skip to main content
DOE PAGES title logo U.S. Department of Energy
Office of Scientific and Technical Information

Title: High Areal Energy 3D-Interdigitated Micro-Supercapacitors in Aqueous and Ionic Liquid Electrolytes

Abstract

The fabrication of high performance on-chip 3D micro-supercapacitors (MSCs) based on MnO 2 pseudocapacitive binder-free thin film electrodes (< 500 nm thick) with interdigitated topology is reported. An original technological process easily scalable to pilot production line is proposed on 3-inch silicon wafers. High areal energy (> 10 μWh.cm -2) and power densities (> 10 mW.cm -2) are reached on small footprint micro-supercapacitors (4 mm 2) tested in aqueous electrolyte (0.8 V). Furthermore, the cell voltage of such MSC can be increased up to 1.5 V with EMI TFSI ionic liquids but at the expense of the areal capacitance. The performance in ionic liquid is in the same order of magnitude than the one obtained for aqueous electrolyte. The benefit from the 3D topology is clearly demonstrated when the surface performance are normalized to the electrode thickness allowing to obtain an interesting energy vs power tradeoff (> 10 μWh.cm -2 μm -1 and > 1 mw.cm -2 μm -1). Here, this paper aims at improving the energy density of MSCs while keeping high power capability, by combining the use of ionic liquids and the deposition of MnO 2 thin film onto robust and efficient 3D scaffolds.

Authors:
 [1];  [2];  [3];  [4];  [2];  [2];  [2];  [5]
  1. Univ. de Lille, Lille (France). Inst. d'Electronique, de Microelectronique et de Nanotechnologies; Univ. de Nantes, Nantes (France). Inst. des Materiaux Jean Rouxel (IMN); Reseau sur le Stockage Electrochimique de l'Energie (RS2E), Amiens (France)
  2. Univ. de Nantes, Nantes (France). Inst. des Materiaux Jean Rouxel (IMN); Reseau sur le Stockage Electrochimique de l'Energie (RS2E), Amiens (France)
  3. Reseau sur le Stockage Electrochimique de l'Energie (RS2E), Amiens (France); Univ. de Picardie Jules Verne, Amiens (France)
  4. Argonne National Lab. (ANL), Argonne, IL (United States). Advanced Photon Source (APS)
  5. Univ. de Lille, Lille (France). Inst. d'Electronique, de Microelectronique et de Nanotechnologies; Reseau sur le Stockage Electrochimique de l'Energie (RS2E), Amiens (France)
Publication Date:
Research Org.:
Argonne National Lab. (ANL), Argonne, IL (United States)
Sponsoring Org.:
USDOE Office of Science (SC), Basic Energy Sciences (BES) (SC-22)
OSTI Identifier:
1426213
Alternate Identifier(s):
OSTI ID: 1375651
Grant/Contract Number:  
AC02-06CH11357
Resource Type:
Accepted Manuscript
Journal Name:
Advanced Materials Technologies
Additional Journal Information:
Journal Volume: 2; Journal Issue: 10; Journal ID: ISSN 2365-709X
Publisher:
Wiley
Country of Publication:
United States
Language:
English
Subject:
77 NANOSCIENCE AND NANOTECHNOLOGY; 3D silicon microtubes; interdigitated electrodes; micro-supercapacitors; pseudocapacitance; X-ray nanotomography

