Journal of Chemical Technology and Biotechnology J Chem Technol Biotechnol 79:927–934 (online: 2004)

DOI: 10.1002/jctb.1082

Recycling of nickel–metal hydride batteries.

II: Electrochemical deposition of cobalt and
nickel
N Tzanetakis and K Scott∗
School of Chemical Engineering and Advanced Materials, University of Newcastle upon Tyne, Newcastle upon Tyne, NE1 7RU, UK

Abstract: A combination of hydrometallurgical and electrochemical processes has been developed for
the separation and recovery of nickel and cobalt from cylindrical nickel–metal hydride rechargeable
batteries. Leaching tests revealed that a 4 mol dm−3 hydrochloric acid solution at 95 ◦ C was suitable to
dissolve all metals from the battery after 3 h dissolution. The rare earths were separated from the leaching
solution by solvent extraction with 25% bis(2-ethylhexyl)phosphoric acid (D2EHPA) in kerosene. The
nickel and cobalt present in the aqueous phase were subjected to electrowinning. Galvanostatic tests on
simulated aqueous solutions investigated the effect of current density, pH, and temperature with regard to
current efficiency and deposit composition and morphology. The results indicated that achieving an Ni–Co
composition with desirable properties was possible by varying the applied current density. Preferential
cobalt deposition was observed at low current densities. Galvanostatic tests using solutions obtained from
treatment of batteries revealed that the aqueous chloride phase, obtained from the extraction, was suitable
for recovery of nickel and cobalt through simultaneous electrodeposition. Scanning electron micrography
and X-ray diffraction analysis gave detailed information of the morphology and the crystallographic
orientation of the obtained deposits.
 2004 Society of Chemical Industry

Keywords: nickel–metal hydride batteries; rare earth elements; liquid extraction; recycling; electrodeposition;
nickel

1 INTRODUCTION very large, representing an important source of envi-

The worldwide market of rechargeable batteries is
growing at a record pace due to increased con-
sumer demand for portable devices. The nickel–metal
hydride (NiMH) battery is one of the most pop-
ular rechargeable batteries for use in portable
devices, power tools, phones, camcorders and portable
computers.1 – 3 The high energy density and long cycle
life of this battery make it a leading technology for the
power source for electric vehicles.4 – 7
Commercial production of NiMH began in 1993
with 100 million cells. By the year 1999 more than
900 million cells, corresponding to 20 000 tonnes of
batteries were manufactured world-wide.8,9 In the year
2000, the one billion mark was passed, representing
4% of the world-wide rechargeable battery production,
with a market of £720 million. In the year 2010, NiMH
batteries are expected to comprise 29% of the total
battery market, with a world-wide battery market of
£9 billion.10
Since the use of NiMH batteries is large, the
expected amount of scrap at the end of their life is
ronmental pollution if spent batteries are thrown away.
Recycling of batteries is necessary both from an envi-
ronmental point of view and from the fact that NiMH
cells have a valuable metal content of nickel, cobalt,
and rare earth elements. Various investigations for
recovering valuable metals from NiMH rechargeable
batteries have been reported,11 – 18 most of which use
a combination of mechanical and hydrometallurgical
processes including dissolution in inorganic acids,11
solvent extraction, and precipitation.14,15
There are many cell types of nickel–metal hydride
cells available on the market (ie cylindrical, prismatic,
and button cell). Since battery composition and
materials differ between manufacturers, the work
reported here describes what can be expected from
a hydrometallurgical and electrochemical treatment
of NiMH batteries. The present study evaluates
the recycling of NiMH rechargeable batteries using
hydrometallurgical processes with electrowinning for
the recovery of nickel and cobalt. An aim of this work is
to recover a nickel–cobalt alloy, from spent batteries,

