Vertically Aligned Carbon Nanotubes Grown on Copper Foil as Electrodes for Electrochemical Double Layer Capacitors

Nwanno, Chinaza E.; Gotame, Ram Chandra; Watt, John Daniel; Kuo, Winson Chun Hsin; Li, Wenzhi

doi:10.3390/nano15191506

Vertically Aligned Carbon Nanotubes Grown on Copper Foil as Electrodes for Electrochemical Double Layer Capacitors

Journal Article · Wed Oct 01 04:00:00 EDT 2025 · Nanomaterials

DOI:https://doi.org/10.3390/nano15191506· OSTI ID:2998256

^[1]; ^[1]; ^[2]; ^[2]; ^[1]

Florida International Univ. (FIU), Miami, FL (United States)
Los Alamos National Laboratory (LANL), Los Alamos, NM (United States). Center for Integrated Nanotechnologies (CINT)

This study reports a binder-free, catalyst-free method for fabricating vertically aligned carbon nanotubes (VACNTs) directly on copper (Cu) foil using plasma-enhanced chemical vapor deposition (PECVD) for electrochemical double-layer capacitor (EDLC) applications. This approach eliminates the need for catalyst layers, polymeric binders, or substrate pre-treatments, simplifying electrode design and enhancing electrical integration. The resulting VACNTs form a dense, uniform, and porous array with strong adhesion to the Cu substrate, minimizing contact resistance and improving conductivity. Electrochemical analysis shows gravimetric specific capacitance (C_grav) and areal specific capacitance (C_areal) of 8 F g⁻¹ and 3.5 mF cm⁻² at a scan rate of 5 mV/s, with low equivalent series resistance (3.70 Ω) and charge transfer resistance (0.48 Ω), enabling efficient electron transport and rapid ion diffusion. The electrode demonstrates excellent rate capability and retains 92% of its initial specific capacitance after 3000 charge–discharge cycles, indicating strong cycling stability. These results demonstrate the potential of directly grown VACNT-based electrodes for high-performance EDLCs, particularly in applications requiring rapid charge–discharge cycles and sustained energy delivery.

View Accepted Manuscript (DOE)

Research Organization:: Los Alamos National Laboratory (LANL), Los Alamos, NM (United States)

Sponsoring Organization:: USDOE National Nuclear Security Administration (NNSA); USDOE Office of Science (SC), Basic Energy Sciences (BES). Scientific User Facilities (SUF); National Science Foundation (NSF)

Grant/Contract Number:: 89233218CNA000001

OSTI ID:: 2998256

Report Number(s):: LA-UR--25-22265; 10.3390/nano15191506; 2079-4991

Journal Information:: Nanomaterials, Journal Name: Nanomaterials Journal Issue: 19 Vol. 15; ISSN 2079-4991

Publisher:: MDPI AGCopyright Statement

Country of Publication:: United States

Language:: English

References (65)

