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Waste Management 28 (2008) 1159–1167

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Recovery of nickel, cobalt and some salts from spent Ni-MH batteries
M.A. Rabah *, F.E. Farghaly, M.A. Abd-El Motaleb
Chemical and Electrochemical Mineral Processing Department, Central Metallurgical R&D Institute, P.O. Box 87, Helwan, 11421 Cairo, Egypt

Accepted 11 June 2007

Available online 21 August 2007

Abstract

This work provides a method to help recover nickel, cobalt metals and some of their salts having market value from spent nickel-metal
hydride batteries (SNiB). The methodology used benefits the solubility of the battery electrode materials in sulfuric or hydrochloric acids.
The results obtained showed that sulfuric acid was slightly less powerful in leaching SNiB compared to HCl acid. Despite that, sulfuric
acid was extremely applied on economic basis. The highest level of solubility attained 93.5% using 3 N sulfuric acid at 690 °C for 3 h.
The addition of hydrogen peroxide to the reacting acid solution improved the level of solubility and enhanced the process in a shorter
time. The maximum recovery of nickel and cobalt metals was 99.9% and 99.4%, respectively. Results were explained in the light of a
model assuming that solubility was a first order reaction. It involved a multi-step sequence, the first step of which was the rate determin-
ing step of the overall solubility. Nickel salts such as hydroxide, chloride, hexamminenickel chloride, hexamminenickel nitrate, oxalate
and nickel oleate were prepared. With cobalt, basic carbonate, chloride, nitrate, citrate, oleate and acetate salts were prepared from
cobalt hydroxide Cost estimates showed that the prices of the end products were nearly 30% lower compared to the prices of the same
chemicals prepared from primary resources.
Ó 2007 Elsevier Ltd. All rights reserved.

1. Introduction contains nickel and other metals of value, namely cobalt

Recycling of spent nickel-metal hydride batteries is
considered a public service responsibility. Recycling of
the batteries complies with the constraints raised by the
Law and related legislation assigned to protect the envi-
ronment from hazardous wastes. The world demand for
metals is progressively increasing, while primary resources
are being depleted. Recovery of metals of concern from
secondary resources would partly satisfy such world
demand. Conventional rechargeable batteries often fail
the needs of consumers and equipment designers in terms
of their size and weight, operating time of use, availabil-
ity and environmental acceptability. Lupi and Pilone
(2002) showed that a type of sealed nickel-metal hydride
battery is offers significant improvements over conven-
tional rechargeable batteries. This type, as they claimed,
*
Corresponding author. Tel.: +20 2 2501 0642; fax: +20 2 37603735.
E-mail addresses: Rabah05@gmail.com, rucmrdi@rusys.eg.net (M.A.
Rabah).
and lithium. Processing of that type of battery reduces
environmental threats and may profit low cost recovery
of Ni, Co, Li, and rare earth metals. Wronski (2001)
showed that the positive electrode material consists of
Ni(OH)2. The negative active material is nickel hydride,
NiH2. This metal alloy is capable of undergoing a revers-
ible hydrogen absorbing/desorbing reaction as the battery
is charged and discharged, respectively.
Lupi and Pasquali (2003) studied extraction of nickel
from lithium ion batteries containing LiCoxNi1xO2 as
one of the cathode materials. Nickel was recovered by
galvanostatic and potentiostatic electrowinning after sep-
arating nickel from cobalt by solvent extraction (SX)
methods using Cyanex 272. Recovery of nickel from
Ni-MH batteries by hydrometallurgical processes was
reported. Frohlich and Sewing (1995), Pietrellii and Bel-
lomo (1999) and Zhang et al. (1999a) developed some
hydrometallurgical processes to recover metals from
spent phone batteries. The spent batteries were processed
at low temperature to suppress the chemical reactions

