Grant

Heileman

Fall 2016
CBE 577 Term Paper

Electrolytic Capacitors
&
Porous Electrodes

Introduction

The charge transfer mechanisms, of electrolytic capacitors, are well-studied

phenomena. Fundamental electrokenetic theories have established working
boundaries; through which, macroscopic geometry and constitutive parameters
determine the capacitors characteristics. These boundaries are investigated as
nano-processing techniques mature; however, effects of nano-scale physics are
difficult to evaluate and can be computationally expensive over large domains.
Luckily, keen observations and careful approximations can yield surprising
analogies and intuitive results. These new characteristics can be used to adapt
current models and may prove useful when deepening our understanding of the
fundamental physics involved.

History

The entire history, of any single fundamental science, is difficult to trace; yet
the pillars of interdisciplinary fields offer a unique insight into the marvel of the
scientific progress. Specifically, the intricacies of electrophysicochemical theory
developed in conjecture with its constituents. Leading to a rich and welldocumented history. Although initial experiments and theories generated by
physics and chemistry gave a glimpse into the possibility of this interdisciplinary
field, bioelectric-physiology was the first field to verify the theories
interconnectedness (Kumar).
In 1791, Luigi Galvani proposed and experimentally verified a theory
concerning animal electricity. He concluded that
electrocution of nerve cells stimulates organic
functions, such as muscle spasms; and despite
some misconceptions, within his theory, an
appreciation for the physiological implications
developed, culturally. It still took generations, of
scientific advancement, to develop the electric
Double Layer (DL) model needed to explain his
phenomena. Serendipitously Michael Faraday was
born the same year De Viribus Electricitatis in Motu
Musculari Commentarius was written (Galvani).

Galvani

Grant Heileman

Faraday

Fall 2016
CBE 577 Term Paper

During the next two centuries substantial
advancements were made in the electrochemistrys
physical (e.g. Thermodynamic, Electromagnetic, etc.)
theories. Faraday addressed a hand full of problems
out of the multiple scientific disciplines. Verifying his
hypothesis through a myriad of unique and ingenious
experiments: thus laying the foundations through
which his theories could make mathematical
approximations. Ironically, Faradays background did
not equip him with the techniques needed to express
retarded potentials. Despite this lack of mathematical
sophistication, in the theories, his raw talent as an
experimentalist earns him a place amongst some of
the most brilliant minds ever.

Arguably, Faradays most influential
contribution was the hypothesis that electromagnetic
force lines were vibrations that transmit via
contiguous particles. Monumental scientists such as
James Clerk Maxwell, Josiah Willard Gibbs, and
Hermann von Helmholtz used this postulate. Maxwell
and Gibbs had no problem considering particulate
theories and made momentous strides in statistical
thermodynamics. Leading the way to Gouy-Chapman
DLs.
On the other hand Helmholtz had difficulty
accepting a theory that did not involve ether (Kumar).
This did not stop him from conceptualizing a
tremendously complicated physical problem. Despite
glaring contradictions with his underlying EM beliefs,
he proposed the idea of counter-ions. He concluded
Helmholtz
that the counter-ions layer formed on charged
surfaces would act similarly to capacitors. This meant the electrolytic solution could
be treated like a dielectric (). With the system, as a whole, having a differential
capacitance proportional to the ratio of electrode distance () and integrated
surface area.

! =

4

Approximately 50 years later, Louis Georges Gouy and David Leonard
Chapman independently developed significantly more accurate models containing
two layers. By taking a one-dimensional Poisson potential,

!
!
=

!

Grant Heileman

Fall 2016
CBE 577 Term Paper

With ! being the volume charge density that obeys a Boltzmann statistics as
follows,
! =

! ! =

! !,! !

!! !"
!"

A new equation for differential capacitance can be acquired. One, which not only
takes into account the applied potentials but also, considers the statistical effects of
an electrolytes ion concentration. Integration, of the Poisson potential, then yields
!

