Journal of Power Sources 362 (2017) 202e218

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Journal of Power Sources

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Review article

A review of the processes and lab-scale techniques for the treatment

of spent rechargeable NiMH batteries
Valentina Innocenzi a, *, Nicolo
 Maria Ippolito b, Ida De Michelis a, Marina Prisciandaro a,
Franco Medici b, Francesco Veglio a
a
Department of Industrial Engineering, Information and Economy, University of L'Aquila, Via Giovanni Gronchi 18, Zona industriale di Pile, 67100 L'Aquila,
Italy
b
Department of Chemical Engineering, Materials and Environment, Sapienza University of Rome, via Eudossiana 18, Rome 00184, Italy

h i g h l i g h t s

Review of the main technologies for the recycling of NiMH batteries is presented.

The industrial pyrometallurgical processes allow to mainly recover metals as Nickel.

Rare earths are lost in sludge during the pyrometallurgical treatments.

Rare earths are recovered by hydrometallurgical processes.

The hydrometallurgical processes need to be implemented for industrial applications.

a r t i c l e i n f o a b s t r a c t

Article history: The purpose of this work is to describe and review the current status of the recycling technologies of
Received 26 April 2017 spent NiMH batteries. In the first part of the work, the structure and characterization of NiMH accu-
Received in revised form mulators are introduced followed by the description of the main scientific studies and the industrial
16 June 2017
processes. Various recycling routes including physical, pyrometallurgical and hydrometallurgical ones
Accepted 11 July 2017
are discussed. The hydrometallurgical methods for the recovery of base metals and rare earths are mainly
developed on the laboratory and pilot scale. The operating industrial methods are pyrometallurgical ones
and are efficient only on the recovery of certain components of spent batteries. In particular fraction rich
Keywords:
Review
in nickel and other materials are recovered; instead the rare earths are lost in the slag and must be
Spent NiMH batteries further refined by hydrometallurgical process to recover them. Considering the actual legislation
Recycling processes regarding the disposal of spent batteries and the preservation of raw materials issues, implementations
Resource recovery on laboratory scale and plant optimization studies should be conducted in order to overcome the in-
Rare earths elements dustrial problems of the scale up for the hydrometallurgical processes.
© 2017 Elsevier B.V. All rights reserved.

1. Introduction As known, the capacity of the batteries to storage energy it is very

In the last years the consumption of Nickel-metal hydride
(NiMH) batteries has increased because they have replaced the
Nickel - Cadmium accumulators for several technological and
environmental advantages. These accumulators were commer-
cialized in Japan in 1990 and the main benefits are the high elec-
trochemical capacity, their versatility, low maintenance, safety,
good environmental compatibility and low self-discharge rates [1].
* Corresponding author.
E-mail address: valentina.innocenzi1@univaq.it (V. Innocenzi).
important as by discussed by several authors in the last period a
renaissance and evolution are represented by the redox flow bat-
teries [2e4]. According to the market data provided by the Euro-
pean Union the amount of the batteries that each year are placed on
the community is: 800,000 tons of automotive batteries, 190,000
tons of industrial batteries and 160,000 tons of portable cells (30%
of rechargeable) [5]. The major use of the NiMH batteries is in the
production of hydride cars, (Hybrid Electric Vehicles, HEV). Some
reports summarize the sales data of this type of vehicles for
example in the United Kingdom 32.715 (20.5% more than in 2012)
were sold in the 2013, 7600 in Germany 2013 [7]. In Italy, more than
14.800 cars were sold in 2014, more than 30% respect to 2013 [8].

