Aabc18 R&D3 180129 Cea MC1

Simulation of a Thin Porous PbO2 Electrode with Fast and Inexpensive Computation Tool
Mikaël CUGNET, Jérémy LANNELONGUE, Angel KIRCHEV, Denys DUTYKH
|1
INTRODUCTION
• Thin-plate lead-acid battery design
Benefits of this new technology Pending issues

 Lower current density  lower polarization o Positive grid corrosion
 Thinner separators  lower ohmic drop o Faster degradation of PAM1
 Faster diffusion  high rate performance o Growth of dendrites
 Spiral-cell design  enhanced compression o NAM sulfation (HRPSoC)
• Examples
• Thin-plate prismatic and spirally wound AGM-VRLAB using pasted grids (plate thickness ~0.8-1 mm)
• Boulder TMF technology2: double-side coated lead foils (plate thickness ~0.25 mm)
1 PAM = Positive Active Material

2 R.C. Bhardwaj and J. Than, “Lead acid battery with thin metal film (TMF®) technology for high power applications”, J. Power Sources 91 (2000) 51-61
8th AABC Europe R&D Symposium 3, January 29, 2018, Mainz, Germany | Mikaël CUGNET, Jérémy LANNELONGUE, Angel KIRCHEV, Denys DUTYKH | 2
ALTERNATIVE CURRENT COLLECTOR FOR THIN POSITIVE PLATE OF AGM-VRLAB
• Selection of corrosion-resistant materials Electroplated PbO2

Ti mesh
Positive paste (~ 400 µm)
Positive
paste
Titanium PbO2
SnO2
Positive plate
Positive paste: 3BS
WHY BOTHER WITH MODELING?
• For the same reasons we practice science:

• to understand how things work
• to be able to predict their behaviors without having to repeat over and over the same experiments
• When a model reproduce experimental data, it proves that we understand the modeled system and
that we don’t need to make experiments anymore (knowledge  freedom)
• To design storage systems dedicated to specific applications

• Transportation, grid, building, health, military…
• To manage the storage systems inside the application

• Best charging procedure, equalization, balance of the cells/modules
• Diagnostic/prognostic tools (if you know how the battery should work then you can detect any change)
• In the specific case of LAB, does modeling matter?

• Yes, more than any other technology, because it is widely used in very different ways
• Despite the huge number of modeling works done, we are still unable to accurately simulate LAB
• And if we are not done with its regular behavior, I let you imagine what we know about its aging
HOW I ENDED UP MODELING THE POSITIVE ELECTRODE OF THE LAB
• PhD in Control engineering

• I started working on SLI LAB for a car manufacturer  diagnostic tool
• I learnt electrochemistry (from a mathematics-based point of view)
• I understood that I would make no progress if I was not able to understand/simulate the LAB behavior
• Post-doc at the Hawaii Natural Energy Institute

• I began working on Li-ion batteries that were supposed to be easier to deal with (not true)
• I kept working on LAB in parallel because I don’t like unfinished work (unwise when you’re a scientist)
• I started to use a fancy computation tool called COMSOL Multiphysics
• Research Engineer for the French Atomic Energy Commission

• I worked on Li-ion, Na-ion, Na-MCl2, Ni-MH, and still Pb-acid modeling and management
• I started to use another computation tool called Battery Design Studio from CD-adapco (Siemens)
• I suddenly realized that it will take time to understand any battery technology and that I should go back
to my first problem and try to solve it instead of jumping to the next opportunity (procrastination)
WHY NOT USING ALREADY EXISTING COMPUTATION SOFTWARE?
• When you know how long it takes to code

the program solving partial differential
equations (PDE) by yourself…
• You demonstrate to your manager that it would
be a waste of time trying to reinvent the wheel
• You then pick a software and pay a license
looking for some “plug and play” experience
• Finally what really happens…

• Your experience quickly turns out to be closer
to “cry and drop” than “plug and play”
• You start thinking that if you really want the job
done, you better know what you’re doing
• Either you do it yourself with tools you know
• Or you pay somebody else to do it for you
(much more expensive than the software license)
THE SIMPLER THE BETTER: START WITH A SINGLE ELECTRODE
• Don’t reinvent the wheel!