0956-053X/$ - see front matter Ó 2007 Elsevier Ltd. All rights reserved.
doi:10.1016/j.wasman.2007.06.007
1160 M.A. Rabah et al. / Waste Management 28 (2008) 1159–1167
involved to form a cake. Dissolution of metals present in
the cake was examined using sulfuric acid or alkali
caustic solutions. From the resulting solution, nickel
was separated. It was shown that the recovery efficiency
and metal(s) purity were more than 94% on a weight
basis. In another way, Ni-MH batteries were processed
by mechanically separating the individual materials (plas-
tic, hydrogen and nickel) within a vacuum chamber to
prevent the escape of hydrogen. The output of this pro-
cess was a product with high nickel content (Waste
watch, Internet, 2004). Also, Zhang et al. (1999b)
reported a hydrometallurgical method for the separation
and recovery of nickel, cobalt and rare earths from spent
nickel-metal hydride batteries. The electrode material was
dissolved in 2 M sulfuric acid at 95 °C. Rare earths were
recovered from the liquor so formed by means of a sol-
vent extraction circuit. Cobalt and nickel in the raffinate
were recovered as oxalate using oxalic acid. The overall
recoveries of cobalt and nickel were over 96% and
99.8%, respectively. When considering nickel electrowin-
ning, one of the problems encountered in the metal depo-
sition is the competing hydrogen reduction reaction that
decreased the current efficiency, resulting in curling and
cracking of the obtained metal(s) (Holm and O’Keefe,
2000). However, the electrowinning process faced other
technical problems. Rydh and Karlström (2002) showed
that recovered nickel and cadmium from spent portable
nickel-cadmium batteries would save up to 75% energy.
The authors recommended use of cadmium in products
that are likely to be collected at the end of their life.
Tan and Shen (2000) recovered nickel and cobalt from
waste alloys. A flow sheet comprised of acidic leaching
precipitating copper, iron and chromium was tested.
The recovery of cobalt amounted to 91.8% and that of
nickel to 97.2%. Xu et al. (2000) studied the leaching
kinetics of nickel and cobalt in spent cadmium-nickel bat-
teries. The recovery process was controlled by surface
chemical reaction. Xie et al. (2005) recovered nickel, cop-
per and cobalt from low grade Ni-Cu sulfide tailings by
leaching with nitric-sulfuric acid solutions. It was shown
that iron removal from the leaching solution enriched
the dissolved Ni, Cu and Co. Seggiani et al. (2006) used
macro-porous resins containing iminodiacetic acid groups
for uptake of nickel ions from sulfate solution at pH 4.
The resin showed high Ni uptake capacity of 1.32 mmol
of Ni/g at 40 °C. Extraction of the adsorbed nickel was
obtained using 10 wt.% H2SO4 and the elute contained
about 13 g/L of nickel. Tenório and Espinosa (2002)
studied a process for the recovery of valuable metals
from spent Ni-MH batteries. Batteries were manually dis-
mantled to classify its components. The electrodes were
separated applying a mineral processing route during
the manual dismantling and characterized by X-ray dif-
fraction (XRD) analysis. A significant fraction of the bat-
teries, around 37 wt.%, was Ni-based alloy. The spent
batteries were treated using laboratory equipment. The
overall metal yield was in the order of 86%.
The aim of this work was to recover pure nickel and
cobalt metals and/or some of their valuable salts from
spent Ni-MH batteries. The applied experimental route
used a combined hydrometallurgical and pyrometallurgical
technique. Nickel and cobalt metals were prepared by
reducing their respective oxides with hydrogen gas. The
prepared salts were technically pure by frequent selective
separation operations using solvent extraction circuit.
The kinetic and the activation energy values of the reac-
tions involved were determined.
2. Experimental
2.1. Materials
Spent rechargeable battery samples were supplied by
The International Cleaning and Environmental Affairs
Co. About a 5 kg sample was visually examined and
flushed with compressed air. Batteries were then disman-
tled and the components were separately freed. The nickel
barrier materials in (or adhered to) the positive and nega-
tive electrodes, Ni-MH, were only used in this work to
recover Ni, cobalt metal and some of their salts.
2.2. Chemicals
The chemicals used in this work were of technically pure
grade. These were:
1. Sulfuric acid 98% with specific gravity of 1.98 g/mL.
2. Hydrochloric acid 6 N.
3. Nitric acid 10 N.
4. Ammonium hydroxide 30% ammonia.
5. Anhydrous ammonium carbonate.
6. Sodium hydroxide flakes.
7. Diacetyldioxime was used as Ni precipitant.
2.3. Equipment
1. Leaching experiments were executed using a glass reac-
tor fitted with four openings. These serve to fit a
mechanical stirrer (4-blade impeller, maintained at a
constant 150 rpm), solution of the required chemical
reagent or water inlet and a digital thermometer of a
thermostat. The fourth opening served as the outlet of
the leaching products and was connected to a vacuum
filtration facility.
2. Filtration was undertaken using sintered glass Nr. 4 fil-
tration flask. Suction was performed with the help of a
vacuum pump. Filtration took place under a vacuum
of 15 mm Hg.
3. Precipitation of nickel was carried out by reacting nickel
and cobalt sulfate solution with Diacetyldioxime,
ammonium hydroxide, carbonate, or caustic soda solu-
tions. The obtained precipitate was washed, dried and
examined. The precipitate was ignited to produce nickel
and cobalt oxide.
 M.A. Rabah et al. / Waste Management 28 (2008) 1159–1167 1161

