Journal of Power Sources 295 (2015) 268e274

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Journal of Power Sources

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Short communication

Enhancing the performance of leadeacid batteries with carbon e In

pursuit of an understanding
Patrick T. Moseley a, *, David A.J. Rand b, Ken Peters c
a
International Lead Zinc Research Organization, 1822 East NC Highway 54 Suite 120, Durham, NC 27713, USA
b
CSIRO, Private Bag 10, Clayton South, Victoria 3169, Australia
c
Glen Bank, Worsley, Manchester M28 2GG UK

h i g h l i g h t s

Conflicting notions of the beneficial effect of carbon are reconciled.

The evidence underpinning mechanisms is reviewed and rationalised.

A combination of different forms of carbon offers maximum benefit.

a r t i c l e i n f o a b s t r a c t

Article history: The inherently poor dynamic charge-acceptance of the leadeacid battery can be greatly improved by the
Received 8 April 2015 incorporation of additional carbon to the negative plate. An analysis is undertaken of the various ways by
Received in revised form which the carbon may be introduced, and of the proposed mechanisms whereby its presence proves to
16 June 2015
be beneficial. It is intended that such an investigation should provide a guide to the selection of the
Accepted 5 July 2015
Available online xxx
optimum carbon inventory.
© 2015 Elsevier B.V. All rights reserved.
Keywords:
Carbon
Dynamic charge-acceptance
Leadeacid batteries
Mechanisms
Negative plate

1. The challenge of high-rate partial state-of-charge (HRPSoC)
duty
The emerging application of leadeacid batteries for the storage
of energy from regenerative braking in various types of electric
vehicle requires the best possible recovery of charge during high-
rate partial-state-of-charge (HRPSoC) duty.
Micro-hybrid vehicles, which are fitted with stop‒start features
both to improve fuel economy and to reduce emissions, employ
batteries that operate under PSoC conditions and are charged by
energy recuperation from the regenerative braking system. The
schedule is a micro-cycle of short bursts of discharge and charge,
each at a high rate, with the charge from regenerative braking
supplementing that from the generator. The PSoC amplitude is just
* Corresponding author.
E-mail address: pmoseley@ilzro.org (P.T. Moseley).
a few percent. The current accepted by the battery during the
charge periods should be sufficient, when efficiently used, to
convert discharge product to the active state and thereby ensure
availability of stop‒start and other essential functions. This charge
current has been defined [1] as the ‘dynamic charge-acceptance’,
DCA, and is the average current over the initial charging period,
which is usually between 3 and 20 s. The parameter is quoted in
terms of amperes (A) per ampere-hour (Ah) of battery capacity, i.e.,
A Ah1. Standardized industry specifications are in the course of
preparation (CENELEC Standard EN50342-6: Lead‒acid Starter
Batteries for Micro-cycle Applications).
The DCA of new leadeacid batteries generally lies between 0.5
and 1.5 A Ah1, although some applications may require higher
values. For effective fuel savings and low-emission features, this
value should be sustained. After relatively short service under PSoC
conditions, however, recent work [2,3] has found the DCA to
decrease to around 0.1 A Ah1 and, after brief periods of parking, to
even lower levels. Resolution of this problem is essential if the

