Journal of Chemical Technology and Biotechnology

J Chem Technol Biotechnol 79:919926 (online: 2004)

DOI: 10.1002/jctb.1081

Recycling of nickelmetal hydride batteries.

I: Dissolution and solvent extraction of metals
N Tzanetakis and K Scott
School of Chemical Engineering and Advanced Materials, University of Newcastle upon Tyne, Newcastle upon Tyne, NE1 7RU, UK

Abstract: Nickelmetal hydride batteries contain valuable metallic components and although they are not
considered a hazardous waste, recovery of these materials is necessary from an economic point of view. In
this work a hydrometallurgical method for the dissolution and separation of the metals from cylindrical
nickelmetal hydride rechargeable batteries was investigated. Hydrochloric acid was employed as the
leaching agent to dissolve the metals from the batteries. Dissolution of metals was investigated as a
function of acid concentration, leaching time and temperature. Suitable conditions for maximum metal
dissolution were 3 h leaching with 4.0 mol dm3 hydrochloric acid solutions at 95 C. Extraction of 98% of
nickel, 100% of cobalt and 99% of rare earth elements was achieved under these conditions. Separation of
the rare earths from nickel and cobalt was preliminarily investigated by single batch solvent extraction
with 25% bis(2-ethylhexyl)phosphoric acid. Efficient separation via complete extraction of the rare earths
was obtained at a pH of approximately 2.5 while leaving nickel and cobalt in the raffinate. A shrinking
particle model which can enable, under certain conditions, evaluation of the extent of metal dissolution
present in nickelmetal hydride batteries was developed. A proposed electrochemical recovery of nickel
and cobalt is also briefly discussed.
2004 Society of Chemical Industry

Keywords: nickelmetal hydride batteries; rare earth elements; recycling; leaching; liquid extraction; nickel

NOTATION
C
C0
d
D
KL
m
m0
p
Re
S
Sc
Sh
t

Concentration of species (mol m3 )

Initial concentration of species (mol m3 )
Equivalent diameter
Diffusivity (m2 s1 )
Mass transfer coefficient (m s1 )
Mass of solid (kg)
Initial mass of solid (kg)
Random number
Reynolds number
Surface area (m2 )
Schmidt number
Sherwood number
time (s)
Density (kg m3 )
Current efficiency

1 INTRODUCTION
The use of rechargeable batteries has increased
considerably over recent years due to continuous
demand for use in portable electrical devices. The
nickelmetal hydride (NiMH) battery is one of the
most promising rechargeable power sources for use

in a range of portable devices such as power tools,

mobile and cordless phones, camcorders and portable
computers.1,2 The high energy density, power density
and capacity and the long cycle life of this battery
make it also a leading choice of power source for
electric vehicles.3,4
Commercial production of NiMH started in 1993
with 100 millions cells while in 1999, 900 millions
cells, corresponding to 20 000 tonnes of batteries were
manufactured world-wide.5,6 In 2000, the one billion
mark was passed, representing 4% of the world-wide
rechargeable battery production, with a market of
720 million. By the year 2010, nickelmetal hydride
batteries are expected to comprise 29% of the total
battery market, with a world-wide battery market of
9 billion.7
Since consumption of NiMH batteries is large and
considering that the average cycle life of these batteries
is 2 years, it can be concluded that an appreciable
amount of spent batteries is generated every year.
Their safe disposal is becoming more and more a key
issue. Recycling of batteries at the end of their life is
necessary both due to the increased requirement for
environmental protection and from the fact that these
batteries have a valuable metal content. NiMH cells
contain approximately 37% (w/w) of nickel as well as

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 20 June 2003; revised version received 27 January 2004; accepted 15 April 2004)
Published online 28 July 2004

