grant/Contract Number:  
AC02-06CH11357
Resource Type:
Accepted Manuscript
Journal Name:
Advanced Materials
Additional Journal Information:
Journal Volume: 31; Journal Issue: 39; Journal ID: ISSN 0935-9648
Publisher:
Wiley
Country of Publication:
United States
Language:
English
Subject:
25 ENERGY STORAGE; Li-CO2 batteries; flexible electrodes; metal-free bifunctional catalysts; nitrogen-doped carbon nanotubes; self-powered systems

Citation Formats

Li, Xuelian, Zhou, Jingwen, Zhang, Junxiang, Li, Matthew, Bi, Xuanxuan, Liu, Tongchao, He, Tao, Cheng, Jianli, Zhang, Fan, Li, Yongpeng, Mu, Xiaowei, Lu, Jun, and Wang, Bin. Bamboo–Like Nitrogen–Doped Carbon Nanotube Forests as Durable Metal–Free Catalysts for Self–Powered Flexible Li–CO2 Batteries. United States: N. p., 2019. Web. doi:10.1002/adma.201903852.
Li, Xuelian, Zhou, Jingwen, Zhang, Junxiang, Li, Matthew, Bi, Xuanxuan, Liu, Tongchao, He, Tao, Cheng, Jianli, Zhang, Fan, Li, Yongpeng, Mu, Xiaowei, Lu, Jun, & Wang, Bin. Bamboo–Like Nitrogen–Doped Carbon Nanotube Forests as Durable Metal–Free Catalysts for Self–Powered Flexible Li–CO2 Batteries. United States. doi:10.1002/adma.201903852.
Li, Xuelian, Zhou, Jingwen, Zhang, Junxiang, Li, Matthew, Bi, Xuanxuan, Liu, Tongchao, He, Tao, Cheng, Jianli, Zhang, Fan, Li, Yongpeng, Mu, Xiaowei, Lu, Jun, and Wang, Bin. Fri . "Bamboo–Like Nitrogen–Doped Carbon Nanotube Forests as Durable Metal–Free Catalysts for Self–Powered Flexible Li–CO2 Batteries". United States. doi:10.1002/adma.201903852.
@article{osti_1574295,
title = {Bamboo–Like Nitrogen–Doped Carbon Nanotube Forests as Durable Metal–Free Catalysts for Self–Powered Flexible Li–CO2 Batteries},
author = {Li, Xuelian and Zhou, Jingwen and Zhang, Junxiang and Li, Matthew and Bi, Xuanxuan and Liu, Tongchao and He, Tao and Cheng, Jianli and Zhang, Fan and Li, Yongpeng and Mu, Xiaowei and Lu, Jun and Wang, Bin},
abstractNote = {The Li-CO2 battery is a promising energy storage device for wearable electronics due to its long discharge plateau, high energy density, and environmental friendliness. Furthermore, its utilization is largely hindered by poor cyclability and mechanical rigidity due to the lack of a flexible and durable catalyst electrode. Herein, flexible fiber-shaped Li-CO2 batteries with ultralong cycle-life, high rate capability, and large specific capacity are fabricated, employing bamboo-like N-doped carbon nanotube fiber (B-NCNT) as flexible, durable metal-free catalysts for both CO2 reduction and evolution reactions. Benefiting from high N-doping with abundant pyridinic groups, rich defects, and active sites of the periodic bamboo-like nodes, the fabricated Li-CO2 battery shows outstanding electrochemical performance with high full-discharge capacity of 23328 mAh g-1, high rate capability with a low potential gap up to 1.96 V at a current density of 1000 mA g-1, stability over 360 cycles, and good flexibility. Meanwhile, the bifunctional B-NCNT is used as the counter electrode for a fiber-shaped dye-sensitized solar cell to fabricate a self-powered fiber-shaped Li-CO2 battery with overall photochemical-electric energy conversion efficiency of up to 4.6%. Along with a stable voltage output, this design demonstrates great adaptability and application potentiality in wearable electronics with a breath monitor as an example.},
doi = {10.1002/adma.201903852},
journal = {Advanced Materials},
number = 39,
volume = 31,
place = {United States},
year = {2019},
month = {8}
}

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Works referenced in this record:

A Li–O2/CO2 battery
journal, January 2011

  • Takechi, Kensuke; Shiga, Tohru; Asaoka, Takahiko
  • Chemical Communications, Vol. 47, Issue 12, p. 3463-3465
  • DOI: 10.1039/c0cc05176d

Energy Storage Technologies for Small Satellite Applications
journal, March 2018

  • Chin, Keith B.; Brandon, Erik J.; Bugga, Ratnakumar V.
  • Proceedings of the IEEE, Vol. 106, Issue 3
  • DOI: 10.1109/JPROC.2018.2793158

The Li–CO2 battery: a novel method for CO2 capture and utilization
journal, January 2013