4. Reduction of nickel and cobalt oxide was carried out in
a tube furnace using hydrogen gas at temperature up to
1350 °C.
2.4. Description of the method
2.4.1. Leaching experiments
Fig. 1 shows a conceptual flow diagram of the successive
steps carried out in this study. The spent batteries were
freed from the plastic container with the help of a disc cut-
ter rotating at 2900 rpm. The spent batteries were then split
longitudinally with the help of a thin rotating cutting disc
fitted with HSS (high speed steel alloy No. 10) teeth. The
bedplate of the machine is movable that can be adjusted
in three coordinates. The batteries were fed with their long
axes to allow the cutter to just split the outer metal casing
with a depth of 400–450 lm. The casing was then removed
and brushed. The brushed powder and the inner battery
components were collected, milled and sieved to pass
72 lm openings. Magnetic susceptible contaminants were
picked out with the help of a magnetic separator having
a high magnetic field. The components obtained were
battery electrodes together with nylon separator. These
were charged in the leaching reactor that contained

Spent mobile phone batteries

Manual separation of Ni-MH batteries

Removal of plastic casing

Plastic casing to be crushed for recycling Spent Ni- batteries

Crushing to release battery component

Steel casing Battery electrodes Nylon separator

Acid leaching Filtration Metals in filtrate

Separation of Cu, Co, and Fe

Cu separates as CuS in acid medium, Fe and Al separates at pH 4-5,
by NH4OH, Co separates as Co2O3.3 (H2O) at pH, 6-8.

Co2O3 3(H2O) ppt. Filtration Ni solution

Roasting at 500º Dimethylglyoxime

CoO Reduction Ni Dioxime ppt

Co Metal
Roasting to NiO Acid treatment

Reduction with hydrogen Refining & Crystallization

Ni Metal Pure Ni salts (SO42-, Cl-, oxalate )

Fig. 1. Conceptual flow sheet for Ni recovery from spent Ni-MH batteries.
1162 M.A. Rabah et al. / Waste Management 28 (2008) 1159–1167

thermo-stated leaching solution(s). Leaching processes
were conducted under constant stirring conditions (150
rpm) throughout the experimental program. Leaching
parameters such as acid and H2O2 concentration, tempera-
ture and time were adjusted and kept constant throughout
each experiment. At the end of each experiment, the leach-
ing products were filtered. The contents of nickel and other
metals in the leachate were determined.
2.4.2. Separation of some other valuable metals
Copper and iron, if present, were first removed by pre-
cipitation as sulfide and hydroxides in presence of ammo-
nium chloride, respectively. Cobalt was precipitated as
Co2O3Æ3 (H2O), whereas nickel in the remaining solution
was precipitated as Ni-dioxime complex. Other nickel
salts were prepared by reacting Ni-dioxime with the
respective acid followed by crystallization at a tempera-
ture <80 °C.
2.4.3. Preparation of nickel and cobalt metals
Pure nickel and cobalt metals were prepared from their
oxide (by roasting Ni-dioxime at 350 °C and cobalt
hydroxide at 500 °C). The reduction process for nickel
and cobalt was conducted using hydrogen gas in a tube fur-
nace at 1350 °C and 1500 °C, respectively.
2.5. Measurement of the physical and chemical properties
1. Analysis of the spent batteries, metal ions; Co, Fe, Cu in
solution and end products was carried out by a chemical
method and with the help of an emission spectropho-
tometer type 3460-880 ARL, Seuces. A computerized
Philips X-ray diffraction equipment model PW/1710
with Ni-filter, Cu radiation (k = 1.5405 Å) at 40 kV,
30 mA, and scanning speed 2° in 2h min1 was used to
identify the battery components and only verify nickel
sulfate quality. The diffraction charts and relative inten-
sities obtained were compared with JCPDS files.
2. Determination of weight distribution was carried out
gravimetrically.
3. Determination of the extent of metal dissolution,
recovery and reduction percentage was computed
gravimetrically.
3. Results
Figs. 2 and 3 show that negative and positive electrodes
contain cobalt oxides (CoO, Co2O3), nickel hydroxide and
nickel cobalt sulfide as depicted from the X-ray pattern.
Table 1 shows the experimentally detected components of
homogenized collected spent batteries under investigation.