• Start with what is already available in the literature1 because a lot
has been done on LAB modeling
• Equations on the right apply for the positive electrode and come
from one of the first complete modeling work2 performed of LAB,
not only dealing with discharge, but also rest and recharge
• Don’t forget the goal

• Getting simulation results does not mean that the job is complete
• The job is really done when you are able to reproduce experimental
data and there are much less literature available about it
1 M. Cugnet and B. Y. Liaw, “Mathematical Modeling of Lead-Acid Batteries,” in Lead-Acid Battery Technologies
(J. Jung, L. Zhang, and J. Zhang, eds.), ch. 9, pp. 229-318, Boca Raton, FL: CRC Press, 2016.
2 H. Gu, T. V. Nguyen, and R. E. White, J. Electrochem. Soc., 134 (12), 2953 (1987).
THE SIMPLER THE BETTER: START WITH A 1D MODEL
• One-dimensional modeling of LAB

• One domain (line) and two boundaries (points)
• The domain is the electrolyte active material soaked with electrolyte
(mix of 2 phases: solid PAM & liquid sulfuric acid solution)
• Left boundary: current collector
• Right boundary: separator
• Numerical method
• In 1D, each PDE can be written in the following form:
• u is the unknown of the PDE
• ux the first-order spatial derivative of u
• F is the flux term
• S is the source term
UNDERSTAND THE EQUATIONS TO USE THEM PROPERLY
• Electrode porosity
• Volume change induced by the transformation of PbO2 in PbSO4
• Material balance
• H2SO4 concentration change induced by the
• consumption of species by the electrochemical reaction
• transport of species by migration, diffusion, and convection
• Ohm’s laws in solids and liquids + electrode kinetics

• In fact a unique equation of conservation of charge that is split in
three equations leading to an ill-posed problem
A WELL-POSED PROBLEM IS ALREADY HALF-SOLVED!
• A well-posed problem (in the sense of Hadamard) satisfies 3 properties

• A solution exists
• The solution is unique
• The solution’s behavior changes continuously with the initial conditions
• Ohm’s laws in solids and liquids + electrode kinetics

• Electrode kinetics is not an equation by itself but simply the source term of the conservation of charge
• Instead of Ohm’s law, let’s use a conservation of charge for each phase:
EQUIPOTENTIAL SOLID PHASE
• The problem we face can be summed up briefly:

• We try to solve two unknowns (electric potentials in solid and liquid phases, respectively) from a single
equation expressing the conservation of charge.
• The solution existed before the problem:

• A solution to this problem has been proposed by Simonsson1 in 1973 through the following
hypothesis: “the solid phase can be regarded as equipotential”
• Tiedemann and Newman2 made the same hypothesis as Simonsson in their model published in 1979
• A valid hypothesis for lead-acid batteries

• The conductivity of solid phase is 3 orders of magnitude higher than the conductivity of liquid phase
1D. Simonsson, “A mathematical model for the porous lead dioxide electrode,” J. Appl. Electrochem. 3 (4), 261 (1973)
2W. H. Tiedemann and J. S. Newman, “Mathematical Modeling of the Lead-Acid Cell,” in Battery Design and Optimization PV 79-1 (S. Gross, ed.), (Penington, NJ), pp.
23-38, The Electrochemical Society Softbound Proceedings, 1979.
THE SIMPLEST PHYSICS-BASED MODEL OF LAB
• Only three PDEs • 31 parameters

• Conservation of volume • 13 are physical constants
• 12 are experimentally measured
• Only 6 remain adjustable
• Conservation of charge
• Conservation of species
SIMULATION RESULTS FROM THE SIMPLEST PHYSICS-BASED MODEL OF LAB
• Objectives
• Reproduce experimental discharge voltage
curves obtained at various rates ranging from
C/20 to 5C (2 orders of magnitude difference)
• Reference electrode
• Data have been collected with an Ag/Ag2SO4
reference electrode at 6 mol/kg
• Analysis of the simulation results

• The thin porous PbO2 electrode does not
behave as expected and shows a polarization of
30 mV whatever the discharge current
• Is this coming from the fact that we are dealing
with a thin electrode on a titanium mesh?
Not so sure…
“IF THE FACTS DON'T FIT THE THEORY, CHANGE THE FACTS” A. EINSTEIN
• The 30 mV missing at low rates

• It will not be possible to get a 30 mV polarization
independent from the discharge current with a
single electrochemical reaction
• A bad solution…
• Decrease the initial condition regarding the
sulfuric acid concentration to lower the voltage
• Reduce the exchange current density to lessen
the polarization at high rates
• …and its limits

• It will be impossible to reproduce the higher
voltage values at the BOD* for low rates
• Voltage values during the rest period following
the discharge will be far too low *BOD: Beginning of Discharge
AT LEAST THE THERMODYNAMIC EQUILIBRIUM IS CORRECT
• Temporal evolution of the voltage curve for each discharge rate
• It’s still not perfect but we know where to look  reaction kinetics
TOO SIMPLE TO BE TRUE
• What about two 1-electron steps instead of the usual 2-electron step?
• The simplest way to write the electrochemical reaction of the LAB positive electrode
• The two 1-electron steps derived from the work of Hampson et al.1 (1968)
• Proton incorporation inside the lead dioxide
• Sulfation of hydrated lead dioxide
• Two Butler-Volmer equations and

an unknown Gibbs energy for Pb(OH)2+
1 N. A. Hampson, P. C. Jones, and R. F. Phillips, Can. J. Chem., 46, 1325 (1968)
SIMULATION RESULTS WITH TWO ELECTROCHEMICAL REACTIONS
• It does not solve our problem  what about a dissolution-transport mechanism?

