Journal of Energy Storage 15 (2018) 196–204

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Journal of Energy Storage

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The external surface area of carbon additives as key to enhance the

dynamic charge acceptance of lead-carbon electrodes
J. Setteleina,* , J. Oehma , B. Bozkayaa , H. Leichta , M. Wienerb , G. Reichenauerb , G. Sextla,c
a
Fraunhofer Institute for Silicate Research ISC, Neunerplatz 2, 97082 Würzburg, Germany
b
Bavarian Center for Applied Energy Research (ZAE Bayern), Magdalene-Schoch-Strasse 3, 97074 Würzburg, Germany
c
University of Würzburg, Chair of Chemical Technology of Materials Synthesis, Röntgenring 11, 97070, Würzburg, Germany

A R T I C L E I N F O A B S T R A C T

Article history:
Received 5 September 2017 The dynamic charge acceptance (DCA) of modern lead-carbon batteries is one of the key parameters for
Received in revised form 18 November 2017 their future application in micro- and mild-hybrid cars. This work elucidates the impact of the external
Accepted 18 November 2017 surface area of carbon additives on the electrochemical performance of lead-carbon electrodes with
Available online 25 November 2017 respect to the DCA. Five specially synthesized amorphous hard carbon powders with different specific
external surface area ranging from 13 m2 g
1 to 192 m2 g
1 were added to the negative active material of
Keywords: laboratory lead-carbon test cells. Results from cyclic voltammetry reveal that the specific external surface
Lead-acid batteries area of amorphous carbons exhibits a clear correlation to the electrochemical activity of lead-carbon
Carbon additives
electrodes. Firstly, an almost linear increase of the activity of the hydrogen evolution reaction with
Dynamic charge acceptance
increasing specific external surface area of the carbon additive can be found. Secondly, the specific
External surface area
Double-layer capacity double-layer capacity of the negative active material is directly linked to the specific external surface area
Hydrogen evolution of the additive, as well. Thirdly, a clear correlation to the DCA can be established. In conclusion, a high
specific external carbon surface in the negative active material seems to be a key to improve the dynamic
charge acceptance of modern lead-carbon batteries.
© 2017 Elsevier Ltd. All rights reserved.

1. Introduction The classical lead-acid battery was not developed for an

Since the introduction of micro- and mild-hybrid powertrains
into the automotive market, new requirements for lead-acid
batteries have been established [1]. Due to braking energy
recuperation functions and stop/start-systems, the car battery is
no longer fully charged most of the time and additionally suffers
from an increased amount of charge/discharge events [2–4]. The
rechargeability of the car battery is essential for providing reliable
stop/start functionality and a maximum of recuperation energy
but strongly depends on the state-of-charge (SOC), the tempera-
ture and the short-term history of battery operation [4–6]. In order
to account for the variable recharge ability of those batteries, the so
called dynamic charge acceptance (DCA) was introduced [7]. With
the help of a new, harmonized test protocol, the EN standard EN
50342-6 now provides a more realistic validation of the
recuperation currents of lead-acid batteries [6,8].
* Corresponding author.
E-mail address: jochen.settelein@isc.fraunhofer.de (J. Settelein).
application including a partial state of charge cycling regime at
high charge and discharge rates. Therefore, an early battery failure
and a disabling of the hybrid functions in the car was very often
observed [4,5]. As was shown in recent years, the negative
electrode is most often responsible for the low charging power of
the battery due to its low specific surface area and an irreversible
PbSO4 crystal growth in partial state of charge [9,10]. However,
adding small amounts of carbon additives, such as carbon black or
graphite, to the negative active material (NAM) seems to be a facile
and low-cost way to improve the DCA [11–13]. These so-called
lead-carbon electrodes exhibit a higher electrochemical activity
and are able to increase the cycle-life and the charging power
significantly. Several mechanisms have been proposed about the
function of the carbon additives in the NAM. The most prominent
are the increase of electrode surface area and double-layer capacity
as well as the improved electrode microstructure due to additional
nucleation sites and steric effects [12]. Yet, it is neither fully
understood nor proven which of these effects actually make a
difference in the electrical performance of the batteries, especially
on the DCA, and how their impact can be enhanced. A direct link