http://dx.doi.org/10.1016/j.jpowsour.2015.07.009
0378-7753/© 2015 Elsevier B.V. All rights reserved.
 P.T. Moseley et al. / Journal of Power Sources 295 (2015) 268e274
intended benefits are to be achieved. Factors that influence these
inconsistencies in battery performance have been investigated,
namely: local current distribution, state-of-charge, temperature,
and variable acid strength due to stratification [4]. The progressive
decrease in DCA can be attributed to rate-limiting processes that
include the accumulation of lead sulfate in the negative plates with
subsequent effects on concentration and potential gradients within
the porous matrix.
New leadeacid batteries can be recharged effectively at high
rates of charge because the freshly-discharged product, lead sulfate,
has a small crystallite size which facilitates rapid dissolution d a
requirement that is fundamental to subsequent recharge via the so-
called ‘solution‒precipitation’ mechanism (reaction [3] in Fig. 1).
On the other hand, if the battery is left at a PSoC for a significant
length of time after discharge from top-of-charge, the lead sulfate
crystals have the opportunity to grow progressively via the ‘Ost-
wald Ripening’ process. Consequently, the charge-acceptance of the
battery declines, particularly at the negative plate which offers less
surface-area (0.5e1 m2 g1) than the positive (4e5 m2 g1).
The immediate history of the battery affects the charge-
acceptance quite markedly when micro-cycling is performed over
a narrow range of PSoC, with no excursions to top-of-charge [5,6]. A
small discharge produces some new (small) lead sulfate crystals,
which can support a high rate of recharge so that a relatively
healthy DCA can be achieved. Immediately after a charge event,
however, the small crystals of lead sulfate will have been consumed
so that only material of low surface-area remains and poor DCA is
observed.
Lacking a construction that is purpose-designed for HRPSoC
duty, valve-regulated lead‒acid (VRLA) batteries typically lose at
least 50% of their initial capacity after operating in a simulated
hybrid electric vehicle (HEV) mode for a relatively short time. The
loss of capacity has been attributed to a progressive build-up of lead
sulfate on the negative plate, especially at the bottom. Since the
battery is not brought to a full state-of-charge in PSoC duty, there is
no routine method available to remove this lead sulfate.
On charging a leadeacid cell, the fundamental reaction at the
positive electrode may be accompanied by oxygen evolution and
that at the negative by hydrogen evolution. All four reactions are
independent. The only requirement is that the currents at the two
electrodes are equal. The end-point of a completed charge is always
water electrolysis during which gas evolution predominates. The
Fig. 1. Discharge and charge reactions at the negative plate of a leadeacid cell.
269
rates of other possible side-reactions, such as grid corrosion, ozone
formation and the decomposition of organic additives, are low and
usually neglected. With new freshly-formed cells, negative elec-
trodes can be charged efficiently over a range of current densities
and temperatures with little gas evolution, whereas under similar
conditions positive electrodes evolve oxygen from the outset [7].
At high rates of charge, it becomes difficult to sustain the mass
and charge balances that are necessary for the solution‒precipita-
tion charging mechanism to proceed. While the lead sulfate crystals
are small, the fluxes of ions to the reaction sites may be rate-
determining [8]. With increasing crystallite size, however, the
discharge product may become resistant to the charging and, as a
consequence, the potential rises and charge current is diverted to
the parasitic reaction of hydrogen evolution. Ultimate battery fail-
ure occurs when the negative plate remains in the discharged state.
It has been found [9] that some forms of carbon, when present in or
on the negative active-material, can be very beneficial in mini-
mizing the irreversible formation of lead sulfate.
2. Previous notions about the function of carbon
It is standard practice in the manufacture of leadeacid batteries
to add to the negative plate a combination of barium sulfate, an