2004 Society of Chemical Industry. J Chem Technol Biotechnol 02682575/2004/$30.00

919

N Tzanetakis, K Scott

appreciable amounts of cobalt and rare earth elements

(REE).
There is an increasing motivation nowadays for
the safe management of many toxic and hazardous
metal ions arising from industrial process streams
and scrap electrical equipment.8 In the case of used
batteries they are either land-filled or treated by
pyrometallurgical processes. An alternative is to use
hydrometallurgical processes which can offer reliable,
environmental friendly, low energy routes with low
wastewater generation for the treatment of spent
batteries.
Hydrometallurgical techniques have been previously
developed for the recovery of cadmium, cobalt and
nickel, and cobalt and lithium from spent NiCd,9 and
Li-ion10 secondary batteries respectively.
Various researchers have investigated the recovery
of the valuable metallic components from NiMH
rechargeable batteries.11 18
Lyman and Palmer investigated a method in
which they dissolved the NiMH battery in sulfuric,
hydrochloric, and nitric acids. They found that
4 mol dm3 HCI was the best acid medium. The
lanthanides were recovered as phosphate precipitates
from the resulting chloride solution. Cobalt and
nickel were recovered after precipitation with oxalic
acid.11,12
Yoshida et al 13 proposed a basic recycling process
in which the valuable metals were recovered through
a combination of mechanical and hydrometallurgical
processing, including solvent extraction, precipitation
and electrowinning of nickel and cobalt.
Zhang et al 14,15 recovered the rare earths by
precipitation with oxalic acid. The cobalt and nickel
were separated by selective extraction of cobalt, while
the individual cobalt and nickel metals were recovered
as oxalates by the addition of oxalic acid.
Tenorio and Espinosa16 suggested mineral processing techniques, which involved hammer and knife
milling, magnetic and size separation for the recovery
of nickel-based alloys from spent batteries.
A chemical treatment and a smelting process have
also been tested for regenerating the hydrogen storage
alloy from these batteries.17 The regenerated alloy
had discharge and cycle properties comparable to the
original one.
Pietrelli et al 18 recovered 80% of the REE contained
in spent batteries through precipitation as insoluble
double sulfate salts.
In the present study, investigation of the hydrochloric acid dissolution of valuable metallic constituents
present in NiMH batteries is described. Separation of
the rare earths from the leaching solution by solvent
extraction is examined. Preliminary investigation of
the electrowinning of nickel and cobalt from the raffinate obtained from leaching is also reported. Figure 1
shows a simplified schematic flowsheet of the proposed
laboratory-scale recycling scheme for the recovery of
metal values from NiMH batteries.
920

NiMH spent batteries

Ni,Co,Mn,Fe,Al,Zn,REE
Mechanical Processing

Steel Case

Leaching with HCI acid

Solvent Extraction with D2EHPA
Filtration

Raffinate
Ni,Co,Mn

Electrodeposition of Ni and Co

Residue
(separator, iron grid)

Organic Phase
REE, Mn, Fe, Al, Zn

Precipitation of REE

Figure 1. Schematic diagram of the nickelmetal hydride

recycling process.

2 EXPERIMENTAL
2.1 Materials
Cylindrical AA NiMH batteries (1.2 V), manufactured
in Japan (Toshiba), with the dimensions diameter
14 mm and height 50 mm were used. The batteries
consisted of a positive nickel hydroxide electrode,
a negative metal hydride electrode employing an
AB5 rare earthnickel-type alloy and a polypropylene
separator, spirally wound together inside a stainless
steel case which acted as the negative terminal. The
electrolyte was KOH and the cell was sealed by
connecting a lid (positive terminal) to the case with an
intermediate plastic gasket. Since battery composition
and materials differ among manufacturers, the work
reported here describes what can be expected in
general, from the hydrometallurgical treatment of
NiMH batteries.
2.2 Dissolution tests
The battery rolls, which weighed an average of 23 g,
were first cut in half longitudinally. After removal
of the external case, the lid and the plastic gasket,
the internal battery components, consisting of the
spirally wound positive (7 g) and negative electrode
(9 g), the separator and the electrolyte, were leached
in HC1 acid solutions. Decanning renders the internal
components more easily attacked by the acid and
also prevents unwanted iron from entering the process
stream. Hydrochloric acid was employed as an agent
due to its relatively low cost and also due to the
suitability of extracting nickel ions from chloride
solutions by electrodeposition or separating cobalt
from nickel. Leaching tests were carried out in a
1.0 dm3 spherical flask, fitted with a condenser to avoid
evaporation when elevated temperatures were used.
Elevated temperatures were achieved with a heating
mantle and the temperature controlled with a digital
thermometer. In all dissolution tests a 1/10 solid/liquid
ratio was used. After leaching, the leachate and
insoluble materials (polypropylene separator and iron
grid) were separated by filtration. Total concentrations
of the chemical constituents of the battery roll were
J Chem Technol Biotechnol 79:919926 (online: 2004)

