E3122 Journal of The Electrochemical Society, 164 (11) E3122-E3131 (2017)

JES FOCUS ISSUE ON MATHEMATICAL MODELING OF ELECTROCHEMICAL SYSTEMS AT MULTIPLE SCALES IN HONOR OF JOHN NEWMAN
Performance Modeling and Design of Ultra-High Power
Microbatteries
James H. Pikul,a,∗,z Paul V. Braun,b,c and William P. Kingb,c
a Department of Mechanical Engineering and Applied Mechanics, University of Pennsylvania, Philadelphia,
Pennsylvania 19104, USA
b Department of Mechanical Science and Engineering, University of Illinois at Urbana - Champaign, Illinois, 61801,
USA
c Department of Materials Science and Engineering, University of Illinois at Urbana-Champaign, Illinois, 61801, USA

High power density microbatteries could enable new capabilities for miniature sensors, radios, and industrial electronics. There is,
however, a lack of understanding on how battery architecture and materials limit power performance when battery discharge rates
exceed 100 C. This paper describes the development and application of an electrochemical model to predict the performance of
microbatteries having interdigitated bicontinuous microporous electrodes, discharged at up to 600 C rates. We compare predicted
battery behavior with measurements, and use the model to explore the underlying physics. The model shows that diffusion through
the solid electrodes governs microbattery power performance. We develop design rules that could guide the development of improved
batteries.
© The Author(s) 2017. Published by ECS. This is an open access article distributed under the terms of the Creative Commons
Attribution 4.0 License (CC BY, http://creativecommons.org/licenses/by/4.0/), which permits unrestricted reuse of the work in any
medium, provided the original work is properly cited. [DOI: 10.1149/2.0151711jes] All rights reserved.

Manuscript submitted February 1, 2017; revised manuscript received April 24, 2017. Published May 4, 2017. This paper is part of
the JES Focus Issue on Mathematical Modeling of Electrochemical Systems at Multiple Scales in Honor of John Newman.

High power density microbatteries would enable new capabilities
for miniature sensors, radios, and industrial electronics.1–4 Recent im-
provements in electrode architectures, materials, and fabrication tech-
nologies have enabled microbatteries with power densities as high as
7.4 mW cm−2 μm−1 , which is about 100 times greater than power den-
sities provided by larger conventional format batteries.5–9 The ultra-
high power densities were achieved by the simultaneous reduction of
ion and electron transport resistances across the anode, cathode, and
electrolyte. Fabricating electrodes with increasingly fine nanostruc-
tures that provide shorter ion and electron transport paths has been the
main strategy for reducing transport resistances.2,5–7,10–18 However, as
the electrode dimensions decrease, electrode fabrication and incorpo-
rating large volume fractions of high capacity materials into the nano
architectures (important for obtaining high energy densities) become
more difficult. Additionally, the larger surface area leads to increased
SEI formation during battery fabrication. To realize both high power
and high energy density, it is important to understand how battery ar-
chitecture and materials affect the physical processes that limit power
density and improve energy density, and to develop experimentally
validated design rules that address the many engineering constraints
in full battery assemblies.
Simulations of battery operation, considering ion transport across
both the anode and cathode regions, can be used to assist in battery
design and optimization. A key parameter in understanding battery
discharge is the C rate, where the time it takes to discharge a battery
in one hour is 1 C rate. An X C rate discharge corresponds to a current
density X times the 1 C rate current density. The validity of battery
discharge models has rarely been explored above discharge rates of
25 C,19–32 with only a few exceptions.33–37 To our knowledge, there is
no published work that validates models for batteries discharged at the
100–1000 C rates relevant to high power microbatteries. There is thus
a need for an experimentally validated battery model that describes
the physical processes that limit battery performance at high C rates.
Such a model would provide valuable insights for future high power
microbattery designs and fabrication, as well as guide the design of
macroscopic battery architectures.
In this paper we present a 1-D electrochemical model that ac-
curately predicts the power performance of batteries discharged at
up to 600 C rates. The predictions were compared to discharge data
∗ Electrochemical Society Student Member.
z
E-mail: pikul@seas.upenn.edu
from high power microbatteries we previously reported.5 The model
enables the study of local lithium concentration and overpotentials,
which indicate that diffusion through the solid electrodes most limits
the microbattery performance. Using the validated model, we propose
design rules for high power batteries that optimize battery perfor-
mance.
System Description and Modeling Approach
Figures 1a and 1b show a schematic and SEMs of the high power
battery modeled in this work.5 The battery has interdigitated elec-
trodes composed of a highly porous bicontinuous nickel current col-
lector (blue) conformally coated with electrochemically active mate-
rials (active materials). The active material is nickel-tin (red) in the
anode and lithiated manganese oxide (yellow) in the cathode. The
electrolyte fills the volume between the electrodes and inside the elec-
trode pores. Figure 1c shows the lithium and electron transport paths
during discharge. Lithium is stored at a high energy state in the anode.
An oxidation reaction at the anode-electrolyte surface releases lithium
ions and electrons that flow to the lower energy state cathode where
they undergo reduction. Electrons do not travel through the electrolyte
and instead travel from the anode active material surface through the
anode active material, anode current collector, external circuit where
they power a load, cathode current collector and cathode active mate-
rial until they react at the cathode surface (black). Lithium ions flow
from the anode to the cathode through the electrolyte (light blue). As
lithium ions are released or inserted into the active material, lithium
stored in the active material bulk diffuses toward or away from the
active material surface according to the concentration gradient (dark
blue). The microbattery architecture achieves high power density by
simultaneously reducing the ion and electron transport lengths.
The battery power performance depends upon the battery voltage,
which is the difference in anode and cathode electrochemical poten-
tials minus any internal voltage drops. The electrochemical potential
difference depends on the lithium concentrations at the active material
surfaces. Internal voltage drops are due to the ohmic conduction of
electrons through the electrodes, the ohmic conduction of ions across
the electrolyte, and the electrochemical kinetics at the anode and cath-
ode surface. Energy density is the product of the battery voltage and
amount of charge transferred between electrodes per battery volume.
Power density is the product of the battery voltage and charge transfer
rate between electrodes per battery volume. As the charge transfer