http://dx.doi.org/10.1016/j.jpowsour.2017.07.034
0378-7753/© 2017 Elsevier B.V. All rights reserved.
 V. Innocenzi et al. / Journal of Power Sources 362 (2017) 202e218
Although the sale of HEV is still a niche compared to the traditional
machines the number will increase in the future and consequently
also the waste coming from the exhausted batteries of the hybrid
cars.
As said, NiMH batteries are similar to the NiCd accumulators
with the difference that the anode is constituted by an alloy instead
of cadmium, while the cathode is nickel hydroxide for both types of
accumulators. A NiMH battery can have two or three time the ca-
pacity of NiCd having the same size. The “metal” of anode is inter-
metallic compound; actually two are the main used classes of
intermetallic compound AB5 and AB2. The most common one is AB5
where A is a mixture of elements of rare earths as La, Ce, Nd and Pr,
instead B is nickel, cobalt, manganese and aluminum. Fewer bat-
teries have electrodes based on AB2 compound. In this case, A is
titanium and/or vanadium and B is zirconium or nickel modified
with chromium, cobalt, iron and/or manganese. Each of these
compounds reversibly produces a mixture of metal hydrides (MH).
The hydrides are ionic substances where the hydrogen has the
oxidation number equal to 1, hence it reduced getting an electron.
When the hydrogen ion is removed from the electrolyte as a
consequence of the voltage applied during charging, the hydrides
are formed that avoid the formation of gaseous hydrogen. During
the discharge of the battery the same ions are released by partici-
pating in the reverse reaction. The alkaline electrolyte of the NiMH
batteries is usually potassium hydroxide. Except the electrodes,
there is a separator of non-woven polyolefin fibers and the elec-
trolyte solution [9].
The reactions of the NiMH batteries were described by Eqs. (1)
and (2) [10,11]:
NiOOH þ H2O þ e / Ni(OH)2 þ OH, cathode reaction
MH þ OH / M þ H2O þ e, anode reaction
Where M is hydrogen absorbing alloy.
The total reaction is described by Eq. (3):
MH þ NiOOH / M þ Ni(OH)2,
The discharge reaction is described by the forward reaction.
Entering in the detail on the characterization, the NiMH batte-
ries are rich in REEs. The typical composition (%wt) is: 36e42% of
Ni, 3e4% Co and 8e10% of rare earths (La, Ce, Pr and Nd) [12].
Instead the HEV batteries have 36% steel, 23% nickel, 18% plastics,
9% electrolytes, 7% rare earths elements (REEs), 4% of cobalt and 3%
of other materials [6]. Just to mention, for example, every battery
pack of Toyota Prius contains about 2.5 kg of REEs.
The uses of rare earths in the NiMH batteries can be explained
by their capacity to store hydrogen by anode. This capacity, as said,
was covered by cadmium in the older Ni-Cd batteries. The elec-
trodes type AB5 can be LaNi5 or a multicomponents alloys as
La0,8Nd0,2Ni2,5Co2,4Si0,1, La0,8Nd0,2Ni2,5Co2,4Al0,1, or a mixture of
metals (M) as MNi3,55Co0,75Mn0,4Al0, or MNi3,5Co0,7Al0,8 [13]. LaNi5
is capable to absorb relevant amounts of H2 and forms LaNi5H6. One
meter cubic of metal hydride contains an amount of hydrogen,
88 kg, higher than the same volume of liquid hydrogen, 71 kg. The
composition of the electrodes influences the capacity to storage
hydrogen, in fact the multicomponents alloys have a lower
hydrogen storage capacity than LaNi5 but at the same time have a
much higher chemical stability in alkaline solution and lower
tendency for pulverization [14]. Several authors discussed in their
works the characterization of the NiMH batteries. Following a list of
the main results about this aspect was reported.
Bertoul et al. [15] studied various types of NiMH batteries,
prismatic and cylindrical devices. The characterization was carried
203
out through manual opening. The first type of batteries has an
external case containing the negative, positive electrodes and the
separators. The negative electrode is a plate symmetrically perfo-
rated and covered by a dark paste; instead the positive electrode is
constituted by a fine metallic film and dark paste. The second type
of batteries, cylindrical one, has three coiled layers in the form of a
bobbin. The first coat, that is the negative electrode, consists of a
plate perforated and covered with a dark paste. The second layer
contains the separator, finally the third one that is the positive
electrode, has the dark paste. The characterization experiments
showed the electrodes represented more than 50%wt of the accu-
mulators for all batteries and for the cylindrical batteries around
70%wt of them. The semi-quantitative and quantitative analysis on
the metallic parts of the batteries showed that nickel and cobalt
were present in great amounts. On average, the positive electrodes
contained (% wt) 31% of Ni, 28% Co, 2% Mn, 10% K, 0.5% Fe, 16% Zn
and traces of other metals. The negative electrodes contained rare
earth with a concentration more than 50% wt. The REEs found in
these metallic components were: cerium, lanthanum, neodymium
and praseodymium with average concentrations (% wt) of 24%, 27%,
10% and 2%, respectively. Other metals found in the negative elec-
trodes were (% wt) 18% Co, 9% Mn, 4% K, 1.5% Fe, 0.8% Zn and traces
of other elements. These concentrations were confirmed in other
papers [8,9]. The characterization of the black paste, containing
positive and negative parts of the batteries, coming from an in-
dustrial scale grinding process after a preliminary sieving
(<500 mm) showed that the most concentrated metals (% wt) were
29% Ni, 13% Mn, 8% Zn and 5% of rare earths. Other elements were
iron, potassium and cobalt with a total concentration of around
2.5% [9].
(1) The exhausted NiMH batteries coming from automotive appli-
cation and other uses are a dangerous waste, for the presence of the
(2) listed metals, and they must be properly disposed according to a
specific legislation that for European Union is the European
Directive n.66 of 2006 and its revisions. An inappropriate waste
handling can cause: ecological risk and human health problems,
following releases and dispersion of dangerous substances; eco-
(3) nomic problems, in fact no entry of spent batteries in the recycling
process involves a loss of metals such as nickel, manganese, zinc but
more important are rare earths elements (REEs). In addition, the
development of the recycling industry should lead to an increase of
employment with considerable benefits for the local economy. The
Batteries Directive set the goals that must be achieved regarding
the collection and recycling: 45% of spent batteries had to be
collected in September 2016 and the recycling processes had to
ensure a recycling of the batteries equal or greater than 50% respect
to the weight of the devices. Moreover, the legislation prohibits the
marketing of accumulators that contain hazardous substances and
improves the environmental performance of all operators involved
from the producers, distributors, and those operators involved in
the recycling treatments [16].
Regarding the collection recycling of the spent NiMH batteries
Eurostat provides a series of data related to 2013 that show Belgium,
Luxembourg, Sweden and Austria are the most virtuous European
countries with a ratio from collected spent batteries and market
batteries of more than 50%, instead other Country as Portugal,