Recycling of nickelmetal hydride batteries. I

3 RESULTS AND DISCUSSIONS

3.1 Leaching tests
The relationship between the amounts of metals
dissolved and the different experimental parameters is
shown in Figs 25. The metal constituents, in the form
of their oxides or hydroxides as electrode materials,
react with acid to give chloride salts. The variation
in concentration of the leached metal obtained after
dissolution with 4 mol dm3 HCl solution at 22 C,
with time is given in Fig 2. The results are plotted
in terms of the natural logarithm of the total initial
amount of metal over the amount remaining at the
time of analysis. Linearity of this quantity over time
J Chem Technol Biotechnol 79:919926 (online: 2004)

Ln(C0/C0-C)

4.0
3.0
2.0
1.0
0.0
0

5
, nickel

10
15
Time/hours
, cobalt

20

25

, rare earth elements

Figure 2. Effect of dissolution time on the natural logarithm of initial

over unreacted amount of metals. Leaching conditions: 4 mol dm3
HC1 (200 cm3 ) at 25 C.

120
100
Percent leached/%

2.3 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 typically for 30 min, until
equilibrium was achieved. A solution of 25% bis-(2ethylhexyl)phosphoric acid) (D2EHPA) (Aldrich) was
chosen as an acidic extractant due to the feasibility of
selective complexation and extraction of rare earths at
low pH, but not of nickel and cobalt.19 22 Alternative
extractants such as a phosphonic acid, eg Ionquest
801, may be used and could offer higher loadings of
the REE. The extractant was dissolved in distilled
kerosene (boiling point 165190 C). All reagents
were used as received without further purification.
The pH of the aqueous and organic solution was
adjusted to the desired value, before extraction by
drop-wise addition of concentrated sodium hydroxide.
The pH adjustment was performed slowly and under
slow stirring to avoid formation of metal hydroxides.
After shaking, the two phases were allowed to
disengage completely in separating funnels and then
separated into raffinate and organic phases. All these
experiments were carried out at room temperature.
The concentrations of metals in the organic phase
were calculated from the difference between their
concentration in the aqueous phase before and after
extraction. Analysis of metal content was made by
either AA or ICP spectroscopy.

5.0

80
60
40
20
0
1

HCl/M
, nickel

, cobalt

, rare earth elements

Figure 3. Effect of acid molarity on the amount of metal dissolved.

Leaching conditions: 200 cm3 acid at 25 C, 3 h dissolution time.

4.7
4.6
4.5
Ln % leached

determined after their complete dissolution in aqua

regia. Leaching test data were compared against this
standard.
The concentrations of Ni, Co, Mn, Fe, Al and Zn
were determined by atomic absorption spectroscopy,
using a Unicam 929 AA spectrometer. The rare
earths were analysed by inductively coupled plasmaatomic emission spectroscopy using a Unicam 701 ICP
emission spectrometer. Errors in the determination of
the concentration of metals were 2%.
The parameters investigated in this study were:
acid concentration, dissolution time and temperature.
The standard conditions for leaching were 4 mol dm3
HC1 (200 cm3 ), ambient temperature and 3 h dissolution time.

4.4
4.3
4.2
4.1
4.0
0.0025

0.0027

0.0029
T-1

, nickel

0.0031

0.0033

0.0035

-1

/Kelvin
, rare earth elements

, cobalt

Figure 4. Effect of dissolution temperature on the amount of metal

extracted. Leaching conditions: 4 mol dm3 HC1 (200 cm3 ), 3 h
dissolution time.

would reveal first order kinetics. The data showed nonfirst order behaviour although, after the first hour, a
linear relationship was obtained. The divergence from
921

N Tzanetakis, K Scott
5.0

KMn,Zn = 4.6 h-1 X KCo, REE = 2.3 h-1

Ln(C0/(C0-C))

4.0
KNi = 1.5 h-1
3.0
2.0

KFe = 0.5 h-1

1.0
0.0
0.0

0.5

1.0

1.5
2.0
Time/hours

, nickel

, cobalt

, manganese

, iron

2.5

3.0

3.5

, rare earth elements

X,

zinc

Figure 5. Natural logarithms of initial of remaining amounts of metals,

versus time for dissolution experiments performed at 95 C. Leaching
conditions: 4 mol dm3 HC1 (200 cm3 ).