Citation Formats

Eustache, Etienne, Douard, Camille, Demortière, Arnaud, De Andrade, Vincent, Brachet, Mylene, Le Bideau, Jean, Brousse, Thierry, and Lethien, Christophe. High Areal Energy 3D-Interdigitated Micro-Supercapacitors in Aqueous and Ionic Liquid Electrolytes. United States: N. p., 2017. Web. doi:10.1002/admt.201700126.
Eustache, Etienne, Douard, Camille, Demortière, Arnaud, De Andrade, Vincent, Brachet, Mylene, Le Bideau, Jean, Brousse, Thierry, & Lethien, Christophe. High Areal Energy 3D-Interdigitated Micro-Supercapacitors in Aqueous and Ionic Liquid Electrolytes. United States. doi:10.1002/admt.201700126.
Eustache, Etienne, Douard, Camille, Demortière, Arnaud, De Andrade, Vincent, Brachet, Mylene, Le Bideau, Jean, Brousse, Thierry, and Lethien, Christophe. Mon . "High Areal Energy 3D-Interdigitated Micro-Supercapacitors in Aqueous and Ionic Liquid Electrolytes". United States. doi:10.1002/admt.201700126. https://www.osti.gov/servlets/purl/1426213.
@article{osti_1426213,
title = {High Areal Energy 3D-Interdigitated Micro-Supercapacitors in Aqueous and Ionic Liquid Electrolytes},
author = {Eustache, Etienne and Douard, Camille and Demortière, Arnaud and De Andrade, Vincent and Brachet, Mylene and Le Bideau, Jean and Brousse, Thierry and Lethien, Christophe},
abstractNote = {The fabrication of high performance on-chip 3D micro-supercapacitors (MSCs) based on MnO2 pseudocapacitive binder-free thin film electrodes (< 500 nm thick) with interdigitated topology is reported. An original technological process easily scalable to pilot production line is proposed on 3-inch silicon wafers. High areal energy (> 10 μWh.cm-2) and power densities (> 10 mW.cm-2) are reached on small footprint micro-supercapacitors (4 mm2) tested in aqueous electrolyte (0.8 V). Furthermore, the cell voltage of such MSC can be increased up to 1.5 V with EMI TFSI ionic liquids but at the expense of the areal capacitance. The performance in ionic liquid is in the same order of magnitude than the one obtained for aqueous electrolyte. The benefit from the 3D topology is clearly demonstrated when the surface performance are normalized to the electrode thickness allowing to obtain an interesting energy vs power tradeoff (> 10 μWh.cm-2 μm-1 and > 1 mw.cm-2 μm-1). Here, this paper aims at improving the energy density of MSCs while keeping high power capability, by combining the use of ionic liquids and the deposition of MnO2 thin film onto robust and efficient 3D scaffolds.},
doi = {10.1002/admt.201700126},
journal = {Advanced Materials Technologies},
number = 10,
volume = 2,
place = {United States},
year = {2017},
month = {8}
}

Journal Article:
Free Publicly Available Full Text
Publisher's Version of Record

Citation Metrics:
Cited by: 5 works
Citation information provided by
Web of Science

Save / Share:

Works referenced in this record:

Destructuring ionic liquids in ionogels: enhanced fragility for solid devices
journal, January 2014

  • Guyomard-Lack, A.; Delannoy, P. -E.; Dupré, N.
  • Phys. Chem. Chem. Phys., Vol. 16, Issue 43
  • DOI: 10.1039/C4CP03187C

Continuous carbide-derived carbon films with high volumetric capacitance
journal, January 2011

  • Heon, Min; Lofland, Samuel; Applegate, James
  • Energy Environ. Sci., Vol. 4, Issue 1
  • DOI: 10.1039/C0EE00404A

TomoPy: a framework for the analysis of synchrotron tomographic data
journal, August 2014

  • Gürsoy, Dogˇa; De Carlo, Francesco; Xiao, Xianghui
  • Journal of Synchrotron Radiation, Vol. 21, Issue 5
  • DOI: 10.1107/S1600577514013939

True Performance Metrics in Electrochemical Energy Storage
journal, November 2011


Atomic Layer Deposition Alumina-Passivated Silicon Nanowires: Probing the Transition from Electrochemical Double-Layer Capacitor to Electrolytic Capacitor
journal, April 2017

  • Gaboriau, Dorian; Boniface, Maxime; Valero, Anthony
  • ACS Applied Materials & Interfaces, Vol. 9, Issue 15
  • DOI: 10.1021/acsami.7b01574

Influence of the configuration in planar interdigitated electrochemical micro-capacitors
journal, May 2013


High-power lithium ion microbatteries from interdigitated three-dimensional bicontinuous nanoporous electrodes
journal, April 2013

  • Pikul, James H.; Gang Zhang, Hui; Cho, Jiung
  • Nature Communications, Vol. 4, Article No. 1732
  • DOI: 10.1038/ncomms2747

Engineering three-dimensional hybrid supercapacitors and microsupercapacitors for high-performance integrated energy storage
journal, March 2015

  • El-Kady, Maher F.; Ihns, Melanie; Li, Mengping
  • Proceedings of the National Academy of Sciences, Vol. 112, Issue 14
  • DOI: 10.1073/pnas.1420398112

Ultrahigh-power micrometre-sized supercapacitors based on onion-like carbon
journal, August 2010

  • Pech, David; Brunet, Magali; Durou, Hugo
  • Nature Nanotechnology, Vol. 5, Issue 9, p. 651-654
  • DOI: 10.1038/nnano.2010.162