Poland and Latvia with less than 30% [17]. The data for the collection
in Italy have shown that 31.8% of batteries and accumulators were
properly collected, 4% more than in 2012 [18]. Regarding the recy-
cling of spent automotive and industrial batteries generally has net
economic benefits. It is estimated that in the current situation
90e100% of the collected automotive and industrial batteries and
accumulators are sent to recycling plants. After collection of these
spent batteries, appropriate processes are necessary to avoid the
diffusion and loss of materials into the environmental.
204 V. Innocenzi et al. / Journal of Power Sources 362 (2017) 202e218
The recycling treatments can be classified as pyrometallurgical
and hydrometallurgical processes. The second one consists of ma-
terial dissolution using reagents (acids or bases) and recovery of
dissolved metals by selective precipitation, solvent extraction,
crystallization and other chemical operations. Pyrometallurgical
processes consist of recovering materials using furnaces that work
at high temperatures to produce metal slag for re-alloying during
the production of commercial metals.
In this paper a review of main research works, industrial treat-
ments and patents about the spent NiMH batteries recycling is
reported. It will be described the conventional pyrometallurgical
processing techniques and the more recent progresses on hydro-
metallurgical processes, mainly developed in laboratory scale.
2. Recycling processes
In this section the main research activities in the development of
the spent NiMH batteries recycling treatments were summarized.
They are divided in physical/mechanical, pyrometallurgical and
chemical processes. The complexity of the treatments and the
number of operations are function of the metals that can be
recovered. From the analysis, it was noticed that the literature is
rich of the chemical processes respect to the other types of the
treatments. The chemical processes that included acid leaching and
several steps of selective precipitations or solvent extractions have
the advantages to recover both base metals and rare earths. Instead
the materials recovered by mechanical and thermal treatments are
mainly base metals or a slag of metals that needs to be refined.
Hence, usually, these steps are used for the pretreatment of the
accumulators to obtain suitable fine materials for the chemical
processes. Following the details of these methods were presented.
2.1. Chemical processes
2.1.1. Solid-liquid extraction
The fine powder recovered after pretreatments of the spent
NiMH batteries, is leached by acid solutions in order to dissolve the
metals of interest. The scientific works can be divided in two main
groups: the processes that include the recovery of the metals (as Ni,
Co and Mn) and other that describe the recovery of rare earths and
metals, both. The leaching of NiMH powders is carried out by
inorganic acids, as sulfuric acid and hydrochloric acid.
The efficiency of sulfuric acid was studied by Zhang et al. [1],
Innocenzi et al., 2012a [9]]; Pietrelli et al. [19,20], Mantuano et al.
[21], Bertoul et al. [22], Li et al. [23], Rodrigues and Mansur [24],
Bertoul et al. [25] and Gasser and Aly [26]. Alonso [28], and
Meshram et al. [28,29]. From the analysis of the cited literature the
chemical reactions involved during the leaching with sulfuric acid
can be described by Eqs. (4)e(6)
M2þ þ H2SO4 ¼ MSO4 þ 2Hþ
Where: M ¼ Ni, Co, Cd, Zn, Mn
2 Al3þ þ 3H2SO4 ¼ Al2(SO4)3 þ 6Hþ
þ
2 REE þ 3H2SO4 ¼ REE2(SO4)3 þ 6H
The authors studied the leaching yields of rare earths and base
metals varying several factors. In particular, the operative condi-
tions varied in the following range: 1e4 M of sulfuric acid,
20e95  C, 1e4 h and solid/liquid ratio of 0.5/10e1.5/10 (in mg/L).
The dissolution of the base metals could reach high values, close to
100% with one stage instead, in some studies it was described that
two stages of dissolution were necessary to completely leach the
rare earths [9,24,26,28,29]. Mantuano et al. [21], described the re-
sults about a series of leaching tests according to a full factorial
plan. The factors investigated were: H2SO4 concentration (2, 5 and
8%vv), S/L ratio (1/10, 1/30 and 1/50 g/mL) and H2O2 concentration
(0, 2 and 4%, v/v). The experiments were conducted at 50  C for 1 h.
H2SO4 and solid/liquid ratio were significant with positive effect for
cobalt, manganese and nickel. H2O2 was not significant. Rodrigues
and Mansur [24] studied the dissolution varying several operating
conditions. The investigated factors were: H2SO4 concentration (2,
4, 6, 8 and 10% (v/v)), H2O2 concentration (0, 1, 3, 5 and 7% (v/v)),
temperature (30, 40, 50, 60 and 70  C) and solid/liquid ratio (1/10,
1/20, 1/30, 1/40 and 1/50 g mL1). The results showed that a good
extraction yields, 95% for Co, 82% for Ni and 84% for Cd, were ob-
tained using 6%v/v of sulfuric acid in presence of 3% v/v of hydrogen
peroxide, solid/liquid ratio of 1/30 for 1 h. Temperature and solid/
liquid ratio seemed to have no influence on dissolution in the
investigated conditions. Sulfuric acid concentration had a positive
effect for nickel dissolution and leaching yield of 97% was obtained
using 8%v/v of H2SO4. For the other metals the leaching was not
influenced by the acid concentration. The presence of H2O2 influ-
enced mainly the dissolution of cadmium. The leaching operations
were also studied in our previous research activities [9]. The ex-
periments were conducted according to a 23 full factorial design.
The investigated factors were sulfuric acid concentration (2e4 M),
temperature (40e80  C) and citric acid concentration (0e30 g/L).
Citric acid was used as reducing agent to increase the metals ex-
tractions. In each tests pulp density of powder was 15%. The average
extraction yields were about 88% for zinc, 33% for cerium and
lanthanum, 93% for manganese, 90% for nickel and about 69% for
aluminum. The statistical analysis showed that the dissolution of
the metals of interest was not significantly influenced, except for
aluminum, by the factors investigated. Temperature had a positive
effect for Mn extractions in presence or not of reducing agent.
An alternative of the leaching system was, recently proposed by
Alonso et al. [27] that reported their studies in which the dissolu-
tion of electrodes from spent NiMH batteries was performed using
sulfuric acid in The leaching of spent NiMH batteries was also
carried out by hydrochloric acid and nitric acid as reported some
authors. The reactions involved in the hydrochloric acid dissolution
are:
M2þ þ 2HCl ¼ MCl2 þ 2Hþ (7)
Where: M ¼ Ni, Co, Cd, Zn, Mn
Al3þ þ 3HCl ¼ AlCl3 þ 3Hþ (8)
REE þ 3HCl ¼ RECl3 þ 3Hþ (9)
The reactions involved in the nitric acid dissolution are:
(4)
M 2þ
þ 2HNO3 ¼ M(NO3)2 þ 2Hþ (10)
Where: M ¼ Ni, Co, Cd, Zn, Mn
(5)
Al3þ þ 3HNO3 ¼ Al(NO3)3 þ 3Hþ (11)
(6)
RE þ 3HNO3 ¼ RE(NO3)3 þ 3Hþ (12)
The efficiency of hydrochloric acid instead discussed by Zhang
et al. [30], Tzanetakis and Scott [31]; Fernardes et al. [32] and Yand
et al. [33].
Zhang et al. [30] studied the effect of four variables on leaching
yields. The investigated factors were HCl concentration, tempera-
ture, time and solid/liquid ratio. The acid concentration had a
 V. Innocenzi et al. / Journal of Power Sources 362 (2017) 202e218 205