Thermal and Electrical Conductivity of 99.9% Pure Copper Processed via Selective Electron Beam Melting : Conductivities of Pure SEBM-Copper Raab, Sebastian J.; Guschlbauer, Ralf; Lodes, Matthias A. Advanced Engineering Materials, Vol. 18, Issue 9 https://doi.org/10.1002/adem.201600078	journal	July 2016
Role of Oxygen Functional Groups in Carbon Nanotube/Graphene Freestanding Electrodes for High Performance Lithium Batteries Byon, Hye Ryung; Gallant, Betar M.; Lee, Seung Woo Advanced Functional Materials, Vol. 23, Issue 8 https://doi.org/10.1002/adfm.201200697	journal	June 2012
Energy Storage Data Reporting in Perspective—Guidelines for Interpreting the Performance of Electrochemical Energy Storage Systems Mathis, Tyler S.; Kurra, Narendra; Wang, Xuehang Advanced Energy Materials, Vol. 9, Issue 39 https://doi.org/10.1002/aenm.201902007	journal	August 2019
Monitoring oxidation of multiwalled carbon nanotubes by Raman spectroscopy Osswald, Sebastian; Havel, Mickael; Gogotsi, Yury Journal of Raman Spectroscopy, Vol. 38, Issue 6 https://doi.org/10.1002/jrs.1686	journal	January 2007
Fabrication of completely filled carbon nanotubes with copper nanowires in a confined space Kokai, F.; Shimazu, T.; Adachi, K. Applied Physics A, Vol. 97, Issue 1 https://doi.org/10.1007/s00339-009-5339-3	journal	July 2009
Growth of carbon nanotubes on aluminium foil for supercapacitors electrodes Kavian, Reza; Vicenzo, Antonello; Bestetti, Massimiliano Journal of Materials Science, Vol. 46, Issue 5 https://doi.org/10.1007/s10853-010-4950-1	journal	October 2010
Nitrogen plasma functionalization of carbon nanotubes for supercapacitor applications Hussain, Shahzad; Amade, Roger; Jover, Eric Journal of Materials Science, Vol. 48, Issue 21 https://doi.org/10.1007/s10853-013-7579-z	journal	August 2013
MXene Enhanced 3D Needled Waste Denim Felt for High-Performance Flexible Supercapacitors Fan, Wei; Wang, Qi; Rong, Kai Nano-Micro Letters, Vol. 16, Issue 1 https://doi.org/10.1007/s40820-023-01226-y	journal	November 2023
Carbon nanotubes: synthesis, properties and engineering applications Gupta, Nikita; Gupta, Shipra Mital; Sharma, S. K. Carbon Letters, Vol. 29, Issue 5 https://doi.org/10.1007/s42823-019-00068-2	journal	July 2019
Vertically aligned carbon nanotubes-coated aluminium foil as flexible supercapacitor electrode for high power applications Ghai, Viney; Chatterjee, Kingshuk; Agnihotri, Prabhat K. Carbon Letters, Vol. 31, Issue 3 https://doi.org/10.1007/s42823-020-00176-4	journal	August 2020
Electrochemical performance of various activated carbon-multi-walled carbon nanotubes symmetric supercapacitor electrodes in aqueous electrolytes Thillaikkarasi, Dhanapal; Karthikeyan, Srinivasan; Ramesh, Rajendran Carbon Letters, Vol. 32, Issue 6 https://doi.org/10.1007/s42823-022-00386-y	journal	August 2022
X-ray diffraction characterization on the alignment degree of carbon nanotubes Cao, Anyuan; Xu, Cailu; Liang, Ji Chemical Physics Letters, Vol. 344, Issue 1-2 https://doi.org/10.1016/S0009-2614(01)00671-6	journal	August 2001
Electrochemically Deposited Nanograin Ruthenium Oxide as a Pseudocapacitive Electrode Gujar, T. P.; Kim, Woo-Young; Puspitasari, Indra International Journal of Electrochemical Science, Vol. 2, Issue 9 https://doi.org/10.1016/S1452-3981(23)17102-1	journal	September 2007
Synthesis and field emission properties of Cu-filled vertically aligned carbon nanotubes Thapa, Arun; Wang, Xuewen; Li, Wenzhi Applied Surface Science, Vol. 537 https://doi.org/10.1016/j.apsusc.2020.148086	journal	January 2021