!
2! !
! = 2 cosh
, =

2

The hyperbolic curve indicates a decrease in potential over a highly concentrated
region of electrolyte. Thus, Gouy-Chapman DL theory takes into account
thermodynamic diffusion: at the time an infantile concept, which took another
generation to further mature (E. Gongadze).

This generation, circa 1885, bore brilliant scientists such as Julius Tafel, Otto
Stern and Peter Debye, whom took the next developmental steps in electrochemical
DL modeling. Debyes contribution gave rise to better diffusion models,
contributing to the Debye-Hckel law. Tefel, using the concept of overpotentials,
elucidated irreversible electrochemical reactions that, at the time, could not be
explained via thermodynamic processes. All while, Stern concluded a layer made of
counter-ions exists, distinctly separate from diffusion activities.

Classical double layer models

The foundations for modern electrochemistry were set, and in the following
century exceedingly innovative expositions, and rigorous analytic procedures were
formed. John Alfred Valentine Butler, Max Volmer, and Erdey-Gruz Tibor began the
development of electrochemical kinetics, an approach that became seminal in the
realization of civilized DL theories. This theory leads to model adaptations that are

Grant Heileman

Fall 2016
CBE 577 Term Paper

traditionally considered outside the scope of chemical analysis. For instance a

precursor to this paradigm would be Revaz Dogonadze or Rudolph Marcus
quantum electrochemical theories (Kumar). Currently, the rule of thumb for a DL
model to be considered civilized is that ion and solvent size must be considered;
however, this is not to say that other multi-physics approximations could be
considered; such as Lars Osager and Samaras use of electrolyte polarization in
limitation laws (Dufreche). Even as a fully matured subject mater, DL physics is
poised to make significant advancements with help from the advanced technologies
of the 21st century.

Materials

The foundations established, during electrochemistrys adolescents, reviled

the importance of parameters such as electrolytic concentration and electrode
geometry. Consequently, the primary conclusions drawn, from contemporary
experiments, are highly dependent on the ability to produce regulated
nanostructures. Therefor a thorough understanding, of material characteristics, is
needed to extend double layer theories; and because of this, the forefronts of
material science offer inimitable perspectives.

In 2004 Dr. Geim and Dr. Novoselov
isolated the carbon allotrope Graphene.
Consequently wining a Nobel Prize by simply,
muching about in the lab with a piece of
scotch tape and some block Graphite
(Institute of Physics). Graphene has a single
atom layer hexagonal lattice structure. This
yields promising material characteristics,
such as impeccable heat conduction and
electrical conductivity. Theoretically, single
layer graphene exhibits super conductive
characteristics; which, in and of it self is an
Graphene structures
interesting phenomena. When used in
capacitors, the near zero resistivity can greatly improves functionality (University of
Manchester). Unfortunately, producing large batches of Single Layer Graphene
(SLG) is currently expensive and impractical; however, production of Reduced
Graphene Oxides (RGOs) can be used to, more easily, manufacture stagnated
graphene layers. While RGOs yield less than idyllic graphene structure, the
phenomenological properties mimic SLG and the manufacturing practicality makes
ROGs a viable market solution. Ideally the graphene can be formed into structures
such as Nanotubes or Bucky Balls.

As the material sciences are probed
for quantifiable adaptations to DL theory it
is important to remember that some of our
most basic understandings of capacitance
are established through constitutive
!"
equations. The equation = ! equates the

Pore-size definitions

Grant Heileman

Fall 2016
CBE 577 Term Paper

capacitance, of a parallel plate capacitor, to the physical properties plate-distance

(), surface area (), and dielectric permittivity (). The physical limitations
bounding the variable are insurmountable; however, research, in high surface
area to volume materials, is testing the limits of porosity. One method, for creating
high porosity materials, is to manufacture an aerogel. Aerogels are a substance that
are treated, in such a way, as so prescribed fillers are evacuated; leaving a structure
of porous material. Subsequently, designs that contain highly porous electrodes
should perform well beyond the operating ranges of traditional electronics.