https://doi.org/10.1016/j.est.2017.11.016
2352-152X/© 2017 Elsevier Ltd. All rights reserved.
 J. Settelein et al. / Journal of Energy Storage 15 (2018) 196–204
between carbon parameters, electrode properties and dynamic
charge acceptance would allow tailoring the synthesis of carbon
additives for high-DCA-batteries and could result in a significant
improvement of advanced lead-acid batteries, thus, providing a
more cost-efficient hybridization of the car market.
In this work, we try to establish a correlation between the
external surface area of carbon additives, the electrochemical
activity of lead-carbon electrodes and the dynamic charge
acceptance (DCA). For this, we synthesized amorphous carbon
powders that have a significant difference in their mean primary
particle size but exhibit a similar microporosity [14]. Thus, we are
able to investigate the effect of the specific external surface area of
carbon additives on the electrochemical performance of lead-
carbon electrodes systematically. The comparison to a non-
microporous commercial lamp black is used to validate the results
and to discuss the impact of microporosity as well.
2. Experimental
2.1. Preparation of amorphous carbon powders
The amorphous carbon particles used as carbon additives
within the framework of this study were prepared according to the
procedure given in detail in reference [15]. Briefly, organic aqueous
suspensions of resorcinol-formaldehyde particles were synthe-
sized in a sol formation process in an aqueous solution at very low
concentration of the reactants resorcinol (R) and formaldehyde (F)
((mass (R + F))/(total mass of solution) <20) thus suppressing the
formation of a gel network. Largely different particle sizes were
initiated by changing the molar ratio of resorcinol to catalyst (0.1 n
Na2CO3) in the aqueous starting solution from 700 to 3000. After
aging of the solution for 24 h at 85  C, the particles were extracted
from the suspension by convective drying at ambient temperature
for several days. Eventually, the organic powder was pyrolized at
800  C under Argon.
2.2. Structural characterization
The structural characteristics of the synthetic carbon particles
were derived by scanning electron microscopy and nitrogen
adsorption analysis.
Scanning electron micrographs were taken with a ZEISS
SUPRATM SEM using the secondary electron detector at an
electron-energy of 6 keV and a working distance of 6 mm.
N2-adsorption measurements at
196  C were performed for all
samples with a commercial volumetric adsorption instrument
(ASAP2020, Micromeritics). Prior to analysis, the samples were
degassed at 300  C for at least 12 h at pressures below 10
3 mbar.
The resulting adsorption isotherms were analyzed by BET theory
[16] for the specific surface area SBET according to the recom-
mendations for microporous materials given in the respective ISO
standard [17]. Furthermore, the t-plot method was applied [18];
hereby, the reference isotherm of Magee was used [19]. This
approach yields the specific external surface area Sext, i.e. the
envelope surface area of the microporous carbon particles, and the
specific micropore volume Vmic. Combining the results obtained
Table 1
Structural properties of the synthesized amorphous carbon powders and the
commercial lamp black.
EAC1 EAC2 EAC3 EAC4 EAC5
mean particle size dpart [nm] 352 118 81 37 22
SBET [m2 g
1] 717 734 755 742 765
Vmic [cm3 g
1] 0.271 0.267 0.275 0.245 0.229
Sext [m2 g
1] 12.9 38.3 56.4 120 192
197
from the t-plot method with the density of the nonporous carbon
phase rc = 2.06 g cm
3 [20], the average particle diameter was
calculated with the following relationship assuming spherical
particle geometry:
dpart = 6/Sext*(Vmic + 1/rc). (1)
2.3. Electrochemical characterization of carbon powders
The electrochemical properties of pure carbon powders were
investigated by an electrochemical three electrode setup including
a rotating disc electrode (Pine Research Instrumentation) and an
Autolab potentiostat (PGSTAT101, Metrohm Germany). As electro-
lyte, one molar sulfuric acid was used that was permanently
purged by argon gas in order to prevent the presence of dissolved
oxygen from the atmosphere. With help of a jacketed glass cell, a
constant electrolyte temperature of 25.0  C  0.1  C was provided.
The three electrode setup consisted of a glassy carbon working
electrode, a standard platinum counter electrode (Pine Research
Instrumentation) and a reversible hydrogen reference electrode
(Gaskatel, Germany). An average amount of 50 mg carbon powder
was drop-casted from aqueous dispersion onto the glassy carbon
electrode and dried under laminar flow in order to get a thin and
homogeneous carbon layer. The dispersion was produced by
ultrasonic mixing of 50 mg carbon powder with 10 ml bi-distilled
water and 40 ml Nafion1 solution (5%, Sigma-Aldrich). For the
cyclic voltammetry study, a scan rate of 100 mV s
1 was applied
and the rotation speed of the working electrode was set to
1600 min
1.
2.4. Electrode fabrication and electrical testing