a linear behaviour, ie high initial slope during the first

hour, is due to rapid reaction of the metal particles
with the acid, caused by the porous nature of the
electrode materials.
It can be seen in Fig 2 that the leaching of cobalt
proceeded very rapidly, reaching completion after
10 h. The value of 4.605 in the natural logarithm
corresponds to 99% dissolution. Total dissolution of
rare earth elements was obtained after 24 h leaching.
On the other hand, relatively slow and incomplete
dissolution of nickel was observed even after 24 h.
At that time, 94% of the nickel initially present was
leached. It is apparent that under these conditions an
increase in the reaction time is necessary to increase
the amount of nickel leached.
Because cobalt removal is complete after 10 h, it
may be possible to adopt a strategy in which a twostage leaching is used. In this way more effective
separation of REE, Ni and Co may be achieved. The
first leachant would contain mainly Co and subsequent
separation of Ni and REE would be more effective.
The second leaching would recover most of the REE
and Ni and thus subsequent separation by extraction
would produce a near pure Ni and pure REE leaching
phase.
Figures 3 and 4 illustrate the effects of acid
concentration and temperature, respectively, on
the percentages of metals dissolved. At ambient
temperature the dissolution of nickel, cobalt and
rare earths did not significantly depend on acid
concentration, under the conditions examined (Fig 3).
Although there was no pronounced increase in percent
extraction of cobalt, with 4 and 6 mol dm3 HC1,
slightly higher dissolution of nickel and rare earths
were achieved. The maximum leaching percentages
achieved using 6 mol dm3 HC1 were 90 and 95%
for cobalt and rare earths respectively. As mentioned
previously, the main drawback was the low dissolution
rate of nickel which reached a maximum of 70% when
using 6 mol dm3 HC1.
922

The dissolution of metals was found to depend

significantly on leaching temperature (Fig 4). The
results are presented with an Arrhenius plot of
the natural logarithm of the percentage of metal
leached against the reciprocal of temperature. Nearly
complete dissolution occurred for nickel, cobalt and
rare earths after 3 h at 95 C. Figure 4 illustrates that
at low temperature, for instance at 40 C, the percent
of nickel leached could only reach approximately
73%, whereas leaching was almost complete at a
temperature of 95 C. The dissolution of cobalt
and the rare earths also varied with temperature,
attaining completion at 80 C. The dissolution of other
metals (Mn, Zn, Al, Fe) was far less dependent on
temperature, over the range examined.
Higher temperature generally improved the kinetics
of the dissolution reactions. Essentially complete
leaching could be achieved at 95 C for cobalt,
nickel, rare earths, zinc, and manganese after 3 h
(Fig 5). The results are plotted in terms of the
natural logarithm of the initial over the unreacted
amount of metal versus time. The maximum value
of 4.605 in the natural logarithm corresponds to
over 99% dissolution. It seems that the dissolution
of metals at such high temperatures followed first
order kinetics approximately, as seen in the linearity
between ln((C0 -C)/C) and time (Fig 5). Equilibrium
was attained faster in the case of Mn and Zn followed
by Co and REE as indicated by the higher rate
constants obtained from the slopes of the lines. A
low amount of iron dissolution of the electrode grids
was desirable for minimal contamination during the
recovery steps of nickel and cobalt. It is quite beneficial
that incomplete iron leaching took place. However due
to the need for high nickel recovery, some extraction
of Fe was unavoidable.
It can be concluded that the order of the dissolution
rate, under the above experimental conditions, was
Mn, Zn > Co > REE > Ni > Fe. Based on the above
results the best leaching conditions were 4 mol dm3
HC1 at 95 C and a leaching time of 3 h. Thereafter, a
leaching procedure of nickelmetal hydride batteries
based on the above conditions was followed. Under
these conditions 98% nickel, <99% rare earths and
100% cobalt were dissolved. At the same time,
however, the other elements were also completely
dissolved in the solution.
After filtration of the leaching solution the resulting
dark green chloride solution had a pH close to 0 and
had a composition of (in g dm3 ): 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.
This solution had to be further processed to separate
the rare earth elements from nickel and cobalt.
3.2 Modelling
A shrinking particle model was proposed to evaluate the extent of metal dissolution under certain
conditions. The focus was to give quantitative information concerning the leaching mechanism of metals
in NiMH batteries.
J Chem Technol Biotechnol 79:919926 (online: 2004)

Recycling of nickelmetal hydride batteries. I

The model considers the situation that dissolution

is controlled by a kinetic (or mass transport) effect
at the surface of the solid particles. The shrinking
model initially assumed that the dissolution rate was
proportional to the surface area of the materials
leached, ie:
dm
(1)
= KL S

dt
where KL is a mass transfer (or rate) coefficient and S
the surface area. The negative sign denotes reduction
in the size of the solids.
The next assumption was that the active materials
of the electrodes in NiMH batteries were identical
size, homogeneous, uniformly distributed spherical
particles. The mass of a sphere is given by m =
( d 3 /6) and the equivalent diameter is given by


6m
d= 3

where is the density of the dissolved particle.

