batteries

Article
Developing Electrolyte for a Soluble Lead Redox
Flow Battery by Reprocessing Spent Lead Acid
Battery Electrodes
Keletso Orapeleng *, Richard G. A. Wills and Andrew Cruden
Energy Technology Group, University of Southampton, Southampton SO17 1BJ, UK;
rgaw@soton.ac.uk (R.G.A.W.); a.j.cruden@soton.ac.uk (A.C.)
* Correspondence: ko1d13@soton.ac.uk; Tel.: +44-(0)23-8059-6727

Academic Editor: Joeri Van Mierlo

Received: 8 March 2017; Accepted: 27 April 2017; Published: 3 May 2017

Abstract: The archival value of this paper is the investigation of novel methods to recover lead (II) ions
from spent lead acid battery electrodes to be used directly as electrolyte for a soluble lead flow battery.
The methods involved heating electrodes of spent lead acid batteries in methanesulfonic acid and
hydrogen peroxide to dissolve solid lead and lead dioxide out of the electrode material. The processes
yielded lead methanesulfonate, which is an electrolyte for the soluble lead acid battery. The lead (II)
ions in the electrolyte were identified using Inductively Coupled Plasma Mass Spectroscopy and
their electrochemistry confirmed using cyclic voltammetry. The concentration of lead (II) ions was
determined and it was found that using the higher concentration of hydrogen peroxide yielded the
highest concentration of lead (II) ions. The method was therefore found to be sufficient to make
electrolyte for a soluble lead cell.

Keywords: lead recovery; electrolyte; soluble lead flow battery; energy storage

1. Introduction
Energy storage is essential to enable uptake of renewable energy [1]. Lead acid batteries,
a well-established technology that is accessible world-wide, emerged as a convenient technology
for renewable energy storage applications in [2]. Despite being a mature technology and relatively low
priced (£150/kWh), lead acid batteries are sensitive to incorrect use. They are sensitive to temperatures
above the design 25 ◦ C; releasing more energy at high temperatures but also deteriorating more quickly,
which reduces battery life by as much as 50% for each 8–10 K temperature increase [2,3]. Discharging
beyond 25% depth of discharge for starting, lighting and ignition (SLI) batteries results in accelerated
deterioration [4]. Lead acid batteries need to be stored fully charged to avoid sulfation, and storage
temperatures should not exceed 25 ◦ C to slow down self-discharge [3]. When used with isolated PV
systems, it is not always possible to charge the battery before storage as availability of electricity is
dependent on local weather [2]. Even when used as recommended, the longest lasting lead acid (valve
regulated) batteries last a maximum of five years, well before other components of a power generation
system need replacing [2–5]. Redox flow batteries are emerging as a viable option for stationary energy
storage [6–8]. This type of battery, depending on the technology, offers a complement of qualities
superior to those of the conventional lead acid battery, including higher cycle-life, tolerance to deep
cycling [8], tolerance to wider temperature ranges, better temperature control and faster charge and
discharge rates [6]. Table 1 compares these qualities for selected redox flow batteries and the lead
acid battery.

Batteries 2017, 3, 15; doi:10.3390/batteries3020015 www.mdpi.com/journal/batteries

Batteries 2017, 3, 15 2 of 13

Table 1. Comparison of the lead acid battery to commercial flow batteries on energy density, cell voltage,
cycle life and depth of discharge, energy efficiency and estimated cost.

Soluble Lead All Vanadium/

Technology Lead Acid Zinc–Bromine
Flow Battery Vanadium–Bromine
Cell voltage, V 2.0 [5] 1.78 1.4/1.0 [1] 1.8
Energy efficiency, % 75–85 [9] 65% [10] (80–85)/(60–70) [11] 65–75
Cycle life 200–2000 2000 [12] 12,000 [13] 10,000
@ Depth of Discharge 70%–30% 100% 100% 100%
Recommended operating
20–25 35–55 (5–40)/(0–50) [11] 20–50
temperature range, ◦ C
Cost, €/kWh 50–150 [14] - 140–400 [15] 800

Unlike the vanadium and the zinc bromine redox flow batteries, the soluble lead flow battery
(SLFB) uses comparatively cheap and non-corrosive materials in redox flow technology. The SLFB is a
well-researched technology [10,16–18] that uses electrolyte made from methanesulfonic acid (MSA)
and Pb2+ in the form of lead methanesulfonate. The electrochemistry is based on two redox couples;
Pb/Pb2+ and PbO2 /Pb2+ [10]. The reactions are shown below in Equations (1)–(3) [16,19].
Positive electrode:
discharge
PbO2 + 4H + + 2e− → Pb2+ + 2H2 O (1)

Negative electrode:
discharge
Pb → Pb2+ + 2 e− (2)

Overall:
discharge
Pb + PbO2 + 4H + → 2Pb2+ + 2H2 O, E = 1.5 versus SHE (3)

where, SHE is standard hydrogen electrode.

During charge, lead metal is deposited on the negative electrode while lead (IV) oxide is deposited
on the positive electrode. During discharge, the deposit from both electrodes is stripped back into the
electrolyte as Pb2+ ions. Lower concentrations of lead ions in the electrolyte were found to be ideal
for uniform and adherent deposit on both electrodes [20]. On the other hand, for higher cell charge
capacities, higher concentrations are required. A concentration of 1.0 mol·dm− 3 Pb2+ was sought as
a compromise.
Since lead acid batteries, including automobile batteries, are globally available, there is
an opportunity to use the lead contained therein in soluble lead flow batteries. Traditionally, lead acid
batteries are recycled to recover lead and re-use it in making new batteries [21,22]. The most common
method is the pyrometallurgic, which is energy intensive with operation temperatures above 300 ◦ C
and produces slag and air contaminants such as sulfur oxide, nitrous oxide and fumes [22]. This paper
presents a method to make electrolyte for a soluble lead flow battery by harvesting lead directly from
end-of-life lead acid batteries.