The lead-carbon electrodes were prepared on laboratory level.
The active material was pasted manually onto lead grids (Sn/Ca-
alloy) with a geometrical area of 10 cm2 and a dimension per grid
section of approx. 5 mm  10 mm. After pasting, the electrodes
were cured at a defined temperature of 45  C and a humidity of 100
% and eventually dried. For the production of the active material, all
paste components were mixed by a SpeedMixerTM (DAC 400,
Hauschild, Germany). The total mixing time was 10 min. The paste
composition comprised 80 wt.-% leady oxide (from ball mill
process), 11 wt.-% distilled water, 6.5 wt.-% diluted sulfuric acid
(50 wt.%), 0.6 wt.-% BaSO4 (Merck) and 0.2 wt.-% sodium-lignosul-
fonate (Vanisperse A, Borregaard LignoTech). The relative amount
of the respective amorphous carbon powder was 1.6 wt.-%.
Three laboratory test cells for each carbon powder were
assembled including one negative lead-carbon electrode sur-
rounded by two commercial positive electrodes. A commercial
polyethylene separator for enhanced flooded batteries was
employed as well as a Ag/Ag2SO4 reference electrode (0.71 V vs.
RHE) [21]. The electrodes were electrochemically formed by
container formation at a constant current of 0.1 C and an acid
density of 1.14 g cm3. After formation, the electrolyte density was
adjusted to 1.28 g cm3. The discharge capacity of the final
laboratory cells was limited by the negative electrode at around
1 Ah at 20 h discharge rate.
Electrochemical performance of the lead-carbon electrodes was
determined via cyclic voltammetry with a Solartron 1470 E
potentiostat at 25  C at a state of charge (SOC) of 100%. For
measuring the charge acceptance of the test cells, the DCA test
protocol from European standard for batteries for micro-hybrid
LB
application DIN EN 50342-6:2015 was adopted [8]. Voltages were
104 scaled by factor 1/6 to account for the 2 V laboratory test cell. The
28
respective currents were downscaled from an assumed 60 Ah, 12 V
nd
28 battery to the 1 Ah cell level. The complete test procedure can be
198 J. Settelein et al. / Journal of Energy Storage 15 (2018) 196–204
Fig. 1. SEM images of the five synthesized amorphous microporous carbon particles and the commercial lamp black LB.
found in the specification [8]. In principle, the charge acceptance is
measured in three different ways: Firstly, by taking an average of
the charging current Ic of a pulse profile (20 charge pulses at 2.47 V
for 10 s each) after the battery was charged from 0% SOC to 80%
SOC. Secondly, by measuring analogously the average charging
current Id after discharge from 100% SOC to 90% SOC. Thirdly, an
average charging current Ir is determined via a simulated real-
world drive cycle of one week including various rest periods and
discharge events. In between, the battery is undergoing a total of
six regenerative charging pulses per day, each five seconds long.
More details can be taken from the European standard [8].
3. Investigation of the synthesized amorphous carbons
3.1. Structural and physical properties
The wet chemical synthesis of the amorphous carbon powder
allows for adjusting the mean particle size of the carbon particles
almost without changing other physical or chemical properties. In
this work, five different electrochemical active carbon powders
(EAC) were synthesized with clear difference in mean particle size
ranging from around 400 nm (EAC1) up to 20 nm (EAC5), see also
Table 1. Fig. 1 shows SEM images of all five carbon powders
investigated in this work plus a commercially available lamp black
(LB, LAMP BLACK 101, Orion Engineered Carbons) serving as
reference material.
In addition to the particle size, the microporosity and the
specific surface area of the carbon powders were investigated in
detail by nitrogen sorption measurements. The results of the
analysis are listed in Table 1 along with the calculated mean
particle diameter (see Section 2.2). In terms of the specific BET
surface area, almost no change in value with the variation of the
particle size in the EAC series is observed. This finding is in line
with measurements on carbon xerogels synthesized by similar
synthesis route [15]. It is assumed that the bulk of the carbon
particle is comprised of turbostratically ordered microcrystalline
 J. Settelein et al. / Journal of Energy Storage 15 (2018) 196–204
Fig. 2. Current-potential-relationship of four different amorphous carbon powders
in one molar sulfuric acid solution at 25  C. The scan rate was set to 100 mV s
1, the
lower and the upper vertex potential were kept constant at
2 V vs. RHE and 2.3 V
vs. RHE. a) shows the first 15 cycles, b) compares the 15th cycle of the four different
carbon powders.
carbon with a high amount of accessible micropores in between
the microcrystallites [22]. Due to the identical precursor material
and pyrolysis process for all five powders within the framework of
this study, the bulk structure of the particles is expected to be very
similar. Thus, the specific amount of microporosity (specific
micropore volume) and the specific surface area generated by