In hopes of merging these concepts
Kansas State University has developed a
method of 3D printing graphene aerogel.
This is done by suspending RGO in water and
printing this solution on a cold plate. When
finished the sample is heated to evaporate
the water, leaving a 3D printed graphene
aerogel. Although, KSUs procedure is
spectacular; either, the advances in
manufacturing graphene or processing
aerogel are monumental in their own right.
Nonetheless, when these advances are paired
with well-designed experiments, the
limitations and predictions of the double
layer theory can be tested. As seen in the
past, this experimentation leads to model
adaptation and in turn these adaptations help
produce more effective technologies
(Qiangqiang Zhang).

3D printed Graphene Aerogel technique

Simulation and
Modeling

Computer simulations and mathematical models allow us to gain an intuition
regarding electrochemical phenomena. The Gouy-Chapman model, containing a
Stern layer, is a highly successful interpretation that takes into account diffusion
layers and some ion specificities. Consequently, the Stern layer is ill equip to
describe phenomena occurring in regions where surface geometry is on the order of
counter-ion size. These scenarios require model adaptations. Luckily, the electrical
properties of graphene result in convenient approximations that simplify
calculations of surface charge distribution in nano-porous devices. Combining this
superconductive approximations with know chemical and geometric constrains;
helps improve electrolytic capacitor models. Dr. Huang, Sumpter, and Meunier
developed a thought experiment where an Electric Double Layer Capacitors (EDLC)
is basically compactified about the electrolytic interface axis. This forms an Electric
Double Cylinder Capacitor (EDCC). When electrolyte and solvent size are taken into
account and the EDCC can be reduced to a cylinder the size of a single ion, creating
an Electric Wire-in-a-Cylinder Capacitor (EWCC) model (Jingsong Huang Dr.).

Grant Heileman

Fall 2016
CBE 577 Term Paper

From left to right: EWCC, EDCC, and EDLC

The EDCC model contains its own intriguing problems and insights. For
instance, as the cylinder becomes smaller the amount of electrolyte in the center is
reduced. As the amount of supporting electrolyte decreases we eventually reach a
size in which the Stern layer on one side of the cylinder interacts with the adjacent
Stern layer. If this reduction in size continues, we reach a point at which material
approximations can extend the EDCC model to an EWCC model.

EWCC modeling takes EDCC one step further, by making the pore sizes of the
same order as the ion size. An array of graphene nano-tubes could be used: allowing
ion conductivity, at the surface, to be analogous to charge running through a wire.
This is a significant conclusion as the theory allows us to utilize equations establish
for cylindrical capacitors. The equation below demonstrates a simple
approximation for EWCC normalized capacitance (/! ),
,

! !
=

ln( /! )

Where is the pore size and ! is the size of the ion inside the pore. Obviously the
singularity at ! = needs to be analyzed; in order, to determine why this theory
begins to diverge from empirical observations. Nevertheless, this yields accurate
results for pores sizes down to 0.5nm. At these scales partial desolations of the ion
from solution is required and Brunauer-Emmett-Teller (BET) theory is needed to
explain surface absorptions. BET is a physical explanation of gas absorption at solid
interfaces and is analogous to double, with the twist being the infinite number of
stochastic absorption layers (Tobias). The surface absorption can then be simply
considered as another explanation for particulate energy exchange of physical
phenomena.

Experimental Results

Although the EWCC model clearly reduces computational cost, some of the
quantum interactions are not well understood. This leads to the unique
opportunity; where classical theories do not match current experimental results.
Universit de Toulouse and Drexel and currently engaged in experimental research
demonstrating inconsistencies within classical models while agreeing quite will
with EWCCs predictions.