∗ Correspondence to: K Scott, School of Chemical Engineering and Advanced Materials, University of Newcastle upon Tyne, Newcastle
upon Tyne, NE1 7RU, UK
E-mail: k.scott@ncl.ac.uk
Contract/grant sponsor: EPSRC/HEFCE; contract/grant number: JIF4NESCEQ
(Received 2 February 2004; revised version received 25 March 2004; accepted 15 April 2004)
Published online 28 July 2004
 2004 Society of Chemical Industry. J Chem Technol Biotechnol 0268–2575/2004/$30.00 927
N Tzanetakis, K Scott
with good properties, suitable for various technological
applications.
Electrodeposition of nickel–cobalt alloys has been
widely studied due to their excellent properties, such
as hardness and strength, and various applications in
the electronic, mechanical, magnetic, and aerospace
industries.19 – 23
A study of the influence of deposition parameters
was carried out to assess the effect of these
parameters both on the electrochemical response
and energy consumption, and morphology and
composition of the obtained deposit. Optimum
operating conditions for alloy electrodeposition were
experimentally established.
2 EXPERIMENTAL
2.1 Dissolution tests
Cylindrical AA-size NiMH batteries, manufactured
in Japan (Toshiba) were used in this work. The
batteries, which weighed an average of 23 g, were
cut in half longitudinally and after removal of the
external stainless steel case, were leached in aqueous
HC1 solutions. Hydrochloric acid was employed as
a leaching agent due to the feasibility of extracting
nickel ions from chloride solutions. After dissolution,
the leachate and insoluble materials, such as the
polypropylene separator and the iron grid, were
separated by filtration.
2.2 Solvent extraction tests
Solvent extraction tests were conducted on the
chloride solutions obtained from leaching. The
extractions were performed by mechanical shaking
of 500 cm3 conical flasks each containing 100 cm3
of the aqueous and organic solutions. A solution of
25% bis-(2-ethylhexyl)phosphoric acid (D2EHPA) in
kerosene was chosen as a solvent for the feasibility of
selective complexation and extraction of rare earths, at
low pH, but not of nickel and cobalt.24 – 27 The pH of
the aqueous and organic solution was adjusted to the
desired value by drop-wise addition of concentrated
sodium hydroxide solution. After shaking, the two
phases were allowed to disengage completely and then
separated into raffinate and organic phases.
2.3 Electrodeposition tests
Electrochemical experiments were performed in a
rectangular acrylic flow cell with removable electrodes.
A platinum oxide-based coated titanium anode and a
stainless steel cathode, each of 35 cm2 area, were used
with a saturated calomel electrode as a reference.
The cell was divided into two compartments by a
NafionR 117 membrane. Figure 1 shows the design
characteristics of the flow cell used for the tests.
Prior to each experiment the stainless steel cathode
was abraded with silicon carbide paper (P600), rinsed
with acetone and then distilled water. Electrochemi-
cal experiments were accomplished with a potentio-
stat/galvanostat (Sycopel Scientific) controlled with
928
Saturated Calomel Electrode
Cation-Exchange Membrane
Working Electrode
2 cm Counter Electrode
10 cm
Catholyte Outlet
Anolyte Outlet
22 cm
Anolyte Inlet
Catholyte Inlet Flow Distribution
3 cm
Figure 1. Design characteristics of the two-compartment acrylic
electrodeposition cell.
Sycopel Scientific electrochemistry software. During
the test, cell voltages were continuously recorded with
a multimeter.
The simulated solutions were prepared from
analytical grade metal sulfate salts (Aldrich). Boric
acid, concentration of 0.15 g dm−3 , was used as a
buffer and 1 mol dm−3 Na2 SO4 as an anolyte. Each
experiment was carried out using a fresh solution
which was deoxygenated with nitrogen for 30 min
prior to electrolysis.
The solutions were circulated from the two 1 dm3
glass reservoirs to the cell by a peristaltic pump at a
flow rate of 0.12 dm3 min−1 . Throughout the tests the
solutions in the reservoirs were stirred with magnetic
stirrers. Samples were taken from the catholyte every
hour and the amount of deposited metal was calculated
by difference from the initial value. Small amounts
of metal ions migrated into the anolyte after long
term electrolysis and these amounts were allowed for
in determining the current efficiencies and deposit
compositions. Depending on the charge passed, up to
approximately 300 and 35 ppm of nickel and cobalt
respectively, diffused into the anolyte.
The electrochemical equivalent of the deposit, ie
the charge used for total metal deposition (practical
charge), was determined from its composition. The
value was then compared with the electric charge
passed through the system (theoretical charge) to
determine the current efficiency. The metal ion
content of various elements was determined by
atomic absorption analysis, using a Unicam 929 AA
spectrometer.
The morphology and the crystal structure of the
deposits were examined using a Hitachi S-2400
scanning electron microscope and a Philips X’ Pert
Pro diffractometer respectively.
3 RESULTS AND DISCUSSIONS
3.1 Leaching tests
The Parameters investigated during the dissolution
tests were acid concentration, dissolution time, and
J Chem Technol Biotechnol 79:927–934 (online: 2004)