the micropores are not affected significantly by the particle size.
What is changing, however, are the inter-particular pores and the
specific external surface area (envelope surface area of the
particles). As the theoretical surface-area-to-volume ratio of a
sphere is indirectly proportional to its diameter, the specific
external surface area can be increased linearly by decreasing the
particle diameter (see Eq. (1)). In comparison, the reference lamp
black has a non-detectable (nd) micropore volume; therefore, its
specific surface area can be assumed to be totally external in
nature.
3.2. Electrochemical properties
The electrochemical properties of four selected carbon powders
were investigated by measuring the current-potential-relationship
of thin carbon layers in one molar sulfuric acid solution at 25  C. In
order to achieve steady-state conditions, all electrodes were cycled
15 times within the potential window of the electrolyte. The scan
199
rate was set to 100 mV/s, the lower and the upper vertex potential
were kept constant at
2 V vs. RHE and 2.3 V vs. RHE, respectively.
The corresponding voltammograms are plotted in Fig. 2a. A
comparison of the 15th cycle is shown for the different carbon
powders in Fig. 2b.
Looking at the current-potential-relationship for negative
potentials, a cathodic region including the physisorption and
chemisorption of oxygen and hydrogen species is found. For
potentials lower than
1.7 V vs. RHE, an exponential increase in the
current value is observed, which is caused by entering the
hydrogen evolution reaction (HER). Almost symmetrically with
respect to zero potential, an anodic region can be observed for
positive potential values comprising chemisorption processes of
oxygen compounds between 0 V and 2 V vs. RHE and CO2 evolution
for potentials greater than 2.2 V vs. RHE. With cycling, the
chemisorption peak intensity is decreasing and stabilizing towards
a constant level. On the other hand, HER and CO2 evolution are
constant over time and seem not to be affected by the
electrochemical treatment. A qualitative comparison of the CVs
in Fig. 2b, however, clearly reveals an influence of the carbon
structure.
The data show that smaller electrochemical active carbon
particles with higher specific external surface area tend to yield a
more pronounced chemisorption on the electrode. Though, the
specific BET surface is similar for all the investigated carbon
additives, one can observe significantly higher peak values of the
sorption processes as carbon additive particles become smaller in
mean diameter. As known from literature, the above mentioned
reactions are directly linked to the electrochemically active surface
area of an electrode [23]. Therefore, it can be concluded that the
external surface area, rather than the surface area located in the
micropores, of the carbon particles is relevant for contributing to
the electrochemically active surface area in this electrochemical
system. If the BET surface area was the determining parameter,
EAC1 would exhibit a pronounced chemisorption peak as well. The
onset-potential and the faradaic current of the HER and the CO2
evolution seem not to be affected by the size of the carbon
structure. Only the underlying offset currents from capacitive
reactions induce differences in the absolute currents.
4. Investigation of lead-carbon electrodes
4.1. Structural properties of lead-carbon electrodes
Negative electrodes with 1.6 wt.-% addition of the six different
carbon powders were investigated after formation of the active
material. The microscopic images of the bulk of the negative
electrodes in Fig. 3 demonstrate the structure of the active material
including the different sized carbon particles. It can be found that
the carbon powder is homogeneously dispersed inside the
electrode and the particles are surrounded uniformly by the lead
skeleton. The small particles tend to form agglomerates that are
most obvious in case of EAC5. There is no evidence for a significant
influence of the different sized carbon particles on the morphology
of the lead skeleton.
4.2. Electrochemical activity of lead-carbon electrodes
In order to elucidate the effect of carbon particle size and
specific external surface area on the electrochemical activity of
lead-carbon electrodes, the current-potential-relationship of the
fully charged negative electrodes was investigated. By cycling
between the equilibrium potential, which is defined by the Pb/
PbSO4 redox couple, and the decomposition of the electrolyte due
to the HER, one obtains important information about the capacitive
200 J. Settelein et al. / Journal of Energy Storage 15 (2018) 196–204
Fig. 3. SEM images of lead-carbon composite electrodes with different sized carbon particle additives (EAC1 to 5 and LB). The total amount of carbon powder was 1.6 wt.-% in
all cases. As guide to the eye, exemplarily carbon particles are highlighted in circles.
and faradaic activity of the negative active material in the potential
region of interest for the later application in the battery. In Fig. 4a