Grant Heileman

Fall 2016
CBE 577 Term Paper

TiC-derived, natural, and synthetic porous activated carbons (TiC-CDC,
NPAC,& SPAC) were used in their experiments. Changing each manufacturing
process duration and temperature made samples with pore sizes, varying from 0.61.2nm. From there, BET absorption measurements were taken and used to infer the
samples effective surface area. After quantification of the material, an electrolyte
tailored for the material is selected. In this case an Acrylonitrile-base electrolyte
contacting 1-mole ! ! was used, having solvated ions, of !! 7 and
!! 9, that are 1.3 and 1.2nm respectively (Simon). Bellow, the normalized
capacitance is compared to pore size; remarkably, showing significant deviation
from traditional simulations.

Experimental results compared to traditional theory

This unconventional increase could be explained by the fact that as partial
desolvation occurs the ions can access smaller pores, thus reducing the distance
between the charge carrier and the electrode. By accepting this fact, we conclude
that traditional DL physics cannot be used in sub-nanometer pores simply because a
defuse layer cannot form. This also point towards the need for civilized models to
be used. Obviously, the effects of ion desolvation need to be taken into account.
Which means, factors such as ion confinement are much more intimately involved,
with the underlying physics, than previously thought. These adaptations will be
needed, in order to get a more accurate accounting of each energy conversion
processes involved.

Grant Heileman

Fall 2016
CBE 577 Term Paper

Market Viability

As techniques for manufacturing unflawed EWCC devices mature, some
rudimentary production methods are being utilized to supply current technological
demands. With patents being held for a multitude of designs and fabrication
processes; such as interlaced porous fibers, and additives for device life extension.
For instance, see figures 6 and 7 in which a
patented application for a porous button
electrode is shown. These types of
supercapacitors are currently in use today!
This gambit of new technology, ranging
from implementation in energy harvesters
to automatic door operation, is
revolutionizing the electronics market (H.
Probstle; Shantanu Das; Akihiko Yoshida).
Patented button capacitor

Some of the challenges facing
the wide scale adaptation, of this
technology, are manufacturing
difficulties and durability.
Unfortunately the material strength
high porosity graphene aerogels is
fairly delicate and not currently
ready for high risk or fault
susceptible applications (WIREs).
Yet, contemporary research is
showing that addition of acrylics can
significantly increase the cycling
performance of graphene electrodes.
(Hailiang Wang; Maher F. El-Kady).
Along with continuing advances in
material sciences it is imaginable
that, in the near future, precise
EWCC capacitors could be a common
commodity.
Porous structures on button capacitor electrodes

Future Technologies

As this field develops and new generations of technology are rolled out it is

exciting to look at the exponentially advancing forefront. Reaching from faster

computer to influencing paradigm shifts; the technologies and theories mentioned
produce systemic changes in our day-to-day life. The most relevant of which is the
application to power management.

Grant Heileman

Fall 2016
CBE 577 Term Paper

A single electrical power storage device is incapable of supplying large

specific powers over a complete range of specific energy requirements. For
instance, although high quality dielectric capacitors can be used to harvest high
frequency energy, from low power
sources, they cannot leverage this
energy for applications requiring high
specific energy. EWCC supercapacitors
can help bridge this gap. One way is to
use Buck and Boost converters. They
are low energy pulsed power circuits
that exclusively increases voltage or
current, while reducing the other, by
cycling a high efficiency resonate circuit.
The circuit outputs a high frequency
pulsed signal that is approximated as DC
(Vamsi Talla).
Another possibility is that
specific electrode structures could be
leveraged to produce unique effects on
the ions. Since, it has been proven that
nano-pores effectively change an
electocapacitors properties: it is not
hard to imagine a more complex
structure yielding exciting and exotic
results. In a sense this would be a
metamaterial; however, instead of
having structures that influence EM
propagation the structures would act on
Ragone Plot
the electrolytes ion species.
The models, recently introduced, bring up questions fundamental in our
understanding of classical theories. The physics described in EWCC most likely
points toward surface interactions at quantum mechanical scales. However, it is
hard to say where the limitations of this theory will take us. In new experiments, we
could find that the solvents atomic fine structure adjusts to fit favorable surface
constraints. This would point towards experimentally verifiable hypotheses
regarding chromodynamics.

