Optimization of Porosity and Thickness of a Battery

Electrode by Means of a Reaction-Zone Model

John Newman*
Energy and Environment Division, Lawrence Berkeley Laboratory, and Department of Chemical Engineering,
Uniw,rsity of California, Berkeley, California 94720

ABSTRACT
If electrode kinetics are fast and concentration gradients can be ignored, the reaction in a battery electrode is confined
to a narrow zone, which moves through the electrode as the battery is discharged. During this process, the ohmic resistance
increases, and the cutoff potential may signal the end of the discharge. It is desirable to have a matching of the capacity
of the electrode (and hence its thickness) with the time ta of discharge. Assuming that there is a certain specified separator
thickness and that the electrolyte of the separator is the same as that permeating the positive electrode, it is possible to
obtain the optimum porosity as a compromise between the desire to have active material present and the necessity to have
a conduction path through the pores of the electrode. For a system with a foil negative electrode and an open-circuit
potential which is independent of state of charge, this optimum value depends on one principal parameter T = UK,ta/q+L~,
one which involves the time of discharge, the open-circuit potential U, the conductivity K~,and thickness L~ of the separator,
and the capacity q+ per unit volume of solids in the positive electrode. There is one other parameter: the ratio of the cutoff
potential to the open-circuit potential. Other parameters are introduced to account for a more complex structure of
the battery.

The development of lithium/polymer batteries prompts application with a shorter discharge time, such as an elec-
us to reconsider an ohmically limited system. Let us think tric vehicle, or even for starting a ear, we know that we need
of a system with a lithium foil negative electrode, a solid to slice the electrodes much thinner than for the slow-dis-
polymer separator, and a positive eleetrede consisting of a charge application. Compensating for this possibly low
positive active material, such as manganese dioxide or conductivity can be the high capacity q+ per unit volume
cobalt oxide, and an admixture of filler or material to en- and the high open-circuit potential U. These parameters
hance the electronic conductivity of the solid matrix, and are brought together here in a single dimensioniess group.
with the pores in the positive electrode filled with the same Table I gives some typical values of critical parameters
polymer electrolyte that constitutes the separator. Such a for two systems to set a perspective for the magnitude of T
system was treated by Doyle et al. 1 Let us further suppose that might be encountered. The small separator thickness
that the rate is not limited by concentration gradients for the lithium/polymer system has probably been chosen
either in the positive solid material or :in the electrolyte. to compensate for the low electrolyte conductivity in that
(Successful efforts to make polymers wit]h a unity transfer- system. The value of q+ for the lead-acid system is probably
ence n u m b e r for lithium ions would assure an ohmically overstated by a factor of two since all the PbO2 cannot be
limited system. Reference 2 covers modeling of such sys- discharged without ruining the structure of the electrode.
tems.) In such a case, with the further assumption that the With this adjustment, the values of T would be comparable
reaction is not kinetieally limited at the interface between for the two systems.
the solid particles and the electrolyte, the reaction-zone The optimization involves a trade-off between increasing
model of Tiedemann and Newman 3 becomes applicable. the capacity of the system and increasing the mass and
While sophisticated models of batteries have proliferated ohmic potential drop. For longer discharge times, one can
over the years, it may be instructive to optimize the battery increase the electrode thickness more or decrease the
thickness and porosity with the reaction-zone model even porosity more before reaching this balance between in-
though more detailed computer models with much less re- creasing capacity and increasing mass and ohmic potential
strictive assumptions would be used for the final design. In drop. What is a large or small discharge time is determined
this particular case, with the mass of other battery compo- by its magnitude in relationship to the other parameters
nents being regarded as negligible, a new dimensionless (q+, U, K~, and L~) making up the dimensionless parameter.
group emerges as being important for governing the opti- Once the concept and method of the optimization are
m u m thicknesses. This quantity is UK~td/q+L~,denoted T. It clear, it is relatively simple to relax a few of the restrictions.
has the desirable feature of bringing in explicitly the time For example, the density of the positive active material
of discharge td, which can be regarded as the most impor- (after accounting for any solid thefts) is likely to be larger
tant parameter of the intended applieatio:n that governs the
design of an actual system. At the same time, the parameter Li foil
LJK~, with units of [1 9em 2, is combined with the discharge
ele~/trode
time to show what we know intuitively after many years of Positive electrode
considering battery design: systems with poor conductivity
are better suited for applications with a long discharge
time. If such a system of poor conductivity is used for an

* Electrochemical Society Active Member.

