Porous Electrodes: From Theory to

Applications in Electrosythesis

By:

Nimrah Anwar

Syed Mustafa Hassan Zaidi

Instructor:

Dr. Elod Gyenge

Electrochemical Science, Engineering and Technology (CHBE 577)

Chemical and Biological Engineering (CHBE)

University of British Columbia

March, 2017
 Abstract
Porous electrode theory provides a macroscopic picture of battery cycling behavior by microscopic
physical models of the electrode materials rather than the empirical circuit approximation. It
basically accounts for the porous microstructure. The general equations describing the behavior
of porous electrodes were first developed by UC Berkeley professor John Newman in a landmark
paper Theoretical analysis of current distribution in porous electrodes in 1962. The theory relies
on a separation of length scale to describe transport in the electrode coupled with insertion (or
intercalation) of small active material particles between the layers of the crystal lattice of the
porous electrode material. These small active materials are usually described as solid solution
particles with transport and surface reactions driven by concentration fields where as the
thermodynamics of the system is incorporated through fitting of the open circuit potential.

In this article, we give a detailed background of porous electrode theory that is pioneered by John
Newman, we derive the first porous electrode theory and extend it for non-ideal active materials,
including those capable of phase transformations. We relate the cell voltage, ionic fluxes, and
faradaic charge-transfer kinetics to the variational electrochemical potentials of ions and
electrons. The Butler-Volmer exchange current is consistently expressed in terms of the activities
of the reduced, oxidized and transition states, and the activation over-potential is defined relative
to the local Nernst potential. Depending on the applied current and porous electrode properties,
the dynamics can be limited by electrolyte transport, solid diffusion and phase separation, or
intercalation kinetics.

Introduction: What is Porous Electrode Theory?

Porous electrode theory, pioneered by J. Newman and collaborators, provides the standard
modeling framework for electro synthesis applications especially battery simulations today. As
reviewed in the next section, this approach has been developed for over half a century and applied
successfully to several electrochemical systems.

A simple electrode has a well-defined interface between the metal electrode and the adjacent
electrolytic solution, and the electrode reaction is restricted to this interface, which is often a
plane surface. A large class of industrially important electrochemical reactions, however, involves
the use of electrodes consisting of porous matrix. An electrolytic solution penetrates the void
spaces of the porous matrix (Newman & Tiedemann, 1975).

Relative to solid electrodes, porous electrodes provide much larger contact areas per unit volume
between electrolyte, solid (or gaseous) reactant, and electronic conductor. Their use is widespread
in primary and secondary batteries and in continuous feed galvanic cells. At any given time, there
will be a large range of reaction rates within the pores. The distribution of these rates will depend
on physical structure, conductivity of the matrix and of the electrolyte, and on parameters
characterizing over-potential phenomena. In galvanic cells, this rate distribution directly influences
the net power available for external use.

In order to perform a theoretical analysis of such a complex problem, it is necessary to establish a

model which accounts for the essential features of an actual electrode without going into exact
geometric detail. Further, the model should be described by parameters which can be obtained
by simple physical measurements.

In this article, we discuss the extended porous electrode theory to non-ideal active materials,
including those capable of phase transformations. For thermodynamic consistency, the faradaic
reaction rate is also related to electrochemical potential differences between the oxidized,
reduced, and transition states, leading to a generalized Butler-Volmer equation suitable for phase
separating materials. These elements are integrated in a general porous electrode theory, where
the active material is described by a Cahn-Hilliard phase-field model. This allows us to describe
the nonequilibrium thermodynamics of porous electrodes in terms of well-established physical
principles for ion intercalation in nanoparticles.

Historical Significance
We begin by reviewing volume-averaged porous electrode theory, which has been the standard
approach in battery modeling for the past 50 years. The earliest papers dealing with porous
electrode theory were published in the late 1950's and early 1960's, by Ksenzhek and Stender and
Euler and Nonnenmacher. A few years later, Newman and Tobias introduced the well-known
equation for mass conservation inside a porous electrode undergoing reactions. Around the same
time, de Levie published his work modeling diffusion inside pores, capacitance effects, and
combined effects of double layer capacitance, diffusion, and kinetics. Another notable paper is by
Ksenzhek, which incorporated concentrated solution theory in the transport equations inside a
porous electrode, and referred to gradients in electrochemical potential as the driving force for
transport. Much of the earlier work on modeling porous electrodes relied on deriving the volume
averaged governing equations as well as some analytical results for small over potential (i.e.
linearized) or high over potential (i.e. Tafel) regime kinetics.