2. Experimental

2.1. Chemical Reagents

The chemicals used to make the electrolyte were methanesulfonic acid, lead methanesulfonate,
and hydrogen peroxide. Aqueous solutions of the chemicals were prepared using de-ionised water
from a Purite water purifier. Ethylenediaminetetrascetic acid (EDTA) was used in titration, as well as
Eriochrome Black T indicator, ammonium hydroxide, ammonium chloride, tartaric acid, and sodium
chloride. The chemicals are listed in Table 2, along with their purities as well as the chemical suppliers.
Chemicals were used as received.
Batteries 2017, 3, 15 3 of 13
Batteries 2017, 3, 15 3 of 13

Table 2. Chemical reagents used in lead recovery as well as those used in titration. The chemical name
and purity
Table is givenreagents
2. Chemical where appropriate, as well asasthe
used in lead recovery supplier’s
well as those name.
used in titration. The chemical name
and purity is given where appropriate,
Molecular as well as the supplier’s name.
Chemical Purity/Concentration Supplier
Formula
Chemical acid
Methanesulfonic Molecular Formula Purity/Concentration Supplier
CH3SO3H 99% Sigma Aldrich, London, UK
(MSA)
Methanesulfonic acid
CH3 SO3 H 99% Sigma Aldrich, London, UK
(MSA)
Lead methanesulfonate Pb(CH3SO3)2 50% w/w Sigma Aldrich
Lead methanesulfonate
Hydrogen peroxide Pb(CH SO )
H2O3 2 3 2 50%
30% w/ww/w Sigma
SigmaAldrich
Aldrich
Hydrogen peroxide H 2 O2 30% w/w Sigma Aldrich
EDTA C10H16N2O8 99.4–100.6 Sigma Aldrich
EDTA C10 H16 N2 O8 99.4–100.6 Sigma Aldrich
Eriochrome Black T
Eriochrome Black T
C 20H12N3NaO7S
C20 H12 N3 NaO7 S
- - Sigma Aldrich
Sigma Aldrich
Ammonium
Ammoniumhydroxide
hydroxide NH
NH4OH4 OH 28.0–30%
28.0–30% NH
NH3
3
SigmaAldrich
Sigma Aldrich
Ammonium
Ammoniumchloride
chloride NH
NH44ClCl 99.5%
99.5% SigmaAldrich
Sigma Aldrich
Fisher
FisherScientific,
Scientific,Loughborough,
Loughborough,
Potassiumchloride
Potassium chloride KCl
KCl 99.5%
99.5% UKUK
Tartaricacid
Tartaric acid CC44H
H66OO6 6 99.5%
99.5% Sigma
SigmaAldrich
Aldrich

2.2.
2.2. Sample
Sample
End-of-life
End-of-life Yuasa
Yuasa NP7-12L,
NP7-12L, 77 AhAh 1212 VV Valve
Valve Regulated
Regulated Lead
Lead Acid
Acid (VRLA)
(VRLA) batteries
batteries were
were
disassembled extractlead
disassembled to extract leadfrom
fromthe
thebattery
battery electrodes.
electrodes. Each
Each battery
battery comprised
comprised six cells
six cells of ~2ofV~2 V
each
each as shown
as shown in Figure
in Figure 1, each
1, each of which
of which hadnegative
had five five negative andpositive
and four four positive electrodes
electrodes separated
separated by an
by an Absorbed
Absorbed Glass Glass Mat (AGM).
Mat (AGM). The electrodes
The electrodes were were
mademade of a mixture
of a mixture of carbon
of carbon and lead
and lead oxide,oxide,
and
and the grids
the grids a lead
a lead calcium
calcium alloy.
alloy. TheThe separatorwas
separator wassoaked
soakedinin33.3%
33.3% dilute
dilute sulfuric acid.
acid. Physical
Physical
dimensions
dimensions of
of the
the battery
battery were
were151
151mmmm× × 65 mm ××9494mm
mmandandaamass
massofof2.8
2.8kg
kg[23].
[23].

Figure 1.
Figure 1. A
A 12
12 V
V lead
lead acid
acid battery
battery with
with its
its lid
lid sawn
sawn off
off to
to show
show the
the six
six compartments
compartments containing
containing five
five
negative and
negative and four
four positive
positive electrode
electrode sets
sets each.
each. Lead
Lead current
current collectors
collectors are
are connected
connected to
to each
each electrode
electrode
and the positive connections connected together, as are the negative electrodes. The
and the positive connections connected together, as are the negative electrodes. The connection is connection is
maintained along the six cell in series, and terminate at two external
maintained along the six cell in series, and terminate at two external leads. leads.