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 Journal of The Electrochemical Society, 164 (11) E3122-E3131 (2017) E3123

Figure 1. a) A diagram of a microbattery with interdigitated electrodes that consist of an electrochemically active layer (red and yellow) coated on an electrically
conductive porous bicontinuous nickel scaffold (blue). b) Electron microscope image of the interdigitated battery electrodes. c) Diagram of a unit cell of the lithium
ion microbattery electrodes showing the key transport paths. d) The simulation domain of this microbattery.

rate increases, the electrochemical potential difference decreases and
the internal voltage drops increase, so that the battery voltage falls
below its equilibrium value and reaches a cutoff voltage before all
of the energy can be fully extracted. The reduced battery voltage at
high charge transfer rates decreases power performance, or amount of
energy extracted at a given power density.
Here, we model the power performance of high power interdigi-
tated bicontinuous microbatteries using a 1-D model of ion and elec-
tron transport.19,20 Figure 1d shows the model space, which includes
the porous anode, porous cathode, and separator. The model space sim-
plifies the interdigitated electrode design to two electrodes bounded
by the electrode centerlines with a symmetric boundary condition.
The electrodes are approximated as rectangular, with widths (Wneg
and Wpos ), height (H), and cross sectional areas equal to the mea-
sured cross sectional areas of the experimental electrodes. Fig. 1d
shows the 1-D transport of ions and electrons. Ion transport through
the electrolyte is governed by migration and diffusion using concen-
trated solution theory,19,20 and electron transport is ohmic. The total
current through each differential length, dx, along the battery is the
sum of the current due to local conduction of electrons and ions and is
constant across the entire pitch. At each differential length in the elec-
trodes, 1-D diffusion models predict lithium concentration through
the active materials. The active material coating is approximated as a
thin film with zero lithium flux to the nickel scaffold and flux at the
electrode-electrolyte interface determined by Fick’s law. The amount
of lithium inserted or removed from the active material is determined
by Butler-Volmer kinetics which link the electrolyte simulation to the
electrochemical potential determined by the active material surface
concentration. The model space and boundary conditions are cho-
sen to match conventional battery formats so that the results can be
generalized to other electrode architectures.
The nickel current collector volume fraction, ε N i , active material
volume fraction, εact , and electrolyte volume fraction, εe , are important
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model inputs that determine the energy density of the batteries and
impact the transport of ions and electrons. ε N i , εact and εe depend on the
bicontinuous electrode structure and are calculated from a geometric
model of self-assembled polystyrene (PS) spheres organized in a FCC
unit cell. The current collector volume is the cubic unit cell volume
minus the void volume left by the sintered PS spheres after PS etching,
Vvoid . The active material volume, Vact , is the volume of a thin layer
coated on the current collector, calculated from thickness t. Figures
2a and 2b show an inverse opal unit cell and the simplified geometry
of two neighboring spheres used to calculate the volume fractions.
PS spheres in contact after opal self-assembly are represented by
circles with radius R and have 0.74 volume fractions. Sintering the PS
increases the radius from R to Rn such that neighboring radii overlap
by a length b. Vvoid is the volume of 4 sintered PS spheres of radii Rn
in a FCC unit cell minus the volume of 48 overlapping spherical caps
of height h or
4 1
Vvoid = 4 πRn 3 − 48 πh 2 (3Rn − h) , [1]
3 3