Three-Dimensional Battery Architectures
journal, October 2004

  • Long, Jeffrey W.; Dunn, Bruce; Rolison, Debra R.
  • Chemical Reviews, Vol. 104, Issue 10, p. 4463-4492
  • DOI: 10.1021/cr020740l

Scalable fabrication of high-power graphene micro-supercapacitors for flexible and on-chip energy storage
journal, February 2013

  • El-Kady, Maher F.; Kaner, Richard B.
  • Nature Communications, Vol. 4, Issue 1
  • DOI: 10.1038/ncomms2446

High temperature carbon–carbon supercapacitor using ionic liquid as electrolyte
journal, March 2007


Fast and Reversible Surface Redox Reaction in Nanocrystalline Vanadium Nitride Supercapacitors
journal, May 2006

  • Choi, D.; Blomgren, G. E.; Kumta, P. N.
  • Advanced Materials, Vol. 18, Issue 9
  • DOI: 10.1002/adma.200502471

Nanotubular metal–insulator–metal capacitor arrays for energy storage
journal, March 2009

  • Banerjee, Parag; Perez, Israel; Henn-Lecordier, Laurent
  • Nature Nanotechnology, Vol. 4, Issue 5
  • DOI: 10.1038/nnano.2009.37

Solvent-Free Electrolytes for Electrical Double Layer Capacitors
journal, January 2015

  • Nègre, L.; Daffos, B.; Taberna, P. L.
  • Journal of The Electrochemical Society, Vol. 162, Issue 5
  • DOI: 10.1149/2.0061505jes

Ionogels, ionic liquid based hybrid materials
journal, January 2011

  • Le Bideau, Jean; Viau, Lydie; Vioux, André
  • Chem. Soc. Rev., Vol. 40, Issue 2
  • DOI: 10.1039/C0CS00059K

Materials for electrochemical capacitors
journal, November 2008

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

To Be or Not To Be Pseudocapacitive?
journal, January 2015

  • Brousse, Thierry; Bélanger, Daniel; Long, Jeffrey W.
  • Journal of The Electrochemical Society, Vol. 162, Issue 5
  • DOI: 10.1149/2.0201505jes

3D RuO 2 Microsupercapacitors with Remarkable Areal Energy
journal, September 2015

  • Ferris, Anaïs; Garbarino, Sébastien; Guay, Daniel
  • Advanced Materials, Vol. 27, Issue 42
  • DOI: 10.1002/adma.201503054

Scientific data exchange: a schema for HDF5-based storage of raw and analyzed data
journal, October 2014

  • De Carlo, Francesco; Gürsoy, Dogˇa; Marone, Federica
  • Journal of Synchrotron Radiation, Vol. 21, Issue 6
  • DOI: 10.1107/S160057751401604X

Realization of an Asymmetric Interdigitated Electrochemical Micro-Capacitor Based on Carbon Nanotubes and Manganese Oxide
journal, January 2015

  • Dinh, Ty Mai; Mesnilgrente, Fabien; Conédéra, Véronique
  • Journal of The Electrochemical Society, Vol. 162, Issue 10
  • DOI: 10.1149/2.0431510jes

3D hierarchical assembly of ultrathin MnO2 nanoflakes on silicon nanowires for high performance micro-supercapacitors in Li- doped ionic liquid
journal, May 2015

  • Dubal, Deepak P.; Aradilla, David; Bidan, Gérard
  • Scientific Reports, Vol. 5, Issue 1
  • DOI: 10.1038/srep09771

Silicon-Microtube Scaffold Decorated with Anatase TiO 2 as a Negative Electrode for a 3D Litium-Ion Microbattery
journal, January 2014

  • Eustache, Etienne; Tilmant, Pascal; Morgenroth, Laurence
  • Advanced Energy Materials, Vol. 4, Issue 8
  • DOI: 10.1002/aenm.201301612

Microsupercapacitors as miniaturized energy-storage components for on-chip electronics
journal, November 2016

  • Kyeremateng, Nana Amponsah; Brousse, Thierry; Pech, David
  • Nature Nanotechnology, Vol. 12, Issue 1
  • DOI: 10.1038/nnano.2016.196

3D Printing of Interdigitated Li-Ion Microbattery Architectures
journal, June 2013

  • Sun, Ke; Wei, Teng-Sing; Ahn, Bok Yeop
  • Advanced Materials, Vol. 25, Issue 33, p. 4539-4543
  • DOI: 10.1002/adma.201301036