Summary

The theories and practices regarding double physics and electrolytic
capacitors have developed unprecedentedly, during the last decade, due to advances
in nano-porous device manufacturability. Leading to an exciting revolution in the
traditional theories governing electrolytic capacitors. As this scientific revolution
unearths hidden physical realities, the intense focus on manufacturability will allow
for nearly instantaneous market implementations. Overall the progress of porous
electrolytic capacitors is both scientifically enlightening and economically enriching.

Grant Heileman

Fall 2016
CBE 577 Term Paper

Works Cited

Akihiko Yoshida, Atsushi Nishino, Ichiro Tanahashi, Yasuhiro Takeuchi. Electric double layer capacitor and
method for producing the same. USA: Patent US4597028 A. 24 Jun 1986.

Dufreche, Jean-Francois. Ions at Interfaces. 2014-2015. 2016
<http://www.icsm.fr/Local/icsm/files/418/JFD_RECYCLING_19-02-2015.pdf>.

E. Gongadze, S. Petersen, U. Beck, U. van Rienen. "Classical Models of the Interface between an Electrode and an
Electrolyte." Milan: COMSOL Conference, 2009. 7.

Galvani, Luigi. Aloysii Galvani De viribus electricitatis in motu musculari commentarius. Bononiae : Ex
Typographia Instituti Scientiarium, 1791.

H. Probstle, C. Schmitt, J. Fricke. "Button Cell Supercapacitors with Monolithic Carbon Aerogels." Journal of
Power Sources 105 (2002): 6.

Hailiang Wang, Li-Feng Cui, Yuan Yang, Hernan Sanchez Casalongue, Joshua Tucker Robinson, Yongye Liang, Yi
Cui, and Hongjie Dai. "Mn3O4Graphene Hybrid as a High-Capacity Anode Material for Lithium Ion Batteries."
Jornal of the American Chemical Society (2010).

Institute of Physics. All about Graphene. 12 2016 <http://www.physics.org/article-questions.asp?id=67 >.

Jingsong Huang Dr., Bobby G. Sumpter Dr., Vincent Meunier Dr. "Theoretical Model for Nanoporous Carbon
Supercapacitors." Angewandte Chemie 47.3 (2007): 4.

Kumar, A.K. Shukla and T. Prem. Pillars of Modern Electrochemistry. Fall 2008. The Electrochemical Society.
<https://www.electrochem.org/dl/interface/fal/fal08/fal08_p31-39.pdf>.

Maher F. El-Kady, Veronica Strong, Sergey Dubin, Richard B. Kaner. "Laser Scribing of High-Performance and
Flexible Graphene-Based Electrochemical Capacitors." Science 335.6074 (2012): 4.

Qiangqiang Zhang, Feng Zhang, Chi Zhou, Dong Lin. "Three-Dimensional Printing of Graphene Aerogel." Small
(2016): 7.

Shantanu Das, N. C. Pramanik. "Indigenous Development of Carbon Aerogel Farad Super-capacitors and
Applications in Electronic circuits." BARC Newsletter 339 (2014): 10.

Simon, Patrice. "Charge storage mechanism in nanoporous carbons and its consequence for electrical double
layer capacitors." Philosophical Transactions of The Royal Society 368 (2010): 10.

Tobias. zumbuhllab.unibas.ch. <https://zumbuhllab.unibas.ch/pdf/talks/080425_Tobias_BET.pdf>.
University of Manchester. Graphene, Manchester's Revolutionary 2D Material. 2016
<http://www.graphene.manchester.ac.uk>.

Vamsi Talla, Bryce Kellogg, Benjamin Ransford, Saman Naderiparizi, Shyamnath Gollakota and Joshua R. Smith.
"Powering the Next Billion Devices with Wi-Fi." (2015).

WIREs Energy Environ 2013. doi: 10.1002/wene.102

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