The surface area of a sphere is equal to:
S = d =

6m

2/3

By substituting the value of the surface area of a sphere

into eqn (1) the following expression was derived:
dm
= KL d 2

dt

(2)

In the case of a free convection at a sphere, the

mass transfer coefficient (KL ) varies with the Reynolds
number,23 eg:
Sh =

KL d
n
= 2 + cRm
e Sc
D

Substituting this mass transfer coefficient value into

eqn (2) gives:
dm
= 2D d

dt
and

dm
= 2D
dt

6m

which gives after integration:

 1/3
6
m1p = 2(1 p)D
2/3 t + m1p
0

1/3
(4)

(8)

The mass of unreacted solid particles during the

dissolution process could then be calculated by the
following equation:


 1
 1/3
1p
6
1p
m = 2(1 p)D
2/3 t + m0

(3)

where D is the diffusivity, d the equivalent diameter

and c is a constant.
For stationary fluids Re = 0 and the above equations
gives:
2D
KL =
d

(6)

The time dependencies of the metal dissolution

rate predicted from the above model (eqn (6)) and
obtained from experimental data are given in Fig 6.
As can be seen this model prediction did not show
good agreement with the experimental data. In fact,
the experimental values were much lower than the
calculations, resulting in an overall disagreement by a
factor of 2.
Nonetheless it was considered essential that a
different approach to the shrinking particle model
should be adopted. In synthesising a closer and
more effective mathematical representation of the
dissolution rate, a strategy was evaluated of assuming
that the mass of the solid was not proportional to
the power of 1/3 as is the case in eqn (5) but to
a random power p. The value of p had then to be
guessed to give the best fit between experimental
and modelling data. Consequently, by applying this
assumption into eqn (5), the rate of dissolution of
metal was expressed as:
 1/3
 t
 m
dm
6
2D
2/3 dt
(7)
p =

m0 m
0

(9)

The best agreement was obtained when p was

equal to 0.95. The value of p was fixed at
0.06
model
experiment

0.05
0.04
Mass/kg


2

which leads to the relationship:

 1/3
6
4
2/3
2/3 t + m0
m2/3 = D
3

0.03
0.02
0.01

The above equation considers particle shrinkage

by dissolution, where the reaction interface moves
towards the centre of the sphere.
Rearranging this equation for integration gives:


m
m0

dm
=
m1/3


0

 1/3
6
2D
2/3 dt

J Chem Technol Biotechnol 79:919926 (online: 2004)

(5)

0.00
0

10

15
20
Time/hours

25

30

Figure 6. Comparison of experimental values of undissolved nickel

mass, obtained from leaching tests and theoretical data derived from
a sequence of mathematical equations.

923

N Tzanetakis, K Scott
Table 1. Effect of extraction time and aqueous:organic phase ratio on
the amount of metals extracted

0.06
model
experiment

0.05

Time (min)
15
30
180
360
30
30

0.03
0.02
0.01
0.00
0

10

15

20

25

30

Time/hours
Figure 7. Comparison of experimental values of undissolved nickel
mass, obtained from leaching experiments and theoretical data
derived from an empirical model.

0.95 and the modelling data were obtained from

eqn (9). Figure 7 plots the unreacted mass of nickel
during the dissolution tests, as a function of time,
derived from theoretical calculations and experimental
measurements. Validation of the model has been
examined only in the case of nickel dissolution,
because nickel is the predominant component of
NiMH batteries.
It is clear that the empirical model gives a reasonable
prediction of dissolution of the solid. The ratedetermining step seems to be controlled by acid
diffusion into the solid matrix. The dissolution, as
derived from experimental measurements, showed an
initially high rate during the first 3 h, probably due to
faster acid diffusion within particles with rather large
specific surface area. Additionally the high initial slope
in the case of experimental measurements might be
attributed to the ease in dissolving the nickel oxides
or hydroxides present in the positive electrode. The
decline in the slope after this point might be due to
the dissolution of nickel from the negative electrode,
which was more difficult due to the presence of metal
hydrides.
3.3 Solvent extraction
Preliminary extraction tests, using simulated leaching
solutions were performed to optimise the influence of
contact time and aqueous to organic phase ratio on
metal selectivity. The simulated solutions contained
nickel, cobalt, manganese, lanthanum, and cerium in
concentrations one-tenth of those expected after the
dissolution tests. The single-batch extraction tests are
summarised in Table 1.
Experiments investigating the effect of time on
metal extraction revealed that 30 min was sufficient
to reach equilibrium for the rare earths, with
minimal contamination from nickel and cobalt. Longer
times increased indiscriminately the extraction of
manganese, nickel, and cobalt. Tests performed at
higher organic to aqueous phase ratios, which were
aimed at increasing the amount of Mn extracted,
resulted in higher extraction of all metals and thereby
924