organic extract of wood, and carbon. Collectively known as ‘ex-
panders’ and usually in total comprising less than 1 wt.% of the
negative mass, the additives not only increase the available capacity
(especially when cells are discharged at high current densities and
low temperatures) but also reduce capacity loss during cycling. The
mechanism by which expanders prove effective was studied
extensively during the last century [10‒14]. Barium sulfate is
considered to act as a seed for the precipitation of lead sulfate due
to the isomorphous structure of the two salts. The organic additives
d usually sulfonated derivatives of lignin (a natural product
extracted from wood pulp) d are surfactants that absorb both on
the surface of lead and on the lead sulfate crystals as they are
formed during discharge. This action inhibits crystal growth during
the dissolutioneprecipitation reaction and thereby helps to main-
tain a high surface-area by preventing contraction and solidifica-
tion of the ‘spongy’ lead active-material.
The function of carbon additions to the negative active-material
has been the subject of much debate. At one time, the presence of
finely-divided amorphous carbon, otherwise known as ‘lampblack’
270 P.T. Moseley et al. / Journal of Power Sources 295 (2015) 268e274
(or ‘gas carbon black’) was thought to improve the conductivity of
the discharge product and to assist in the formation of pasted plates
during manufacture. On the other hand, no benefits of carbon
addition were found during a study in which flooded cells were
cycled with different levels of overcharge [15].
In summary, the combination of expander additives counteracts
the tendency for the spongy lead to densify during cycling and
thereby imparts sustainable low-temperature and high-rate capa-
bilities to the negative plate.
The benefits of including additional carbon in the negative
active-material were eventually demonstrated by the work of
Nakamura and Shiomi [16,17], who made negative plates that
contained up to ten times the customary level of carbon. The actual
amounts were not disclosed but, based on normal practice, were
believed to be about 2.0 wt.% of the negative mass. The trials, which
were directed towards both electric vehicle and photovoltaic power
applications, were undertaken with VRLA batteries that operated
under PSoC conditions to minimize overcharge effects. Each of the
applications was likely to have entailed relatively short bursts of
charge at high current densities. Batteries with standard levels of
carbon failed quickly due to the build-up of lead sulfate in the
negative plate. In contrast, the associated positive plate was fully
charged. Batteries with extra carbon enjoyed appreciably longer
operating lives.
A study conducted by CSIRO under the auspices of the Advanced
LeadeAcid Battery Consortium (ALABC) showed [18] that HEV duty
cycles cause the exterior layers of negative plates to become almost
completely sulfated. With, presumably, further crystal growth
during open-circuit, the eventual result is pore blocking and acid
starvation inside the plates. As pointed out much earlier [19] and
given the high surface-area of positive active-material compared
with that of the negative (v.s.), a full discharge results in a 0.025 mm
thick layer of lead sulfate, overall, on the positive and a 0.3 mm layer
on the negative. Little wonder that there is pore blocking, a much-
reduced flux of sulfate ions during high-rate charging, acid star-
vation and poor charge-acceptance.
More recent developments have revealed that the additional
carbon enhances charge efficiency under high-rate charging con-
ditions such as occur in vehicles with regenerative braking. It has
also become clear that supplementary carbon can enable cell
voltages to remain far more uniform in battery banks used for the
storage of renewable energy where the charge is limited, for
example, in remote-area power supplies which employ photovol-
taic arrays and/or wind turbines.
Whereas the advantages have been demonstrated, an un-
equivocal understanding of the means by which carbon assists the
recharge of leadeacid batteries has yet to be reached. Such
knowledge will provide a deeper appreciation of the functional
relationship between product and required duty, which is essential