2.3. Equipment
2.3. Equipment
An LD300
An LD300 DC DC electronic
electronic load
load (Huntington,
(Huntington, UK)
UK) was
was used
used toto discharge
discharge the
the sample
sample batteries;
batteries;
Solartron equipment
Solartron equipment 1470E
1470E CellTest
CellTest (West
(West Sussex,
Sussex, UK)
UK) was
was used
used toto measure
measure the
the battery
battery on
on open
open
circuit, and to charge and discharge the batteries. For heating purposes, a water bath and Yellow
circuit, and to charge and discharge the batteries. For heating purposes, a water bath and Yellow Line Line
MST basic C stirrer (Boutersem, Belgium) with a coated chemical-resistant heating
MST basic C stirrer (Boutersem, Belgium) with a coated chemical-resistant heating base were used,base were used,
and aa TC
and TC 33 electronic
electroniccontact
contactthermometer
thermometerwas wasused
usedtoto monitor
monitor thethe mixture
mixture temperature.
temperature. A Sigma
A Sigma 2-
2-6E
6E centrifuge machine (Osterode am Harz, Germany) was used for liquid/solids separation.
centrifuge machine (Osterode am Harz, Germany) was used for liquid/solids separation. For mass For mass
measurements,aabalance
measurements, balancewith
withprecision
precisiongg±± 0.001
0.001 was used. Elemental
was used. analysis was
Elemental analysis was performed
performed using
using
the Element 2XR Inductively Coupled Plasma Mass Spectrometer (ICP-MS, Thermo
the Element 2XR Inductively Coupled Plasma Mass Spectrometer (ICP-MS, Thermo Fisher Scientific, Fisher Scientific,
Waltham,MA
Waltham, MAUSA).
USA). Cyclic
Cyclic voltammetry
voltammetry was was performed
performed on an on an Autolab
Autolab potentiostat
potentiostat (Metrohm,
(Metrohm, Utrecht,
Utrecht, The
The Netherlands).Netherlands).

2.4. Development
2.4. Development of
of Lead
Lead Recovery
Recovery Method
Method
Low energy
Low energy chemical
chemical and
and mechanical
mechanical methods
methods were
were favoured
favoured for
for lead
lead recovery.
recovery. The
The following
following
subsections explain the choice of treatment methods.
subsections explain the choice of treatment methods.
Batteries 2017, 3, 15 4 of 13

2.4.1. Use of Methanesulfonic Acid

The ability to dissolve the redox couple at both charged and discharged states is an important
feature of an electrolyte [24]. Lead methanesulfonate solubility in water is high, at 2.6 mol·dm− 3 ,
compared to lead sulfate which saturates at 0.004 mol·dm− 3 , lead hydroxide at 0.034 mol·dm− 3 , or lead
nitrate at 1.64 mol·dm− 3 [25]. MSA retains good conductivity (275 S·cm− 2 ·mol−1 ), and has lower
toxicity than other solvents. Where nitric acid reacts with metals to evolve hydrogen, MSA does not.
MSA does not attack organic compounds nor does it require pre-disposal treatment like H2 SO4 [25].
Therefore, MSA was used to make lead (II) methanesulfonate electrolyte.
The lead found in lead acid battery electrodes occurs as PbO2 , PbSO4 and Pb metal. MSA reacts
chemically with these forms in the following ways:

PbO2 + 2CH3 SO3 H → Pb(CH3 SO3 )2 + H2 O + O2 , (4)

Pb + 2CH3 SO3 H → Pb(CH3 SO3 )2 + H2 , (5)

PbSO4 + 2CH3 SO3 H → Pb(CH3 SO3 )2 + H2 SO4 , (6)

Empirically, the solubility limit of Pb in MSA is indicated at 1.25 mol·dm− 3 Pb2+ in 2.5 mol·dm− 3
MSA at 25 ◦ C [19,25], while the solubility of lead methanesulfonate is inversely proportional to the
concentration of methanesulfonic acid [19]. Reference [16] also shows that conductivity of electrolyte
made from methanesulfonic acid increases with high acid concentrations and low lead concentration.
On the other hand, more lead is required to yield more energy from the cell. The electrolyte acidity also
reduces during discharge, as the concentration of Pb2+ ions in the electrolyte increases. It is therefore
important to balance the concentrations to avoid precipitation of lead methanesulfonate salt into the
cell when it is fully discharged. Pletcher et al. [26] recommend that the acidity of electrolyte made
from Pb2+ and MSA should be limited to 2.4 mol·dm− 3 MSA to prevent formation of flaky deposits
in an electrochemical cell. Therefore, the concentration of MSA in this experiment was limited to
2.5 mol·dm− 3 , which would yield 1.0 mol·dm− 3 Pb2+ ions.

2.4.2. Heating
Lead (IV) oxide reacts with warm acids to form more stable lead (II) ions and release oxygen [27].
Heat was used to speed up the reaction between MSA and PbO2 . As a preliminary measure, the heating
temperature was limited to 50 ◦ C to minimise energy use.

2.4.3. Use of Hydrogen Peroxide

Hydrogen peroxide (H2 O2 ) is capable of acting as a reducing agent as well as an oxidising agent
in acidic conditions [28] (p. 600). It was used to reduce Pb (IV) oxide to Pb (II) ions in MSA, shown in
Equation (7). It was also used to catalyse the oxidation of Pb metal to Pb (II) ions in MSA in Equation (8).
These reactions occur faster than the oxide and metal reactions with acid. H2 O2 has also been used to
recondition a soluble lead cell to remove PbO2 sludge build-up [18].