In 1975, Newman and Tiedemann published a review of porous electrode theory. This paper
summarized mass and charge conservation equations and kinetic equations for batteries and
other types of electrochemical systems (Newman & Tiedemann, 1975). A few years later, Atlung
et al. investigated the dynamics of solid solution (i.e. intercalation) electrodes for different time
scales with respect to the limiting current. Pollard and Newman investigated the transient
behavior of porous electrodes at high exchange current densities (i.e. small overpotential). Up to
this point, the literature was predominantly based on linearized Butler-Volmer and exponential
Tafel kinetics, due to limited computational power.

As computers and numerical methods advanced, so did simulations of porous electrodes. West et
al. demonstrated the use of numerical methods to simulate discharge of a porous TiS2 electrode
(without the separator), and how the main limiting factor is the depletion of the electrolyte. About
ten years later, Doyle, Fuller and Newman modeled a separator and porous electrode under
constant current discharge. This paper was one of the first to model the reaction rate with the
Butler-Volmer equation, instead of linearized kinetics or a Tafel equation.

Most recently, Bazant Research group at MIT is working intensely on identifying nonlinearities in
porous media. His group has worked on various applications such as lithium ion battery simulation,
electro deposition, desalination via shock electro dialysis and developing meso-scale models of
porous media. On 28 February 2017, Bazant and coworker published a Multiphase porous
electrode theory that models multiphase porous electrodes using the non-equilibrium
thermodynamics for the first time (Smith & Bazant, 2017).
 Theory of Porous Electrodes
In this section, we will describe a modified porous electrode theory that combines a modified form
of the Butler-Volmer equation with concentrated solution theory and the classical Porous
Electrode Theory equations to create a set of thermodynamically consistent equations that can be
used to model phase separating battery materials. We begin with mass and charge conservation
to derive the classical porous electrode theory equation. Then a modified form of the Butler-
Volmer equation will be derived using the general reaction rate equation. Finally, an overview of
non-dimensionalization and scaling will be presented (Ferguson, 2012).

The foundations of porous electrode theory are mass and charge conservation to model transport
and kinetics inside a porous electrode (Vidts, 1997). First, we postulate the electrochemical
potential of a charged particle as:

, = + +

Where = equilibrium chemical potential, =boltzman constant, = temperature, =activity = species

charge number (in this case, the absolute value), = charge per electron, and = local potential .

We can derive the expression of flux from the classical concentrated solution theory (not
described here due to limited space) as following:

Where = mass flux (mass transfer/surface area), = species mobility = (velocity/force), & = species concentration.

By inserting the electrochemical potential into the concentrated solution theory equation for the
flux, we can obtain the Nernst-Planck equation as:

, = , +

Where chemical potential is scaled to the thermal voltage = /, = porosity of the porous
media, and , is the chemical diffusivity of species i. and it is given as

, =

Where = dilute limit diffusivity, =activity and = activity coefficient of the transition state which is basically a
state that a particle experience when it is travelling from one state to another state while diffusing.
Now, we make some assumptions regarding the electrolyte of this porous electrode in order to
simplify some of the equations.

1. First, we assume that the bulk is electro-neutral, with a non-zero current density.
2. Furthermore, we assume the electrolyte can be modeled as binary, although we do not
assume it is symmetric.

For a binary system, we can write the cation and anion conservation equations as:

+
= . (,+ + + + + + ) +

= . (, + )

Where is the volumetric consumption of the species via faradaic reaction.

The first assumption of Electroneutrality approximates the charge density as zero and relates
the cation and anion concentrations as

= + + = 0

Hence the neutral concentration variable can be defined as:

= + + =

In this binary system, the current density is given by the sum of the fluxes times the charge carried
by the species. The current density is given as

=
=0

Where N is the number of species.