where Rn = (b/2)2 − R 2 and h is Rn – R. Vact is the volume of
4 spheres with radius Rv subtracted from Vvoid , where Rv is Rn – t.
Additionally, the volume where the active material does not deposit,
marked with hatching, is integrated and subtracted out of Vact , but not
including the volume of the spherical cap marked by h2.
  2
b 2
Rv R
4 Rn
Vact = Vvoid − 4 π(Rv )3 − 48 π − t − x2
3 0 2
1
d x + 48 πh22 (3Rv − h2) , [2]
3
 E3124 Journal of The Electrochemical Society, 164 (11) E3122-E3131 (2017)

Figure 3. Equilibrium voltage profiles used for the anode and cathode mate-
rials in the simulation. During discharge, the cathode voltage decreases and
anode voltage increases. The black line shows the difference between the
cathode and anode equilibrium voltages.

normalized to 1, such that

εN i εact
σe f f = σN i + σact . [7]
ε N i + εact ε N i + εact
σepos
ff
is 3.3 × 106 S m−1 and σneg ef f
is 1.1 × 107 S m−1 . k e f f is then
corrected for the porosity of the electrode with a Bruggeman exponent
of 1.5.
The model uses electrolyte material properties from available elec-
trolyte data. The experimental electrolyte is 1:1 ethylene carbonate:
dimethyl carbonate (EC:DMC) with initial 1000 mol m−3 LiClO4
concentration, ce0 . The electrolyte interdiffusion coefficient is approx-
imated as 2.6 × 10−10 m2 s−1 based on 1 M LiClO4 in propylene
Figure 2. Model of the electrode showing key parameters. a) Unit cell of carbonate (PC).38 The electrolyte conductivity depends on concen-
the microbattery electrode with some geometric parameters. b) Model used to tration and is taken from data on LiClO4 in EC:PC,39 where the 8.5
calculate the polystyrene radius (R), active material thickness (t), and volume × 10−3 S cm−1 maximum conductivity, σe , is close to that of 1 M
fractions of the current collector and electrochemically active materials. LiClO4 in EC:DMC.40,41 The lithium transference number, t+ , is 0.363
based on LiPF6 in EC:DMC because the transference number depends
on the solvation radius of the anion, which is similar for PF6 − and
where h2 is Rv (1 – R / Rn ). ε N i , εact and εe are calculated
√ from the Vact ClO4 − .19,40,42 The electrolyte conductivity and diffusivity through the
and Vvoid normalized by the unit cell volume, (2R 2)3 . porous electrodes are corrected for the increased path length using a
Vvoid Bruggeman exponent of 1.5.19,20 Changes to the pore shape or volume
εN i = 1 −  √ 3 , [3] fraction in the microbattery electrodes would change the tortuosity
2R 2 and affect the Bruggeman exponent.8
The following are material properties for the electrochemically
active materials. Figure 3 shows the open circuit voltage (OCV),
Vact
εact =  √ 3 , [4] versus lithium, as a function of the state of charge for the anode
2R 2 and cathode active materials. The OCV is measured from batter-
ies discharged at low rates. The maximum capacity of the cathode,
−3
and cmax
pos , is 23,000 mol m based on a 145 mAh g−1 manganese oxide
cathode. The initial cathode concentration, c0pos , is approximated as
43
εe = 1 − εact − ε N i . [5]
50 mol m−3 for all batteries. The nickel-tin anode is composed of
Equations 3–5 calculate ε N i , εact and εe from fitting parameter t and 80% tin. At a full state of charge, the anode OCV corresponds to
experimental measurements of R and b. ε N i = 0.12 for the experimen- Li3 Sn with a 55,000 mol m−3 volumetric capacity.44 cneg 0
is set so that
tal batteries where b is 200 nm and R is 500 nm. the low rate voltage plateau matches between predicted and measured
An effective electrode conductivity across the electrode width, batteries.
k e f f , is approximated by equating the conductance across the width Table I shows the active material thickness, t, and diffusivity, D,
to the conductance down the length, using used to simulate each battery in addition to experimentally measured
parameters. The active material thickness and diffusivity are fitting
ke f f L H σe f f W H
= , [6] parameters bound by half the interconnect pore size (100 nm) and
W L PITT diffusivity measurements in the anode and cathode materials.
as electrical conduction occurs primarily down the length (normal to Measured anode diffusivities varied between 9.34 × 10−18 and 8.51
the model space in Fig. 1d), L, in the interdigitated architecture. The × 10−17 m2 s−1 , with an average of 3.35 × 10−17 m2 s−1 . Cathode
bicontinuous electrode conductivity, σe f f , is approximated by con- diffusivities varied between 1.57 × 10−19 and 1.14 × 10−16 m2 s−1 ,
duction through the two media in parallel with their volume fractions with an average of 1.83 × 10−17 m2 s−1 . The anode and cathode