CV curves are plotted exemplarily to demonstrate the current-
potential relationship of NAM with 1.6 wt-% EAC3. The black line
shows the first 10 cycles between the open circuit potential and
hydrogen evolution at a scan speed of 10 mV s
1; moreover, the
colored lines indicate the rate-dependent charging and discharg-
ing behavior of the electrolytic double-layer. The currents were
normalized to the 20 h discharge capacity of the electrode. A very
high stability of the electrochemical response can be observed. In
general, three potential regions can be defined: One is the region of
the main reaction, which is the reversible redox couple Pb/PbSO4 at
around
1.0 V vs. Ag/Ag2SO4. Depending on how much lead is
oxidized in the prior cycle, the consecutive lead reduction peak is
affected in its peak height and width. A second potential region can
be attributed to the decomposition of the electrolyte via the HER.
The onset of this region starts at around
1.3 V vs. Ag/Ag2SO4. A
third potential region is the double-layer region between regimes
one and two, where almost no faradaic processes occur and the
main current contribution originates from the capacitive charging
and discharging of the electrolytic double-layer and a constant, yet
negligible cathodic offset-current due to the oxygen reduction
reaction of approx.
2 mA Ah
1. Here, one recognizes a significant
current difference between forward and backward scan direction
and a linear relationship between current and scan rate.
Fig. 4b summarizes the 10th cycle of 18 fully charged negative
electrodes comprising the six different kinds of carbon additives.
For statistical reasons, every measurement was replicated with
three separate laboratory cells. The scan speed was set to 10 mV s
1
and the potential range was adjusted from the Pb/PbSO4
equilibrium potential at
1.0 V vs. Ag/Ag2SO4 to the onset potential
of the hydrogen evolution reaction at
1.5 V vs. Ag/Ag2SO4. As can
be seen from Fig. 4b, the Pb/PbSO4 reaction exhibits no clear
correlation to the different carbon additives. On the other hand, the
electrochemical activity of the HER seems to be strongly influenced
by the respective carbon additive. It is observed that the carbon
particles with small particle size (high specific external surface
area) trigger an earlier onset of the HER.
In order to get a deeper insight in the HER region, Tafel plots of
the double-layer corrected current-potential-relationship from
Fig. 4b are shown in Fig. 5a. As expected, all electrodes exhibit an
exponential behavior in this potential region that fits to the
transposed Tafel equation:
lnj ¼ lnj0 þ bh: ð1Þ
 J. Settelein et al. / Journal of Energy Storage 15 (2018) 196–204
Fig. 4. Current-potential-relationship of fully charged negative electrodes with
different EAC as additive. The currents are normalized to the 20 h discharge capacity
of the electrode. a) The black line represents the first 10 cycles between open circuit
potential and hydrogen evolution at a scan speed of 10 mV s
1 for a lead-carbon
electrode with EAC3 as additive. The colored lines display the double-layer charging
of the same electrode at different scan rates between 1 mV s
1 (red, low currents)
and 100 mV s-1(blue, high currents). b) The 10th cycle as measured from three
separate laboratory cells for each carbon material. The scan speed was set to
10 mV s
1 and the potential range was adjusted to be between the Pb/PbSO4
equilibrium potential at
1.0 V vs. Ag/Ag2SO4 and the onset potential of the
hydrogen evolution reaction at
1.5 V vs. Ag/Ag2SO4. (For interpretation of the
references to colour in this figure legend, the reader is referred to the web version of
this article.)
Here j is the measured current, j0 the exchange current, b the
inverse Tafel slope and h the reaction overpotential. The Tafel
slopes were fitted between
10 mA and
100 mA for each
electrode and the fit parameters are summarized in Table 2.
Obviously, the slopes are very similar for all active materials. The
deviation from a theoretical Tafel slope of 118 mV per decade
calculated for the HER on metallic lead surface is an often observed
behavior in real battery electrodes and can be explained by mass
transport limitations due to the porous electrode structure as well
as a non-ideal measurement situation for such sensitive kinetics
due to the relative large size of the electrodes. [24]
Analyzing the absolute current values in the Tafel plot from
Fig. 5a, one observes a constant current offset of the curves over the
whole potential region between each of the different active
material variants. The absolute current difference is changing over
one order of magnitude when comparing the electrodes with the
smallest carbon particles and the ones with the biggest particles
(Fig. 5b and Table 2). As obvious from the Tafel equation, this
absolute current difference is directly linked to the exchange
201
Fig. 5. a) Tafel plots of the hydrogen evolution region of the cyclic voltammo-
gramms of the 18 lead-carbon electrodes from Fig. 4b. b) Absolute current values at