N= Ni Co2S4 ATSM Card 20-782

C= CoO, Co2O3 ATSM Card 9-402, 2-770
N
N
N

C C C
N C
N C

28 32 36 40 44 48 52 56 60 64 68 72 76 80 84
2θ

Fig. 2. X-ray of the negative electrode powder from spent batteries.

N= Ni (OH)2 ATSM Card 14-117

C= CoO ATSM Card 9-402
N N
C

C C C
N
N
N N N
C N
N C C
C

18 22 26 30 34 38 42 46 50 54 58 62 66 70 74 78
2θ

Fig. 3. X-ray of the positive electrode powder from spent batteries.

 M.A. Rabah et al. / Waste Management 28 (2008) 1159–1167 1163

Table 1 of temperature. It can be seen that the leaching yields

Components of homogenized collected spent batteries
Material
Outside plastic case
Metallic case
Cap + insulating ring
Plastic wrapper
Negative electrode (Cobalt metal + Co2O3
+ rare earth, Ni metal)
Positive electrode Nickel-metal + Ni(OH)2
Nylon separator
Total
Average weight of the battery (g)
It is shown that nickel and nickel hydroxide are available
mainly in the positive electrode. This information finds
support from the results given by Pietrellii and Bellomo
(1999). Table 2 shows the weight percentage of the metals
available in the +ve and ve electrodes. It is seen that
the total nickel amounts to 18 g. On the other hand, the
value with cobalt amounts to 1.9 g. Worth noting is that
the detected rare earth metals were not considered for the
time being. Fig. 4 shows the solubility extent of nickel in
3 N sulfuric acid at different times up to 3 h as a function
amounts to about 40% at 20 °C and increases gradually
Wt. % with the corresponding increase in temperature. The leach-
29.61 ing yields amounts to about 71% and 82% at 80 °C and
11.42 95 °C, respectively. The leaching yields acquired a maxi-
3.82 mum value after 2 h (93.5% at P90 °C). However, a fur-
1.16
27.65
ther increase in time up to 3 h was found immaterial.
Measurements of the dissolution extent of cobalt under
24.53 the same conditions applied with nickel dissolution are
1.81 depicted in Fig. 5. Results show that the same pattern is
100 acquired. However, the extents of dissolution with cobalt
66.92 are comparatively lower than with nickel. For example,
81.3% of cobalt dissolved in 3 N sulfuric acid at 90 °C after
3 h of treatment, while 93.5% nickel dissolution takes
place.
The use of hydrochloric acid to dissolve the electrode
materials was tested. Results are given in Fig. 6. It is seen
that 3 N hydrochloric acid dissolves both nickel and cobalt
more readily compared to sulfuric acid under the same con-
ditions. Despite that, sulfuric acid was extremely applied
on economic basis.
Fig. 7 shows the effect of time on the leaching yields of
nickel and cobalt using 3 M sulfuric acid at 90 °C. It can be

1h 2h 3h
Table 2 85
Metal content in the spent Ni-MH battery
Dissolution yields, wt%

80
Metal (as free metal) Weight, g % (of total metals) 75
70
Ni 18.090 87.20
65
Co 1.950 9.40
60
Fe 0.109 0.50 55
Zn 0.335 1.10 50
Al 0.139 0.67 45
Rare earths 0.39a 1.12 40
Cu, Cd and Cr Traces 0.7 35
Total 21.013 99.99 20 40 60 80 100
a Dissolution temperature, ºC
Not determined.
Fig. 5. Effect of dissolution temperature for periods up to 3 h on the
extent of dissolution of cobalt (3 N sulfuric acid, S/L ratio = 1/1.5).

