Mit10 626S14

10.426/10.
626 Electrochemical Energy Systems

Spring 2014 MIT, M. Z. Bazant
Problem Set 1 – Equivalent Circuit Models
© Macmillan Publishers Limited. Huskinson, B., M. P. Marshak, et al. "A Metal-free Organic–inorganic
Aqueous Flow Battery." Nature 505 (2014): 195–98. All rights reserved. This content is excluded from
our Creative Commons license. For more information, see http://ocw.mit.edu/help/faq-fair-use/.
HBr Laminar Flow Battery

W. Braff, MZB, C. Buie
H2 (gas)
s)
Micropo
Microporous anode H2 2e-
(Pt catalyst)
2H+
HBr (aqueous)
G
Br2 2HBr
Br 2 Graphite cathode
HB
r+
2e- -
Figure 1: Comparison of two new bromine flow battery technologies. Top: Proton-exchange mem
brane based Quinone-Bromine Flow Battery (QBFB) of Huskinson et al., Nature (2014). Bot
tom: Membraneless Hydrogen-Bromine Flow Battery (HBFB) of Braff et al., Nature Com
munications (2013). Left: Cell schematics. Right: Experimental polarization curves.
© Macmillan Publishers Limited. Braff, W. A., M. Z. Bazant, et al. "Membrane-less Hydrogen Bromine Flow
Battery." Nature Communications 4, no. 2346 (2013). All rights reserved. This content is excluded from
our Creative Commons license. For more information, see http://ocw.mit.edu/help/faq-fair-use/.
1
1. Bromine Flow Battery Comparison: Performance See Figure 1. In the following
assume 50% SOC for the QBFB and 3M Br2 for the HBFB.
(a) Which cell has the higher open circuit voltage?

(b) Which cell shows some signs diffusion limitation? Explain your reasoning.
(c) Estimate the internal resistance Rint and of each cell in Ω·cm2 , and assume Rint is
constant in the following calculations. Which cell has higher internal resistance, and
why?
(d) Calculate the maximum power density Pmax (W/cm2 ) and the corresponding current
density Imax (A/cm2 ) of each cell on discharge. Which cell has greater power?
(e) Calculate the voltage efficiency of charge/discharge cycles at 25% and 100% of ±Imax
for each cell. Which cell is more efficient?
2. Bromine Flow Battery Comparison: Cost See Figure 1. In the following assume 50%
SOC and 1M quinone for the QBFB and 3M Br2 for the HBFB.
(a) Estimate the power cost ($/kW) for each cell discharging at 0.2 W/cm2 . Assume hard
ware costs of $0.003/cm2 per active area for both cells. The Nafion 212 membrane in
the QBFB costs $0.26/cm2 , while no membrane is needed for the HBFB. The anode
catalyst in the HBFB (platinum) costs $0.01/cm2 , while no anode catalyst is needed for
QBFB. Neither cell needs any catalyst for bromine reduction at the cathode. Which cell
is cheaper per power? Can either one beat lead-acid and Li-ion batteries (≈ $200/kW)?
(b) Estimate the capacity cost or energy cost ($/kWh) for each cell, assuming slow cycling
near the open circuit voltage. In flow batteries, the capacity cost is dominated by that of
the active materials stored in large separate tanks and the cost of the tanks themselves.
The quinones cost $4.74/kg with molecular mass 100 g/mol per electron transferred
(where 2 electrons are transferred per mole of quinone). Hydrogen (H2 ) costs $120/kg
and has mass 1 g/mol per electron transferred. Bromine (Br2 ) costs $1.76/kg and has
mass 80 g/mol per electron transferred. The cost to store H2 in tanks at 10,000 PSI is
$500/kg, cost to store the bromine and quinone is $1.5/L. The cost to operate a liquid
pump for bromine or quinone is $0.03/(L*min), and pumps are operated for 1 hour per
cycle. Which cell is cheaper per energy stored? Can either one beat the lead-acid battery
(≈ $200/kWh) or the Li-ion battery (≈ $400/kWh)? Can either cell beat the cost target
$100/kWh to make solar or wind energy more competitive?
2
3. Battery discharge at constant load. Consider a battery whose open-circuit voltage
varies with charge Q(t) stored in the cathode as VO (Q) = V 0 (1 − αQ − βQ2 ), where α, β > 0.
Consider slow discharge against an external resistance R from Q(0) = 0, and neglect any
internal resistance.
(a) What is the maximum capacity Qmax (α, β) for galvanic discharge?
(b) Solve for the voltage profile, V (t) if β = 0.
(c) Solve for V (t) with α, β > 0.
4. Super-capacitor polarization. As shown in the figure, a super-capacitor, consisting of

two parallel-plate porous metal electrodes soaked in an electrolyte, can be modeled by a
transmission-line equivalent circuit. Assume a symmetric situation of two identical porous
electrodes of thickness L, and thus focus on only one, in the region 0 < x < L. The electrolyte-
filled pore space has a constant volume-averaged resistance per length R and constant capac
itance per unit length C. Neglect any resistance in the porous metal electrode or the thin
gap between the electrodes.
metallic electrode matrix

double-layer
capacitance C dx
electrolyte-filled R dx (x,t)
pores
(a) Show that the mean potential in the pores satisfies a linear diffusion equation
∂φ ∂2φ
RC =
∂t ∂x2
with boundary conditions φ(0, t) = V (t), ∂φ∂x (0, t) = I(t)R, and

∂φ
∂x (L, t) = 0, where V (t)
is (half of) the voltage across the electrodes.
(b) Suppose the supercapacitor begins fully charged at voltage V and for t > 0, the voltage is
suddenly removed, V = 0 (short circuit). Find a separable solution, φsep (x, t) = Φ(t)θ(x)
up to a multiplicative constant, which is valid at long
�
times. What is the time scale for
discharging? Estimate the constant by requiring L1 0L φsep (x, 0)dx = V .
3
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10.626 Electrochemical Energy Systems

Spring 2014
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10.426/10.

626 Electrochemical Energy Systems

Problem Set 1 – Equivalent Circuit Models

HBr Laminar Flow Battery

(a) Which cell has the higher open circuit voltage?

4. Super-capacitor polarization. As shown in the ﬁgure, a super-capacitor, consisting of

metallic electrode matrix

with boundary conditions φ(0, t) = V (t), ∂φ∂x (0, t) = I(t)R, and

10.626 Electrochemical Energy Systems

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