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Novel current collector and active mass carrier of the zinc electrode for
alkaline nickel-zinc batteries

Article  in  Bulgarian Chemical Communications · January 2016

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Bulgarian Chemical Communications, Volume 48, Number 1 (pp. 61– 65) 2016

Novel current collector and active mass carrier of the zinc electrode for alkaline
nickel-zinc batteries
R. Raicheff1*, M. Mladenov1, L. Stoyanov1, N. Boshkov2, V. Bachvarov2
1
Institute of Electrochemistry and Energy Systems - BAS, G. Bonchev Street, bl.10, 1113 Sofia, Bulgaria
2
Institute of Physical Chemistry - BAS, G. Bonchev Street, bl.11, 1113 Sofia, Bulgaria
Received January 13, 2015, Revised July 30, 2015

A new current collector and electrode mass carrier based on copper foam is developed and applied in constructing
pasted zinc electrode for alkaline nickel-zinc batteries. It is suggested that the microcellular structure of the foam matrix
assures uniform volume conductivity of the zinc electrode mass, facilitates the electron transport between the
electrochemically active electrode material and the current collector, improves the mechanical stability of the electrode,
also helping to minimize dendrite formation during charging. It is shown that the surface modification of the electrode
foam matrix by duplex tin/zinc coating leads to considerable reduction of gas evolution on the current collector during
the charging process. The investigation on the performance of nickel-zinc battery cells has definitely proved the
possibility of application of the newly developed current collector and active mass carrier for pasted zinc electrodes in
nickel-zinc batteries.
Keywords: current collector, electrode mass carrier, copper foam, zinc electrode, nickel-zinc batteries

INTRODUCTION for improving electrochemical performance (e.g.

calcium hydroxide, bismuth oxide, indium oxide,
The interest to rechargeable alkaline nickel-zinc
carbon additives, conductive ceramic materials,
batteries is largely stimulated by the advantages
etc.) of the anode. However, the zinc electrode
offered by this electrochemical system – high
suffers from a short cycle life due to degradation of
specific energy density (55 – 85 Wh kg-1), high
the zinc anode material because of dendrite growth
power density (140 -200 W kg-1), high voltage
during the charging process (penetrating the cell
(1,73 V), abundant low-cost materials and
separator and causing internal short circuits), high
environmentally acceptable chemistry. There is no
solubility of the ZnO (a discharge product of the
use of heavy metals (Hg, Pb, Cd), no flammable
zinc anode) and the metal zinc in highly alkaline
active materials and electrolytes and a simple
battery electrolytes. The electronic conductivity of
recycling process of the metal recovering. Besides,
ZnO is also rather poor and this is the main reason
the electrochemical system Ni-Zn is similar to the
for the electrochemical heterogeneity of the anode
widely used in the practice Ni-Cd system and
mass. Besides, the zinc electrode loses active
battery technology but is advantageously
surface area during charge/discharge cycling, which
environmentally friendly by replacing the toxic
results in gradual changes in the electrode shape
cadmium with common zinc [1-5].
and loss of capacity [1,3,7,8].
Since the zinc electrode also demonstrates fast
As current collectors and electrode mass carriers
electrochemical kinetics, the battery is ideally
of the zinc electrode usually copper or copper
suited to high discharge rate applications such as
alloys in the form of grid, foil, perforated plate or
power tools, household appliances, toys, electric
rugged strip are used. Serious disadvantage of those
bikes and hybrid electric vehicles. Nickel-zinc
carriers is the possibility of intensive gas evolution
batteries are the ideal choice when there is a need
on the electrode during charging due to the low
for a small, lightweight power source at a cost
overpotential of hydrogen evolution on those
significantly lower than lithium-ion battery [1,5,6].
metals which results in decreasing the effectiveness
The battery life is largely determined by the life
of the charging cycle and especially – of the
of the zinc anode – usually a paste type electrode
mechanical stability of the electrode mass, thus
with an electrochemically active composite
reducing the life of the zinc electrode.
electrode mass based on powder ZnO and additives
The aim of the present paper is to develop a new
current collector and active mass carrier for the zinc
* To whom all correspondence should be sent: electrode of nickel-zinc alkaline rechargeable
E-mail: r.raicheff@gmail.com battery using modified copper foam.
 2016 Bulgarian Academy of Sciences, Union of Chemists in Bulgaria 61
 R. Raicheff et al.: Novel current collector and active mass carrier of the zinc electrode for alkaline nickel-zinc…