Separator
Table I. Typical parameter values far three battery systems.

Lead Lithium Cd/

acid polymer NiOOH
Reacted ~ Uareacted l
L~, cm 0.1 0.005 0.03
K~,S/cm 0.8 0.0906 0.34 Narrow Current
q+, C/cm3 7563 1888 3124
U, V 2.14 4 1.3 reaction zone collector
T for td = 15 s 0.34 0.76 2.36
T for to = 3 h 244 549 1698 Fig. 1. Pictorial of the battery system.
d. Electrochem. Soc., Vol. 142, No. 1, January 1995 9 The Electrochemical Society, Inc. 97
Downloaded on 2014-10-21 to IP 130.15.241.167 address. Redistribution subject to ECS terms of use (see ecsdl.org/site/terms_use) unless CC License in place (see abstract).
 98 J. Electrochem. Soc., Vol. 142, No. 1, January 1995 9 The Electrochemical Society, Inc.
Acdvr rnalenaJ
any current collector or other sheets between the cells. The
second term is the mass of the separator, and the third term
is the mass of the positive electrode, including the elec-
trolyte within the pores. This mass analysis might be par-
ticular]y appropriate to a bipolar system.
0 When the thickness of the negative electrode is to be ad-
justed to maintain a specified ratio of positive capacity to
Separaol Hleclrolyte
negative eapaeity, the mass of the negative electrode would
be removed from the residual mass p~LI.and included in a
Fig. 2. Equivalent-circuit representation for the reaction-zone model. term proportional to the thickness of the positive electrode.
Equation 4 might be replaced by
than the density of the electrolyte. The calculations are just M = prLr + p~L~ + [p_q+(1 - e)/q_ + eps + (1 - e)p+]L+ [5]
as easy to carry out; the real complication is that there is
We shall use Eq. 4 in the examples in this work.
now an additional parameter, p+/p~, the ratio of the density
When carrying out the optimizations, it is best to be clear
of the positive active material to that of the electrolyte, and
about what is to be optimized and what is to be held fixed.
results should be presented as this parameter is varied.
We wish to maximize the value of the energy per unit mass
Another example is the mass of the balance of the system.
for given discharge time td, open-circuit potential U, sepa-
We shall attempt to cover two of these parameters after
rator thickness Ls, positive-electrode capacity density q.,
presenting the method and the basic results.
and separator conductivity Ks. The parameters Pr, Lr, p~, and
Analysis p+ are also supposed to be fixed. The parameters which are
Figure 1 shows one example of the system being treated. free to be varied to attain the m a x i m u m are the discharge
On the left we see an Li foil negative electrode; next to it is current density i, the thickness L. of the positive electrode,
and the porosity 9 representing the volume fraction of the
the separator, taken here to have a porosity of unity. On the
right is the positive electrode, divided into two regions, the electrolyte in the positive electrode. The effective conduc-
tivity K of the electrolyte phase in the positive electrode is
reacted and the unreacted regions. A bipolar partition com-
assumed to be given by the Bruggeman equation 4
pletes the cell sandwich. The ionic current must flow from
the negative electrode, through the separator, and through K ---- K0 9 [6]
the pores of the reacted region up to the reaction zone.
Figure 2 shows the same thing in an equivalent circuit. The where K0is the conductivity of the pore electrolyte when 9=
upper conductor represents the high conductivity of the 1. Because the porosity of the separator 9 was taken to be
positive-electrode matrix. The lower conductor represents unity, ~0 = K~, and the p ar am et er es is not considered explic-
the resistance of the separator on the left and of the elec- itly in this work.
trolyte in the pores of the positive electrode on the right. It is easiest to maximize first with respect to the dis-
The terminal on the left represents the negative electrode; charge current for given L. and 9 because the value ob-
that on the right represents the current collector or bipolar tained is then independent of the mass parameters. We
partition. Within the positive electrode are ideal battery shalt make the current density dimensionless with the
elements (with fast reaction kinetics); the three on the left short-circuit current at full charge; thus, I = iLjK~U. Maxi-
toward the separator are shown open because the active mization of Eq. 3 w~th respect to I gives
material has been exhausted there. As the current moves 1
through the network from left to right, it takes the first Iop~ = / 3 Ut~K~ ~~/~ [7]
opportunity to transfer from the pore electrolyte to the ma- 1 + ~1 + 2K(1 - 9
trix because this represents the low-resistanee path. Where
this transfer occurs, just to the right of the exhausted por- However, there are two constraints to consider. At the end
tion, constitutes the reaction zone. of discharge, the cell potential V must be greater than the
The distance x~ that the reaction zone has penetrated into cutoff potential Vo. This requires that
the positive electrode depends on the amount of charge
passed, as follows 2(1 - VJU)
Iopt -< / 4 ( U - Vr ~/2 [8]
it 1+ ( 1.----~'
z~ - (1 - e)q+ [1] K(1 - 9 )