1.5 V vs. Ag/Ag2SO4 of the various lead-carbon electrodes plotted vs. the specific
external carbon surface area of the respective carbon additive including a linear fit
as guide to the eye.
current density which is a measure for the activity of the material
and its electrochemical active surface area. As the specific
micropore volume and thus the related surface area of the carbon
additives is very similar for all synthesized carbon additives
(Table 1), it seems very likely that the external surface area of the
carbon particles has a major impact on the electrochemical activity
of the electrode and especially on the HER. Additional proof gives
the current-potential relationship of the electrodes including the
reference lamp black. Though, LB’s BET area is significantly lower
than that of EAC1, the measured HER is far more active than that of
EAC1 electrodes. Furthermore, the HER activity of LB is close to the
one of EAC2 which has a similar Sext. The pronounced change in the
electrochemical activity with carbon additive regarding the HER
displays a nearly linear relationship with the specific external
surface area of the carbon powder. The overcharge current at
1.5
V tends towards zero for zero specific external surface area in
Fig. 5b. This seems reasonable, as the hydrogen evolution reaction
is strongly impeded on metallic lead surface and therefore the HER
should mainly take place on the external surface of the carbon
particles at such potentials.
Besides the faradaic electrolyte decomposition, it is also
interesting to investigate the capacitive region in more detail in
order to find out how the specific double-layer capacity of the
active material is affected by different sized carbon particles. For
that purpose, the differential electrochemical double-layer
capacities CDL normalized to the amount of active material were
202 J. Settelein et al. / Journal of Energy Storage 15 (2018) 196–204