EXPERIMENTAL Electrochemical properties of the new current

collector
Design of a current collector and active mass
carrier of the zinc electrode based on copper foam The main objects of study are the corrosion
matrix behavior of the modified electrode matrix and the
hydrogen evolution on that matrix applying
The current collector and electrode mass carrier of
electrochemical polarization techniques. The
the zinc electrodes for prismatic type nickel-zinc
investigation is performed in an alkaline electrolyte
batteries is a rectangular matrix of copper foam
normally used in nickel-zinc batteries [9] with
covered with electrodeposited tin (base) and zinc
composition: KOH (400 g/l), NaOH (35 g/l),
layers. The microcellular structure of the foam
LiOH.H2O (18 g/l), KF.2H2O (30 g/l),
assures uniform volume conductivity of the zinc
Na3PO4.12H2O (50 g/l). As model electrode matrix
electrode mass, facilitates the electron transport
samples of copper plate (dimensions 2.0 × 1.0 cm)
between the electrochemically active mass and the
with different coatings are used. The
current collector and improves the mechanical
potentiodynamic curves of the samples are obtained
stability of the electrode as a whole. It also helps to
by linear polarization method (scanning rate of 1
minimize formation of dendrites during charging
mV/s) using VerStat 4 PAR apparatus and a
process. The zinc coating and especially – the tin
conventional three-electrode electrochemical cell
coating isolate the copper substrate from the battery
with platinum plate as a counter electrode and
electrolyte and assure minimal gas evolution on the
saturated calomel electrode as a reference electrode.
electrode during charging because of the high
All measurements are carried out at room
hydrogen overpotential on those two metals.
temperature.
Besides, the zinc layer is an additional source of
metallic zinc for the current generation reaction Preparation and testing of the pasted zinc electrode
which would have a beneficial effect on the in an experimental nickel-zinc cell
magnitude and stability of the electrode capacity
A matrix of copper foam (Circuit Foil
during charge/discharge cycling of the battery.
Luxembourg Sarl, Luxembourg) with dimensions
The electrode matrix is cut from copper foam in
5.0 × 3.0 cm and thickness 0.15 cm is used for
rectangular form with appropriate dimensions,
current collector and active mass carrier of the zinc
enforced along one of the longer edges by welding
electrode. The electrodeposited tin and zinc layers
a copper strip bar with a tail for electric contact,
on the foam matrix have thickness of 5 and 10 μm,
and then subjected to electrochemical deposition,
respectively. The active electrode mass in the form
first of tin coating (5-10 μm thick) and after that of
of paste with composition: ZnO – 85,0%, Ca(OH)2
zinc coating (10-20 μm thick) [9].
– 4,0 %, Bi2O3 – 4,0%, Acetylene black – 2,0%,
Electroplating of tin and zinc layers on the copper polytetrafluoroethylene – 4,0 % and
foam matrix carboxymethylcellulose – 1,0 % is uniformly
incorporated into the cellular structure of the
The electrode matrix is first subjected to a
matrix. The pasted electrode is dried at 70 0C for 2
conventional surface treatment: degreasing in
h, pressed at 30 MPa and then mounted into double
ethanol solution, washing, pickling in dilute
separator pockets made of separators Celgard
solution of hydrochloric acid and washing. The
C3501 and PGA-Text. The electrode-separator
electroplating of the tin layer is performed from an
assembly is soaked with battery electrolyte under
electrolyte containing H2SO4, SnSO4 and wetting
vacuum for 10 min before mounting in the battery
additive ZC-1. The zinc layer is deposited from an
cell. The composition of the electrolyte is: KOH -
electrolyte containing ZnSO4.7H2O, NH4Cl, H3BO3,
400 g/l, NaOH - 35 g/l, LiOH.H2O - 18 g/l,
wetting additive ZC-1 and brightener ZC-2. The
KF.2H2O - 30 g/l, Na3PO4.12H2O - 50 g/l, the
electroplating is realized using a shaking bar for
balance - H2O, and is saturated with ZnO (approx.
continuous reflexive movement of the sample with
20 g/l) [9].
an aim for a better penetration of the electrolyte
Sintered type of nickel electrodes (CLAIO,
into the foam volume. The surface morphology of
Poznan, Poland) with dimensions 5.0 × 3.0 cm and
the copper foam electrode matrices without and
thickness 0.12 cm are used for cathodes in the
with tin and zinc coatings is studied using scanning
experimental nickel-zinc battery cell. The
electron microscope JEOL JSM-6390 for SEM
electrodes are wetted directly with the electrolyte
analysis.
before mounting in the cell using the same
evacuation procedure.