Efficient diffusion barrier layers for the catalytic growth of carbon nanotubes on copper substrates García-Céspedes, J.; Thomasson, S.; Teo, K. B. K. Carbon, Vol. 47, Issue 3 https://doi.org/10.1016/j.carbon.2008.10.045	journal	March 2009
Study on the mechanical and electrical properties of twisted CNT yarns fabricated from CNTs with various diameters Inoue, Yoku; Hayashi, Kohei; Karita, Motoyuki Carbon, Vol. 176 https://doi.org/10.1016/j.carbon.2021.01.139	journal	May 2021
An intrinsically non-flammable organic electrolyte for wide temperature range supercapacitors Li, Shaohui; Tian, Qingyong; Chen, Jingwei Chemical Engineering Journal, Vol. 457 https://doi.org/10.1016/j.cej.2022.141265	journal	February 2023
Enhancing charge transfer utilizing ternary composite slurry for high-efficient flow-electrode capacitive deionization Yan, Lvji; Issaka Alhassan, Sikpaam; Gang, Haiyin Chemical Engineering Journal, Vol. 468 https://doi.org/10.1016/j.cej.2023.143413	journal	July 2023
Outstanding adsorption performance of high aspect ratio and super-hydrophobic carbon nanotubes for oil removal Kayvani Fard, Ahmad; Mckay, Gordon; Manawi, Yehia Chemosphere, Vol. 164 https://doi.org/10.1016/j.chemosphere.2016.08.099	journal	December 2016
Hollow SnO2 microspheres and their carbon-coated composites for supercapacitors Ren, Suzhen; Yang, Ying; Xu, Meiling Colloids and Surfaces A: Physicochemical and Engineering Aspects, Vol. 444 https://doi.org/10.1016/j.colsurfa.2013.12.028	journal	March 2014
FTIR studies of nitrogen doped carbon nanotubes Misra, Abha; Tyagi, Pawan K.; Singh, M. K. Diamond and Related Materials, Vol. 15, Issue 2-3 https://doi.org/10.1016/j.diamond.2005.08.013	journal	February 2006
RF-PECVD growth and nitrogen plasma functionalization of CNTs on copper foil for electrochemical applications Hussain, Shahzad; Amade, Roger; Moreno, Harold Diamond and Related Materials, Vol. 49 https://doi.org/10.1016/j.diamond.2014.08.006	journal	October 2014
Preparation of carbon nanotube-activated carbon hybrid electrodes by electrophoretic deposition for supercapacitor applications Huq, Mohammad Mahmudul; Hsieh, Chien-Te; Ho, Chia-Yin Diamond and Related Materials, Vol. 62 https://doi.org/10.1016/j.diamond.2015.12.014	journal	February 2016
Supercapacitor electrodes by direct growth of multi-walled carbon nanotubes on Al: a study of performance versus layer growth evolution Zhao, Fu; Vicenzo, Antonello; Hashempour, Mazdak Electrochimica Acta, Vol. 150 https://doi.org/10.1016/j.electacta.2014.10.129	journal	December 2014
High-performance supercapacitors based on the carbon nanotubes, graphene and graphite nanoparticles electrodes Aval, L. Fekri; Ghoranneviss, M.; Pour, G. Behzadi Heliyon, Vol. 4, Issue 11 https://doi.org/10.1016/j.heliyon.2018.e00862	journal	November 2018
In situ growth of self-supported and defect-engineered carbon nanotube networks on 316L stainless steel as binder-free supercapacitors Lei, Rui; Ni, Hongwei; Chen, Rongsheng Journal of Colloid and Interface Science, Vol. 532 https://doi.org/10.1016/j.jcis.2018.08.035	journal	December 2018
Electrochemical properties of ultra-long, aligned, carbon nanotube array electrode in organic electrolyte Zhang, Hao; Cao, Gaoping; Yang, Yusheng Journal of Power Sources, Vol. 172, Issue 1 https://doi.org/10.1016/j.jpowsour.2007.07.060	journal	October 2007