Table 2
Electrochemical properties of negative active material with different carbon additives EAC1-5 and LB.

Sext in SBET in HER Tafel slope in HER Current at
1.5 V in Diff. double-layer capacity at
1.2 V and a scan rate of 100 mV s
1 in
m2 g
1 m2 g
1 mV dec
1 mA Ah
1 mF Ah
1
EAC1 12.9 717 152  8
18  2 404  17
EAC2 38.3 734 153  3
42  3 536  8
EAC3 56.4 755 160  2
102  1 631  16
EAC4 120.2 742 171  1
235  54 752  22
EAC5 191.8 765 180  3
338  19 894  74
LB 28 28 143  5
44  2 501  32

calculated for various electrode potentials between 1.15 V and
1.25 V vs. Ag/Ag2SO4 and plotted in Fig. 6a. A reproducible CDL,
indicated by the small error bars, is observed for the different lead-
carbon electrodes with only small variation between the three
samples of each EAC. All electrodes exhibit a slight increase of the
CDL towards higher potentials which is originating from the
marginal overlap with the faradaic lead reaction. The graph in
Fig. 6a indicates that there is a clear distinction in the CDL for
carbon additives with different specific external surface area over
the whole potential region. Exemplarily, values at
1.2 V vs. Ag/
Ag2SO4 (see column 5 in Table 2) are plotted in Fig. 6b vs. the
specific external surface area.
By increasing SExt (by decreasing the particle size) of the carbon
additives, the CDL can be increased significantly due to an enlarged
electrochemical active surface area. The enhancement of the CDL,
however, is not as pronounced as compared to the HER. While the
current density for the HER is increased with specific external
surface area of the carbons by almost one order of magnitude, only
a doubling of the CDL between EAC1 and EAC4 is observed. This
increase is still significant; however, the mechanism appears to be
different. In contrast to the HER, where the reaction seems to take
place primarily on the external carbon surface, the double-layer
charging can be assumed to occur on the lead surface as well.
According to the results plotted in Fig. 6b, a CDL of around 300 to
350 mF Ah
1 can be expected even at negligible external carbon
surface that originates from the lead skeleton. The fact that the
electrodes including the LB exhibit a higher CDL than the ones for
EAC1 indicates that the micropores of the carbon additives do not
play a significant role for the capacitive reaction which is in line
with the results from Section 3.2. The micropores seem to be
inaccessible or rather the diffusion kinetics to the storage sites
within the microporous particle are hindered [25].