for the future development and design of cells for new and
emerging applications. Possible mechanisms for the ‘extra-carbon
effect’ are discussed below in Section 4.
3. Types of battery configuration
The configuration of the negative plate in a conventional
leadeacid battery is compared in Fig. 2 with alternatives in which
additional carbon has been incorporated in various ways, as
follows.
(i) Conventional leadeacid batteries (see Fig. 2(a)) with no
additional carbon, i.e., above that typically included in the
expander formulation, exhibit a sharply-declining DCA dur-
ing HRPSoC operation. This restriction of the charge reaction
is due to the limited solubility of lead sulfate, as described
earlier in Section 1. Individual lead‒acid cells in long strings
are also likely to suffer a divergence in state-of-charge during
PSoC cycling at any charge/discharge rate.
(ii) The simplest way to incorporate additional carbon in a
conventional leadeacid battery is to mix it with the basic
ingredients of the negative plate and then paste in the
normal way (see Fig. 2(b)), although it must be acknowl-
edged that supplementary water is required to maintain a
satisfactory rheology. Batteries with such plates exhibit a
somewhat improved DCA but small carbon particles may
become isolated and lose efficacy, as described below.
(iii) Axion Power International Inc [20]. offers the PbC® battery
that has a negative plate with carbon as the sole active ma-
terial; see Fig. 2(c). All other components are similar to those
found in a conventional leadeacid battery. Given that there is
no lead sulfate to limit charge-acceptance at the negative
plate (the reaction involves the storage of protons, Hþ), the
technology sustains DCA well. The carbon acts as a capacitor
to provide not only a high degree of DCA but also to enable
self-balancing of series-connected cells during PSoC cycling.
The PbC® battery does, however, suffer from two disadvan-
tages, namely, a specific energy lower than that of the con-
ventional counterpart and a voltage that varies with the
state-of-charge.
(iv) The UltraBattery® d a CSIRO invention that is under com-
mercial development by Furukawa Battery Co. (Japan), Ltd.,
East Penn Manufacturing (USA), and Ecoult (Australia) d has
a compound negative plate in which one section consists of
the usual sponge lead active-material and the other is
composed of supercapacitor-grade carbon. As with the Axion
PbC® design, all other components of the battery are con-
ventional; see Fig. 2(d). In addition to providing a sustained
DCA during high-rate HRPSoC operation, the UltraBattery®
provides self-balancing of individual cells in long series-
connected strings in the same manner as does the Axion
PbC®.. A road test [21] of a Honda Insight medium-hybrid in
which the original nickelemetal-hydride (Ni‒MH) battery
had been replaced by an UltraBattery® of the same voltage
(144 V) was continued for 100 000 miles at the Millbrook
Proving Ground in the UK. At the end of the test, the battery
was still fully-functional. Moreover, the 12 individual 12-V
modules were matched together better than at the start of
the test and, moreover, without the intervention of any
external equalization [21]. A similar project, which involved
the replacement of a Ni‒MH battery in a Honda Civic with an
UltraBattery®, ran for 150 000 miles in Arizona [22,23] and
again the individual modules remained fully-balanced
without any electronic support. Self-balancing of the Ultra-
Battery® has also been observed in stationary energy-storage
applications by the Ecoult Company.
(v) A concept evolved by ArcActive Limited [24] has the lead grid
replaced by a porous carbon material which has been ‘acti-
vated’ by an electric-arc process; see Fig. 2(e). The result is a
configuration that might be viewed as analogous to the
UltraBattery® but with the carbon layer under the negative
active-material instead of above. Similar designs have been
proposed by Kirchev et al. [25], Czerwinski et al. [26] and
Firefly [28], respectively. The ArcActive cell sustains DCA
well, as shown in Fig. 3, but its behaviour in long strings has
yet to be reported.
4. Progress in understanding the ‘carbon effect’
In recent years, there has been much discussion over the
 P.T. Moseley et al. / Journal of Power Sources 295 (2015) 268e274 271