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 Journal of The Electrochemical Society, 164 (11) E3122-E3131 (2017) E3125

Table I. Parameters used for the simulation of batteries 1 through 5.

Battery

Parameter 1 2 3 4 5
Dneg [m2 s−1 ] 3.0 × 10−17 1.0 × 10−17 3.0 × 10−17 3.5 × 10−17 4 × 10−17
Dpos [m2 s−1 ] 1.3 × 10−17 5.0 × 10−18 6.0 × 10−18 3.9 × 10−17 6.0 × 10−18
tneg [nm] 30.0 17.0 30.0 21.0 27.0
tpos [nm] 55.0 37.0 20.0 29.5 13.3
cneg 0 [mol m−3] 54,500 54,500 21,000 54,500 15,700
H [μm] 14.9 9.9 14.9 12.6 14.9
Wneg , Wpos [μm] 12.6 8.4 12.6 10.7 12.6
P [μm] 45 27 45 45 45

diffusivities in the simulation vary by a maximum of 3.35 and 3.66
X the average measured diffusivities for each battery. The model was
simulated in COMSOL using a 1-D battery module.
Modeling Results
Figure 4 shows predicted and experimental discharge curves of
Batteries 1–4, which have the highest combined energy and power
densities of our previously tested microbatteries.5 At low C rates,
predictions and measurements compare very well. At greater than 30
C rate discharges, there is a slight departure between prediction and
measurement, up to 3 percent of total capacity. The measured and
predicted discharge curves for Batteries 2 and 3 closely overlap at low
and high discharge rates, but the higher predicted capacities at 8.6
and 20 C rates are likely due to error in the thin film approximation
as the amount of capacity extracted from a thin film is larger than
the concave geometries in the curved electrode pores at moderate
discharge rates. The lower average voltages of the discharge curves
in Battery 3 indicate that the anode was not fully charged before
cycling, which caused to cathode to be overcharged when Battery 3
was charged to a 4.0 volt cutoff. The overcharging caused a higher
voltage for the first 0.15 Ah m−2 of experimental discharge. The
overall good agreement between predicted and measured discharge
curves indicates that the model captures the major physics for high
rate discharging and that the 1-D transport model provides an accurate
foundation for design studies of batteries discharged at up to 600 C
rates.
We use the calculated lithium concentration throughout the battery
to understand how different parameters affect battery performance.
Figure 5a shows the electrolyte concentration in Battery 1 at the end of
discharge at multiple C rates. The change in electrolyte concentration
increases as the C rate increases, except at 457 C, where the battery
quickly shuts off before a significant amount of ions can be removed
from the electrolyte. This quick shut off is due to limits in the solid
active material diffusion and will be discussed later. The maximum
concentration change is 250 mol m−3 at 146 C, which decreases the

Figure 4. Comparison of predicted and measured discharge curves in Batteries 1 through 4. The capacity is normalized by the separator area.