temperature. Detailed description of this work is
given in another communication.28 It is important
to mention that dissolution of all metals was found to
depend significantly on leaching temperature. Nearly
complete dissolution occurred for cobalt, nickel, rare
earths, zinc and manganese after 3 h using 3 mol dm−3
HC1 at a temperature of 95 ◦ C. Low iron dissolution
of the electrode grids was desirable for minimal
contamination of Ni and Co during recovery. However
some extraction of Fe was unavoidable due to the need
for high nickel recovery. After filtration of the leaching
solution the resulting green chloride solution had a pH
close to zero and a composition of (in g dm−3 ): 55.7
Ni, 5.7 Co, 2.2 Mn, 0.99 Zn, 2.8 Fe, 1.1 Al, 6.4 La,
6.2 Ce and 2.5 Nd.
3.2 Solvent extraction experiments
Solvent extraction using 25% D2EHPA (0.75 mol
dm−3 ) as an extractant, demonstrated the feasibility
of recovering the rare earths, while leaving Ni, Co
and Mn in the aqueous phase to later undergo
electrowinning. Extraction tests over a wide range
of aqueous pH (0–3) indicated that, at a pH close to
2.5, all the rare earths and most of the iron could be
extracted into the organic phase and hence separated
from nickel and cobalt.28 Extraction of manganese,
aluminium and zinc was relatively low over the whole
range of acidity possibly as a result of preferential
extraction of rare earths and iron.14
3.3 Electrochemical deposition
This is a preliminary study to illustrate the feasibility
of using electrodeposition for the recovery of nickel
and cobalt from the leach solutions from spent
NiMH batteries and initially investigation of the
voltammetric characteristics of the systems was
carried out.
Studies using simulated solutions were performed
to evaluate the effect of current density, pH, and
temperature on the composition and morphology of
the electrodeposits. The results are then compared
with those obtained using solutions derived from the
hydrometallurgical treatment of batteries.
3.3.1 Voltammetric studies
Figure 2 shows typical linear sweep voltammograms
(LSVs) obtained for the nickel, cobalt, and simulated
battery solutions containing Ni, Co and Mn, and
for the solution obtained from hydrometallurgical
treatment of the batteries.
The curves for the simulated solutions revealed clear
nucleation processes followed by hydrogen evolution
at more negative potentials. The current–potential
curves showed only a small difference in the nucleation
potential for nickel and cobalt.
Electrochemical reduction of nickel and cobalt
began at a potential of approximately −850 mV vs
SCE, while hydrogen reduction occurred at potentials
more negative than −1100 mV. The ‘limiting’ current
densities for nickel, cobalt, and simulated battery
J Chem Technol Biotechnol 79:927–934 (online: 2004)
Recycling of nickel–metal hydride batteries. II
-30
Nickel
-25 Cobalt
Simulated solution
Battery solution
-20
J/mA cm-2
-15
-10
-5
0
-500 -700 -900 -1100 -1300 -1500
E/mV vs. SCE
Figure 2. Linear sweep voltammograms of 0.09 mol dm−3 NiCl2 +
1 mol dm−3 NaCl, 0.009 mol dm−3 CoCl2 + 1 mol dm−3 NaCl,
simulated battery solution containing 0.09 mol dm−3 NiCl2 ,
0.009 mol dm−3 CoCl2 , 0.004 mol dm−3 MnCl2 + 1 mol dm−3 NaCl and
actual battery solution. All solutions contained 0.25 mol dm−3 H3 BO3 ,
pH 3, and scan rate 20 mV s−1 .
solutions were approximately 13, 1.5, and 17 mA cm−2
respectively. For the potential range of approximately,
−970 to −1050 mV, the different systems operated
under mass transport control. The LSV of the
simulated battery solution shifts to a potential more
positive than that observed in the pure nickel, which
indicates that the formation of a nickel–cobalt alloy
from the simulated solutions was thermodynamically
favourable.
The voltammogram for the solution, from leaching
of a NiMH battery revealed that deposition in this
case occurred less readily than from simple chloride
solutions and without a clear nucleation overpotential.
The average difference in nucleation potential
between the simulated and the battery solution was
around 200 mV. The low limiting current and the
shift in the reduction potential towards more negative
values in the case of the battery solution was due to
the complexity of this solution and the presence of
impurities from the previous leaching and extraction
steps.
Figure 3 compares cyclic voltammograms from a
solution of only nickel ions, and from simulated,
and actual battery solutions. In all cases the
voltammograms exhibited a single reduction wave and
suggested the presence of a nucleation process which
was less pronounced in the case of the actual battery
solution. The tests with the simulated solution showed
a greater deposition rate, ie larger current densities,
than that of the battery solution. The voltammetric
response associated with the deposition from the
battery solution showed a lower current intensity and a
shift of the hydrogen evolution reaction, towards more
negative potentials.
It is worth re-stating at this point the impurities
that might be present in the case of the actual
battery solution due to the previous hydrometallurgical
treatment. The solution from the solvent extraction
cycle contained, in addition to nickel, cobalt, and
929
N Tzanetakis, K Scott