Carbon nanotube film anodes for flexible lithium ion batteries Yoon, Sora; Lee, Sehyun; Kim, Soyoung Journal of Power Sources, Vol. 279 https://doi.org/10.1016/j.jpowsour.2015.01.013	journal	April 2015
A comparative study of high density Vertically Aligned Carbon Nanotubes grown onto different grades of aluminum – Application to supercapacitors Querne, Corentin; Vignal, Thomas; Pinault, Mathieu Journal of Power Sources, Vol. 553 https://doi.org/10.1016/j.jpowsour.2022.232258	journal	January 2023
Template synthesis and characterization of well-aligned nitrogen containing carbon nanotubes Maiyalagan, T.; Viswanathan, B. Materials Chemistry and Physics, Vol. 93, Issue 2-3 https://doi.org/10.1016/j.matchemphys.2005.03.039	journal	October 2005
Synthesis of tin oxide/graphene (SnO 2 /G) nanocomposite and its electrochemical properties for supercapacitor applications Velmurugan, V.; Srinivasarao, U.; Ramachandran, R. Materials Research Bulletin, Vol. 84 https://doi.org/10.1016/j.materresbull.2016.07.015	journal	December 2016
Growth of Carbon Nano Tubes on Copper Substrate Suitable for Lithium Ion Battery Anode Sepahvand, S.; Safaei, P.; Sanaee, Z. Procedia Materials Science, Vol. 11 https://doi.org/10.1016/j.mspro.2015.11.100	journal	January 2015
Roll-to-roll synthesis of vertically aligned carbon nanotube electrodes for electrical double layer capacitors Arcila-Velez, Margarita R.; Zhu, Jingyi; Childress, Anthony Nano Energy, Vol. 8 https://doi.org/10.1016/j.nanoen.2014.05.004	journal	September 2014
Flexible supercapacitor electrodes with vertically aligned carbon nanotubes grown on aluminum foils Dogru, Itir Bakis; Durukan, Mete Batuhan; Turel, Onur Progress in Natural Science: Materials International, Vol. 26, Issue 3 https://doi.org/10.1016/j.pnsc.2016.05.011	journal	June 2016
The effect of temperature on the growth of carbon nanotubes on copper foil using a nickel thin film as catalyst Atthipalli, G.; Epur, R.; Kumta, P. N. Thin Solid Films, Vol. 519, Issue 16 https://doi.org/10.1016/j.tsf.2011.02.046	journal	June 2011
Aligned CNT Forests on Stainless Steel Mesh for Flexible Supercapacitor Electrode with High Capacitance and Power Density Avasthi, Piyush; Kumar, Akash; Balakrishnan, Viswanath ACS Applied Nano Materials, Vol. 2, Issue 3 https://doi.org/10.1021/acsanm.8b02355	journal	February 2019
Decoding Carbon-Based Materials’ Properties for High CO₂ Capture and Selectivity Mehra, Palak; Paul, Amit ACS Omega, Vol. 7, Issue 38 https://doi.org/10.1021/acsomega.2c04269	journal	September 2022
Direct Growth of Binder-Free CNTs on a Nickel Foam Substrate for Highly Efficient Symmetric Supercapacitors Isacfranklin, Melkiyur; Rathinam, Yuvakkumar; Ganesan, Ravi ACS Omega, Vol. 8, Issue 13 https://doi.org/10.1021/acsomega.2c04998	journal	March 2023
Rational Design of a Redox-Active Nonaqueous Electrolyte for a High-Energy-Density Supercapacitor Based on Carbon Nanotubes Park, Jinwoo; Yoo, Young-Eun; Mai, Liqiang ACS Sustainable Chemistry & Engineering, Vol. 7, Issue 8 https://doi.org/10.1021/acssuschemeng.8b06486	journal	February 2019
Facile Synthesis of Graphene-Wrapped Honeycomb MnO₂ Nanospheres and Their Application in Supercapacitors Zhu, Jiayi; He, Junhui ACS Applied Materials & Interfaces, Vol. 4, Issue 3 https://doi.org/10.1021/am3000165	journal	February 2012
Ion Diffusion and Electrochemical Capacitance in Aligned and Packed Single-Walled Carbon Nanotubes Izadi-Najafabadi, Ali; Futaba, Don N.; Iijima, Sumio Journal of the American Chemical Society, Vol. 132, Issue 51 https://doi.org/10.1021/ja108766y	journal	December 2010