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 E3126 Journal of The Electrochemical Society, 164 (11) E3122-E3131 (2017)
Figure 5. Predicted lithium concentrations for Battery 1 at various discharge
rates. a) Lithium concentration in the electrolyte. b) Lithium concentration in
the solid. c) Lithium concentration across the cathode active material.
electrolyte conductivity from 8.6 × 10−3 S cm−1 to 8.2 × 10−3 S cm−1
in the cathode region and 8.5 × 10−3 S cm−1 in the anode region.
The minimal changes in conductivity indicate that diffusion in the
electrolyte did not limit the power performance of Battery 1. Figures
5b and 5c show the final lithium concentrations in the solid electrode
active materials in Battery 1 at each discharge rate. The differences
in surface and center concentrations increase as the discharge rate
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Figure 6. Diagrams of the microbattery electrodes showing important design
parameters. a) Cross-section of the microbattery showing electrode width,
W, and electrode pitch, P. b) Microbattery electrode architecture showing the
electrode pore size and active material thickness, as well as electron transport
through the bicontinuous nickel scaffold. c) Microbattery top view showing
the interdigitated layout and the electrode length, L.
increases. The surface and center concentrations in the cathode are
22,200 mol m−3 and 2,600 mol m−3 at 30.5 C, which corresponds to a
1.26 volt difference, or 63% of the battery voltage window. At 457 C,
the cathode surface concentration reaches a maximum in 0.17 seconds
and limits the capacity to 0.058 Ah m−2 . The large concentration
differences across the anode and cathode active materials and the
associated overpotential at moderate and high discharge rates show
that diffusion in the active material limits the power performance of
Battery 1. Diffusive limitations in the active materials limit the power
performance of all simulated batteries.
Design and Optimization Considerations
The design process that follows informs how microbattery geom-
etry influences the trade-offs between energy and power density, and
develops design rules that guide these trade-offs. The power density
of a battery is proportional to the energy density times the C rate,
Power ∼ Crate × Energy, so an improved power performance re-
sults from an improved C rate and energy density. Figure 6 shows the
microbattery geometries that govern ion and electron transport. The
electrode width, W, governs diffusion through the electrolyte because
the largest electrolyte concentration gradients occur from depletion
and generation of lithium ions across the electrode width. The elec-
trode pitch, P, governs ionic conduction in the electrolyte. The active
material thickness, t, governs active material diffusion. The particle
radius could function as the thickness in other electrode designs. The
bicontinuous electrode architecture and the electrode length, L, have
the largest impact on electrode electron conduction in this work. Sim-
ulating the energy density of Battery 1 at various C rates for a range
of values of a single geometric component or governing transport
 Journal of The Electrochemical Society, 164 (11) E3122-E3131 (2017) E3127

Figure 7. a) Ragone plot of Battery 1 for various values of electrode width (5, 12.6, and 50 μm) and diffusivity (scaling of 0.04, 0.2, 1, 10, and 25X). b) Predicted
energy density versus electrode width for Battery 1 at 1 to 146 C rate discharges. The dashed line is the design parameter, Wc , for the electrode width, which
corresponds to the complete depletion of lithium ions at the cathode centerline for each C rate. c) Predicted energy density versus electrolyte peak conductivity for
Battery 1 at 1 to 457 C rate discharges. The dashed lines are the design parameter, Ve , for the electrode pitch calculated with 0.1 and 0.3 voltage drops across the
electrolyte for each C rate. d) Ragone plot of Battery 1 showing the effect of a change in electrolyte conductivity by 0.01, 0.1, 1, and 10 for each electrode pitch.
The red dots are experimental data from Battery 1. Black diamonds correspond to inflection points calculated from design parameters.

property isolates the influence of each geometric component on the electrolyte with constant and uniform depletion is
power performance. Data from Battery 1 provides the primary com-
parison between experiment and simulation in many of the design ∂ 2c
D + q̇ = 0. [8]
plots because the experimental microbatteries cover a small subset ∂x2
of geometries compared to the large variation required to cover the
The depletion rate in the electrolyte, q̇, is assumed constant when
simulation range.
discharged at a constant C rate and uniformly distributed throughout
the electrode region. q̇ is the amount of lithium ions that enter the
cathode from the electrolyte, per electrode volume, or
Electrode width (W).—Figure 7a shows the predicted energy and
power density of Battery 1 for various values of the electrode width  Crate
pos − c pos ε pos
q̇ = − cmax 0
. [9]
(5, 12.6 and 50 μm) and electrolyte diffusivity (scaling factor 0.04, 3600
0.2, 1, 5, and 25X from the value in Table I). For batteries with
Equation 9 is valid when the capacities in the battery electrodes
wide electrodes and low electrolyte diffusivities, the Ragone curves
are balanced, or when the cathode limits capacity. The discharge time
show large drops in power density for a given energy density. This
is approximated as the time it takes to fully discharge a battery at a
results from lithium ions severely depleting in the cathode region
constant current density (3600 / Crate). Solving Equation 8 yields the
such that the concentration is near zero in the electrolyte close to the
concentration profile
electrode center. The near zero concentration significantly reduces the
local electrolyte conductivity and causes a large voltage to develop q̇ q̇ W pos
across the electrolyte, which brings the battery to the shut off voltage c=− x2 + x + ce0 , [10]
2De εe 1.5 De εe 1.5
before more energy can be extracted. At higher C rates, the Ragone
curves return to normal because diffusion in the active material causes where x is the distance between the separator, x = 0, and the electrode
the battery to shut off before severe electrolyte depletion occurs. We centerline, x = Wpos . The diffusivity is corrected using the Brugge-
conclude that diffusion in the electrolyte has a minimal effect on the man approximation. The initial concentration of the electrolyte, ce0 , is
battery performance unless the concentration in the cathode region the concentration at x = 0, which is valid for most batteries because
depletes to near zero, at which point the effect is dramatic. the concentration change across the separator is small. A symmetric
The point when the concentration in the cathode region depletes to boundary condition exists at x = Wpos . Equation 10 solves for the
zero is predicted by solving for steady state diffusion in the cathode critical electrode width, Wc , where the steady state electrolyte con-
electrolyte region. The governing equation for 1-D diffusion in the centration depletes to zero by setting x = Wc = W pos when c = 0. Wc