DISSOLUTION-TRANSPORT MECHANISM
• A mechanism proposed by Bernardi et al.1

involving three major steps
• Dissolution of PbO2
• Diffusion of Pb2+ to a reaction site

• Electrochemical conversion to PbSO4
• Not perfect yet but could be the way to go

• Optimize the parameter values
• Work on the simple diffusion of Pb2+ in a
pseudo-steady-state flux
• Introduce a new equation dealing with the
concentration of Pb2+ to fit the “coup de fouet”
seen at the BOD
1 D. M. Bernardi, R. Y. Ying, and P. Watson, J. Electrochem. Soc., 151 (1) A85 (2004)
A FAST AND INEXPENSIVE COMPUTATION TOOL
• Less than 1 s to simulate each discharge and rest (still room for improvement)
PROVIDING ACCESS TO THE BATTERY STATE AT ANY TIME AND POSITION
• Spatial evolution of the acid concentration profile for each time step (from blue to red)
• The higher the current, the higher the concentration gradient

CONCLUSIONS AND PERSPECTIVES
• Conclusions
• The use of expensive commercial computation tools will not solve the modeling issues for LAB
• The strategy is to start from something simple and to add the missing blocks until it fits the data
• We showed today that it is possible to try anything, any kind of mechanism, as long as you know
what you are doing and how to do it properly
• Always check the validity of your simulation through the analysis of the predicted physical values
• Perspectives
• Add more physics to get rid of some assumptions (isothermal, isobaric, isochoric)
• Implement nucleation and growth of PbSO4 to simulate properly the beginning and end of discharge
• Improve the polarization dependence to the current in the dissolution-transport mechanism
• Move to the charge process and change the temperature of operation
THANKS FOR YOUR ATTENTION
ANY QUESTIONS?
mikael.cugnet@cea.fr
Commissariat à l’énergie atomique et aux énergies alternatives INES Site

Alternative Energies and Atomic Energy Commission Institut National de l’Energie Solaire
17 av des martyrs 38000 GRENOBLE France 50 avenue du lac Léman
http://liten.cea.fr 73375 Le Bourget-du-Lac France
+33 4 79 79 20 00
Établissement public à caractère industriel et commercial
Public establishment with commercial and industrial character
RCS Paris B 775 685 019

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Simulation of a Thin Porous PbO2 Electrode with Fast and Inexpensive Computation Tool

Mikaël CUGNET, Jérémy LANNELONGUE, Angel KIRCHEV, Denys DUTYKH

• Thin-plate lead-acid battery design

Benefits of this new technology Pending issues

1 PAM = Positive Active Material

• Selection of corrosion-resistant materials Electroplated PbO2

• For the same reasons we practice science:

• To design storage systems dedicated to specific applications

• To manage the storage systems inside the application

• In the specific case of LAB, does modeling matter?

• PhD in Control engineering

• Post-doc at the Hawaii Natural Energy Institute

• Research Engineer for the French Atomic Energy Commission

• When you know how long it takes to code

• Finally what really happens…

• Don’t reinvent the wheel!

• Don’t forget the goal

• One-dimensional modeling of LAB

• Ohm’s laws in solids and liquids + electrode kinetics

• A well-posed problem (in the sense of Hadamard) satisfies 3 properties

• Ohm’s laws in solids and liquids + electrode kinetics

• The problem we face can be summed up briefly:

• The solution existed before the problem:

• A valid hypothesis for lead-acid batteries

• Only three PDEs • 31 parameters

• Analysis of the simulation results

• The 30 mV missing at low rates

• …and its limits

• Temporal evolution of the voltage curve for each discharge rate

• Sulfation of hydrated lead dioxide

• Two Butler-Volmer equations and

1 N. A. Hampson, P. C. Jones, and R. F. Phillips, Can. J. Chem., 46, 1325 (1968)

• Temporal evolution of the voltage curve for each discharge rate

• It does not solve our problem  what about a dissolution-transport mechanism?

• A mechanism proposed by Bernardi et al.1

• Diffusion of Pb2+ to a reaction site

• Not perfect yet but could be the way to go

• Temporal evolution of the voltage curve for each discharge rate

• The higher the current, the higher the concentration gradient

Commissariat à l’énergie atomique et aux énergies alternatives INES Site

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