Fig. 2. Schematics of negative-plate configurations without and with additional carbon.

mechanism by which a carbon component of the negative plate can
enhance the performance of a leadeacid battery. As many as eight
different functions have been proposed [27] but the growing body
of evidence points to just three candidates that are the most likely
to have a significant individual effect; the degree of influence varies
according to the design, particularly in the case of the alternatives
depicted in Fig. 2 above. The situation remains complicated,
however, because all three can be operative simultaneously.
The first function of carbon is to serve as a capacitive buffer to
absorb charge current in excess of that which can be accommo-
dated by the Faradaic (i.e., electrochemical) reaction; see Fig. 1. A
conventional negative electrode will itself have an attendant
double-layer but the capacitive function (normally in the range
0.4e1.0 F per Ah) only becomes noticeable when the surface-area is
272 P.T. Moseley et al. / Journal of Power Sources 295 (2015) 268e274
Fig. 3. Dynamic charge-acceptance (DCA) of the ArcActive cell is sustained through
PSoC cycling in contrast to that of a conventional VRLA cell (absorptive glass-mat
technology).
magnified appreciably by the addition of an appropriate form of
carbon. The second effect of carbon is to extend the area of the
electrode microstructure on which the electrochemical charge and
discharge reactions can take place.
For carbon to perform either of these two functions to best ef-
fect, it should be in an sp2 hybridized form, e.g., graphite (v.i.).
The third way in which carbon can modify the behaviour of the
negative active-material is by means of physical effects, for instance
by obstructing the growth of lead sulfate crystals and/or by main-
taining channels for irrigation of the electrode by the electrolyte. In
both these cases, there is no need for the carbon to be in a
conductive form.
Each of the above three actions of carbon is considered in more
detail, as follows.
4.1. Capacitance: current flows during and after a charge event
When a charge event applied to a leadeacid cell is discontinued,
although the external current is zero, the double-layer remains
charged and this results in a local current between the component
materials of the negative active-mass [29]. The current is caused by
the discharging of the double-layer via the Faradaic reaction and
thereby the electrode potential changes to its equilibrium value
with a characteristic time constant. The amount of charge involved
can be substantial if the surface-area of conducting material is
augmented by the inclusion of an appropriate form of carbon. The
time constant, t, for the equilibration process can be estimated by
equating the double-layer discharge current to the charging current
that is going into the Faradaic reaction and can be approximated as:
t ¼ RTC=Fio [1]
where: R is the universal gas constant (8.3145 J mol1 K1); T is the
absolute temperature (K); C is the specific capacitance (F cm2); F is
the Faraday constant (96 458 As mole1); io is the exchange-current
density (A cm2).
Reactions that proceed relatively quickly have a small time
constant, whereas those that are kinetically sluggish result in a
large time constant. By way of example [29], the zinc electrode has
rapid kinetics with an exchange current of around 102 A cm2 that
gives rise to a time constant of the order of 50 ms. Alternatively, the
nickel hydroxide electrode has a time constant of around 5 ms.
Since both these time constants are so short, the involvement of the
equilibration process outlined above has been largely ignored for
both the zinc and the nickel electrode systems. By contrast, the
kinetics of the electrode reactions in a lead‒acid cell are much
slower, namely: 4.0  107 A cm2 at the positive plate, and
4.96  106 A cm2 at the negative [29]. With an augmented carbon
inventory, the negative plate can contribute a specific capacitance
of up to 30 m F cm2 whereby the time constant can be of the order
of seconds and the charge equilibration (shown as reaction 3 in
Fig. 4) can be regarded as a significant process that follows the
removal of the external charging voltage. Under HRPSoC condi-
tions, charge from external events, such as regenerative braking in
vehicle applications, is taken up by the double-layer and thus
boosts DCA efficiency. When the external input is discontinued, this
charge is re-equilibrated between the double-layer and the Fara-
daic reaction.
4.2. Extending the conducting surface-area for the electrochemistry
Cycle tests under HRPSoC conditions of cells that contain extra
carbon have provided strong evidence [30] that the electrochemical
and chemical processes can take place not only on the surface of
lead metal but also on the surface of carbon; see Fig. 5. Subsequent
research [9] has confirmed that two electrical systems are oper-
ating on carbon at the negative plate, namely:
(i) a capacitive system, which involves high-rate charging and
discharging of the electric double-layer;
(ii) the conventional lead electrochemical system, which com-
prises the oxidation of lead to lead sulfate during discharge
and the reverse process during charge.
It has been found that the capacitive process dominates during
cycling with charge and discharge processes each of 5-s duration,
whereas and the electrochemical reactions dominate during
cycling with longer pulses. These observations are consistent with
the above calculation of the time constant for the transfer of charge
between the two component materials of the negative electrode.
4.3. Physical processes
A widely-proposed suggestion [31,32] is that the carbon added
to the negative active-material acts as a steric hindrance to the
crystallization of lead sulfate and thus helps to maintain a high
surface-area for the discharge product. In support of this theory, it
has been observed [33] that HRPSoC cycle-life is enhanced when
titanium dioxide (a poorer electronic conductor), rather than
graphite, is used as the additive. Whereas cycle-life is improved by
using either titanium dioxide or graphite (to different extents), the
effect of the latter is not necessarily due to its conductivity alone.
It has also been advocated [34] that ‘activated’ carbon increases
the porosity of the negative electrode by providing an additional
structural skeleton that facilitates diffusion of the electrolyte so-
lution from the surface to the interior of the plate. As a result,
sufficient sulfuric acid is supplied to keep pace with the electrode
reaction during HRPSoC operation.
The same work has demonstrated [34] that longer cycle-lives
under HRPSoC duty are achieved with carbon of larger particle
size (i.e., micron-size rather than nanometre). This observation has
given rise to the view [35] that small particles of carbon can become
progressively buried within crystals of lead sulfate such that their
effectiveness is lost. Other studies have revealed [9] that carbon
additives can alter the pore structure of the negative electrode and
one consequence is that the access of SO2 4 ions to the innermost
pores is impeded. On the other hand, Hþ ions may still diffuse out of
the pores and allow the pH to rise locally to a value at which a-PbO
is formed. This phase, which is clearly visible in X-ray diffraction
 P.T. Moseley et al. / Journal of Power Sources 295 (2015) 268e274 273