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 E3128 Journal of The Electrochemical Society, 164 (11) E3122-E3131 (2017)

is then

−2ce0 De εe 1.5
Wc = . [11]
q̇
Figure 7b shows the predicted energy densities of Battery 1 dis-
charged at multiple C rates with varying electrode width (3–100 μm)
and constant Wsep = 19.8 μm. The dashed line shows the energy
density of batteries with electrode widths equal to Wc . A maximum
energy density occurs for each C rate because of competition between
the increases in electrode volume fractions (W/P) that improve energy
density and the increase in ion diffusion length through the electrode
width. The energy density at 12, 20 and 30.5 C dramatically decreases
after the maximum energy density is reached because the concentra-
tion of lithium is depleted to near zero in the cathode electrolyte. An
electrolyte with increased or decreased diffusion coefficient would
increase or decrease the electrode width required to deplete to zero
concentration. We conclude that Wc is a good design parameter for the
cathode width as it predicts the largest allowable cathode electrode
width before severe ion depletion occurs.

Electrode pitch (P).—Figure 7c shows the predicted energy den-

sity of Battery 1 discharged at 1–500 C rates with electrolyte conduc-
tivities varied between 4 × 10−5 S cm−1 and 1 × 10−1 S cm−1 . The
electrolyte conductivity was scaled by 1 × 105 to study the effect of
the pitch on power performance without affecting other physics in the
system, and also represents the affect of changing the battery elec-
trolyte. The dashed lines represent a constant potential drop across
the electrolyte calculated using Ohm’s law, where the voltage drop,
Ve , and electrolyte conductivity, σe , are related to the pitch, P, by
I  I P
Ve = I R = ρl = m . [12]
A pos,neg,sep A σe ε1.5
e

The current density is


I F cimax − ci0 εi Wi Crate
= .
A 3600
i is the electrode with the lowest total capacity. m = 0.5 in the positive
and negative electrode region because on average half the current
is transported by ionic conduction and the other half by electron
conduction in the electrode. m = 1 in the separator region. εe is the
volume fraction of the electrolyte in each region. Equation 12 is valid
when the electrolyte concentration has little variance during discharge,
[13]
Figure 8. a) Predicted energy density versus electrode conductivity scaling
factor for Battery 1 at 1 to 457 C rate discharges. The dashed lines are the
design parameter, Vs , for the electrode length and architecture calculated with
0.1 and 0.3 voltage drops across the electrode for each C rate. b) Ragone plot
of Battery 1 as the electrode conductivity is scaled from 10−7 to 100 times the
reference conductivity.
which is true if W pos < Wc . The energy density at each C rate in Fig.
7c remains constant as the conductivity decreases until the voltage
drop in the electrolyte, calculated from Equation 12, is greater than
0.1 volts.
Figure 7d further demonstrates how the electrolyte conductance
affects power performance by plotting power density versus energy
density for various electrode pitches (30, 45, and 120 μm). The elec-
trode separation is held constant. At each pitch, the peak electrolyte
conductivity is scaled by a factor of 0.01, 0.1, 1 or 10X. At low power
density, battery performance has minimal dependence upon electrode
pitch or conductivity. The point at which the power performance be-
gins to rapidly change (marked by a black diamond for each battery)
is predicted by Equation 12 when Ve = 0.1 volts. We conclude that
high power performance microbatteries should be designed so that Ve
< 0.1 volts.
Electrode electron path.—Figure 8a shows how the electrode con-
ductivity affects the energy density of Battery 1 at 1–500 C discharge
rates. The conductivity is varied by up to 1 × 10−8 times the conduc-
tivity in Table I. The dashed lines in Fig. 8a correspond to the energy
density of batteries where the voltage drop across the electrodes, Vs ,
is 0.3 or 0.1 V. The voltage drop is estimated using Ohm’s law,