PbO2 + H2 O2 + 2CH3 SO3 H → Pb(CH3 SO3 )2 + 2H2 O + O2 , (7)

Pb + H2 O2 + 2CH3 SO3 H → Pb(CH3 SO3 )2 + 2H2 O , (8)

2.5. Lead Recovery Method

This section presents the procedure used to disassemble a 7 Ah 12 V VRLA battery and dissolve
lead out of the battery electrodes.
Batteries 2017, 3, 15 5 of 13

2.5.1. Determining Battery State of Health

Before disassembly, the state of health (SoH) of the battery was determined. A 12 V SLI VRLA
battery that 3,maintains
Batteries 2017, 15 only 80% of its rated capacity in Ah is at the end of its service life [29]. According
5 of 13
to the VRLA battery manual, a voltage of 12.6 V corresponds to 100% state of charge (SoC) while an
According
open circuittovoltage
the VRLA battery
under manual,
11.8 V a voltage
indicates 0% SoCof[30].
12.6Therefore,
V corresponds to 100%
the battery state
was of charge (SoC)
galvanometrically
while ten
cycled an times
open between
circuit voltage underand
12.6 V (100%) 11.811.86
V indicates
V (0% SoC),0%charging
SoC [30]. Therefore,
at 0.7 A (C/10)the battery
constant was
current
galvanometrically
for 3 h and discharging cycledatten
thetimes
same between
rate for 312.6
h toVdetermine
(100%) and 11.86
how V (0%
much Ah SoC), charging
capacity atretain.
it could 0.7 A
(C/10)
Its open constant currentwas
circuit voltage for 3measured
h and discharging at the same rate for 3 h to determine how much Ah
after charge.
capacity it could retain. Its open circuit voltage was measured after charge.
2.5.2. Disassembling the Battery
2.5.2.The
Disassembling thewas
sealed battery Battery
disassembled using the procedure below:
The sealed battery was disassembled using the procedure below:
(1) Sulfuric acid was emptied from the battery.
(1) Sulfuric
(2) acid was rinsed
The battery emptied from
with the battery.
distilled water three times.
(2) The
(3) Thebattery wasofrinsed
top cover with distilled
the battery was sawnwater three
off, and times. were retrieved out of each cell chamber
electrodes
(3) The top cover of the battery
as shown in Figure 2a,b. was sawn off, and electrodes were retrieved out of each cell chamber
as shown in Figure 2a,b.

(a) (b)

Figure 2.
Figure 2. (a) A 12
(a) A 12 V
V VRLA
VRLA battery
battery showing
showing extraction
extraction of one of
of one of the
the six
six cells’
cells’ contents;
contents; and
and (b)
(b) The
The
multi-electrode assembly
multi-electrode assembly with
with Absorbed
Absorbed Glass
Glass Matt
Matt separator.
separator.

2.5.3. Dissolving
2.5.3. Lead from
Dissolving Lead from Battery
Battery Electrodes
Electrodes
Each of
Each ofthe
theelectrode
electrodesetssets retrieved
retrieved fromfrom a battery
a battery was weighed
was weighed and in
and placed placed in a container
a separate separate
container to be investigated uniquely. In the first container, 500 mL of 2.5 mol·
to be investigated uniquely. In the first container, 500 mL of 2.5 mol·dm− 3 MSA was added to thedm −³ MSA was added

to the contents
contents and to
and heated heated
30 ◦ C.toChange
30 °C. inChange
densityinofdensity of the
the solution solution
formed wasformed wasand
monitored monitored and
heating was
heating was maintained until the density of the solution plateaued. The procedure
maintained until the density of the solution plateaued. The procedure to monitor density is explainedto monitor density
is explained
in Section 2.6inonsection 0 on measurement.
measurement.
Electrodes in
Electrodes in the
the second
second container
container werewere treated
treated similarly
similarly except
except the
the acid
acid was
was heated
heated to
to 40
40 °C.
◦ C.
For the third experiment, 450 mL of 2.5 mol· dm −−³ MSA was used and 50 mL of 0.09 mol·dm−³
For the third experiment, 450 mL of 2.5 mol·dm MSA was used and 50 mL of 0.09 mol·dm− 3
3
hydrogen peroxide
hydrogen peroxide waswas added.
added. The The contents
contents werewereheated to 30
heated °C. ◦In
to 30 C. the fourth
In the container,
fourth the
container,
temperature
the temperature waswas
increased
increasedto to
40 40
°C.◦ C.
In In
thethe
fifth
fifthand
andsixth
sixthexperiments,
experiments,the thehydrogen
hydrogen peroxide was
peroxide was
diluted at 0.90 mol· dm −³and the mixtures were heated to 30 °C and 40 °C, respectively. The procedure
diluted at 0.90 mol·dm− 3 and the mixtures were heated to 30 ◦ C and 40 ◦ C, respectively. The procedure
is outlined
is outlined in
in Figure
Figure 3.
3.

2.5.4. Electrolyte Preparation

The liquid from dissolving lead battery electrodes was separated from undissolved solids by
centrifuging at 3600 rpm for 20 min. The supernatant liquid was collected and named “recovered
electrolyte” and used as electrolyte in soluble lead cells. The metal composition of the electrolyte was
determined using Inductively Coupled Plasma Mass Spectroscopy (ICP-MS,) The concentration of
the Pb2+ ions was determined using mass measurements as well as titration as outlined in Sections
2.6.2 and 2.6.3, respectively.
Batteries 2017, 3, 15 6 of 13
Batteries 2017, 3, 15 6 of 13

Figure 3.
Figure 3. Lead
Leadrecovery
recoveryplan planforfor
electrolyte preparation.
electrolyte The electrodes
preparation. retrieved
The electrodes from afrom
retrieved spenta VRLA
spent
battery with open circuit voltage less than 11.8 V were each placed in a beaker.
VRLA battery with open circuit voltage less than 11.8 V were each placed in a beaker. An amount An amount of 2.5
of
2.5 mol·dm MSA was added to the electrodes. The contents were heated at either 30 C or 40 ◦the
mol· dm −³ MSA
− 3 was added to the electrodes. The contents were heated at either 30 °C or 40
◦ °C. In C.
first
thetwo cases,
two no H2Ono 2 was added, in the next two cases 0.09 mol·dm−³H2O2 was −3 H added to the beaker
In first cases, H2 O 2 was added, in the next two cases 0.09 mol·dm 2 O2 was added to
while
the the last
beaker whiletwothe
had 0.90
last twomol·
haddm
−³ H2O2.
0.90 mol·dm− 3 H2 O2 .