REE (%)

Mn (%)

Ni (%)

Co (%)

1:1
1:1
1:1
1:1
1:1.5
1:2

80
100
100
99
100
100

20
40
45
54
50
60

0
1
3
9
6
15

0
1
2
4
3
12

Tests performed using simulated solutions containing (mol dm3 ):

NiC12 (0.09), CoC12 (0.009), MnC12 (0.004), LaC13 (0.005) and CeC13
(0.004). pH = 2 for all runs.

no efficient separation could be achieved. Tests

using lower solvent concentrations showed a marked
decrease in REE loading while concentrations of
D2EHPA above 1 mol dm3 were not suitable due
to its high viscosity.
The above data indicate that D2EHPA shows higher
selectivity for REE over nickel and cobalt and also
requires only a single contact with a 1:1 aqueous to
organic phase ratio.
Solvent extraction of solutions obtained from
dissolution of batteries, using 25% D2EHPA
(0.75 mol dm3 ) as extractant, demonstrated the feasibility of recovering the rare earths in the solvent
stream, while leaving Ni, Co, and Mn in the raffinate stream. Single-batch extraction tests over a wide
range of aqueous pH (03) values were performed to
establish the influence of acidity on metal extraction.
The results indicated that, at a pH close to 2.5, the
extractant showed strong selectivity over the REE and
thus all of the rare earths and most of the iron could
be extracted into the organic phase (Fig 8).
It is apparent that the extraction of rare earths
increased linearly with increase in pH in the range
02.5, reaching completion after this point. On
the other hand, in this range, extraction of nickel
and cobalt was low. Additionally it was observed
that the distribution of metals between the organic
120
100

Metal extraction/%

Mass/kg

0.04

Aq/org

80
60
40
20
0
0.0

0.5

1.0

1.5
2.0
Equilibrium pH

, nickel

, cobalt

, Zinc

, iron

2.5

3.0

3.5

-, manganese
, rare earth elements

Figure 8. Extraction of metals from the leaching solution as a

function of equilibrium pH (aq:org ratio 1:1, extraction time 30 min).

J Chem Technol Biotechnol 79:919926 (online: 2004)

Recycling of nickelmetal hydride batteries. I

and aqueous phases was highly dependent on the

hydrogen ion concentration of the aqueous phase. A
higher pH was required, in the case of the solution
obtained from dissolution of batteries, compared with
the tests using simulated solutions, to achieve a
sufficient separation. This was probably attributed to
the different complexation between the metals in the
leachate.
A decrease in the aqueous phase pH was apparent
after all extraction tests, indicating the exchange of
protons from the phosphoric acid extractant with
extracted metal species.
Table 2 shows distribution coefficients and separating factors for the rare earth elements, nickel and
cobalt. The separation factor (SM1/M2 ) between two
metals is determined as the ratio of their distribution
coefficients (DM ). The distribution coefficient, which
controls the degree of transfer of the solute, is derived
from the metal concentration in the solvent stream
divided by its concentration in the raffinate stream.
The high separation factors, at pH 2.5, indicate the
feasibility of extracting the REE from the leaching
solution with minimal contamination from nickel and
cobalt.
Figure 8 shows that insufficient extraction of
manganese, aluminium, and zinc took place under
the whole range of acidity. It might have been
possible that the preferable extraction of rare earths
and iron, prevented take up of aluminium, zinc
and manganese into the organic phase. Moreover
incomplete extraction may be attributed to the
presence of undissociated metal compounds such as
oxides or hydroxides in the aqueous phase. Inevitably
the resulting effect is that only a very small amount
of manganese (17%) is transferred to the organic
phase. However, it was previously shown14 that by
increasing the organic-to-aqueous phase ratio and
by using multistage extraction, complete elimination
of manganese from the solution could be potentially
achieved.
3.4 Recovery of metals
The recovery of the rare earths from the organic phase,
as shown in the proposed recycling scheme (Fig 1), is
not examined in this study. Previous researchers have
shown that the rare earth elements can be recovered
by precipitation, following stripping, from the organic
phase. Zhang et al 14 found that almost quantitative
Table 2. Distribution coefficients and separating factors for solvent
extraction tests at different equilibrium phase pH values at 1:1
ratioaqueous:organic phase ratio