where i is the current density (taken to be constant), t is the Furthermore, the capacity of the positive electrode must
time since the beginning of the discharge, 9 is the porosity not be exhausted, and this can be expressed as
of the positive electrode, and q+ is the capacity per unit
volume of active material (including any solid additives in
L§ - e)q+ [9]
Iop~ <- Utd~
the volume calculation). The cell potential at any given
time is the open-circuit potential U minus the ohmic drop The smallest of the three values must be used. One can
required for the ionic current to flow across the separator reason that, after optimization with respect to L+, the last
and through the pores in the positive electrode up to the condition could be replaced by an equality, since otherwise
region x= where the reaction is taking place there would be unused capacity and the situation couId be
improved by reducing L+ until the equality held. We did not
v=u-i ~+ =~J---i
Ks K(1 - - e)q+
[2] implement this in the optimization procedure, but the re-
sults obtained satisfy this equality condition..
The energy E (per unit of separator area) delivered is the The dimensionless specific energy to be maximized now
integral of the instantaneous power being delivered takes the form

E=fVidt=(u-L~i) itd i3t~ [3] Ep~ (1 - I)IT - I3T2/2e~a(1 - 9 [10]

Ks 2K(I - e)q+
Finally, the mass M per unit of separator area can be ex-
MUq§ prL~
--+i+
p~L~
L+
E
9149 [ p.
P:
]
pressed as where I is taken as the m i n i m u m value governed by Eq. 7 to
M = p~.Lr + p~L~ + [9 + (1 - 9247 [4] 9 and

Here the first term on the right represents the remainder of T= UK~td [11]
the system, such as the lithium foil negative electrode and q+Ly

Downloaded on 2014-10-21 to IP 130.15.241.167 address. Redistribution subject to ECS terms of use (see ecsdl.org/site/terms_use) unless CC License in place (see abstract).
 J. Electrochem, Soc., Vol. 142, No. 1, January 1995 9 The Electrochemical Society, Inc. 99

I I I |
2.5 0,6
0.5
o.4 z " - . . . . / / . . . . . . . -" . . . . . .
,; / / //
I
2.0 a = 0.3 .,',, / ( . / . _ . . . .... :f~ /................