Using the Nernst-Planck equation for a binary electrolyte, along with the electroneutrality
approximation, the current density is given by

= (,+ , )c e(+ + + ) c
Due to electroneutrality, we can eliminate electric field and consequently solving for c, we
can obtain

(,+ , )
c = c
+ + + e(+ + + )

Using this expression along with our electroneutrality approximation and conservation equations,
we can obtain

c + + +
= . ( ) . ( ) + .
2 2 2

Where is given as

+ + , ,+
=
+ + +

We can use charge conservation e(+ + + ) = . to eliminate the anion reaction rate to
give us the conservation equation as

c +
= . ( ) . ( ) + +

If we consider the case of lithium ion batteries, and if we assume that only the cation reacts (which
is reasonable if solid electrochemical interface (SEI) formation at the graphite anode is ignored),
then cation reaction rate can be replaced as

+ + =

Where is the active particle area per active particle volume and is the reaction rate (typically as a function of
local concentrations and potential).

This substitution recovers the classical Porous Electrode Theory mass conservation equation
(Newman & Tobias, 1962)

c +
+ = . ( ) . ( )

To complete the reaction-diffusion equation, a suitable model for the reaction rate is needed. In
electrochemistry, the Butler-Volmer equation is the standard for modeling reaction kinetics. The
Butler-Volmer equation combines two Tafel expressions to handle the forward and reverse
reaction rates. To account for a more complex porous electrodes that exhibits complicated
behavior such as phase separation, surface energy and coherency strain, modified Butler Volmer
equation and Nernst equations are given as below (derivation not shown).

+
Nernst Equation: = + ln ( ) =

Where = equilibrium potential difference, = standard potential, and = chemical potential of oxidant and
reductant, = Boltzmann constant, = temperature

( )1
: = exp((1 )) =

Where = exchange current density, A= electrode area, = reaction rate constant, and =charge transfer coefficient.

After faradaic reaction kinetic modeling, first we need to do the modeling of potential drop in solid
conducting phase which can be done by finding ohmic drop current density through conductivity
of solid matrix. Second we will need to model diffusion in the solids which requires a suitable free
energy equation to model the transport inside the solids. This could be done through the regular
solution model if the material is homogeneous and if the material is phase separating material
then we could model the transport inside the material though Cahn-Hillard free energy functional.
Once we obtain all sets of the equations to model reaction rate throughout porous electrode
including mass and charge conservation equations governing the dynamics of the porous
electrode inside the electrolytic cell, modified BV equation with the Nernst Potential and potential
drop in the solid conducting phase for the volume averaged continuum modeling, and complicated
dynamics such as phase separation using concentrated solution theory inside the particles, we can
do suitable scalings of the equations that allow dimensionless quantities to be identified in order
to solve these equations.

Applications -Water Desalination using Porous Carbon Electrodes

Theory and benefits:
Desalination via porous electrodes is a promising technology that is energy efficient and can be
explained by the capacitive deionization (CDI) and electro dialysis (ED) (Deng, 2015). Due to
increasing scarcity of fresh water in the world, there has been a great push during the last decade
to develop technologies like CDI and ED that can deliver fresh water economically and efficiently.

A CDI cell consists of a pair of porous electrodes (static/flow) with a separator (an open channel/
porous dielectric material) in the middle. The electrodes are typically porous carbon, and the feed
water flows either between or through the charging electrodes. The porous electrode pair is
charged to typically 11.4 V, and salt ions present in the feed migrate into electrical double layers
(EDLs) along the pore surfaces at the carbon/water interface, removing salt from the feed water
(electrosorption). An electrical double layer is a structure of charge accumulation and charge
separation that always occurs at the interface when an electrode is immersed into an electrolyte
solution. In the case of CDIs, salt ions are electrostatically held in the double layer until the
discharging step, where the external power supply is shorted or its polarity reversed. During
discharge, the release of ions results in a brine stream, and the charge leaving the cell can be
leveraged to recover energy.