1h 2h 3h
100 sulfuric acid hydrochloric acid
90 100
Dissolution yields wt%.

90
Dissolution yields, wt%

80
80
70
70
60
60
50
50
40 40
30 30
20 40 60 80 100 20 40 60 80 100
Dissolution temperature, ºC Temperature, ºC
Fig. 4. Effect of dissolution temperature for periods up to 3 h on the Fig. 6. Extent of dissolution of the electrodes in 3 N hydrochloric acid as
extent of dissolution of nickel. (3 N sulfuric acid, S/L ratio = 1/1.5). compared to 3 N sulfuric acid for 1 h (S/L ratio = 1/1.5).
1164 M.A. Rabah et al. / Waste Management 28 (2008) 1159–1167

Ni, in sulfuric acid Ni, in hydrochloric acid Figs. 9 and 10 illustrate the effect of adding hydrogen
Co, in sulfuric acid Co inhydrochloric acid peroxide to H2SO4 acid on the leaching yields of both
100 nickel and cobalt at 50 °C and for 1 h. It is seen that hydro-
Dissolution yields wt%

90
gen peroxide enhanced the acid dissolution particularly
when the process is executed in a short time. For 1 h of
80 the H2SO4 treatment having more than 8% H2O2, the
70 nickel or cobalt dissolution diminished. Fig. 11 shows the
weight of nickel goes into solution, as well as the weight
60
of nickel that remains undissolved. A minimum weight of
50 nickel undissolved occurred after about 2 h. With longer
0 1 2 3 periods of H2SO4 treatment, dissolution of nickel does
Time of dissolution, h.
not take place any more. Nickel ions that went into solu-
Fig. 7. Extent of dissolution of nickel and cobalt in 3 N sulfuric and 3 N tion display a mirror image. Results with cobalt metal con-
hydrochloric acids as affected by time up to 3 h (T = 90 °C, S/L ratio = 1/ firm the same criterion. It is also worthy to note that the
1.5).
concentration of nickel and cobalt ions that went into solu-
tion was far below the saturation point. Figs. 12 and 13
seen that the leaching yields increase gradually with show the Arrhenius plot of the sulfuric dissolution process
increase in time, approaching a constant plateau after of both nickel and cobalt, respectively. An activation
2 h. The maximum dissolution extent amounts to 93.5% energy value amounting to 5036 J/mol was obtained with
with nickel and 81.3% with cobalt. It is worthy to note that nickel and 5260 J/mol with cobalt.
the maximum leaching yields attained at 90 °C are not Nickel was separated as dimethyldioxime compound,
affected by increasing the acid concentration >2 N as washed with hot water and dried. The compound was
shown in Fig. 8. decomposed by heating to 400 °C. Fig. 14 illustrates the
thermal decomposition of nickel dimethylglyoxime upon
heating to 400 °C for 1 h (a time found sufficient to achieve
Ni Co
100 1h 1.5 h 2h
Dissolution yields of cobalt wt%
Dissolution yields wt%

90
95
80
85
70
75
60
65
50
55
40
0 1 2 3 4 45
Sulfuric acid concentration, N
0 2 4 6 8 10 12 14
Fig. 8. Effect of sulfuric acid normality at 90 °C for 2 h (S/L ratio = 1/1.5) Volume of H2O2 added, %.
on the extent of dissolution nickel and cobalt.
Fig. 10. Effect of hydrogen peroxide addition to sulfuric acid (S/L
ratio = 1/1.5) on the extent of dissolution of cobalt.