Equilibrium pH

DREE

DNi

DCo

S REE
Ni

S REE
Co

1.0
1.5
2.0
2.4
2.5
3.0

0.85
1.50
4.00
15.7
99.0
99.0

0.04
0.04
0.05
0.06
0.06
0.15

0.03
0.03
0.03
0.05
0.05
0.14

21.3
37.5
75.5
262
1650
660

28.4
50.0
133
314
1980
707

J Chem Technol Biotechnol 79:919926 (online: 2004)

stripping could be accomplished with 2 mol dm3

HC1 in a single contact at an organic:aqueous ratio
of 5:1. The mixed rare earths were precipitated by
the addition of concentrated ammonia, followed by an
excess of saturated oxalic acid solution. Calcination
of the oxalate resulted in a mixed rare earth oxide
product. It should be noted that stripping of iron will
be difficult with 2 mol dm3 HCl and usually higher
concentrations of acid (eg 6 mol dm3 ) are typically
required.
Preliminary tests were performed in the present
work to investigate the feasibility of recovering nickel
and cobalt from the raffinate of the solvent extraction
circuit by electro-deposition. Batch electro-deposition
tests lasting 10 h, or until a specific electrical charge
had passed, were performed. Table 3 presents the
composition of cathodic deposits obtained for tests
performed at different current densities. These had a
dendritic appearance, especially at the higher current
density, possibly due to the presence of impurities in
the bath.
The rate of deposition for both nickel and cobalt
was increased by operating at higher current densities.
After 10 h electrolysis, 82% and 68% of nickel
and cobalt were deposited at a current density of
50 A m2 with a current efficiency of 82%. Overall
these data show the feasibility for the electrochemical
recovery of Ni and Co from spent NiMH batteries. A
more comprehensive study of this aspect is reported
elsewhere.24

4 CONCLUSIONS
Dissolution and solvent extraction can, potentially,
provide an efficient process for recycling the valuable metallic components of spent rechargeable
nickelmetal hydride batteries. Dissolution parameters such as time, acid concentration, and temperature
were varied to study their effect on leaching of metals.
The dissolution tests showed that maximum extraction can be established with 4 mol dm3 HC1 at 95 C
and a dissolution time of 3 h or less. An empirical
model was developed for metal dissolution that provides results which are in reasonable agreement with
the experimental observations.
Rare earth element separation from nickel and
cobalt was evaluated with a single stage solvent
Table 3. Effect of current density on current efficiency and
composition of the deposit obtained from electrodeposition tests
using the aqueous phases solutions remaining after solvent extraction
(all tests were conducted at ambient temperatures, at pH 3 and
0.25 mol dm3 H3 BO3 added as buffer)

Current
density
(A m2 )


(%)

Ni
(%)

Co
(%)

Mn
(%)

Al
(%)

Fe
(%)

Zn
(%)

Rare
earths (%)

10
50
100

100
82
39

83.0
76.2
82.0

14.1
12.0
11.2

0.0
7.0
3.0

1.0
4.0
0.7

1.2
0.0
0.5

0.7
0.0
1.4

0.0
0.8
1.2

925

N Tzanetakis, K Scott

extraction process using D2EHPA as extractant

at an optimum pH value close to 2.5. Effective
electrochemical recovery of nickel and cobalt from
the aqueous phase of the solvent extraction circuit can
be potentially achieved.

ACKNOWLEDGEMENT
The work was performed in research facilities provided
through an EPSRC/HEFCE Joint Infrastructure Fund
award, no JIF4NESCEQ.