CDIs have multiple benefits over traditional desalination process such as reverse osmosis, e.g. CDIs
allow removal of salt at low (sub-osmotic) pressures and room temperatures, requires low cell
voltage and is dependent on the size of the operation and doesnt need high pressure pumps and
heat sources that increase scaling all of which leads to significant savings. Secondly, the ions can
be directly removed from the feed similar to electrodialysis. Finally, CDIs can act as capacitors
depending on the flow current giving CDIs the unique ability to acts not only as desalination
systems but also as energy storage systems.

History:
The initial theory of CDI was presented in the 1960s by Blair and Murphy and the focus during the
time was the development of cation and anion selective electrodes. At the time, scientists
believed ions are only removed from after when there are specific chemical groups present on the
surface that can either be oxidized or reduced, forming an ionic bond between ions and the groups
present on electrode surface. The electric double layer model presented in the 1970s was a
breakthrough in terms of understanding what happens on the electrode. More work was done in
the 1990s that led to commercialization of this technology mainly for water softening purposes.
The diagram below shows the evolution of the CDI technology.
 (Porada, 2013)

Design of the electrode:

There is a great deal of on-going research on the materials to be used for the electrodes. The most
suitable choices are activated carbon or carbon nanogels but research is being done on using
carbon nanotubes and composite materials. The key metrics to be looked when designing the
electrode and the CDI cell as a whole, are listed in the table below.
The Gouy-Chapman-Stern theory of the electrical double layer can describe the charge profile of
the electrode. This model is better than the one presented by Helmholtz as with porous electrodes
ions do not condense next to the surface rather they are distributed in a layer close to the
electrode known as the Gouy-Chapman layer. The pores are electrolyte-filled, and we assume
locally averaged ion concentrations (described by the Donnan model). The large and continuous
interparticle pores (macropores) transport salt across the electrode thickness and are charge
neutral, with salt concentration c, while in the (intraparticle) micropores , the excess ionic charge
is charge-compensated by electrical charge located in the carbon matrix. At equilibrium, the ion
concentration profiles can be described in first approximation by the Boltzmann distribution which
is at the basis of the PoissonBoltzmann equation. The figure below provides a visualization of the
processes in effect at the electrode (Schlumpberger, 2015).

Most of the work being done with CDI involves placing two porous carbon electrodes (typically
100-500 m) parallel to each other allowing feed water to flow in the gap. Various geometries are
presently being investigated and are shown in the diagram below (Porada, 2013).
The features desirable for the electrode are the inhibition of electrochemical reactions within the
water electrolysis voltage window and high specific capacitance, which are also desirable features
for capacitors. The understanding of the impact of average pore size and pore size dispersity on
energy storage performance developed by the supercapacitor industry can be applied towards
improving desalination performance. However, one important difference between CDI and
supercapacitor electrode materials is the electrodes charge efficiency which is the number of
electrosorbed ions per invested charge. In order to minimize energy requirements for desalination
we minimize co-ion expulsion which can be done adding ion exchange membranes as seen below.

(Suss, 2015)

Challenges and Opportunities:

In order to optimize the CDI cells, it is important to build a robust and predictive 2D model that
accurately describes the movement of ions at constant voltage and current. Available CDI process
models consider the capacitive nature of ion storage but dont consider Faradaic effects. It is
important to develop theoretical methods that also address transport and adsorption of protons
and hydroxyl ions as they can alter the pH of the filtered water leading to quality and scaling issues.
Additionally, further research needs to be carried out to identify the most appropriate pore size
and pore size distribution. The ideal electrode would contain a large population of micropores for
ion immobilization with an carefully designed network of mesopores which act as transport
channels.

Carbon electrodes have a high CDI performance, are abundant, and are available at low to
moderate costs. However, other possibilities such as polymers and metals should not be ignored
as they are very specific. CDIs are used for low salinity feed waters and the cost is directly
proportional to the concentration of ions. It is important for the cost to be minimized if CDI is to
move towards large scale commercialization. An important area of improvement would be the
electrode design itself. Various options such as fiber mats, wires and foams are available and more
research has to be put in in order to design more robust CDI cells. The integration of nanoparticles
and advanced system engineering has the potential of addressing many of the problems
associated with CDI cells.

It is possible that as this technology matures the CDI theory can be applied to recover lithium from
seawater, phosphate from agricultural sources, and valuable metal ions in metallurgical
operations. Additionally, CDI cells can be used where ever there is a need to capture and harvest
valuable ions from a solution, or to remove undesired ions which may be harmful or poisonous.