4.3. Correlation to the dynamic charge acceptance

From a scientific point of view, the influence of the carbon

Fig. 6. a) Evaluation of the specific differential double layer capacity at 100 mV s-1 in
a potential region between
1.15 V and
1.25 V vs. Ag/Ag2SO4. b) Relationship
between the specific external carbon surface area and the differential double-layer
capacity of the various lead-carbon electrodes containing the respective carbon
additive (dotted line as guide to the eye).
particle size on the electrochemical properties of lead-carbon
electrodes was already discussed. An increase in CDL of the negative
active material at high scan rates as well as an activation of the HER
can be achieved by carbon additives with high specific external
surface area.
In terms of the application of lead-carbon composite electrodes
in batteries for micro- and mild-hybrid cars, however, it is most
important to identify a structure-property relationship for the final
performance values of the battery. As described in the introduc-
tion, despite the standard cycle life tests, the test of the charge
acceptance is nowadays of particular importance for providing a
high efficiency of the car‘s recuperation function. In order to
evaluate the impact of the size of the carbon additive particles in
this application, the laboratory test cells were subject to the new
DCA test protocol for batteries of micro-hybrid cars. For statistical
reasons, every measurement was repeated for each carbon
additive in three different laboratory cells. The results of the
different charging currents for the various carbon additives are
plotted in Fig. 7 vs. the specific external surface area of the carbon
additives. There are two main observations: Firstly, the different
charging currents Ic, Id and Ir corresponding to the average charging
currents at 2.47 V after charge history, discharge history and in a
drive cycle profile, respectively, behave analogue when comparing
the various active materials with each other. Secondly, the
charging currents can dramatically be improved with carbon
additives that have a high external surface area or small primary
particles. The DCA value IDCA, defined as the weighted sum of all
three charging currents of the respective laboratory test cell can be
increased from 0.2 A Ah
1 up to 0.7 A Ah
1 using the smallest
carbon particles.
This large difference in the charge acceptance values can be
achieved, even though the exact same amount of the synthesized
 J. Settelein et al. / Journal of Energy Storage 15 (2018) 196–204
Fig. 7. Correlation between the specific external surface area of the carbon
additives and the charge acceptance from the DCA test according to the EN standard.
carbon powder with a similar specific BET surface area of about
750 m2 g-1 was mixed into the various negative active masses. This
finding is of high importance, as it is clearly indicating that the
specific external surface area of the carbon additives affects the
charging behavior of the negative electrode predominantly rather
than their BET surface area. Interestingly, also the electrodes with
non-porous lamp black fit perfectly into the observed relationship
supporting the negligible influence of the microporosity regarding
the charge process.
Altogether, it can be concluded that the electrochemical activity
of the negative active mass is a surface area related property that
can be influenced by the non-microporous surface area of the
carbon additive. By using additives with high Sext the charging
ability of a lead-carbon electrode can be improved significantly.
5. Conclusion
In summary, the impact of the specific external surface area or
the particle size of amorphous carbon additives on the electro-
chemical performance of negative lead-carbon electrodes was
investigated. Five amorphous carbon powders with distinct
differences in their average particle sizes ranging from about
20 nm up to 400 nm were synthesized by sol-gel processing. The
physical investigation of the powders revealed a similar specific
BET surface area of about 750 m2 g
1 for all powders. However, due
to the difference in primary particle size, the ratio between surface
area generated by micropores and the external (envelope) surface
area Sext of the carbon spheres could be varied over a wide range. To
our knowledge, this approach allowed for the first time to
investigate the effect of the external surface area or particle sizes
of carbon additives on the electrochemical properties of lead-
carbon electrodes.
Cyclic voltammetry on pure carbon electrodes demonstrated
that Sext of the carbon powders is clearly correlated with the
specific double-layer capacity. Thus, increasing the specific
external surface area by decreasing the carbon particle diameter
results in higher capacitive currents.
Preparation of negative active material comprising 1.6 wt.-% of
the respective amorphous carbon powder revealed that the
electrochemical response of lead-carbon electrodes is clearly
varying with the external surface area of the additive. In principle,
one can state that the smaller the carbon particles, i.e. the higher
203
the external surface area, the higher the electrochemical activity of
the lead-carbon electrodes. Cyclic voltammetry shows that both
the hydrogen evolution reaction current and the specific double-
layer capacity at given scan rates can be increased explicitly by
carbon powders with high Sext. The comparison to a non-
microporous commercial lamp black supports the negligible
influence of the micro porosity regarding the electrochemical
activity.
Similar to the electrochemical activity improvement of the
negative electrode, one of the key parameters for future applica-
tion of lead-acid batteries, i.e. the dynamic charge acceptance, can
be significantly increased with carbon additives having a high Sext.
However, the enhanced hydrogen evolution reaction may lead to
increased electrolyte decomposition during overcharge tests and
should be considered for battery production.
In conclusion, the specific (non-microporous) external surface
area of carbon additives in the negative electrode seems to be
highly relevant in order to significantly improve the dynamic
charge acceptance of modern lead-carbon batteries.
Acknowledgements
Funding of the Fraunhofer Research and Development Center
Electromobility Bavaria FZEB received from the Bavarian State
Ministry of Economic Affairs and Media, Energy and Technology
(Grant number: 43-6629/86) is gratefully acknowledged. The
authors would also like to thank Dr. Christian Balzer, ZAE Bayern,
for the careful recording and evaluation of the N2 adsorption data.
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