Nickel Catalyst-Assisted Vertical Growth of Dense Carbon Nanotube Forests on Bulk Copper Atthipalli, Gowtam; Epur, Rigved; Kumta, Prashant N. The Journal of Physical Chemistry C, Vol. 115, Issue 9 https://doi.org/10.1021/jp108624n	journal	February 2011
Direct Growth of Aligned Multiwalled Carbon Nanotubes on Treated Stainless Steel Substrates Masarapu, Charan; Wei, Bingqing Langmuir, Vol. 23, Issue 17 https://doi.org/10.1021/la7012232	journal	July 2007
High Capacity and Excellent Stability of Lithium Ion Battery Anode Using Interface-Controlled Binder-Free Multiwall Carbon Nanotubes Grown on Copper Lahiri, Indranil; Oh, Sung-Woo; Hwang, Jun Y. ACS Nano, Vol. 4, Issue 6 https://doi.org/10.1021/nn100400r	journal	May 2010
Progress in the Raman spectra analysis of covalently functionalized multiwalled carbon nanotubes: unraveling disorder in graphitic materials Rebelo, Susana L. H.; Guedes, Alexandra; Szefczyk, Monika E. Physical Chemistry Chemical Physics, Vol. 18, Issue 18 https://doi.org/10.1039/C5CP06519D	journal	January 2016
Catalyst-free growth of carbon nanotube arrays directly on Inconel® substrates for electrochemical carbon-based electrodes Silva, Ricardo Manuel; Bastos, Alexandre Cunha; Oliveira, Filipe Jose Journal of Materials Chemistry A, Vol. 3, Issue 34 https://doi.org/10.1039/C5TA03734D	journal	January 2015
Carbon materials as oil sorbents: a review on the synthesis and performance Gupta, Shivam; Tai, Nyan-Hwa Journal of Materials Chemistry A, Vol. 4, Issue 5 https://doi.org/10.1039/C5TA08321D	journal	January 2016
Functionalized carbon nanotube (CNT) membrane: progress and challenges Sianipar, Merry; Kim, Seung Hyun; Khoiruddin, Khoiruddin RSC Advances, Vol. 7, Issue 81 https://doi.org/10.1039/C7RA08570B	journal	January 2017
Beta-phased Ni(OH)2 nanowall film with reversible capacitance higher than theoretical Faradic capacitance Lu, Zhiyi; Chang, Zheng; Zhu, Wei Chemical Communications, Vol. 47, Issue 34 https://doi.org/10.1039/c1cc13796d	journal	January 2011
Comparison of GO, GO/MWCNTs composite and MWCNTs as potential electrode materials for supercapacitors Aboutalebi, Seyed Hamed; Chidembo, Alfred T.; Salari, Maryam Energy & Environmental Science, Vol. 4, Issue 5 https://doi.org/10.1039/c1ee01039e	journal	January 2011
Advances and challenges for flexible energy storage and conversion devices and systems Li, Lin; Wu, Zhong; Yuan, Shuang Energy & Environmental Science, Vol. 7, Issue 7 https://doi.org/10.1039/c4ee00318g	journal	January 2014
Flexible supercapacitors based on carbon nanomaterials Chen, Tao; Dai, Liming Journal of Materials Chemistry A, Vol. 2, Issue 28 https://doi.org/10.1039/c4ta00567h	journal	January 2014
Low temperature growth of ultra-high mass density carbon nanotube forests on conductive supports Sugime, Hisashi; Esconjauregui, Santiago; Yang, Junwei Applied Physics Letters, Vol. 103, Issue 7 https://doi.org/10.1063/1.4818619	journal	August 2013
Effect of alignment on adsorption characteristics of self-oriented multi-walled carbon nanotube arrays Zilli, D.; Bonelli, P. R.; Cukierman, A. L. Nanotechnology, Vol. 17, Issue 20 https://doi.org/10.1088/0957-4484/17/20/016	journal	September 2006
Using a cut–paste method to prepare a carbon nanotube fur electrode Zhang, H.; Cao, G. P.; Yang, Y. S. Nanotechnology, Vol. 18, Issue 19 https://doi.org/10.1088/0957-4484/18/19/195607	journal	April 2007