positive effect for concentration <2 M. The dissolution of Fe was
influenced by temperature, for other metals temperature had less
influence. Tzanetakis and Scott [25] studied the effect of HCl con-
centration and temperature on metal dissolutions. The results of
the experiments showed that HCl concentration had a positive ef-
fect on extractions; yields of 90% and 95% of dissolution were
obtaining with 6 M of HCl for Co and REEs, respectively. Temper-
ature had a positive effect on dissolution. The leaching 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.
Yang et al. [33] studied the leaching step by hydrochloric acid
varying the acid concentration, time and temperature. The results
indicated that the rare earths dissolution improved increasing
these factors. 95.16% of REE leaching was reached under the
following conditions: 20% HCl, 70  C, 10% pulp density
70  C, 74 mm particle size, and 100 min leaching time.
The efficiency of the three acids was studied by Rabah et al. [34],
Lyman and Palmer [35]. The results of the experiments conducted
by sulfuric acid (3 N) at three hours showed that the temperature
had a positive effect: the nickel extraction yields were 40%, 71% an
82% at 20  C, 80 and 95  C, respectively. The maximum leaching
yields was achieved after 2 h (93.5% at 90  C). The same trend was
reported also for cobalt though the values were lower than Ni
extraction. The results obtained during the leaching with HCl
showed that this reagent was a good substance for the dissolution.
It was more efficient respect to sulfuric acid; anyway, this last acid
was applied on economic basis. Hydrogen peroxide seemed to
improve the dissolution of the metals, mainly when the process is
executed in a short time.
Tables 1 and 2 reports the effect of the operative conditions on
dissolution yields of the metals and some of the best operational
conditions for the leaching of NiMH by different acidic media,
respectively.
2.1.2. Recovery of REEs and metals from leaching solutions
The main methods used to recover metals from leach liquors
are: selective precipitation, solvent extractions, electrochemical
processes [36] and adsorption [26]. The recycling processes often
are a combination of the listed operations as described for example
by Tanong et al. [37].
Chemical precipitation for recycling of spent NiMH batteries is
to use precipitation agents to selectively precipitate rare earths
from leach liquors. The selective recovery of REEs was performed
after leaching by hydrochloric acid adding phosphoric acid [13,35].
Other authors reported the rare earths precipitation after dissolu-
tion with sulfuric adding sodium sulfate [38], or sodium hydroxide
in order to increase the pH until a value less than 2.5e3 [9,19,22].
Yang et al. [33] described the recovery of rare earths as oxalates,
after leaching with HCl. This solid was washed with ammonia and
dilute HCl to remove impurities and finally calcinated at 810  C to
obtain the oxides with high grade of purity (99%).
After REEs recovery, other metals (as Ni, Mn, Zn and Co) could be
recovered by additional precipitation using several agents as NaOH
[22], NH4OH or ammonia solution [27].
The results described in Bertoul et al. [22] research showed that
100% of iron and 70% of zinc were precipitated increasing the pH
until a value of 7, a coprecipitation of 10% of Ni and 9% of Co was
achieved.
Solvent extraction is a more complex operation in which the
leach liquors are put in contact with an organic phase in order to
transfer, selectively, the metallic ions from solutions to organic
phase. After solvent extraction the metals are recovered by strip-
ping with acid solutions and hence recovered by precipitation or
electrolysis. Di e (2-ethylhexyl) phosphoric acid (D2EHPA),
bis(2,4,4-tri-methylpenthyl) phosphinic acid (Cyanex 272), Aliquat
336, TBP, CYanex 923 were usually used to separate the metals after
dissolution [1,9,11,23,24,26,32,39e43]. Good rare earths extraction
yields were obtained using D2EHPA [1,30,31]. Other works were
only concentrated on the extractions of the base metals from leach
solutions: D2EHPA and Cyanex 272 were the extractants more
studied [21,24,39]. For example Mantuano et al. [21] in their work
studied the influence of pH on the extraction of metals using Cya-
nex 272 from sulfuric acid media. The results indicated that the
sequence of the extraction was:
Zn2þ > Al3þ > (Cu2þ z Mn2þ z Co2þ z Cd2þ) > Ni2þ > Liþ. The pH1/
2 values were 2.5e3.0 for zinc and aluminum, 4.0e4.5 for copper,
manganese, cobalt and cadmium, 6.3 for nickel and 8.0 for lithium.
For NiMH batteries, zinc and aluminum were co-extracted the same
occurred with cobalt and manganese, while nickel remained in the
aqueous solution. Rodrigues and Mansur [24] found that D2EHPA
and Cyanex 272 were adequate to separate cadmium, cobalt and
nickel from sulfuric media. In terms of selectivity factors, the
removal of cadmium over cobalt is maximized using 0.5 M of