  • Xu, Shaomao; Das, Shyamal K.; Archer, Lynden A.
  • RSC Advances, Vol. 3, Issue 18
  • DOI: 10.1039/c3ra40394g

3D-Printed Graphene Oxide Framework with Thermal Shock Synthesized Nanoparticles for Li-CO 2 Batteries
journal, October 2018

  • Qiao, Yun; Liu, Yang; Chen, Chaoji
  • Advanced Functional Materials, Vol. 28, Issue 51
  • DOI: 10.1002/adfm.201805899

A reversible lithium–CO 2 battery with Ru nanoparticles as a cathode catalyst
journal, January 2017

  • Yang, Sixie; Qiao, Yu; He, Ping
  • Energy & Environmental Science, Vol. 10, Issue 4
  • DOI: 10.1039/C6EE03770D

Mo 2 C/CNT: An Efficient Catalyst for Rechargeable Li-CO 2 Batteries
journal, May 2017

  • Hou, Yuyang; Wang, Jiazhao; Liu, Lili
  • Advanced Functional Materials, Vol. 27, Issue 27
  • DOI: 10.1002/adfm.201700564

Verifying the Rechargeability of Li-CO 2 Batteries on Working Cathodes of Ni Nanoparticles Highly Dispersed on N-Doped Graphene
journal, November 2017


Identification of cathode stability in Li–CO 2 batteries with Cu nanoparticles highly dispersed on N-doped graphene
journal, January 2018

  • Zhang, Zhang; Zhang, Zongwen; Liu, Peifang
  • Journal of Materials Chemistry A, Vol. 6, Issue 7
  • DOI: 10.1039/C7TA10497A

High performance Li–CO 2 batteries with NiO–CNT cathodes
journal, January 2018

  • Zhang, Xin; Wang, Chengyi; Li, Huanhuan
  • Journal of Materials Chemistry A, Vol. 6, Issue 6
  • DOI: 10.1039/C7TA11015D

Fabricating Ir/C Nanofiber Networks as Free-Standing Air Cathodes for Rechargeable Li-CO 2 Batteries
journal, June 2018


Rechargeable Li/CO2–O2 (2 : 1) battery and Li/CO2 battery
journal, January 2014

  • Liu, Yali; Wang, Rui; Lyu, Yingchun
  • Energy & Environmental Science, Vol. 7, Issue 2
  • DOI: 10.1039/c3ee43318h

The First Introduction of Graphene to Rechargeable Li-CO 2 Batteries
journal, May 2015

  • Zhang, Zhang; Zhang, Qiang; Chen, Yanan
  • Angewandte Chemie International Edition, Vol. 54, Issue 22
  • DOI: 10.1002/anie.201501214

Rechargeable Li–CO 2 batteries with carbon nanotubes as air cathodes
journal, January 2015

  • Zhang, Xin; Zhang, Qiang; Zhang, Zhang
  • Chemical Communications, Vol. 51, Issue 78
  • DOI: 10.1039/C5CC05767A

Highly Rechargeable Lithium-CO 2 Batteries with a Boron- and Nitrogen-Codoped Holey-Graphene Cathode
journal, May 2017

  • Qie, Long; Lin, Yi; Connell, John W.
  • Angewandte Chemie International Edition, Vol. 56, Issue 24
  • DOI: 10.1002/anie.201701826

A Quasi‐Solid‐State Flexible Fiber‐Shaped Li–CO 2 Battery with Low Overpotential and High Energy Efficiency
journal, September 2018


Highly Surface‐Wrinkled and N‐Doped CNTs Anchored on Metal Wire: A Novel Fiber‐Shaped Cathode toward High‐Performance Flexible Li–CO 2 Batteries
journal, January 2019

  • Li, Yinchuan; Zhou, Jingwen; Zhang, Tingbo
  • Advanced Functional Materials, Vol. 29, Issue 12
  • DOI: 10.1002/adfm.201808117

Aligned multi-walled carbon nanotubes on different substrates by floating catalyst chemical vapor deposition: Critical effects of buffer layer
journal, May 2008


The role of nitrogen in carbon nanotube formation
journal, October 2003


A Formation Mechanism for Catalytically Grown Helix-Shaped Graphite Nanotubes
journal, July 1994


Bamboo-like carbon nanotubes produced by pyrolysis of iron(II) phthalocyanine
journal, August 2001


Theoretical studies of icosahedral C60 and some related species
journal, August 1986


Plumbing carbon nanotubes
journal, December 2007

  • Jin, Chuanhong; Suenaga, Kazu; Iijima, Sumio
  • Nature Nanotechnology, Vol. 3, Issue 1
  • DOI: 10.1038/nnano.2007.406

Imaging active topological defects in carbon nanotubes
journal, May 2007

  • Suenaga, Kazu; Wakabayashi, Hideaki; Koshino, Masanori
  • Nature Nanotechnology, Vol. 2, Issue 6
  • DOI: 10.1038/nnano.2007.141