9 0.2 .....................................
J
,C,,'" , " / / 0.7 0.1

,.o o., //.....,,,/ /

l ? ,," ," /
//," i ~ ///

0.0!
0.5 ~ " T=100
10-2 10-1 I0 o I01 10z 10 ] 10 ~
T = UNta/q+L9
0.0 I I I I
0 2 4 6 8
Fig. 5. Optimum electrode thickness as it depends on ~e parame-
L+/Ls, etectrode thickness
ter determined by discharge time, electrode capacity density, open-
circuit potential, and separator parameters.
Fig. 3. Electrode capacity for various electrode thicknesses and
porosities. The maximum capacity is achieved with e = 0.6 (a result
valid 3 for any value of D. trated. At the same time, the optimum electrode thickness
is reduced from L+/Ls = 6 to 1.95. (For these illustrative
cases, we have taken p+ = p~ and prL, = 0. This can be con-
Results strued to constitute an optimization of energy density in-
Optimum specific energy vs. optimum capacity.--In an stead of specific energy.)
earlier work we employed a similar model to show how to
optimize the capacity of a system characterized by a reac-
Optimum thickness and porosity.--Figure 5 shows the
optimum electrode thickness (made dimensionless with the
tion z o n e ) More features were included in that model; the
conductivity of the m a t r i x was not taken to be infinite, and separator thickness), and Fig. 6 shows the optimum posi-
the properties after reaction could be different from those tive-electrode porosity, both as functions of the dimension-
before reaction. The optimization is different because in less parameter, T For these calculations, the ratio of the
the earlier case the mass of the cell was not included in the cutoff potential to the open-circuit potential is taken to be
denominator. 2/3. Also, p+ = p~, and p~L~. = 0.
Figure 3 shows how the electrode capacity depends on Toward the left on these figures (for high-rate dis-
electrode thickness and porosity for T = 100. The capacity charges), the ohmic potential drop is important, and the
increases with thickness until the ohmic potential drop inequality in Eq. 8 becomes an equality. That is, the cell
causes the cutoff potential to be reached; further increase reaches the voltage cutoff at the end of discharge. Above
in thickness does not permit the current density to be in- about T = 50, the voltage cutoff is no longer reached (for
creased to utilize the material. The capacity attains a max- P+ = Ps and prLr = 0); weight considerations become more
imum at a porosity of 0.6, in harmony with the earlier re- important.
sult ~ for the parameters used here. Figures 7 and 8 show the corresponding results for sev-
When we consider the specific energy, as in Fig. 4, the eral values of p+/p~ and a residual mass parameter b defined
mass in the denominator of Eq. 10 contributes an addi- as b = 1 + prLr/p~L~. A larger residual mass pushes the opti-
tional penalty for increasing the thickness of the electrode. mum porosity up toward the value of 0.6 corresponding to
More refined calculations show that the optimum porosity the capacity maximization. At the same time, this permits
is reduced from 0.6 to 0.227 for the value of T = 100 illus- an increase in the optimum electrode thickness because of
the more open electrode. On the other hand, an increase in

e = 0.2 0.3
0.4 /"...""-. .)'.-,. 0.4

,., "-, 0.5 0.4

-<,- ~,~-,,

o 0.3

0 I ..... . N
0.2

7"= IOO
0.1
o.o' I I I I 10 ~ 104 10~ 101 10 2 10 3 10'
0 2 4 6 8
T = UNtd/q+Ls 2
L+/Ls, e l e c t r o d e t h i c k n e s s
Fig. 6. Optimum electrode porosity as it depends on the parameter
Fig. 4. Specific energy for various electrode thicknesses and determined by discharge time, electrode capacity density, open-cir-
porosities. The optimum is e = 0.227 and LJ~ = 1.95. cuit potential, and separator parameters.

Downloaded on 2014-10-21 to IP 130.15.241.167 address. Redistribution subject to ECS terms of use (see ecsdl.org/site/terms_use) unless CC License in place (see abstract).
 100 d. E l e c t r o c h e m . Soc., Vol. 142, No. 1, January 1995 9 The Electrochemical Society, Inc.

10 I I I I I I I I I I t I 6 I~,I I I I I I I I IJ Table II. Values of limiting optimum values for the

positive-electrode porosity for small T and values of
b = 10 ...-'~
-
the fitting coefficient A" for selected values of the
parameters p+/p, and b. Here VJU = 2/3.