Table 1
Summary of the effects of operative conditions for leaching of spent NiMH batteries.

References Factors Effect of factors

[21] H2SO4 (2,5 and 8%v/v) Acid concentration and solid/liquid ratio had significant positive effect on dissolution of Co, Mn and Ni. Hydrogen peroxide
H2O2 (0, 2 and 4%v/v) had not significant effect on leaching yields.
S/L ratio (1/10, 1/30 and 1/50 g/ Other constant conditions: 50  C and 1 h.
mL)
[24] H2SO4 (2,4,6,8 and 10%v/v) Temperature and solid/liquid ratio had not significant effect.
H2O2 (0,1,3,5 and 7% v/v) Acid concentration had significant positive effect for Ni.
Temperature (30,40,50,60 and Hydrogen peroxide had significant positive effect on Cd leaching yields.
70  C)
S/L ratio (1/10, 1/20, 1/30, 1/40
and 1/50 g/mL)
[8] H2SO4 (2e4 M) Temperature had significant effect on Mn dissolution
C6H8O7 (0e30 g/L) Acids concentration, temperature had not significant effect for REEs, Zn and Ni expect for Al
Temperature (40e80  C) Other constant condition: S/L ratio of 1.5/10 g/mL
[30] HCl (0.5e6 M) Acid concentration had a positive significant effect for metals dissolution
Temperature (40e95  C) Temperature had significant positive for Al dissolution
Time (15 min-3 h) Time had a positive effect mainly for Fe, Zn and Ni
Other constant condition: S/L ratio of 0.6/10 g/mL
[31] HCl (2e6 M) The investigated factors had a positive effect for metals dissolution (Co and REEs)
Temperature (25e100  C) Other constant condition: S/L ratio of 1/10 g/mL
Time (0e24 h)
206 V. Innocenzi et al. / Journal of Power Sources 362 (2017) 202e218

Table 2
Summary of some of the best experimental conditions for the leaching of spent NiMH batteries.

References Leaching agent Temperature Time S/L Results

[ C] [h] [g/mL]

[21] 3 M HCl 95 2 1/10 100% Ni, Co, Fe, Mn Zn and REEs

[5] 2 M H2SO4 95 4 0.5/10 96% REEs,
97%Ni
100% Co
[19] [20]; 2 M H2SO4 20 2 1/10 75% Ni, 98% Mn, 94% Co, 80% REEs, 48% Fe (anode material)
97% Ni, Mn, Co;
<1% for Fe (cathode material)
[31] 4 M HCl 95 3 1/10 98% Ni
<99% REEs
100% Co
[24] 8% v/v H2SO4 30 1 1/10 65% Ni,
(Two leaching stages) 96% Co and Cd
87% REEs
[25] 2 M H2SO4 90 4 0.5/10 83% Ce
84% La
86% Nd
80% Pr
83% ni,
92% Co,
96% Zn,
53% Fe
91% Mn
[8] First leaching 80 3 1.5/10 >94% Ni and Zn
2 M H2SO4 25 1 1.5/10 65% Al
Second leaching 100% Mn
1 M H2SO4 35% REEs
100% REEs
100% Co
100% Zn
100% Mn
99% Ni
[26] 2 M H2SO4 25 2 1/10 98% Co (100%with two leaching stages)
85% Ni (100%with two leaching stages)
100% RE (with two leaching stages)
[28] First leaching 75 1 1/10 90% Ni,Zn, REEs
H2O 95 1
Second leaching
NaHSO3/HCl
[29] 2 M H2SO4 75 2 1/10 98.1% Nd
98.4% Sm
95.5% Pr
89.4% Ce
>90% Ni, Co, Zn, Mn
[27] 1 M H2SO4/ozone 25 1 1/12 >90%La, Ce, Nd, Co and Mn
80% Ni

D2EHPA in Exxsol and pH 3.0, the cadmium/cobalt separation extraction was mainly used to recover base metals from leach li-
factors (bCd/Co) was equal to 350, instead the bCo/Ni higher than 1000 quors after precipitation of rare earths. The process has the
obtained using 0.6e0.7 M of Cyanex 272 at pH 5.7. No modifier advantage to selectively separate base metals and recover products
agent was necessary in the organic phase. Counter-current stages with high grade. At the same time it has the disadvantage to be
operations at given controlled pH and room temperature were expensive in relation to the cost of organic solvents and it can
suggested for scale operations. hardly be technologically profitable at industrial level. Table 3 re-
Other solvent extractions systems using PC88A and Cyanex 923 ports some of the best operational conditions for the solvent
were proposed by other authors [32,42]. The details of these studies extraction process.
were described in the next section.
Larsonn and Binnemans [44] studied the liquid-liquid extraction
2.2. Examples of typical combined recycling processes
of metals from chloride and nitrate leaching solutions using Cyanex
923 dissolved in the ionic liquid tricaprylylmethylammonium ni-
2.2.1. Physical, mechanical and thermal processes
trate, [A336][NO3], and a synthetic chloride-based aqueous leach
Tenorio and Espinosa [45] studied the recovery of valuable
solution. The treatment included a complete extraction of transi-
metals from spent NiMH accumulators using mineral processing
tion metals and REEs, the raffinate was rich in nickel instead the
techniques. The batteries were manually dismantled; after the
loaded organic phase was sent to three stripping steps utilizing first
electrodes were separated and carefully characterized. The analysis
nitrate, stripping Co and Mn, the second stripping performing with
showed that 37% of the batteries were constituted by Ni-based
a chloride complexation, stripping the rare earths; followed by last
alloy. The exhausted accumulators were used to carry out a series
stripping of iron and zinc. Cobalt was separated from manganese by
of experiments to develop a simple process to recover valuable
extraction using [A336][SCN].
materials using mechanical techniques. The flow sheet included
From the literature analysis, it was observed that liquid e liquid
hammer milling, magnetic separation to separate the plastic
 V. Innocenzi et al. / Journal of Power Sources 362 (2017) 202e218 207

Table 3
Summary of some of the experimental conditions for the solvent extractions of metals from leach liquors coming from dissolution of spent NiMH batteries.