10 the aqueous phase after extraction. The composition

of the solution (g dm−3 ): 5.57 Ni, 0.57 Co, and 0.
5 22 Mn, was similar to that obtained after diluting the
leaching solution by a factor of 10.
0
Electrowinning experiments from dilute solutions
J/mA cm-2

-5 should generally be operated at the maximum use-

-10
-15
Nickel
-20 Simulated solution
Battery solution
-25
-1400 -1200 -1000 -800 -600 -400 -200 0 200
E/mV vs. SCE
Figure 3. Cyclic voltammograms of 0.09 mol dm−3 NiCl2 + 1 mol
dm−3 NaCl, simulated battery solution containing 0.09 mol dm−3
NiCl2 , 0.009 mol dm−3 CoCl2 , 0.004 mol dm−3 MnCl2 + 1 mol dm−3
NaCl and actual battery solution. All solutions contained
0.25 mol dm−3 H3 BO3 , pH 3. The potential was first scanned
cathodically from the rest potential with a scan rate of 20 mV s−1 .
Arrows indicate the potential scan direction.
manganese, small quantities of iron (0.36 g dm−3 ),
aluminium, zinc (0.66 g dm−3 ), and possibly traces
of rare earth elements (0.1–0.2 g dm−3 ) and the
organic solvent. Due to these impurities, a much
higher overpotential was necessary to begin the
nucleation process in the actual battery solution.
Despite the fact that both the simulated and the
actual battery solutions contained nickel and cobalt
as the major constituents, the presence in the latter
of the above metals was responsible for the different
ful current density at which efficient deposition takes
place. Figure 4 shows the typical effect of current den-
sity on current efficiency and composition of nickel
and cobalt in the deposit. For these experiments the
charge passed (3250 C) was identical. The thickness of
the deposit obtained was approximately 1.7 mm. The
data confirmed co-deposition of nickel and cobalt,
while in all cases the deposit contained no more
than 2% of manganese (Table 1). A greater propor-
tion of cobalt was deposited at low current densities
although the amount was approximately one tenth that
of nickel. Higher cobalt content potentially results in
high strength and hardness of the obtained alloy.19
Overpotentials of 820–1100 mV were observed at the
beginning of the deposition process at current den-
sities of 10–100 A m−2 (Table 1). The overpotentials
decreased by approximately 50–100 mV during the
runs. It is also apparent that the cobalt content in the
deposit decreased when the applied current density
was increased.
The current efficiencies decreased at higher current
densities due to metal ion depletion, which resulted
120 100
Ni
100 80