1h 1.5 h 2h Ni metal Ni ion

Dissolution yields of nickel wt%

100 100 100

Dissolved nickel, wt %

80 80
undissolved, wt %

95
Metal nickel

60 60
90
40 40
85 20 20

80 0 0
0 2 4 6 8 10 12 14 0 0.5 1 1.5 2 2.5 3 3.5 4
Volume of H2O2 added,%. Time of sulfuric acid dissolution, h.
Fig. 9. Effect of hydrogen peroxide addition to sulfuric acid (S/L Fig. 11. Nickel/nickel ion weight percentage during sulfuric acid disso-
ratio = 1/1.5) on the extent of dissolution of nickel. lution (S/L ratio = 1/1.5) of the spent Ni–Ni-MH battery.
 M.A. Rabah et al. / Waste Management 28 (2008) 1159–1167 1165

4.5

Extent of reduction, wt %
Nickel oxide cobalt oxide
ln wt. loss % of nickel 4.4 100
4.3 80
4.2 60
4.1 40
4 20
3.9 0
3.8 1000 1100 1200 1300 1400 1500
3.7 Reduction temperature, ºC.
3.6 Fig. 15. Extent of reduction of NiO and Co2O3 using hydrogen gas for
27 28 29 30 31 32 33 34 35 2 h.
-4
1/K, 10
Fig. 12. Arrhenius plot of dissolution of nickel in 3 N sulfuric acid for 1 h
(S/L ratio = 1/1.5). preparation will be published elsewhere. Fig. 15 shows the
extent of reduction in the weight percentage of both nickel
and cobalt oxide as a function of temperature. It is seen
that the extent of reduction exhibited insignificant value
4.5
upon executing the reduction process at temperatures up
ln wt loss % of cobalt

4.3 to 1100 °C. It can be also seen that the extent of reduction
gradually increases with the corresponding increase of tem-
4.1 perature. Complete reduction took place at 1325 °C with
nickel and 1450 °C with cobalt.
3.9

3.7 4. Discussion
3.5 Complying with the constraints of the Law and related
27 28 29 30 31 32 33 34 35
-4 legislation designed for environmental protection against
1/K,10
hazardous wastes is a must. Recovery confidentiality may
Fig. 13. Arrhenius plot of dissolution of cobalt in 3 N sulfuric acid for 1 h provide beneficial advantages on an economic basis as it
(S/L ratio = 1/1.5). also reserves the national mineral resources. In this work,
losses and release of secondary hazardous by-products
were highly minimized. The collected battery powder (see
80 experimental) was dissolved in the sulfuric acid solution(s)
70 (S/L ratio 1/1.5) under variable conditions of acid concen-
tration, temperature and time. Results given in Figs. 4–8
Weight loss, %.