High-performance supercapacitors based on vertically aligned carbon nanotubes and nonaqueous electrolytes Kim, Byungwoo; Chung, Haegeun; Kim, Woong Nanotechnology, Vol. 23, Issue 15 https://doi.org/10.1088/0957-4484/23/15/155401	journal	March 2012
Synthesis of carbon nanotubes and nanotube forests on copper catalyst Kruszka, Bartosz; Terzyk, Artur P.; Wiśniewski, Marek Materials Research Express, Vol. 1, Issue 3 https://doi.org/10.1088/2053-1591/1/3/035040	journal	September 2014
Direct deposition of multi-walled carbon nanotubes onto stainless steel and YEF foils using a simple electrophoretic deposition for electrochemical capacitor electrode Azam, Mohd Asyadi; Talib, Elyas; Seman, Raja Noor Amalina Raja Materials Research Express, Vol. 6, Issue 1 https://doi.org/10.1088/2053-1591/aae293	journal	October 2018
Anomalous Increase in Carbon Capacitance at Pore Sizes Less Than 1 Nanometer Chmiola, J. Science, Vol. 313, Issue 5794 https://doi.org/10.1126/science.1132195	journal	September 2006
Transition from “Supercapacitor” to “Battery” Behavior in Electrochemical Energy Storage Conway, B. E. Journal of The Electrochemical Society, Vol. 138, Issue 6, p. 1539-1548 https://doi.org/10.1149/1.2085829	journal	January 1991
Comparison Between Electrochemical Properties of Aligned Carbon Nanotube Array and Entangled Carbon Nanotube Electrodes Zhang, Hao; Cao, Gaoping; Yang, Yusheng Journal of The Electrochemical Society, Vol. 155, Issue 2 https://doi.org/10.1149/1.2811864	journal	January 2008
Growth of aligned multiwalled carbon nanotubes on bulk copper substrates by chemical vapor deposition Li, Ge; Chakrabarti, Supriya; Schulz, Mark Journal of Materials Research, Vol. 24, Issue 9 https://doi.org/10.1557/jmr.2009.0339	journal	September 2009
Cytotoxicity of carbon nanotube variants: A comparativein vitroexposure study with A549 epithelial and J774 macrophage cells Kumarathasan, Prem; Breznan, Dalibor; Das, Dharani Nanotoxicology, Vol. 9, Issue 2 https://doi.org/10.3109/17435390.2014.902519	journal	April 2014
Electrodeposited Nanostructured CoFe2O4 for Overall Water Splitting and Supercapacitor Applications Zhang, Chunyang; Bhoyate, Sanket; Zhao, Chen Catalysts, Vol. 9, Issue 2 https://doi.org/10.3390/catal9020176	journal	February 2019
Field Emission Properties of Cu-Filled Vertically Aligned Carbon Nanotubes Grown Directly on Thin Cu Foils Nwanno, Chinaza E.; Thapa, Arun; Watt, John Nanomaterials, Vol. 14, Issue 11 https://doi.org/10.3390/nano14110988	journal	June 2024

Similar Records

An electrochemical double layer capacitor using an activated carbon electrode with gel electrolyte binder

Journal Article · Sat May 01 00:00:00 EDT 1999 · Journal of the Electrochemical Society · OSTI ID:354416

Properties of electric double-layer capacitors with various polymer gel electrolytes

Journal Article · Mon Sep 01 00:00:00 EDT 1997 · Journal of the Electrochemical Society · OSTI ID:556827

High-capacity electric double-layer capacitor with high-density-activated carbon fiber electrodes

Journal Article · Fri Dec 31 23:00:00 EST 1999 · Journal of the Electrochemical Society · OSTI ID:20014482

Related Subjects

25 ENERGY STORAGE
36 MATERIALS SCIENCE
EDLC
PECVD
VACNTs
copper substrate
specific capacitance
supercapacitor

Vertically Aligned Carbon Nanotubes Grown on Copper Foil as Electrodes for Electrochemical Double Layer Capacitors

Citation Formats

References (65)

Similar Records

Related Subjects