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 R. Raicheff et al.: Novel current collector and active mass carrier of the zinc electrode for alkaline nickel-zinc…

The experimental nickel-zinc prismatic battery The main electrochemical properties of the
cell is assembled with two nickel cathodes and one modified copper foam electrode matrix are
zinc anode, prepared as described above. The cell is demonstrated by the polarization curves of the
subjected to electrochemical charge/discharge test model samples of copper plate with different
using a multichannel automated battery testing coatings (tin and duplex tin-zinc) obtained in the
apparatus type CDT10. The apparatus gives a nickel-zinc alkaline battery electrolyte, as shown in
possibility for a complex control and monitoring of Fig. 2. The working zone of the zinc electrode in
the main cell parameters during charge/discharge the nickel-zinc battery – from the maximal potential
cycling - cell voltage and current, reference of charging (-1.7 V, SCE) to the minimal potential
potential, capacity and temperature. of discharging of the electrode (-1.4 V, SCE) is also
shown on the same figure.
RESULTS AND DISCUSSION
The cellular structure of the copper foam
electrode matrix in “as received” conditions
(without coating), with tin coating only and with
duplex tin-zinc coating is illustrated by SEM
images on Fig.1. As seen, the cellular structure of
the foam matrix practically does not change after
plating of the tin coating and the duplex tin-zinc
coating, and both coatings are uniform. This
microcellular structure of the electrode matrix, as
already noted, not only facilitates the electron
transport between the electrochemically active
electrode mass (based on ZnO – a material
characterized with low electron conductivity) and Fig. 2. Potentiodynamic polarization curves of
the current collector, but it also improves the copper plate (1), copper plate with tin coating (2) and
with tin and zinc coatings (3) in the battery electrolyte.
mechanical stability of the electrode as a whole.
The following conclusions can be made from the
results of the polarization studies: (a) the presence
of tin coating, and especially – of zinc coating on
the copper surface significantly shifts the corrosion
potential of the system in negative direction; (b) as
expected, copper shows high corrosion stability in
the highly alkaline battery electrolyte; (c) the rate
a) of hydrogen evolution on the copper surface in the
working zone of the zinc electrode is much higher
(1-2 orders of magnitude) in comparison to the rate
of hydrogen evolution on zinc coating and
especially – on tin coating, and this difference is
better expressed at more negative potentials (higher
potentials of charging of the zinc electrode); (d) the
anodic dissolution of zinc (cf. curve 3) is active in
b) the whole working zone which suggests that the
deposited zinc layer would not only reduce the
hydrogen evolution on the matrix but it could also
serve as an additional source of active zinc for
anodic reaction on the zinc electrode, especially at
prolonged exploitation of the battery. The surface
modification of the copper foam electrode matrix
by tin and zinc coatings would strongly restrict the
c) gas evolution on the matrix; (e) there is practically
Fig. 1. SEM images of copper foam in “as received” no anodic dissolution of tin in the whole working
condition (a), with tin coating (b) and with tin and zinc zone which means that the tin coating is
coatings (c). cathodically protected by the zinc layer and it
would reliably isolate the copper matrix from the
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 R. Raicheff et al.: Novel current collector and active mass carrier of the zinc electrode for alkaline nickel-zinc…