Compartmentalized CNx nanotubes: Chemistry, morphology, and growth
journal, May 2002

  • Trasobares, S.; Stéphan, O.; Colliex, C.
  • The Journal of Chemical Physics, Vol. 116, Issue 20
  • DOI: 10.1063/1.1473195

Tailoring the field emission property of nitrogen-doped carbon nanotubes by controlling the graphitic/pyridinic substitution
journal, January 2010


Controllable Growth, Structure, and Low Field Emission of Well-Aligned CN x Nanotubes
journal, March 2002

  • Wang, Xianbao; Liu, Yunqi; Zhu, Daoben
  • The Journal of Physical Chemistry B, Vol. 106, Issue 9
  • DOI: 10.1021/jp013007r

Carbon-Catalyzed Oxidative Dehydrogenation of n-Butane: Selective Site Formation during sp3-to-sp2 Lattice Rearrangement
journal, March 2011

  • Liu, Xi; Frank, Benjamin; Zhang, Wei
  • Angewandte Chemie International Edition, Vol. 50, Issue 14
  • DOI: 10.1002/anie.201006717

Dual Raman Features of Double Coaxial Carbon Nanotubes with N-Doped and B-Doped Multiwalls
journal, December 2005

  • Yang, Quan-Hong; Hou, Peng-Xiang; Unno, Masashi
  • Nano Letters, Vol. 5, Issue 12
  • DOI: 10.1021/nl051779j

Effect of nitrogen doping on Raman spectra of multi-walled carbon nanotubes
journal, September 2008

  • Bulusheva, L. G.; Okotrub, A. V.; Kinloch, I. A.
  • physica status solidi (b), Vol. 245, Issue 10
  • DOI: 10.1002/pssb.200879592

Tubular structured ordered mesoporous carbon as an efficient sorbent for the removal of dyes from aqueous solutions
journal, October 2010


Li-CO2 Electrochemistry: A New Strategy for CO2 Fixation and Energy Storage
journal, October 2017


Synthesis of N-Doped Graphene by Chemical Vapor Deposition and Its Electrical Properties
journal, May 2009

  • Wei, Dacheng; Liu, Yunqi; Wang, Yu
  • Nano Letters, Vol. 9, Issue 5
  • DOI: 10.1021/nl803279t

Freestanding, Hydrophilic Nitrogen-Doped Carbon Foams for Highly Compressible All Solid-State Supercapacitors
journal, May 2016


Nitrogen-doped carbon nanotubes and graphene composite structures for energy and catalytic applications
journal, January 2014

  • Lee, Won Jun; Maiti, Uday Narayan; Lee, Ju Min
  • Chemical Communications, Vol. 50, Issue 52
  • DOI: 10.1039/c4cc00146j

Identification of Electron Donor States in N-Doped Carbon Nanotubes
journal, September 2001

  • Czerw, R.; Terrones, M.; Charlier, J. -C.
  • Nano Letters, Vol. 1, Issue 9
  • DOI: 10.1021/nl015549q

Heterogeneous nanocarbon materials for oxygen reduction reaction
journal, January 2014

  • Wang, Da-Wei; Su, Dangsheng
  • Energy & Environmental Science, Vol. 7, Issue 2
  • DOI: 10.1039/c3ee43463j

Efficient Electrocatalytic Reduction of CO 2 by Nitrogen-Doped Nanoporous Carbon/Carbon Nanotube Membranes: A Step Towards the Electrochemical CO 2 Refinery
journal, June 2017

  • Wang, Hong; Jia, Jia; Song, Pengfei
  • Angewandte Chemie International Edition, Vol. 56, Issue 27
  • DOI: 10.1002/anie.201703720

Calibration of the basic strength of the nitrogen groups on the nanostructured carbon materials
journal, January 2015

  • Li, Bo; Sun, XiaoYing; Su, Dangsheng
  • Physical Chemistry Chemical Physics, Vol. 17, Issue 10
  • DOI: 10.1039/C4CP05765A

Nitrogen-Doped Hollow Carbon Nanospheres for High-Performance Li-Ion Batteries
journal, April 2017

  • Yang, Yufen; Jin, Song; Zhang, Zhen
  • ACS Applied Materials & Interfaces, Vol. 9, Issue 16
  • DOI: 10.1021/acsami.6b14840

Highly effective sites and selectivity of nitrogen-doped graphene/CNT catalysts for CO 2 electrochemical reduction
journal, January 2016

  • Chai, Guo-Liang; Guo, Zheng-Xiao
  • Chemical Science, Vol. 7, Issue 2
  • DOI: 10.1039/C5SC03695J

Incorporation of Nitrogen Defects for Efficient Reduction of CO 2 via Two-Electron Pathway on Three-Dimensional Graphene Foam
journal, December 2015


Rechargeable Room-Temperature Na-CO 2 Batteries
journal, April 2016


EELS analysis of Nylon 6 nanofibers reinforced with nitroxide-functionalized graphene oxide
journal, April 2014