b 1 3 10

e0 0.503 0.559 0.586

p+/p~ Values of A~

1 1.074 0.992 0.954

3 1.52 1.34 1.1
10 1.179 1.63 1.41

H e r e the density of the positive active m a t e r i a l does not

e n t e r s i g n i f i c a n t l y into the o p t i m u m values of L+ a n d e. The
values of the l i m i t i n g porosity e0 increase t o w a r d 0.6 as the
residual mass of the system is increased, t h u s a p p r o a c h i n g
10 100 1000 the best porosity for o p t i m u m c a p a c i t y of the system.
T = U~ta/q+Ls 2 The trends s h o w n in these a s y m p t o t e s are reflected in the
results s h o w n in Fig. 7 and 8: an increase in b increases the
Fig. 7. Opfmum electrode thickness as it depends on T and on o p t i m u m values of L§ and e at b o t h large and small T; an
several parameters, increase in p./p~ increases 9 a n d decreases L . / L s b u t only in
the a s y m p t o t e for large T.
With these a s y m p t o t e s for small a n d large values of T,
the density of the positive electrode m a t e r i a l increases the results for several sets of p a r a m e t e r values could be p l o t t e d
o p t i m u m porosity b u t reduces the o p t i m u m electrode like Fig. 7 a n d 8 b u t w i t h the axes m o d i f i e d so t h a t the
thickness since these changes can c o m p e n s a t e for the in- a s y m p t o t e s coincide for all cases. This w o u l d p r o v i d e a
creased mass. general correlation of the results for o p t i m u m electrode
A s y m p t o t i c l i m i t s . - - F o r large values of T, the c o m p r o - thickness and porosity. However, the b e h a v i o r of t h e curves
mise b e t w e e n o h m i c drop a n d w e i g h t and c a p a c i t y leads to b e t w e e n the a s y m p t o t e s d e p e n d s on the a d d i t i o n a l
s m a l l e r porosities and t h i c k e r electrodes. The limits are p a r a m e t e r s . An a l t e r n a t i v e is to develop a fitting e q u a t i o n
of the f o r m
L./L~ --> (0.75)1/3b 5/9 ( p ~ 2 , 9 [12] i 1 i i
\ p+/
L+/Ls - ~ToT + ~ + A=T 2/9 [16]
and
w h e r e A0 represents the coefficient of T in Eq. 14, A~ repre-
9 --'> (0"75)2/3b4/9 ( p+ ]2/~ \~T] [13] sents the coefficient of T 2/9 in Eq. 12, and Ai represents an
i n t e r m e d i a t e v a l u e o b t a i n e d from an e m p i r i c a l fit and
S u c h an a s y m p t o t e is s h o w n on Fig. 5. given for some values of the p a r a m e t e r s in Table II.
F o r small values of T, the l i m i t i n g f o r m for the electrode
B r e a d t h o f the m a x i m a . - - I t m a y be impossible to m a n u -
thickness is facture an electrode of the porosity specified by the opti-
L+ --~ 1 - Vc/U T [14] m i z a t i o n procedure. T h e n one should w i s h to o p t i m i z e cur-
Ls i - e0 rent density and electrode thickness subject to a constraint
of specified porosity. We m a y also w i s h to k n o w h o w p r e -
w h e r e the l i m i t i n g v a l u e of the p o s i t i v e - e l e c t r o d e porosity cisely we m u s t hit the o p t i m u m value.
e0 m u s t be o b t a i n e d by solving the e q u a t i o n Figure 9 shows the dimensionless specific energy as a
f u n c t i o n of porosity for T = 5000 (and p. = ps and prL~ = 0).
3 5 4
[15]
e~ "~ - e~ '5 + b (3 - VIVa)
i i i
0.6 , ' , , ''"1 ~ ' ' ' '"~ ' ' ' ' ''''
0."7
b = 10 . -" "" - . Optimized
,' "" - electrode
' "- thickness
0.4

~9 0.6

"=~oe
0.3 0 '"&"~'"i""~-""
"~ ...... P s i
"~ ] electrode
0.21 0.5 [ thickness
' -- 10 /
b=l
[ T = 5000

04 I i
0.0 0.1 0.2 0.3 0.4
lO 100 1000 Porosity, s
T = U%tdq+Ls2
Fig. 9. Breadth of maximum of specific energy for a constant
Fig. 8. Optimum positive-electrode porosity as it depends on Tand electrode thickness (optimized at the optimum porosity) and for an
on several parameters. electrede thickness optimized at each porosity. Here p./p, -- b = 1.

Downloaded on 2014-10-21 to IP 130.15.241.167 address. Redistribution subject to ECS terms of use (see ecsdl.org/site/terms_use) unless CC License in place (see abstract).
 J. Electrochem. Soc., Vol. 142, No. 1, January 1995 9 The Electrochemical Society, Inc. 101
10 a
These relationships are brought into quantitative focus
by starting with a separator of given thickness and conduc-
tivity, as constrained by practical considerations of m a n u -
facturability and reliability.
10 4 Remember that es, p+/ps, Lrpr/Lsp~, and other parameters in
Eq. 5 can also be included in the calculations and in the
resulting graphs with little additional difficulty. Even the
W
o~ conductivities of the matrix, before and after reaction,
could be accounted for. 3 However, the additional parame-
xo-2 Optimized at " ~ I ters may obscure the primary role played by the discharge
...........T=2 ".. ! time and its dimensionless counterpart.
---T=100 ",. i I Note that to maximize the energy density instead of the
c~ .....T = 5000 " , ~ I
specific energy, we would take p~ = p+ = Pr. Then the mass M
\
i 0 "1
becomes the volume (or the thickness of the cell sandwich).
Limitations of mass transfer would force the use of the
I , * .... I . I .*,,.I . ~ | ,lltll t