I L2 L2
= 0.5 ef f
+ ef f
, [14]
A 2σ pos W pos ε1.5
pos 2σneg Wneg ε1.5
neg
where the current density is calculated from Equation 13. Figure 8b
shows predicted power density versus energy density for Battery 1
with varying electrode conductivities. The point at which the power
performance begins to rapidly change (marked by a black diamond
for each battery) is predicted by Equation 14 when Vs = 0.1 volts.
We conclude that high power performance microbatteries should be
designed so that Vs < 0.1 volts.
Active material thickness (t).—The active material thickness in-
fluences the fraction of lithium extracted or inserted into the active
material at a discharge rate. A smaller active material thickness allows
more energy to be extracted in less time; there are however practical
limits on the thickness. Figure 9a shows how the cathode active ma-
terial thickness in Battery 1 affects the energy density at 1–500 C rate
discharges. A maximum energy density occurs because of competing
effects between an increase in the total volume fraction of the ac-
tive material and an increase in the distance that lithium travels. The

maximum can be predicted by comparing the diffusion time, τ, to the
I I W pos Wneg diffusion distance, l. The active material thickness corresponding to
Vs = ρl = 0.5 + ef f
A A k epos
f f 1.5
ε pos kneg ε1.5
neg the maximum power performance, to , is predicted from the diffusivity,

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 Journal of The Electrochemical Society, 164 (11) E3122-E3131 (2017) E3129

Figure 9. a) Predicted energy density versus active material thickness for Battery 1 at discharge rates of 1 to 457 C. The dashed line is the design parameter to
for the active material thickness. b) Ragone plot of Battery 1 as active material thickness is varied. The 15.5 C power curve is the energy and power density of
batteries with varied thicknesses discharged at 15.5 C rate. Colored dots are experimental data. Black diamonds correspond to inflection points calculated from
design parameters. c) Predicted energy density versus pore diameter for Battery 1 at discharge rates of 1 to 457 C. The active material thickness is varied with the
pore size to maintain a constant volume fraction. Dc is the pore diameter corresponding to to . d) Ragone plot of Battery 1 as active material thickness is varied and
volume fraction maintained.

Ds , and C rate using Dτ/l2 , or
 pore diameters in Figs. 9c and 9d are approximately proportional to
Ds 3600
to = n , [15]
Crate
√ the active material thickness past to dramatically reduces the power
where n is 1 for a slab and 5 for a sphere. The dashed line in Fig. 9a is
the energy density corresponding to to , when n = 1, which predicts the
maximum with reasonable accuracy. The amount of lithium extracted
or inserted into the active material is constant for a constant Dτ/l2
when the discharge is stopped at a set surface concentration, which is
valid for batteries discharged at a constant C rate.45 It follows that the
extracted capacity of a microbattery with to active material thickness
is a constant fraction of the total capacity if the shutoff concentration
is set to the maximum concentration in the cathode or minimum in the
anode. The fraction of extracted capacity is 2/3 the maximum when
n = 1 and the active material thickness is to . Figure 9b is a simulated
Ragone plot for Battery 1 with cathode active material thicknesses
varied between 13 and 100 nm. The power curve for 15.5 C shows the
energy and power density of each battery when discharged at a 15.5 C
rate. The maximum power performance occurs at the apex of the 15.5
C power curve and corresponds to to = 55 nm, which is the optimal
active material thickness predicted from Equation 15 at 15.5 C rate.
The energy and power density corresponding to to for each battery is
marked with a diamond. We conclude that power performance is near
optimal when the active material thickness is to .
Figures 9c and 9d show how the active material thickness af-
fects the power performance independent of the volume fraction by
changing the pore diameters. The active material thickness is varied
with the pore size to maintain a constant volume fraction so that the
the active material thickness. The dashed line in Fig. 9c shows bat-
tery performances when the active material thickness is to . Increasing
performance at all C rates, including 1 C. Decreasing the pore size
(PS diameter) improves the power performance because the diffusion
distance through the solid active material is reduced (higher power)
while the active material volume fraction remains the same (constant
energy). A battery fabricated with 109 nm PS diameter particles can
be discharged at 300 C and maintain 55% of its total energy density.
In the simulated batteries, the electrode pores are FCC closed
packed. If the pore distribution deviated from FCC close packed to-
ward random close packed, the nickel volume fraction would increase
and the active material volume fraction would decrease. If the active
material thickness was maintained, and thus the C rate performance
held constant, the power density would still decrease because the
reduced active material volume fraction would decrease the energy
density.
Battery Design Summary
The design parameters (to , Wc , Ve , and Vs ) provide a simple tool
to optimize the power performance of a battery using only battery
geometry and material properties. To illustrate the design utility, we
optimize Battery 1 for a 50 C rate discharge using the design param-
eters and compare the optimized performance to experimental data.