60
50
40
30
20
10
0 ing to:
100 200 300
Temperature, ºC.
Fig. 14. Thermal decomposition curve of nickel dimethylglyoxime to
nickel oxide upon heating up to 400 °C for 1 h (S/L ratio = 1/1.5).
a constant weight loss). It can be seen that the weight loss
values increase with increasing the decomposition temper-
ature. A constant weight loss of 73.9% takes place within
the temperature range of >350–375 °C. With cobalt, the
same shape of thermal decomposition curve was obtained.
Cobalt hydroxide started decomposition at >230 °C. The
maximum extent of weight loss of cobalt hydroxide was
24.5% at 500 °C. Some valuable salts of nickel and cobalt
have been prepared under strict conditions. Details of salt
show that dissolution of the nickel and cobalt-barring
materials (BM) may proceed according to a multi-step pro-
cess. The input BM might undergo oxidation–reduction
reactions ending with the formation of salts of the respec-
tive acid. The dissolution sequence would proceed accord-
400 695 C
ƒƒƒ Ni2þ þ 2e
Ni ƒƒƒ! ð1Þ
2þ þ
Ni þ H2 SO4 ! NiSO4 þ 2H ð2Þ
2Hþ þ 2e ¡H2 ð3Þ
The overall reaction involved the dissolution of nickel and
cobalt to form sulfate salts. Some other metal impurities
such as iron, copper, zinc and rare earths were detected,
as shown in Table 2. Impurities rather than rare earths
readily dissolved in the attacking acid and went into solu-
tion. Legitimately it was reasonable to remove these impu-
rities from the nickel and cobalt solution. In this work, iron
and copper were removed as shown in Fig. 1 (flow chart).
Zinc ions remained in solution, whereas rare earth metals
were sparingly soluble under the applied conditions. The
1166 M.A. Rabah et al. / Waste Management 28 (2008) 1159–1167
filtered solution thus contains nickel, cobalt and zinc (as
impurities).
Reaction (1) of the dissolution sequence may be the rate
determining step of the dissolution process. However,
increasing the dissolution temperature enhanced oxidation
of nickel and cobalt and promoted liberation of their ions
enough to accomplish the next step (2). Results given in
Figs. 4 and 5 reveal that increasing temperature >25 °C
activated reaction (1) in the forward direction. Heating at
90–95 °C attained the optimum leaching yields whereby a
state of equilibrium was established. The leaching yields
therefore were optimum at a stable value. Results given
in Fig. 8 are in a good agreement with the law of mass
action. Increasing the acid concentration enhanced reac-
tion (2) in the forward direction. Acid concentration of
2 N was found to be the most appropriate to attain com-
plete dissolution. However, the effect of time on the leach-
ing yields (Fig. 7) may demonstrate the role of diffusion of
the ionic species. Our experiments were carried out with
constant stirring (150 rpm).
Results given in Fig. 10 show that the nickel ion con-
centration increased rapidly within the early period of
reaction, followed by a slight increase. Within the first
hour of acid attack, nearly 90% of nickel-metal dissolves.
Within the following 30 min, only an additional 5% dis-
solved. After nearly 2 h, nickel ion concentration
approached a constant value. Determination of the
nickel/nickel ion equilibrium of the dissolution process
revealed that it is a chemically controlled process. Disso-
lution was a zero order reaction. Addition of hydrogen
peroxide to the reacting acid satisfied reaction 1 of the
dissolution sequence. Hydrogen peroxide decomposes to
water and nascent oxygen that enhanced the oxidation
step. The dissolution process was readily accomplished
in a shorter time. The DE value of the dissolution of
nickel and cobalt in sulfuric acid as derived from the
Arrhenius plot given in Figs. 12 and 13 amounted to
5036 and 5260 J/mol, respectively.
Thermal decomposition of nickel-glyoxime complex to
nickel oxide took place at 350 °C. Afzal et al. (1993)
claimed that decomposition of Ni dimethylglyoxime
involved the formation of nickel oxides at 618 K
(345 °C). On the other hand, cobalt hydroxide was decom-
posed to cobalt oxide at a relatively lower temperature
range. Thermal reduction of the obtained nickel oxide to
nickel-metal using hydrogen gas was carried out when
nickel was prepared at 1300–1350 °C whereas cobalt was
obtained at 1500 °C. Nickel and cobalt salts of market
value such as sulfate were prepared in this phase or work
by reaction of the respective hydroxide with the required
acid. Other salts will be published elsewhere. Solutions left
behind each final step were distilled, whereby distilled
water and acids were recycled. However, no hazardous
emissions or by-products were detected.
Preparation of nickel and cobalt metals was performed
by thermal reduction of their oxide as shown in Fig. 15.
Results revealed that reduction might proceed via partial
formation of oxides having a lower state of oxidation
before complete reduction took place. With cobalt,
Co2O3 and Co3O4 were formed within the temperature
range 1100–1300 °C, whereas with nickel it was formed at
1100–1250 °C.
5. Cost estimation of the recovery process
The spent batteries were supplied at a price of US$5 per
kg. Cost elements (chemicals, equipment, utilities, labor
salaries, etc.) were considered to estimate the recovery cost
of the products. It was found that the method was feasible
and the prices of the products are 30% lower than the same
products prepared from primary resources. Details of the
cost analysis are to be published elsewhere.
6. Conclusion
Recovery of spent N-MH batteries provides multipur-
pose targets; control the hazardous materials’ protect the
environment against pollution; conserve the mineral
resources and recover pure valuable nickel, cobalt and
chemical compounds needed in the market. The applied
method may be environmentally friendly with no hazard-
ous by-products. The cost of recovered products is compet-
itive with the market price for the same chemicals prepared
from primary resources.
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