References Media Solvent extraction systems Extraction yields

[30] HCl solution 25%v/v D2EHPA in kerosene 98% RE

O/A ¼ 1/3 100% Al, Fe
2 stages 85% Zn
pH 2
[1] H2SO4 solution 25%v/v D2EHPA in kerosene 100% RE, Fe, Al, Zn
O/A ¼ 3/2
2 stages
pH 2.6
[1] H2SO4 solution 20%v/v Cyanex 272 in kerosene 98% Co
O/A ¼ 1.2/1
2 stages
pH 4.75e4.80
[22] HCl solution O/A ¼ 1/3 99% RE
1 stages 54% Mn
pH 2 9% Ni
4% Co
[23] H2SO4 solution 20% Cyanex 272 in kerosene >99.9% Co
O/A ¼ 1/1
2 stages
pH 4.5
[40] H2SO4 solution 0.36 M Aliquat 336 in kerosene 87.5% Co
O/A ¼ 1/1 3.5% Ni
89% Fe
7.3% RE
[39] H2SO4 solution 25%v/v D2EHPA in n-dodecano 100% Zn
O/A ¼ 1/1 95% Mn
2 stages 20% Ni
pH 2.5
[41] H2SO4 solution D2EHPA in kerosene 50% Mn
D2EHPA/Mn ¼ 2/1 <10% Ni, Co
1 stages
pH 4