Enhancement of lithium transport by controlling the mesoporosity of silica monoliths filled by ionic liquids
journal, January 2016

  • Guyomard-Lack, Aurélie; Said, Bilel; Dupré, Nicolas
  • New Journal of Chemistry, Vol. 40, Issue 5
  • DOI: 10.1039/C5NJ03318G

Electrochemical Characteristics and Impedance Spectroscopy Studies of Carbon-Carbon Supercapacitors
journal, January 2003

  • Taberna, P. L.; Simon, P.; Fauvarque, J. F.
  • Journal of The Electrochemical Society, Vol. 150, Issue 3, p. A292-A300
  • DOI: 10.1149/1.1543948

Laser Scribing of High-Performance and Flexible Graphene-Based Electrochemical Capacitors
journal, March 2012


Generalized Titarenko's algorithm for ring artefacts reduction
journal, October 2014


Perspective—A Guideline for Reporting Performance Metrics with Electrochemical Capacitors: From Electrode Materials to Full Devices
journal, January 2017

  • Balducci, A.; Belanger, D.; Brousse, T.
  • Journal of The Electrochemical Society, Vol. 164, Issue 7
  • DOI: 10.1149/2.0851707jes

Solder-reflow resistant solid-state micro-supercapacitors based on ionogels
journal, January 2016

  • Brachet, Mylène; Gaboriau, Dorian; Gentile, Pascal
  • Journal of Materials Chemistry A, Vol. 4, Issue 30
  • DOI: 10.1039/C6TA03142K

Direct laser writing of micro-supercapacitors on hydrated graphite oxide films
journal, July 2011


VN thin films as electrode materials for electrochemical capacitors
journal, September 2014


Charge Storage Mechanism of MnO 2 Electrode Used in Aqueous Electrochemical Capacitor
journal, August 2004

  • Toupin, Mathieu; Brousse, Thierry; Bélanger, Daniel
  • Chemistry of Materials, Vol. 16, Issue 16
  • DOI: 10.1021/cm049649j

On-chip and freestanding elastic carbon films for micro-supercapacitors
journal, February 2016


Fabrication and properties of a carbon/polypyrrole three-dimensional microbattery
journal, April 2008


Supercapacitor Behavior with KCl Electrolyte
journal, April 1999

  • Lee, Hee Y.; Goodenough, J. B.
  • Journal of Solid State Chemistry, Vol. 144, Issue 1
  • DOI: 10.1006/jssc.1998.8128

All Solid-State Symmetrical Activated Carbon Electrochemical Double Layer Capacitors Designed with Ionogel Electrolyte
journal, January 2014

  • Brachet, M.; Brousse, T.; Le Bideau, J.
  • ECS Electrochemistry Letters, Vol. 3, Issue 11
  • DOI: 10.1149/2.0051411eel

MnO 2 Thin Films on 3D Scaffold: Microsupercapacitor Electrodes Competing with “Bulk” Carbon Electrodes
journal, July 2015

  • Eustache, Etienne; Douard, Camille; Retoux, Richard
  • Advanced Energy Materials, Vol. 5, Issue 18
  • DOI: 10.1002/aenm.201500680

Holographic patterning of high-performance on-chip 3D lithium-ion microbatteries
journal, May 2015

  • Ning, Hailong; Pikul, James H.; Zhang, Runyu
  • Proceedings of the National Academy of Sciences, Vol. 112, Issue 21
  • DOI: 10.1073/pnas.1423889112

Effect of Sn-doping on the electrochemical behaviour of TiO2 nanotubes as potential negative electrode materials for 3D Li-ion micro batteries
journal, February 2013


Graphene-based in-plane micro-supercapacitors with high power and energy densities
journal, September 2013

  • Wu, Zhong–Shuai; Parvez, Khaled; Feng, Xinliang
  • Nature Communications, Vol. 4, Issue 1
  • DOI: 10.1038/ncomms3487

    Works referencing / citing this record:

    The Road Towards Planar Microbatteries and Micro‐Supercapacitors: From 2D to 3D Device Geometries
    journal, June 2019


    The Road Towards Planar Microbatteries and Micro‐Supercapacitors: From 2D to 3D Device Geometries
    journal, June 2019


    Water-Soluble Hybrid Graphene Ink for Gravure-Printed Planar Supercapacitors
    journal, June 2018

    • Chang, Quanhong; Li, Lemei; Sai, Liman
    • Advanced Electronic Materials, Vol. 4, Issue 8
    • DOI: 10.1002/aelm.201800059