Amount in deposit/%
Current efficiency/%

electrochemical behaviour. 80
60
The anodic processes revealed a clear oxidation
60
wave in the case of the nickel ion and the simulated
40
solutions, and a smaller one for the battery solution. 40
It can be observed that the simulated solution showed Co 20
similar characteristics to the nickel curve as nickel 20
was the major component of that solution. In the 0 0
case of nickel ion and the simulated solutions, 0 10 20 30 40 50 60 70 80 90 100 110
the voltammetric charge of the cathodic peak was Current density/A m-2
approximately equal to that of its corresponding
anodic peak, which indicated good electrochemical Figure 4. Effect of current density on alloy current efficiency and
composition. Experiments were carried out in baths containing
reversibility for these systems.
0.09 mol dm−3 NiCl2 , 0.009 mol dm−3 CoCl2 , 0.004 mol dm−3 MnCl2 ,
Overall from the voltammetric study it is expected 1 mol dm−3 NaCl and 0.25 mol dm−3 H3 BO3 at 22 ◦ C and at pH 3.
that, in the case of the solution from hydrometallur- Charge passed, 3250 C.
gical treatment of the NiMH batteries, the deposition
process will be inhibited. This inhibition was caused Table 1. Effect of current density on the composition of the deposit,
by substrates, other than the metal ion of interest, the cell voltage and the energy consumption for tests using simulated
present either at the surface of the electrode or in the battery solutions at pH 3
diffusion layer, which hindered the cathodic process
and partially covered the surface of the cathode. They Initial Cell Energy
Current Ni Co Mn Overpotential Voltage Consumption
also affected the overpotential and the texture of the
(A m−2 ) (%) (%) (%) (mV) (V) (kWh mol−1 )
surface.
10 70 30 0 820 2.1 0.109
3.3.2 Simulated solutions 25 83 15 2 850 2.6 0.133
50 87 12 1 900 2.9 0.15
Galvanostatic electrodeposition tests were conducted
75 87 11 2 1050 3.15 0.248
with solutions containing nickel, cobalt, and man-
100 88 10 2 1100 3.44 0.296
ganese ions, the predominant elements expected in

930 J Chem Technol Biotechnol 79:927–934 (online: 2004)


in operating conditions above the limiting current and
greater hydrogen evolution.
When experiments were performed at current
densities higher than 100 A m−2 the deposits included
green nickel hydroxides which would detract from
the properties of the deposit. The nickel hydroxide
was possibly formed due to operation above the
limiting current at which the local pH at the electrode
increased, due to localised formation of OH− ions.
Table 1 shows the cell voltages and energy con-
sumptions obtained at the termination of the elec-
trodeposition experiments. Higher current densities
resulted in significantly greater cell voltages. During
all electrodeposition tests the cell voltage decreased
slightly with time and hence so did the energy con-
sumption.
Experiments carried out to optimise the operating
pH indicated that at a pH between 2 and 4 higher
metal removal at greater current efficiencies and
better quality deposits were obtained (Fig 5). The
composition of the deposit was similar regardless of
the solution pH. However at low pH, reduction of
hydrogen ions was high which led to low current
efficiencies. Since cogeneration of hydrogen with
nickel–cobalt electrodeposition would tend to increase
pH locally at the electrode surface, formation and
inclusion of metal hydroxides into the deposit is likely.
Thus maintaining the pH in the appropriate range
during these experiments was necessary.
Precipitation of metals and occlusion of hydroxides
in the growing deposit was observed during the runs at
pH values above 4.5. The formation of hydroxides
inhibited the deposition process and induced the
formation of cracked non-homogeneous deposits.
During all runs an increase in the catholyte pH was
observed, which was adjusted to the appropriate value
by addition of hydrochloric acid solution.
Figure 6 shows scanning electron microscopic
(SEM) images of the surface morphology of the
final deposits obtained under various electrodeposition
conditions. A constant alloy composition throughout
120
Ni
100
Current efficiency/%
80
60
40
20 Co
0 0
0 1 2 3 4 5
pH
Figure 5. Effect of pH on alloy current efficiency and composition.
Experiments were carried out in baths containing 0.09 mol dm−3
NiCl2 , 0.009 mol dm−3 CoCl2 , 0.004 mol dm−3 MnCl2 , 1 mol dm−3
NaCl and 0.25 mol dm−3 H3 BO3 at 22 ◦ C and at a current
density = 50 A m−2 . Charge passed, 6120 C.
J Chem Technol Biotechnol 79:927–934 (online: 2004)
Recycling of nickel–metal hydride batteries. II
the thickness of the deposit was formed. In all cases
deposits adhered well to the stainless steel substrate.
It is clear that the morphology of the structures varied
significantly with the experimental conditions used.
The grain size became gradually refined on
decreasing the current density and by ensuring
that the nucleation took place slowly. The higher
cobalt content at low current densities increased the
crystalline nature of the alloy and gave a compact,
homogeneous, dense, and fine-grained structure.
At high current densities, the alloy structure
was characterised by large, randomly distributed
grains without visible porosity. Black inclusions were
distinguished in the micrographs while the colour of
the alloy changed from silver to black.
The deposit obtained at higher temperatures
was globular, with variable grain sizes, without a
uniform distribution over the surface. Deposition tests
performed at 40 and 60 ◦ C did not give a significant
improvement in current efficiency.
The structure of the alloy and the size distribution
of the crystallites became more homogeneous as the
pH increased and a metallic deposit was obtained. The
deposit at high pH exhibited a silver foil appearance.
Low pH (<1), on the other hand, provoked inhibition
of the growth process while deposition of hydrogen-
rich alloy possibly occurred. In this case a brittle
deposit, that partially lifted from the electrode,
probably due to hydrogen evolution, was obtained.
3.3.3 Battery solutions
Batch galvanostatic electrodeposition experiments
were performed with solutions obtained after the
dissolution and solvent extraction processing of NiMH
batteries, for 10 h or until a specific electric charge
had passed. Table 2 gives the deposit compositions
obtained for tests performed at three different current
densities. The deposits had a dendritic appearance,
especially at the higher current density, possibly due
to the presence of impurities in the bath.
Figure 7 shows the variations in nickel and cobalt
catholyte concentrations versus charge passed for two
current densities. The rate of deposition for both
100 metals increased at higher current densities. After
10 h electrolysis, approximately 82% and 68% of
80
nickel and cobalt respectively were deposited at a
Amount in deposit/%
current density of 50 A m−2 . As the concentration of
60
metal ions fell during the tests, the current efficiency
and consequently the metal removal rate also fell.
40
For instance for the run at 50 A m−2 , the current
20
efficiency was initially close to 100% and fell to 65%
at the end of the experiment. Under these conditions,
the competing electrochemical reaction of hydrogen
evolution became more dominant, thus using a higher
percentage of the applied current.
In general relatively high current densities are
beneficial, from an industrial point of view, to
achieve fast metal removal. However tests at higher
current densities of 200–500 A m−2 resulted in poor
metal recovery and low current efficiencies (10–20%)
931
N Tzanetakis, K Scott