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 E3130 Journal of The Electrochemical Society, 164 (11) E3122-E3131 (2017)

Figure 10. a) Schematic of a battery architecture optimized for a 50 C discharge rate using the design rules presented here. b) Predicted discharge curve of the
battery. c) Ragone plot of the battery performance compared to previously fabricated batteries. The 50 C rate discharge point is marked. d) Sensitivity analysis of
the optimized battery. The electrochemically active material thickness and electrode width are varied by plus and minus 10 and 25 percent.

Figure 10a shows a diagram of the optimized microbattery. The micro-
battery geometry was chosen by setting the active material thickness
to to and cathode width to Wc , while decreasing the pore size to 250
nm to increase the active material volume fraction. Additionally, the
pitch was set so Ve ≤ 0.1, and the electrode length so that Vs ≤ 0.1.
Figures 10b and 10c show the power performance of the 50 C rate
optimized microbattery. The microbattery capacity at 50 C is 56% of
the 1 C rate capacity, which agrees well with the 2/3 performance
predicted by Equation 15. The 50 C rate optimized design has ∼10 X
increase in energy density compared to Battery 1 at 1,000 mW cm−2
μm−1 power density and ∼10 X increase in power density at 10 μWh
cm−2 μm−1 energy density. The most significant power performance
improvements came from increasing the cathode width and optimiz-
ing the active material thickness while reducing the pore size to 250
nm. Figure 10d shows sensitivity analysis results for the 50 C rate op-
timized design when all combinations of the active material thickness
and electrode width are varied by ±10 and 25%. Microbatteries with
better power performance than the 50 C optimized design are to the
right of the red line. A majority of the microbatteries have lower power
performance than the 50 C rate optimized design. We conclude that
the design parameters can be used to optimize microbattery geometry
for maximum power performance.
The design optimization presented here is for a single porous anode
and cathode separated by electrolyte. Stacking many of these anode,
cathode, and electrolyte sections together would increase the total
battery energy and power, but maintain the same energy and power
density, and thus performance, as long as the electrodes are stacked
so that the geometric properties that control transport (represented by
to , Wc , Ve , and Vs ) remain the same.
Conclusions
In conclusion, the performance of microbatteries with up to 7.4
mW cm−2 μm−1 power densities were predicted using 1-D transport
models combined with a geometric model of the bicontinuous elec-
trodes. The 1-D model showed good agreement between predicted
and measured discharge curves at up to 600 C rate discharges and
indicated that diffusion through the electrochemically active material
limited battery power performance. The accuracy of predictions could
be improved by accounting for material property changes, including
capacitive transport, and accounting for pore wall or surface film mass
transport limitations. The microbattery geometry was related to the
power performance using four design parameters, to , Wc , Ve , and Vs .
The microbattery geometry can be optimized for a desired output
power by setting the active material thickness to to , the cathode width
to Wc , the pitch so Ve ≤ 0.1, and the electrode length so that Vs ≤ 0.1.
A 50 C rate optimized microbattery based on the interdigitated bicon-
tinuous architecture showed a ∼10 X improvement in power per-
formance over the experimental batteries, indicating that significant
improvements in power performance are possible with advances in mi-
crobattery design and fabrication. The 1-D electrochemical model and
design parameters provide a new tool for developing novel material
architectures, nano composites, and full battery cells with improved
power performance, which is critical for the maximum exploitation
of energy storage technologies in many applications. In addition, the
performance limitations and design parameters developed in this work
are based on the same physical models used for macroscopic batteries;
therefore, these design principles might be applicable for improving
the performance of macroscopic batteries.

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 Journal of The Electrochemical Society, 164 (11) E3122-E3131 (2017) E3131

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