Conclusion and Outlook for the Future

Porous Electrode Theory is immensely important in electrochemistry. In this article, we have
derived a modified equation for porous electrode theory, Nernst equation and Butler Volmer
equation taking into account non-equilibrium thermodynamics (Ferguson, 2012). The application
that was discussed was capacitive deionization (CDI) (Suss, 2015). Other applications that could
have been discussed include using porous electrode theory for all types of battery simulations
including Lead-Acid, Lithium Ion, Lithium Iron Di-sulphide (LFP) (Ramadesigan, 2012) and Zinc
Nickel Oxide, Fuel Cells and flow batteries (Tiedemann, 2008), other water desalination technology
such as (shock) Electro dialysis pioneered by Martin Bazant (Schlumpberger, 2015), electro
deposition in porous media, electrosynthesis in porous media, micro fluidic applications and
electro osmotic micro pumps and mixers. The outlook for porous electrode theory includes further
developing equations at macroscopic scale for the porous electrodes, identifying non-linearities in
the electrochemical systems involving porous media, developing better intermediate scale or
mesoscopic models for the porous media, further developing theoretical and computational
models for porous electrodes and alas test these models and apply them to important societal
problems.
 References
De Vidts, Pauline. "Governing Equations For Transport In Porous Electrodes". Journal of The
Electrochemical Society 144.4 (1997): 1343. Web.
Deng, Daosheng et al. "Water Purification By Shock Electrodialysis: Deionization, Filtration, Separation,
And Disinfection". Desalination 357 (2015): 77-83. Web.
Ferguson, T. R., and M. Z. Bazant. "Nonequilibrium Thermodynamics Of Porous Electrodes". Journal of
the Electrochemical Society 159.12 (2012): A1967-A1985. Web.
Lai, Wei, and Francesco Ciucci. "Mathematical Modeling Of Porous Battery ElectrodesRevisit Of
Newman's Model". Electrochimica Acta 56.11 (2011): 4369-4377. Web.
Martin Z. Bazant,. "Desalination And Purification System". 2015: n. pag. Print.
Newman, John S., and Charles W. Tobias. "Theoretical Analysis Of Current Distribution In Porous
Electrodes". Journal of The Electrochemical Society 109.12 (1962): 1183. Web.
Newman, John, and William Tiedemann. "Porous-Electrode Theory With Battery Applications". AIChE
Journal 21.1 (1975): 25-41. Web.
Porada, S. et al. "Review On The Science And Technology Of Water Desalination By Capacitive
Deionization". Progress in Materials Science 58.8 (2013): 1388-1442. Web.
Ramadesigan, Venkatasailanathan et al. "Publisher's Note: Modeling And Simulation Of Lithium-Ion
Batteries From A Systems Engineering Perspective [J. Electrochem. Soc., 159, R31
(2012)]". Journal of The Electrochemical Society 159.5 (2012): S12. Web.
Schlumpberger, Sven et al. "Scalable And Continuous Water Deionization By Shock
Electrodialysis". Environmental Science & Technology Letters 2.12 (2015): 367-372. Web.
Smith, Raymond B., and Martin Z. Bazant. "Multiphase Porous Electrode Theory". (2017): n. pag. Web.
24 Mar. 2017.
Subramanian, Venkat R., Deepak Tapriyal, and Ralph E. White. "A Boundary Condition For Porous
Electrodes". Electrochemical and Solid-State Letters 7.9 (2004): A259. Web.
Suss, M. E. et al. "Water Desalination Via Capacitive Deionization: What Is It And What Can We Expect
From It?". Energy Environ. Sci. 8.8 (2015): 2296-2319. Web.
Tiedemann, William. "Forty Years Of Porous Electrode Theory With Battery Applications". ECS
Transactions (2008): n. pag. Web. 24 Mar. 2017.

Useful Links
Shock Electrodialysis - Martin Z. Bazant
https://www.youtube.com/watch?v=pyFdE6PsIk8
Martin Z. Bazant | Physics of next generation batteries
https://www.youtube.com/watch?v=tE3H63ZuQHY