ID 4 lO a 10 4 1 0 "~
more sophisticated computer programs for system design.
Dimensionless average specific power Limitations of manufacturability may force optimization
of the electrode thickness at a constrained porosity.
Fig. 10. Specific energy vs. average specific power. For three of the Acknowledgment
curves, the electrode thickness and porosity are optimized at the
value of Tgiven. For the envelope curve, the electrode thickness and This work was supported by the Assistant Secretary for
porosity are optimized for each point on the curve. Here p./p~ = Energy Efficiency and Renewable Energy, Office of Trans-
b=l. portation Technologies, Electric and Hybrid Propulsion
Division of the U.S. Department of Energy under Contract
No. DE-AC03-76SF00098.
The solid curve is calculated for a fixed electrode thick- Manuscript submitted June 10, 1994; revised manuscript
n e s s - - t h a t which gives the overall optimum at this value of received Aug. 30, 1994.
T. The dashed curve indicates the specific energy if the Lawrence Berkeley Laboratory assisted in meeting the
electrode thickness is optimized for each value of the publication costs of this article.
porosity. Thus, if manufacturing constraints restrict us to a
porosity of 9= 0.35, we can see what specific energy can be LIST OF SYMBOLS
attained and how much of a penalty there is with respect to b =1 + prLr/psLs
the best possible value. E energy per unit separator area, J/cm 2
i superficial current density, A/cm 2
Ragone plot.--Figure 10 shows a plot of specific energy I =iLs/KsU,dimensionless current density
vs. average specific power; the ratio of these two quantities L+ thickness of positive electrode, cm
is the parameter T. The three lower curves are calculated Lr thickness of residual parts, cm
with fixed values of electrode thickness and porosity, those L~ thickness of the separator, cm
selected as optimum values from Fig. 3 and 4 for the three M mass per u n i t separator area, g/cm 2
values of T = 2,100, and 5000. These curves illustrate how q§ capacity density of solids in the positive electrode,
C/cm s
the compromise between energy and power shifts as one q_ capacity density of the negative electrode, C/cm 3
optimizes for different discharge times. t time, s
Also shown on Fig. 10 is a curve where the electrode td discharge time, s
thickness and porosity are optimized for each point (which T =UK:Jq+L~
corresponds to a given value of T). This curve provides an U open-circuit potential, V
envelope of the best performance attainable and gives some V cell potential, V
perspective to the compromises represented in the other Vc cutoff potential, V
curves. The system will have a natural minimum practical xr distance of reaction zone from separator, cm
discharge time corresponding to a T of about 2 or 5. That is 9 positive electrode porosity
K electrolyte conductivity in positive electrode, after cor-
to say, selection of a value of T significantly less than 2 rection for the porosity, S/cm
makes it impossible to use very much of the capability of K0 inherent electrolyte conductivity, S/cm
the battery to store energy. Ks conductivity of separator, S/cm
p+ average density of the positive solid material, g/cm3
Conclusion p_ density of the negative electrode, g/cm3
The most significant factor affecting the design of a bat- Pr average density of residual parts, g/cm~
tery is its discharge time. (The next most important is its p~ density of the electrolyte, g/cm3
capacity.) It is shown here how the electrode thickness and
porosity are determined by this discharge time for a partic- REFERENCES
ularly simple battery model. Shorter discharge times (high- 1. M. Doyle, T. E Fuller, andJ. Newman, ThisJournal, 140,
power applications) require t h i n n e r electrodes because of 1526 (1993).
2. M. Doyle, T. E Fuller, and J. Newman, Electrochim.
the significant ohmic potential drop within the electrode. Acta, 39, 2073 (1994).
Longer discharge times permit thicker electrodes. They 3. W. Tiedemann and J. Newman, This Journal, 122, 1482
also allow smaller porosities to get more capacity into a (1975).
given volume without incurring a large ohmic penalty. 4. D. A. G. Bruggeman, Ann. Physik, 24, 636 (1935).

Downloaded on 2014-10-21 to IP 130.15.241.167 address. Redistribution subject to ECS terms of use (see ecsdl.org/site/terms_use) unless CC License in place (see abstract).