REFERENCES
1 Bull of British Battery Manufacturers Association, Dec (1996).
2 Ruetschi P, Meli F and Desilvestro J, Nickelmetal hydride
batteries. The preferred batteries of the future. J Power Sources
57:8591 (1995).
3 Soria ML, Chacon J, Hernandez JC, Moreno D and Ojeda A,
Nickel metal hydride batteries for high power applications.
J Power Sources 96:6875 (2001).
4 Zhan F, Jiang LJ, Wu BR, Xia ZH, Wei XY and Qin GR,
Characteristics of NiMH power batteries and its applications
to electric vehicles. J Alloys and Compounds 293295:804808
(1999).
5 Ovshinsky SR, Dhar SK, Fetcenko MA, Young K, Reichman B, Fierro C, Koch J, Martin F, Mays W, Sommers B,
Ouchi T, Zallen A and Young R, presented at 17th International Seminar & Exhibit on Primary and Secondary Batteries,
Ft Lauderdale, Florida, March 69 (2000).
6 Noreus D, Substitution of rechargeable NiCd batteries,
University of Stockholm, August(2000), available at:
http://europa.eu.int/comm/environment/waste/nicd.pdf
7 Stempel RC, in Third Annual Merrill Lynch Global Energy
Technology Conf, New York, May (2002).
8 Scott K, Electrochemical Processes for Clean Technology, The Royal
Society of Chemistry, Cambridge (1995).
9 Nogueira CA and Delmas F, New flowsheet for the recovery of
cadmium, cobalt and nickel from spent NiCd batteries by
solvent extraction. Hydrometallurgy 52:267287 (1999).
10 Zhang P, Yokoyama T, Itabashi O, Suzuki TM and Inoue K,
Hydrometallurgical process for recovery of metal values
from spent lithium-ion secondary batteries. Hydrometallurgy
47:259271 (1998).
11 Lyman JW and Palmer GR, Recycle of nickel hydride battery
scrap. J Metals 3235 (1993).

926

12 Lyman JW and Palmer GR, in Third International Symposium on

Recycling of Metals and Engineered Materials, ed by Queneau PB
and Peterson RD. The Minerals, Metals and Materials
Society, Warrendale, PA, pp 131144 (1995).
13 Yoshida T, Ono H and Shirai R, Recycling of used NiMH
rechargeable batteries, in Third International Symposium on
Recycling of Metals and Engineered Materials, ed by Queneau PB
and Peterson RD. The Minerals, Metals and Materials
Society, Warrendale, PA, pp 145152 (1995).
14 Zhang P, Yokoyama T, Itabashi O, Wakui Y, Suzuki TM and
Inoue K, Hydrometallurgical process for recovery of metal
values from spent nickelmetal hydride secondary batteries.
Hydrometallurgy 50:6175 (1998).
15 Zhang P, Yokoyama T, Itabashi O, Wakui Y, Suzuki TM and
Inoue K, Recovery of metal values from spent nickelmetal
hydride rechargeable batteries. J Power Sources 77:116122
(1999).
16 Tenorio JAS and Espinosa DCR, Recovery of Ni-based alloys
from spent NiMH batteries. J Power Sources 108:7073
(2002).
17 Wang R, Yan J, Zhou Z, Gao X, Song D and Zhou Z, Regeneration of hydrogen storage alloy in spent nickelmetal hydride
batteries. J Alloys and Compounds 336:237241 (2002).
18 Pietrelli L, Bellomo B, Fontana D and Montereali MR, Rare
earths recovery from NiMH spent batteries. Hydrometallurgy
66:135139 (2002).
19 Peppard DF, Mason GW, Driscoll WJ and Sironen RJ, Acidic
esters of orthophosphoric acid as selective extractants for
metallic cations-tracer studies. J Inorg Nucl Chem 7:276285
(1958).
20 Pierce TB and Peck PF, The extraction of the lanthanide
elements from perchloric acid by di-(2-ethylhexyl)hydrogen
phosphate. Analyst 88:217221 (1963).
21 Grimm R and Kolarik Z, Extraction of Cu(II), Co(II), Ni(II),
Zn(II) and Cd(II) by di(2-ethylhexyl) phosphoric acid. J Inorg
Nucl Chem 36:189192 (1974).
22 Sarangi K, Reddy BR and Das RP, Extraction studies of
cobalt(II) and nickel(II) from chloride solutions using NaCyanex 272. Separation of Co(II)/Ni(II) by the sodium salts
of D2EHPA, PC 88A and Cyanex 272 and their mixtures.
Hydrometallurgy 52:253265 (1999).
23 Shelman JR and Tobias CW, Mass-transfer measurements by
the limiting-current technique. Adv Chem Eng 10:211318
(1978).
24 Tzanetakis N and Scott K, Recycling of nickelmetal hydride
batteries. II: Electrochemical deposition of cobalt and nickel.
J Chem Technol Biotechnol 79:927934 (2004).

J Chem Technol Biotechnol 79:919926 (online: 2004)