materials from metals, knife milling, magnetic separation and size
separation. The outputs were the plastic case and the Ni-Alloy that
were recycled. Moreover the paste of electrodes was recovered and
could be sent to a hydrometallurgical section for recovery of valu-
able materials. The mass balance of the process showed that from 1
ton of spent NiMH batteries around 0.33 ton of Ni-alloys was
recovered and 0.52 pastes and fabric. The fraction of plastic case
was 0.15 ton. A preliminary economic analysis was performed and
it showed the feasibility of the process.
Muller and Friedrich [46] described a process to recover metals
from exhausted NiMH batteries. At the first the batteries were
mechanical processed to separate iron and plastic from electrodes
that after were grinded and melt in a dc electric arc furnace to
obtain rare earth oxides slag and a nickel e cobalt alloy. The
treatment was tested in the laboratory and pilot scale performing a
series of tests. The aim of the experiments was to find a suitable
slag system which ensured best separation of REEs oxides and NiCo
alloy. Different oxidic and halogenic slag systems were studied. The
results showed that the slag systems CaOeCaF2 and CaOeSiO2 were
suitable for subsequent pilot plant experiments. The CaOeCaF2
system had shown a better melting behavior than the other system.
The outputs of the process were a slag containing the rare earths
that could be sent to chemistry industry and a flow rich in nickel
and cobalt that needed to be refined in order to remove impurities
such as Fe, Mn, Al or C, finally this flow was sent to electrolysis step
in which Ni and Co were selectively recovered. Huang et al. [47]
focused their work in the mechanical treatments of Ni-Cd and
spent NiMH batteries. The accumulators were mechanically treated
by crushing, size classification, gravity separation, and magnetic
separation. The results showed the efficiency of the crushing step to
separate the metallic parts from pastes and separators. The particle
size was between 0.5 and 2 mm. Gravity separation was important
to improve the concentration of the metals until 90%. The particles
between 0.5 and 2 mm were suitable for magnetic separation
during industrial application, with the recycling efficiency
exceeding 95% using a rotation speed of 30e60 rpm.
Another mechanical method to treat spent NiMH batteries was
proposed by Granata et al. [41] (Fig. 1). The process included two
steps of rotors crushing and sieving at 1 mm. The fraction material
greater than 1 mm was treated at high temperature (300  C) for 2 h.
Finally, a separation with ECS splitter was performed. The experi-
mental results showed that it was possible to recover valuable
fractions (ferrous metals, non-ferrous metals and non-metals). The
outputs were distributed as follows: 49% fine fraction, 33% ferrous
metals, 1% non metals and 6% of non ferrous metals. The electrode
material should be further refined by hydrometallurgical processes.
The advantage of the developed methods was that it could be
adopted for other spent batteries, as Li-ion and primary lithium
batteries, reducing the explosive power of these last.
2.2.2. Combination of acid leaching and chemical precipitation
Pietrelli et al. [19] developed a simple process to recover rare
earths. The treatment combined an acid leaching with sulfuric acid
and selective precipitation of rare earths double sulfate adding
sodium hydroxide until pH 2.5e3. The experimental conditions for
the dissolution were 2 M of sulfuric acid, solid/liquid ratio of 1/10
for 2 h under agitation. The leaching yields for anode material were
77%, 98%, 1%, ~100% for Ni, Co, Fe and Mn; 93% for La and Ce, 92%
and 96% for Pr and Nd. Instead the leaching yields for cathode were
100% for Ni, Co, Mn, Zn, 1% for Fe and around 2% for REEs. In the
leach liquors sodium hydroxide was added to precipitate rare earth
sulfates. The total recovery of rare earths was 82e88%.
Rahab et al. [34] proposed a hydrometallurgical process to
recover metals, mainly nickel and cobalt from spent NiMH batte-
ries. The treatment included manual separation and removal of
plastic from accumulators, crushing of the batteries to release the
208 V. Innocenzi et al. / Journal of Power Sources 362 (2017) 202e218
components and recovery of electrodes from nylon and steel casing.
After dissolution with sulfuric acid the metals were recovered in
several steps: Cu was recovered as copper sulfides in acid medium,
iron and aluminum were precipitated at pH 4e5 by NH4OH, Co was
precipitated as Co2O3 3 H2O at pH 6e8, roasted at 500  C to obtain
CoO and after reduced to Co metal in a furnace using hydrogen gas
at temperature up to 1350  C. Nickel in the leach liquors was
precipitated as nickel dioxime using dymetylglyoxime. This solid
was calcined and after it was sent to the reduction step to obtain Ni
metal. An alternative to this process was to treat the precipitate
with acid and after recover nickel as solid in several forms, for
example as sulfate or oxalate. Preliminary cost estimation showed
that the prices of the end products were nearly 30% lower
compared to the prices of the same chemicals prepared from pri-
mary resources.
More structure was the process described by Kanamori et al.
[48]. The aim was to recover valuable components of the batteries
using chemical processes and to test the efficiency of the recovered
materials for CH4 dry reforming catalysts. The proposed treatment
included a leaching with 2 M of HCl for 24 h. After the dissolution
NaOH was added in the solution to reach pH 12 and precipitate the
metals at room temperature. The solid was dissolved using a so-
lution of NH3 (7.5 M) for 12 h of stirring obtaining a Ni e ammo-
nium complex. The suspension was filtered and the solid and liquid
were sent to two different circuits for the recovery of the valuable
Fig. 1. Mechanical process for the recycling of spent NiMH batteries, Granata et al. [41].
compounds. The liquid was heated until 60  C to cause decompo-
sition of this complex and precipitation of the Ni component as
Ni(OH)2. The solid was recovered and calcined at 1000  C for 1 h to
obtain NiO. The residual solid coming from ammonia solution
leaching was calcined at 1000  C for 1 h and after dissolved with
HCl (2 M) for 24 h. After leaching the suspension was filtered, solid
and liquid were recovered. Solid was cerium oxide instead the so-
lution contained lanthanum that was recovered after precipitation
by NaOH until pH 12. The suspension was filtered and the cake was
calcined to obtain LaCoO3. The total recovery of nickel was around
70% with a purity of 97 mol%. Regarding the purity LaCoO3 con-
tained (in moles) 56.3% of lanthanum, 16.6% cobalt, 14.6% manga-
nese and 12.4% of nickel; instead CeO2 contained (in moles) 62.6%
cerium, 30.7% manganese, 6.1% of neodymium and 0.7% cobalt.
Finally the experimental tests carried out to test the efficiency of
the recovered NiO showed that it was an excellent catalyst for the
CH4 dry reforming process with a catalytic activity greater than to
the regent NiO. The recycling process is schematized in Fig. 2.
2.2.3. Combination of acid leaching, solvent extraction and
chemical precipitation
Zhang et al. [30] proposed a hydrometallurgical process
included the removal of the cases followed by leaching of the
electrodes using hydrochloric acid to extract almost completely
