ECS Transactions, 61 (6) 17-19 (2014)

10.1149/06106.0017ecst ©The Electrochemical Society

Knitted Electrochemical Capacitors Via Natural Fiber Welded Electrode Yarns

David P. Durkin1, Kristy Jost2,4, E. Kathryn Brown1, Luke Haverhals3, Genevieve Dion4,
Yury Gogotsi2, Hugh De Long5, and Paul C. Trulove1

1
U. S. Naval Academy, Department of Chemistry, Annapolis, MD, USA
2
A.J. Drexel Nanotechnology Institute, Materials Science and Engineering Department,
Drexel University, Philadelphia, PA, USA
3
Bradley University, Mund-Lagowski Dept of Chemistry, Peoria, IL, USA
4
Shima Seiki Haute Technology Laboratory, ExCITe Center, Drexel University,
Philadelphia, PA, USA
5
Air Force Office of Scientific Research, Complex Materials and Devices Department,
Arlington, VA, USA

This report presents a novel ionic liquid-based method for

fabricating flexible double layer supercapacitor electrodes utilizing
natural substrates. It investigates the performance of these yarns
knitted as fabrics and with other cellulose-based fibers welded with
carbon particles. Scanning electron microscopy, mechanical
properties testing, conductivity and other electrochemical testing
are performed to characterize both individual yarns and knitted
devices.

Natural fiber welding (NFW) is a process that uses controlled amounts of ionic liquid
(IL) and molecular co-solvents to selectively swell and mobilize biopolymers in fibrous,
natural materials for functional (chemical and physical) modification.1-4 NFW processes
control and minimize the amount of dissolution to fibrous natural substrates. By
carefully regulating the ratio of solvent to substrate, solvent efficacy, time, temperature,
pressure, location of solvent exposure, etc., hydrogen bonding networks are reconfigured
and extended by only mobilizing the outer shell of individual fibers. The result is that
fibers are essentially ‘welded’ together while the cores maintain their native states.

In this work, the traditional fiber welding process has been modified to incorporate
carbon materials into the biopolymer matrix, resulting in flexible carbon containing yarns
for wearable supercapacitor applications. Using a solution of imidizolium acetate (EMI-
Ac) with co-solvent, the yarn's cellulose matrix is opened; the dissolved carbon with
binder is then drawn under pressure into the opened matrix and embedded into the fibers.
A water bath is used to drive out the EMI-Ac and reconstitute the fibers, now embedded
with carbon (Figure 1).

To determine whether the material is a viable candidate for wearable supercapacitors,

the welded carbon-yarns are coated with polymer electrolyte (PVA-H3PO4-SiWA-H2O),
and then twisted with stainless steel yarn (current collector) and electrochemically tested
in a symmetric configuration through cyclic voltammetry, galvanostatic cycling, and
impedance spectroscopy. Electrochemical testing was performed on samples randomly
selected across the entire length of the prepared yarn electrodes, typically 10-20 ft in
length. The yarns yield 8-12 mF/cm, which is comparable with previously reported

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 ECS Transactions, 61 (6) 17-19 (2014)

literature. However, when the cotton is twisted with steel prior to coating, there is a
dramatic increase in capacitance, up to 45 mF/cm, though it is the same material system.
Fabrication can have a dramatic effect on the electrochemical performance. SEM images
also indicate that the coating was consistent, delivering a coated outer shell of carbon,
with some penetration of carbon materials into the yarn’s core.

Figure 1. SEM Analysis of Selected Coated Yarns.

The mechanical properties of the cellulose yarns also play a crucial role when knitting
these capacitive yarns into full fabrics, thus tensile testing of the yarns pre- and post
welding were conducted. Tensile strength and mass load data represent average values of
sample sets from the beginning 3’ and end 3’ of a particular coated yarn. In each case, an
improved strength was seen at the expense of elasticity; the most notable increases in
strength and toughness were measured for the viscose and linen welded samples (Table
I).

Table I. Tensile Testing Summary for Fiber Welded Cellulose Yarns

PERCENT CHANGE FROM NATIVE YARN (%)

Substrate Energy to Break Max Stress at Break (Strength)

(Toughness)
Cotton (11) – ( 31) 6-14
Viscose 22 107
Bamboo (52) no significant change
Linen 22 78

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 ECS Transactions, 61 (6) 17-19 (2014)

Though many of the cotton yarns produced have favorable electrochemical

performance, none were machine-knittable. The linen, viscose, and bamboo yarn
supercapacitors were successfully machine knitted at Drexel’s Shima Seiki Haute Tech
Lab (Figure 2). We currently attribute this to the length of the fibers playing a role in
flexibility and mechanical strength within the yarn. More work is currently underway to
explain this process, and fabricate a welded cotton yarn that can be knitted.

Figure 2. Machine Knitted Activated Carbon Supercapacitor Electrode

To date, we have demonstrated a coating process that is repeatable and scalable

(coating hundreds of feet at a time), inexpensive, and delivers competitive performance to
similar reports in the literature. Given that composites are constructed from a truly
‘green’ substrate (cotton, bamboo, etc.) and utilizing a nonfluorinated binder (cellulose
from cotton), we believe this to be a major breakthrough for the prospects of wearable
energy storage.5-7
Acknowledgements

Portions of this work were funded by the Air Force Office of Scientific Research. Any
opinions, findings, conclusions or recommendations expressed in the material are those
of the authors and do not necessarily reflect the views of the U.S Navy or U.S Air Force.
K. Jost acknowledges support from the DoD National Defense Science and Engineering
Graduate (NDSEG) Fellowship.
References

1. L. M. Haverhals, W. M.Reichert, H. C. De Long, P. C. Trulove, Macromol. Mater. Eng.,

2010,
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H. C. De Long, P. C. Trulove, ECS Transactions, 2010, 33, 79-90.
3. L. M. Haverhals, H. M. Sulpizio, Z. A. Fayos, M. A. Trulove, W. M. Reichert, M. P. Foley,
H. C. De Long, P. C. Trulove, Cellulose, 2012, 19, 13-22.
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6. Jost, K. et al. Energy and Environmental Science 4, (2011) 5060-5067;
7. Jost, K. et al. Energ Environ Sci, 6 (2013) 2698–2705.

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