(a) (b)

(c) (d)

Figure 6. Scanning electron micrographs of deposits obtained under different experimental conditions. (a) CD = 10 A m−2 , pH = 3, T = 25 ◦ C,
(b) CD = 100 A m−2 , pH = 3, T = 25 ◦ C, (c) CD = 50 A m−2 , pH = 3, T = 40 ◦ C, (d) CD = 50 A m−2 , pH = 1.5, T = 25 ◦ C.

Table 2. Effect of current density on the composition of the deposit 6000 1250
and the current efficiency for tests using solutions obtained from
treatment of batteries at pH 3 for all runs 5000 1050

Co concentration/ppm
Ni concentration/ppm

Current 4000
850
density
Ni Co Mn Al Fe Zn Rare earths
3000
(A m−2 ) (%) (%) (%) (%) (%) (%) (%) (%)
650
10 100 83 14.1 0 1 1.2 0.7 0 2000
50 82 76.2 12 7 4 0 0 0.8 1000 450
100 39 82 11.2 3 0.7 0.5 1.4 1.2
0 250

= current efficiency. 0 500 1000 1500 2000 2500 3000 3500 4000
Charge passed/Coulombs
because of re-dissolution of metals, due to their poor , Ni, 20 A m-2 , Co, 20 A m-2
adhesion to the substrate caused by excessive hydrogen , Ni, 50 A m-2 , Co, 50 A m-2
evolution. At such higher current densities the surface
Figure 7. Variation in nickel and cobalt concentrations in the
of the electrode was covered with metal oxides or catholyte with charge passed. Experiments were performed at two
hydroxides which appeared as black or green deposits. current densities at pH 3.
However runs at low current densities were more
successful since deposits adhered well to the electrode The crystal structure of the deposits was affected
and contained lower amounts of impurities (Table 2). by variations in current densities as were the
In this case though, a high electrode area is necessary morphologies shown by the SEM photographs
for efficient metal recovery. Hence a high surface (see Fig 6). The deposits obtained from battery
area (three dimensional) electrode is recommended to solutions showed amorphous structures with irregular
maximise deposition rate and the space time yield. morphology and thus the SEMs are not shown.
Figure 8 shows the X-ray diffraction patterns The deposit obtained at 10 A m−2 had a face-centred
of deposits obtained at three current densities. cubic (fcc) structure with sharp reflections from nickel