Fig. 4. Schematic of the positive current fluxes during and after a short charge event on a negative plate that contains carbon.

Fig. 5. Faradaic reactions of the negative plate can take place on both the lead and carbon surfaces [30]. EAC stands for electrochemically active carbon.

records, is deleterious to the continued function of the negative Table 1

active-material because the formation of the oxide is irreversible. Physical properties of diamond and graphite.

Property Diamond Graphite

5. Properties of carbon Crystal structure Cubic Hexagonal
Orbital hybridisation sp3 sp2
Carbon can be found in various forms with a very wide range of Covalent radius, pma 77 73
physical properties, which depend very strongly on the respective Density, g cm3 3.515 2.267
Mohs hardness 10 ~1
electronic properties of the atoms. The principal allotropes of the Heat capacity, J mol1 K1 6.155 8.517
element are (i) diamond, in which the carbon atoms are sp3 hy- Thermal conductivity, W m1 K1 ~2200 ~150
bridized so that the material is very hard and electronically resis- Resistivity, U m ~1012 ~3  103 (c axis)
tive, and (ii) graphite, in which the atoms are sp2 hybridized and ~4  106 (a axis)
invest the material with a softer, layered structure that exhibits a
picometres; 100 pm ¼ 1 angstrom (Å).
significant conductivity along the planes of its hexagonal structure.
The physical properties of diamond and graphite are listed in
Table 1. A wide range of amorphous, or poorly crystalline, substances
In the context of the materials present in the negative plate of a can be prepared in which both sp2 and sp3 carbon atoms are pre-
leadeacid cell, it is worth noting that the thermal conductivity of sent. Such materials exhibit physical properties that are interme-
graphite is approximately four times that of lead (35.3 W m1 K1) diate between those of the diamond and graphite ‘end-members’,
so the presence of graphite assists heat distribution within the but also are strongly influenced by other parameters associated
negative active-material. The resistivity of graphite (both parallel to with materials. Particle size can be anywhere between a few
and perpendicular to the basal plane, see Table 1) is greater than nanometres and tens of microns, whereas surface-areas can vary
that of lead (2.08  107 U m). Consequently, early theories that the from a few m2 g1 (graphite) to over 2000 m2 g1 (activated car-
benefits gained by the addition of carbon are due to an improve- bons and carbon blacks). Activated carbons are mainly amorphous
ment in the conductivity of the negative active-material appear to with a fine pore structure. Carbon blacks are composed of ag-
be groundlessdexcept when the electrode is so discharged that glomerates of interconnected clusters within which there are re-
almost all of the sponge lead is replaced by lead sulfate. gions that are ordered and have the graphite structure. In the
274 P.T. Moseley et al. / Journal of Power Sources 295 (2015) 268e274
absence of other factors, electrical conductivity is likely to follow
the sequence graphite > carbon blacks > activated carbons. The
surfaces of these materials, however, can accommodate a range of
atoms or groups of atoms [36] that exercise considerable influence
on properties such as wettability, double-layer formation, and
chemical reactivity. Impurity levels are also important. Depending
on the production process, industrial carbons can contain up to
10,000 ppm of ‘foreign’ elements that can include various amounts
of iron, nickel, copper, zinc, silicon, potassium, and sulfur. In view of
the need to restrict the evolution of hydrogen during charging, it is,
of course, particularly important to prevent or minimize the pres-
ence of those impurities that would promote such gassing.
6. The best choice of carbon?
Empirical evidence suggests that there are at least three ways by
which the presence of carbon can modify the performance of the
negative plate of a leadeacid battery, namely, via (i) a capacitive
contribution, (ii) the extension of the surface-area on which the
electrochemical charge and discharge processes can take place, and
(iii) physical processes.
The capacitive process (i) is favoured by carbon that has large
surface-area, is conductive, and is in contact with the current-
collector (grid) via the ‘skeleton structure’ sponge lead that is
present at all states-of-charge. It is not necessary, however, for the
carbon to be mixed intimately with the sponge lead component of
the negative electrode.
The surface-area effect (ii) also requires the carbon to be
conductive and in contact with the current-collector. On the other
hand, given that carbon promotes a bulk rather than a surface
process, the surface-area can be less than that for the capacitive
process.
Carbon deployed to take advantage of the physical processes (iii)
does not have to be conducting, but it must be intimately mixed
with the sponge lead and should not be very finely-divided or its
efficacy will wane over time.
In view of the conflicting requirements for the carbon to func-
tion in these several ways, it is not surprising that workers who are
seeking to optimize the HRPSoC performance of lead‒acid batteries
have resorted to evaluating combinations of different types of
carbon.
Whilst this experimental approach may be beneficial in the
short term, a thorough investigation of the mechanism of the
electrochemical influence of added carbon is desirableda complete
understanding would encourage further enhancement of the per-
formance of lead‒acid batteries in a variety of energy-storage
applications.
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