battery electrolyte and strongly restrict the gas volume conductivity of the active mass, facilitates
evolution in case of partial uncovering of the the electron transport between the
copper surface of the matrix. Thus, the above electrochemically active electrode material and the
results definitely proved the choice of duplex tin- current collector, improves the mechanical integrity
zinc coating on the copper foam current collector. of the electrode, and helps to minimize formation of
dendrites during charging process.
It is established that the modification of the
copper surface with duplex tin/zinc coating results
in a considerable reduction of the rate of the
hydrogen evolution at charging conditions of the
zinc electrode, thus restricting the gas evolution on
the electrode foam matrix during charging cycle. In
addition, the zinc layer is an additional source of
metallic zinc for the current generation reaction
which would have a beneficial effect on the
magnitude and stability of the electrode capacity,
especially at prolonged cycling of the battery.
The electrochemical testing of pasted zinc
Fig. 3. Dependence of the charge and discharge electrodes constructed with modified copper foam
capacity on the number of cycles of the experimental matrix as current collector and active mass carrier
nickel-zinc battery cell at current load procedure C/5 – in an experimental alkaline nickel-zinc battery cell
C/2.5 (C=1.0 Ah is the nominal capacity of the cell). has demonstrated an excellent performance of the
The electrochemical testing of the zinc electrode electrode – good cycleability, high and stable
constructed with modified copper foam matrix as specific discharge capacity, high charge/discharge
current collector and active mass carrier in the efficiency, etc. Thus, all the results proved
experimental nickel-zinc cell is carried out at definitely the possibility of application of the newly
constant current mode from full charged state of the developed current collector and active mass carrier
electrode to full discharge at room temperature. for pasted zinc electrodes in alkaline nickel-zinc
First, a forming cycle at charge/discharge procedure batteries.
C/20 – C/10 and 5 cycles at normalizing procedure
C/10 – C/5 (where C=1.0 Ah is the nominal REFERENCES
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at procedure C/5 (0.2 A) – C/2.5 (0,4 A) up to 250 2. A.K. Shukla, S. Venugopalan, B. Haripkash, J.
cycles. In Fig. 3 the dependence of the charge and Power Sources, 100, 125 (2001).
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figure illustrate well the very good characteristics 4. M. Geng, D.O. Northwood, Int. J. Hydrogen Energy,
28, 633 (2003).
of the zinc electrode – high specific discharge
5. J. Philips, S. Mohanta, M.M. Geng, J. Bartom, B.
capacity (above 100 mAh/g) at high current load McKinney, J. Wu, ECS Trans. 16, 11 (2009).
(0.4 A), high charge/discharge efficiency (above 95 6. G.X. Zhang, ECS Trans., 16, 47 (2009).
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CONCLUSION 8. Y.F. Yann, I.Q Yu, N.M. Wu, J.L. Yang, Y.B. Chen,
S.Y. Guo, J.P. Tu, Electrochim. Acta, 56, 4378 (2011).
New current collector and electrode mass carrier 9. M. Mladenov, R. Raicheff, L. Stoynov, D.
based on copper foam is developed and applied in Kovacheva, BG Patent 111 775 (2014)
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nickel-zinc batteries. It is suggested that the
microcellular structure of the foam assures uniform

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 R. Raicheff et al.: Novel current collector and active mass carrier of the zinc electrode for alkaline nickel-zinc…

НОВ ТОКОВ КОЛЕКТОР И НОСИТЕЛ НА АКТИВНАТА МАСА НА ЦИНКОВ ЕЛЕКТРОД

ЗА АЛКАЛНИ НИКЕЛ-ЦИНКОВИ БАТЕРИИ
Р. Райчев1, М. Младенов1, Л. Стоянов1, Н. Божков2, В. Бъчваров2
1
Институт по електрохимия и енергийни системи – БАН, ул. Г. Бончев, бл. 10, София 1113
2
Институт по физикохимия – БАН, ул. Г. Бончев, бл. 11, София 1113
Постъпила на 13 януари 2015 г.; коригирана на 30 юни 2015 г.

(Резюме)
Нов токов колектор и носител на електродната маса, основан на медна пяна, е разработен и приложен за
конструиране на пастов тип цинкови електроди за алкални никел-цинкови батерии. Микроклетъчната структура
на електродната матрица от медна пяна осигурява равномерна обемна проводимост на цинковата електродна
маса, улеснява преноса на електрони между активния електроден материал и токовия колектор, подобрява
механичната устойчивост на електрода и ограничава образуването на дендрити при зареждане на електрода.
Показано е, че повърхностната модификация на електродната матрица с двуслойно калай/цинково покритие
води до значително намаляване на отделянето на газ върху токовия колектор в процеса на зареждане на
електрода. Изследванията върху работата на никел-цинкови батерии доказват убедително възможността за
прилагане на разработения токов колектор и носител на активната маса на цинкови електроди за никел-цинкови
батерии.

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