2.6. Measurements
2.5.4. Electrolyte Preparation

2.6.1.The liquid from

Inductively dissolving
Coupled Plasmalead battery
Mass electrodes was separated from undissolved solids by
Spectroscopy
centrifuging at 3600 rpm for 20 min. The supernatant liquid was collected and named “recovered
ICP-MS allows analysis of trace elements which may otherwise be difficult to do using other
electrolyte” and used as electrolyte in soluble lead cells. The metal composition of the electrolyte was
analytical methods. The sample is pulverised into plasma using high currents, and the mist created
determined using Inductively Coupled Plasma Mass Spectroscopy (ICP-MS,) The concentration of the
is scanned for trace elements. Detection levels at parts per billion (ppb) can be realised.
Pb2+ ions was determined using mass measurements as well as titration as outlined in Sections 2.6.2
Since the quantity of trace metals other than lead in the recovered electrolyte was expected to be
and 2.6.3, respectively.
low, ICP-MS was used. The manual for the VRLA battery mentioned that the grid of the battery was
made
2.6. of lead-calcium alloy [30]. Literature on lead acid batteries also mentioned that grids may also
Measurements
contain antimony and tin as alloying agents, as well as traces of bismuth [31–33]. The ICP-MS was
2.6.1. Inductively
therefore Coupled
performed Plasma
to check Mass Spectroscopy
the presence of these elements as well as to quantify them.
ICP-MS allows analysis of trace elements which may otherwise be difficult to do using other
2.6.2. Change in Mass of Solution
analytical methods. The sample is pulverised into plasma using high currents, and the mist created is
From
scanned foreach
tracemixture, a sample
elements. waslevels
Detection collected every
at parts perhour and
billion centrifuged
(ppb) at 3600 rpm for 20 min
can be realised.
to separate
Since thethequantity
liquid from the solids.
of trace metals A 10 mL
other thansample ofthe
lead in therecovered
supernatant liquid was
electrolyte wascollected
expectedand its
to be
massICP-MS
low, was measured and
was used. Therecorded.
manual This was
for the usedbattery
VRLA to monitor the change
mentioned in density
that the of the
grid of the solution.
battery was
Assuming
made that the increase
of lead-calcium in mass
alloy [30]. of the
Literature onclear solution
lead acid was also
batteries duementioned
to Pb andthatPbOgrids
2 solids
maybeing
also
converted
contain to Pb²+ ions,
antimony theas
and tin concentration of Pb²
alloying agents, ions as
as+ well was estimated
traces from the
of bismuth change
[31–33]. TheinICP-MS
mass, using
was
Equation performed
therefore (9) below: to check the presence of these elements as well as to quantify them.
∆𝑚
2.6.2. Change in Mass of Solution [𝑃𝑏2+ ] = (9)
𝑉𝑠 𝑀𝑀𝑃𝑏
From each mixture, a sample was collected every hour and centrifuged at 3600 rpm for 20 min
where, [Pb²+] is the concentration of Pb²+ ions, in mol·dm−³; ∆m is the change in mass of recovered
to separate the liquid from the solids. A 10 mL sample of the supernatant liquid was collected and
solution over specific period, in grams; Vs is the volume of the sample weighed, in dm³; MMPb is the
its mass was measured and recorded. This was used to monitor the change in density of the solution.
molar mass of lead, in g·mol−¹.
Assuming that the increase in mass of the clear solution was due to Pb and PbO2 solids being converted
2.6.3. Titration
Batteries 2017, 3, 15 7 of 13

to Pb2+ ions, the concentration of Pb2+ ions was estimated from the change in mass, using Equation (9)
below: h i ∆m
Pb2+ = (9)
Vs MMPb
where, [Pb2+ ] is the concentration of Pb2+ ions, in mol·dm− 3 ; ∆m is the change in mass of recovered
solution over specific period, in grams; Vs is the volume of the sample weighed, in dm3 ; MMPb is the
molar mass of lead, in g·mol− 1 .

2.6.3. Titration
Complexometric titration of the sample with EDTA acid and Eriochrome Black T dye, as described
by Fitch [34], was carried out to determine the concentration of Pb2+ ions in the solution.
The formation constant for the Pb2+ -EDTA complex is high, at 1.1 × 1018 [35] (p. 315). In a basic
buffer solution with pH 10, the formation constant remains high at 3.3 × 1017 . The complex formation
is therefore expected to proceed to completion, according to Reaction (10):

H2 Y 2− + Pb2+ → PbY 2− + 2H + (10)

where H2 Y 2− is the EDTA acid and PbY 2− is the Pb2+ -EDTA complex.
The titration of Pb2+ with EDTA followed these steps:

(1) An aliquot of the Pb2+ solution collected after centrifuging was diluted a 100 times. The solution
was made to 25 cm3 .
(2) To make the solution basic, 5 mm of pH 10 ammonium hydroxide was added to the solution.
This resulted in formation of solid Pb(OH)2 .