932 J Chem Technol Biotechnol 79:927–934 (online: 2004)


(111)
(200)
(220) (311)
Intensity (Arbitrary units)
10 Am-2
50 A m-2
100 Am-2
0 20 40 60
2-Theta (Degrees)
Figure 8. X-ray diffraction patterns of deposits obtained from
solutions obtained from battery treatment, at three current densities,
10, 50 and 100 A m−2 . All runs performed at pH 3.
and cobalt crystalline grains, with very strong (111)
growth orientation (2ϑ = 44◦ ) with significant but
weaker (200), (220) and (311) reflections at 2ϑ values
of 52◦ , 76◦ and 93◦ respectively. This crystallographic
orientation is similar to that observed from pure state
nickel crystallites.29 Moreover the sharp reflections
throughout the spectrum indicated the presence of
large-size crystallites. Single peaks were observed for
nickel and cobalt due to their indistinguishable X-ray
scattering powers. Similarly the spectrum obtained at a
current density of 50 A m−2 exhibited the same (111),
(200), (220) and (311) oriented planes although at a
lower intensity when compared with those at 10 A m−2 .
The two spectrams clearly proved the crystalline
structure of the deposit at low current density.
At higher current densities an increase in the fcc
lattice parameter and an absence of clear diffraction
peaks was observed, which indicated the presence
of inclusions in the deposit. The particle size of the
deposit obtained, especially at higher current densities,
was irregular due to the formation of dendrites.
In addition to some nickel crystallites formed during
electrodeposition, nickel oxides–hydroxides were also
embedded in the deposit. The absence of diffraction
peaks is also partly attributed to the presence of
other metal oxides in the deposit. This speculation is
supported by the amorphous nature of these deposits.
The presence of metal impurities and the adsorption
of oxides into the electrode surface inhibited, to a
great extent, cobalt and nickel reduction by lowering
the limiting current. Future work will focus on
purification of the battery solution which will enable
efficient operations at higher current densities. Iron
and aluminium removal using precipitation steps
prior to the aforementioned deposition tests and
anodic deposition of manganese as an oxide will be
investigated.
4 CONCLUSIONS
A combination of hydrometallurgical and electro-
chemical processes can potentially provide an efficient
process for recycling valuable metal materials from
J Chem Technol Biotechnol 79:927–934 (online: 2004)
Recycling of nickel–metal hydride batteries. II
spent rechargeable nickel–metal hydride batteries.
The work revealed that appropriate leaching can be
performed with 4 mol dm−3 HC1 at a temperature of
95 ◦ C and a leaching time of 3 h or less. Rare earth
elements were separated from nickel and cobalt by
solvent extraction using D2EHPA as an extractant at
a pH close to 2.5.
The feasibility of recovering nickel and cobalt
as an alloy by electrowinning from the raffinate
was demonstrated using simulated and real battery
solutions.
80 100 120 Galvanostatic tests on simulated solutions showed
that composition and surface morphology of the alloy
is largely influenced by modifying the deposition
parameters (mainly pH and current density). The
crystalline nature of the alloy increased as the cobalt
content of the deposit increased. Electrodeposition
tests using solutions obtained after hydrometallurgical
treatment of NiMH batteries showed that recovery
of nickel and cobalt was feasible. Operations at low
current densities gave a deposit with a crystalline
structure at high current efficiencies, while higher
current densities gave amorphous materials with
significant reduction in current efficiencies.
Overall the data reported can be used for the
development of a process which will allow efficient
electrochemical recovery of Ni and Co from spent
NiMH batteries.
ACKNOWLEDGEMENTS
Cumberland Electrochem (Bootle) are thanked for
providing the electrode materials for the project. The
work was performed in research facilities provided
through an EPSRC/HEFCE Joint Infrastructure Fund
award, no JIF4NESCEQ.
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1 Bulletin of British Battery Manufacturers Association, Dec
(1996).
2 Wiaux JP, in 49th ISE meeting, Sept, Kokura, Japan, abstract
K-11-18-02, p 817 (1998).
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