Pb2+ + 2(OH )− → Pb(OH )2 (11)

(3) To keep the Pb2+ ions in solution, a spatula tip of powder tartaric acid was added. Tartaric acid
complexes weakly with Pb2+ ions, keeping the Pb2+ ions aqueous.

Pb2+ + C4 H4 O6 2− → Pb(C4 H4 O6 ) (12)

(4) Before titration, a colour indicator was added to the solution. The indicator was prepared by
grinding 100 mg of Erio Black T with 5 g of KCl. The indicator attaches to Pb2+ ions to form
a reddish violet coloured complex, as indicated by Equation (13):

Pb2+ + In → PbIn (13)

where In is the indicator.

(5) A standard solution of 0.01 mol·dm− 3 EDTA was titrated out of a burette into the solution
under investigation.
(6) The EDTA replaced the indicator from the PbIn complex to form the strongly bonding PbY 2−
until the indicator existed as a free protonated dye with a blue colour. Replacement of the
indicator by EDTA is shown in Equation (14):

H2 Y 2− + PbIn → PbY 2− + H2 In (14)

At the end-point, the colour of the solution changed from violet to blue.
(7) The concentration of lead in the solution was related to the concentration of EDTA by the equation:
h i
CEDTA VEDTA = Pb2+ VPb2+ (15)
Batteries 2017, 3, 15 8 of 13

The concentration obtained from the titration experiments was recorded and compared to the
concentration estimates made from density measurements.

2.6.4. Cyclic Voltammetry

A three-electrode electrochemical cell was used to determine the presence of Pb2+ ions in solution.
A rotating disc electrode was used to control the mass transport properties of the system, and electrolyte
flow was kept laminar. The cell used a vitreous carbon working electrode (WE) with an area of
0.1527 cm2 , a saturated standard calomel electrode (SCE) and a 1.5 cm2 platinum wire mesh counter
electrode
Batteries (CE),
2017, 3, 15 shown in Figure 4. 8 of 13

Figure 4.
Figure Sketch of
4. Sketch of three-electrode
three-electrode cell
cell for
for cyclic
cyclic voltammetry
voltammetry with
with 1.2 cm2 Pt
1.2 cm² Pt wire
wire mesh
mesh reference
reference
electrode, 0.1527 cm 2 vitreous carbon rotating disc working electrode and a saturated calomel
electrode, 0.1527 cm² vitreous carbon rotating disc working electrode and a saturated calomel
standard electrode.
standard electrode.

2.6.5.Cyclic
Flow Cell Testing experiments were carried out on diluted recovered electrolyte. The WE was
voltammetry
polished on a Buehler 736-3 8” microcloth with 0.3 µm alumina suspended in water. The WE was
The recovered electrolyte was subjected to an initial comparison to an electrolyte manufactured
rotated at 800 rpm, and a potential sweep was applied at 25 mV·s− 1 . The −experiments were carried out
from fresh laboratory reagents. Each2+electrolyte comprised 0.9 mol·dm ³ Pb2+ in 0.7 mol·dm−³ MSA.
at room temperature. For the Pb/Pb couple voltammetry, the potential was swept between −0.8 V
The flow cell has been described previously [17] and comprised a parallel plate reactor with electrode
and −0.3 V. For the PbO /Pb2+ , the potential was swept between 0.2 V and 1.9 V. The electrolyte used
2. 2The electrolyte was maintained at room temperature and pumped through
surface areas of 10 cm
was 1 mol·dm− 3 MSA.
the cell at a rate of 0.44 dm3·s−1 using a Watson Marlow 505S peristaltic pump.
2.6.5. Flow Cell Testing
3. Results and Discussion
The recovered electrolyte was subjected to an initial comparison to an electrolyte manufactured
from fresh
3.1. State of laboratory reagents.
Health of Lead Each electrolyte comprised 0.9 mol·dm− 3 Pb2+ in 0.7 mol·dm− 3 MSA.
Acid Battery
The flow cell has been described previously [17] and comprised a parallel plate reactor with electrode
The VRLA battery manual states that at 25 °C, a battery voltage of 12.6 V corresponds to 100%
surface areas of 10 cm2 . The electrolyte was maintained at room temperature and pumped through the
SoC while an open circuit voltage under 11.8 V indicates 0% SoC [30]. Upon testing, the maximum
cell at a rate of 0.44 dm3 ·s−1 using a Watson Marlow 505S peristaltic pump.
battery open circuit voltage measured was 11.6 V, well below the 0% SoC mark. Therefore, these
batteries
3. Results were
andconsidered
Discussionto have reached the end of their lives.
The Ah charge capacity of the batteries was less than 1% of the nominal capacity. This was
3.1. Stateindicator
another of Health that
of Lead
theAcid Battery
batteries had reached the end-of-life. Using this indicator, along with the
open circuit voltage, the batteries were chosen ◦for lead recovery.
The VRLA battery manual states that at 25 C, a battery voltage of 12.6 V corresponds to 100% SoC
while an open circuit voltage under 11.8 V indicates 0% SoC [30]. Upon testing, the maximum battery
3.2. Lead Recovered
open circuit voltage measured was 11.6 V, well below the 0% SoC mark. Therefore, these batteries
were considered to have reached the end of their lives.
3.2.1. Recovered Electrolyte Qualitative Analysis
The presence of metal ions in the recovered electrolyte sample was confirmed using ICP-MS. As
expected for the VRLA battery used, the presence of Ca2+ ions was confirmed. Bi²+, Sn²+ and Sb²+ ions
were also detected and quantified. The average concentration of Pb²+ ions averaged was 0.95 mol·dm−³,
while that of Ca2+ and Sn²+ ions was 2.98 x 10¯6 mol·dm−³and 0.08 x 10−6 mol·dm−³, respectively. Bi²+and
Sb²+ ions had the lowest average concentrations at 0.99 x 10−9 and 0.44 x 10−9 mol·dm−³ each.
Batteries 2017, 3, 15 9 of 13

The Ah charge capacity of the batteries was less than 1% of the nominal capacity. This was another
indicator that the batteries had reached the end-of-life. Using this indicator, along with the open circuit
voltage, the batteries were chosen for lead recovery.

3.2. Lead Recovered

3.2.1. Recovered Electrolyte Qualitative Analysis

The presence of metal ions in the recovered electrolyte sample was confirmed using ICP-MS.
As expected for the VRLA battery used, the presence of Ca2+ ions was confirmed. Bi2+ , Sn2+
and Sb2+ ions were also detected and quantified. The average concentration of Pb2+ ions
averaged was 0.95 mol·dm− 3 , while that of Ca2+ and Sn2+ ions was 2.98 × 10¯6 mol·dm− 3 and
0.08 × 10−6 mol·dm− 3 , respectively. Bi2+ and Sb2+ ions had the lowest average concentrations at
0.99 × 10−9 and 0.44 × 10−9 mol·dm− 3 each.
The concentration of Pb2+ ions in the recovered electrolyte is three orders of magnitude higher
than that of Ca2+ ions. The rest of the ions were present in parts per billion. Based on these quantities,
the presence of the last three ions was considered to be negligible. Electrochemically calcium ions were
not expected to affect performance of the recovered electrolyte.
Batteries 2017, 3, 15 9 of 13
3.2.2. Cyclic Voltammetry
Thecyclic
The cyclicvoltammograms
voltammogramsfor forboth
boththe
thenegative
negativeand
andpositive
positiveelectrodes
electrodesare
areshown
shownininFigure
Figure55
and they are comparable to that found in literature [16].
and they are comparable to that found in literature [16].

(a) (b)

Figure5.5. Cyclic
Figure Cyclic voltammetry
voltammetryresults
resultsofofrecovered
recoveredelectrolyte: 1 mol·
electrolyte: dm·dm
1 mol
−³MSA using a vitreous carbon
− 3 MSA using a vitreous
rotating disk working electrode (WE), rotated at 800 rpm, with a Pt wire reference
carbon rotating disk working electrode (WE), rotated at 800 rpm, with a Pt wire reference electrode
electrode (RF)(RF)
and
standard
and standardcalomel
calomel electrode (SCE),
electrode (SCE),where
wherea apotential
potentialsweep
sweep was applied at
was applied at25
25mVmV·
·s−s 1¹,, at
− atroom
room
temperature. (a) For the Pb/Pb²
2++ couple, the potential was swept between −0.7 V and −0.2 V. (b) For
temperature. (a) For the Pb/Pb couple, the potential was swept between −0.7 V and −0.2 V. (b) For
thePbO
the PbO/Pb2/Pb²
2++, the potential was swept between 0.2 V and 1.9 V.
, the potential was swept between 0.2 V and 1.9 V.
2

The characteristic deposit and anodic stripping of lead on the negative electrode (Figure 5a) is
The characteristic deposit and anodic stripping of lead on the negative electrode (Figure 5a) is
similar to that published by others, as is the behaviour at the positive electrode which is shown in
similar to that published by others, as is the behaviour at the positive electrode which is shown in
Figure 5b [16].
Figure 5b [16].
3.2.3. Comparison of Methods Used to Quantify Lead (II) Ions Recovered
3.2.3. Comparison of Methods Used to Quantify Lead (II) Ions Recovered
Thequantity
The quantityofofPb
Pb² + ions recovered was monitored by checking solution density, as well as by
2+ ions recovered was monitored by checking solution density, as well as by
titration. Table 3 compares sample values of Pb²+ ions concentration calculated using the change in
titration. Table 3 compares sample values of Pb2+ ions concentration calculated using the change
mass of the solution as well as titration. Calculations of [Pb²+] concentrations using mass of the
in mass of the solution as well as titration. Calculations of [Pb2+ ] concentrations using mass of the
solution recovered and using titration were performed using Equation 9 for the mass measurements
solution recovered and using titration were performed using Equation (9) for the mass measurements
and Equation 15 for titration.
and Equation (15) for titration.
Table 3. Comparison of the concentration of Pb²+ ions obtained by mass measurements and by
titration. The variance between the two values is lower than 10% in all cases.

[Pb²+] in mol·dm−³by
%Variance
Mass Measurements Titration
0.65 0.656 0.9
Batteries 2017, 3, 15 10 of 13

Table 3. Comparison of the concentration of Pb2+ ions obtained by mass measurements and by titration.
The variance between the two values is lower than 10% in all cases.

[Pb2+ ] in mol·dm− 3 by
%Variance
Mass Measurements Titration
0.65 0.656 0.9
0.68 0.670 1.5
0.73 0.716 1.9
0.87 0.860 1.2
0.95 0.890 6.3
0.96 0.900 6.3
1.06 0.930 9.7

The concentration of Pb2+ ions calculated from the change in mass of the solution differs from
that obtained by titration measurements by less than 10%. The mass measurements could therefore be
considered a reliable method. The close agreement of the results also confirms that the assumption
that the change in mass of the solution was due to Pb and PbO2 solids being converted to Pb2+ ions
was reasonable.
It is worth noting that the difference between the values from the two methods lessened the longer
the sample was allowed to settle. In those cases, it was not necessary to centrifuge the sample before
aliquots were collected.
There were concerns about interference from calcium (II) ions complexing with EDTA, since
calcium (II) ions complex with EDTA at the same pH as do lead (II) ions. However, because of the
much higher formation constant of Pb-EDTA (1.1 × 1018 ) as compared to Ca-EDTA (5.0 × 1010 ),
the Pb-EDTA complex is expected to reach equivalence before the Ca-EDTA complex is formed,
hence the titration results are considered reliable.

3.2.4. Quantity of Lead (II) Ions Recovered

The methods described in Section 2.5 and by Figure 3 yielded different concentrations of lead
Pb2+ ions. Table 4 shows the results for each method.

Table 4. Amount of Pb2+ ions in the solution made by dissolving solid VRLA battery electrodes.
The temperatures shown are averaged over 6 h.

Method Electrode Material (g) Average Temperature (◦ C) [H2 O2 ] (mol·dm− 3 ) [Pb2+ ] (mol·dm− 3 )
1 250 30 - 0.16
2 250 45 - 0.07
3 250 30 0.09 0.51
4 250 40 0.09 0.75
5 250 30 0.90 1.00
6 250 40 0.90 0.91

The density of the collected samples tended to stabilise after six hours and it was found that
without hydrogen peroxide, the amount of lead (II) ions recovered was lower than 0.2 M. Addition
of 0.09 mol·dm− 3 H2 O2 yielded 0.5 M, which was half the required amount of Pb2+ . Solutions with
the highest concentration of H2 O2 yielded the highest concentration of Pb2+ ions, and the required
1.0 mol·dm− 3 was obtained.
The quantity of hydrogen peroxide was kept at 10% of the total volume to control reaction
volatility. The concentration of recovered electrolyte was limited at 1.0 mol·dm− 3 of Pb2+ ions by
the initial concentration of acid. It was possible to recover more Pb2+ ions by adding more acid and
hydrogen peroxide.
Batteries 2017, 3, 15 11 of 13

3.3. Flow Cell

Comparison of Recovered and Standard Electrolytes

An initial comparison of the recovered electrolyte to a standard electrolyte, manufactured using
fresh laboratory reagents, was carried out in a small (10 cm2 electrode area) flow cell. The voltage profile
was similar for both electrolytes and consistent with previously reported data [16]. Each electrolyte was
subjected to 20 cycles in the flow cell, where each cycle consisted of a 1 h period of charge at 20 mA·cm−2
followed by full discharge at 20 mA·cm−2 . The average charge, energy and voltage efficiency obtained
for each electrolyte is shown in Table 5. There was no difference in the voltage efficiency, although the
recovered electrolyte returned charge and energy efficiencies 4% and 2% respectively lower than the
standard electrolyte. This is a relatively small variation and within deviations typically observed in
the literature [17]. The similarity in performance between the recovered and standard electrolytes is
encouraging and further characterisation of the recovered electrolyte within an operational flow cell
is ongoing.

Table 5. Operational data from 10 cm2 flow cell, comparing electrolyte recovered from conventional
lead acid batteries using the methodology detailed in this paper and standard electrolyte manufactured
from laboratory reagents.

Electrolyte Charge Efficiency/% Energy Efficiency/% Voltage Efficiency/%

Recovered 81 52 64
Standard 85 54 64

4. Conclusions
A novel lead recovery method for making electrolyte for a soluble lead redox flow battery has
been developed by the authors using methanesulfonic acid and hydrogen peroxide. The method
involved dissolving spent lead acid electrodes in warm MSA and using hydrogen peroxide to catalyse
the oxidation and reduction of solid Pb (IV) and Pb, respectively.
The method successfully yielded the amount of lead (II) ions (0.9 to 1.5 mol·dm− 3 ) sought, over
a period of at least 6 h. The methods used to recover lead yielded varying amounts of lead (II)
ions, indicating that some were more favourable than others. The addition of hydrogen peroxide
catalysed the retrieval of lead ions from lead (IV) oxide. As shown by the cyclic voltammetry results,
the recovered electrolyte displays similar electrochemical activity as does the conventional electrolyte
used in soluble lead redox flow batteries developed by others. A lead (II) concentration of 1.5 mol·dm− 3
would give an equivalent storage capacity of 40 Ahr·dm−3 of electrolyte or 60 Whr·dm−3 (at a discharge
voltage of 1.5 V).
A comparison of recovered and standard (made from laboratory reagents) electrolytes in an
operational flow cell showed encouraging performance. Further, detailed characterisation of the
recovered electrolyte in a flow cell environment is planned to enable optimisation of the recovery
process and electrolyte composition. The ability to reprocess waste conventional lead acid batteries at
the end of their useful life offers a novel and low cost route to obtaining an electrolyte for the soluble
lead flow battery. Further work should be carried out to compare the energy requirements for this
process and traditional lead acid recycling. A low cost, abundant supply of electrolyte for the soluble
lead flow battery would have a significant impact on future commercialisation of the technology.

Acknowledgments: This research was carried out with the financial support of the Government of Botswana as
well as the Botswana International University of Science and Technology.
Author Contributions: Richard G. A. Wills and Andrew Cruden conceived and designed the experiments,
Keletso Orapeleng performed the experiments and analyzed the data, Richard G. A. Wills contributed reagents
and materials, Andrew Cruden contributed laboratory equipment and Keletso Orapeleng wrote the paper. Andrew
Cruden and Richard G. A. Wills proof-read.
Batteries 2017, 3, 15 12 of 13

Conflicts of Interest: The authors declare no conflict of interest.

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