REEs, Co and Ni. Complete dissolution for all metals (Ni, Co, Fe, Mn,
Zn and REEs) was obtained using 3 M of HCl, 95  C, 2 h and S/L equal
to 1/10 g/mL. Then the suspension was filtered and sent to a solvent
extraction phase by 25%v/v of D2EHPA in kerosene. The extraction
was conducted in two stages in counter current with organic/
aqueous phase of 3/1 at pH of 2. The organic phase that contained
rare earths, zinc, manganese and traces of cobalt was sent to a
scrubbing section to remove Co with 0.3 M of HCl and organic/
aqueous ratio of 22/1. Stripping of REEs with 2.0 M of hydrochloric
acid and organic/aqueous phase of 5/1 was performed, and then
rare earths were recovered with oxalic acid as oxalates that were
roasted to obtain oxide with purity of 99%. The total recovery of
REEs was 98%. The raffinate coming from the first extraction was
sent to another step of extraction with 25%v/v TOA in kerosene,
three stages in counter current, O/A phase ratio of 2/1. Nickel
remained in the aqueous phase and after recovered by precipitation
with ammonium oxalate. The purity and the final recovery of nickel
were 99.9% and 96%, respectively. Organic phase rich in cobalt was
sent to stripping phase with 0.01 M of HCl to strip the metal in a
single stage at an organic/aqueous phase ratio of 4/1. Finally, cobalt
was precipitated as oxalates using ammonium oxalate. The purity
and the final recovery of cobalt were 99.9% and 98.6%, respectively.
The process described by the same authors [1] included several
steps, first all the removal of the cases after a series of leaching,
liquid e liquid extraction and precipitation steps to recover rare
earth oxides, CoC2O4 and NiC2O4. The first leaching of the elec-
trodes was performed using 2 M of sulfuric acid, 95  C and S/L ratio
of 0.5/10 g/mL for 4 h. Then the suspension was filtered obtaining a
liquid with 10.6 g/L of Ni, 0.85 g/L of Co, 1.70 g/L of Fe, 0.36 g/L of Zn,
0.21 g/L of Al, 0.54 g/L of Mn and rare earths with a total concen-
tration of 3.29 g/L. The dissolution yields were 96%, 97% and 100%
for RE, Ni and Co, respectively. The operations for the recovery of
rare earth oxides were: solvent extraction 25%v/v D2EHPA in
kerosene at pH 2.6, scrubbing with 0.15 M of sulfuric acid, stripping
with 1 M of sulfuric acid and precipitation using oxalic acid. The
rare earths oxalates were roasted to obtain the oxides with a purity
grade of 99.8% and a recovery of 93.6%. The residual organic phase
was sent to another liquid extraction step to separate nickel and
cobalt using 20%v/v Cyanex 272 in kerosene. The organic phase rich
in cobalt was sent to scrubbing and stripping section where sulfuric
acid was fed (0.5 M). Cobalt as oxalate was recovered adding oxalic
 V. Innocenzi et al. / Journal of Power Sources 362 (2017) 202e218
acid with a purity of 99.6%. The aqueous phase was sent to another
step of precipitation with the same precipitation agent to recover
NiC2O4 with a purity of 99.8%. The overall recoveries were over 96%
for cobalt and nickel, both. The process is described in Fig. 3.
The process described by Nayl [40] included a leaching of the
electrodes using sulfuric acid under the following conditions 2 M,
80  C, solid/liquid ratio of 1/6 for three hours. After filtration and
washing the solutions were sent to solvent extraction step. The
liquid extraction was performed using R4NeSCN in kerosene at
25  C with organic/aqueous ratio of 1/1 for 20 min. The extraction
yields were 87.5% cobalt, 3.5% nickel, 89% iron, and 7.3% lanthanides
(Ln) together with less than 22% of other metal impurities. The
raffinate that contained mainly nickel and lanthanides was sent to
another step of extraction with R4NeSCN in kerosene at 25  C with
organic/aqueous ratio of 1/1 to separate lanthanides from nickel
that remained in the organic phase. The lanthanides were recov-
ered by precipitation adding oxalic acid, the rare earths oxalates
were calcined to obtain oxides with purity greater than 99.5%. The
organic phase was sent to scrubbing section with 0.1 M HCl and
Fig. 2. Recycling of negative electrodes from spent NiMH batteries, Kanamori et al. [48].
209
0.3 M HNO3 and after to stripping section using 0.2 M of sulfuric
acid, organic/aqueous phase of 4/1. Nickel was recovered by pre-
cipitation as oxalates and after calcined for 3 h at 400  C to obtain
nickel oxide pure at 99.6%. The organic phase coming from the first
solvent extraction, rich in cobalt, was sent to scrubbing section with
0.4 M of HNO3 and 0.1 M of HCl, and after it was sent to stripping
step with water at 50  C with an aqueous/organic phase ratio of 1.
Cobalt was recovered as oxalates and roasted at 500  C for three
hours to obtain Co oxide with purity greater than 99.5%. The mass
balance of the process showed that from 8.7 g of electrodes con-
taining 5.56 g of Ni, 0.43 g of Co and 1.47 g of Ln, it was recovered
5.2 g of Ni, 0.34 g of Co and 1.39 g of Ln. Hence the final recoveries
were 93% for Ni, 80% for Co and 95% for Ln. The process is described
in Fig. 4.
Li et al. [20] proposed a hydrometallurgical process (Fig. 5) that
included after separation of electrodes from the other parts of the
batteries (cases and electrolyte) a series of chemical operations as
leaching, solvent extractions and precipitations. The electrodes
were leached under the following conditions: 3 M of sulfuric acid,
210 V. Innocenzi et al. / Journal of Power Sources 362 (2017) 202e218
for 4 h at different temperatures (30e95  C) with a pulp density of
13%. The results showed that the dissolution yields of the rare
earths decreased with rising temperature. For the other metals (Ni,
Co, Fe, Mn, Zn) the yields were comprised between 85 and 99% at
30  C and 95  C, respectively. For rare earths the leaching yields
were comprised between 55 and 5%, at 30  C and 95  C, respec-
tively. The leach liquors obtained at 95  C and under the cited
conditions contained 60.9 g/L of Ni, 0.80 g/L of REEs, 5.07 g/L of Co,
1.69 g/L of Mn, 2.19 g/L of Zn and 0.34 g/L of Fe. REEs were
precipitated as sulfates with a recovery yield of 94.8%. REEs were
transformed in hydroxide dissolved with 1 M of HCl and after
recovered as rare earths chlorides. Then iron, zinc, manganese and
the residual rare earths were completely separated from nickel and
cobalt by solvent extraction with 20% P204. REEs were recovered
after two steps of scrubbing with 0.1 M and 0.5 M of sulfuric acid,
respectively and stripping with 2 M HCl. The raffinate contained
cobalt and nickel was sent to another solvent extraction step with
20%v/v Cyanex 272. Cobalt was extracted and recovered as sulfate
after scrubbing with 0.1 M of sulfuric acid and stripping with 1 M of
the same acid. Nickel in the aqueous phase was recovered after
concentration as spherical nickel hydroxide. The total recovery for
rare earths, cobalt and nickel exceeded 98%.
In the process described by Fernandes et al. [32] a method to
recover cobalt, nickel and rare earths coming from leaching with
HCl was proposed. The materials were separated by the other
components (mainly plastic) of the accumulators after dismantling,
fed into a milling machine to reduce the fraction until < 1 mm and
finally dried at 105  C for three hours. The dried mass was leached
with 12 M of hydrochloric acid in a closed glass reactor. The ex-
periments were carried out at 40  C with a solid/liquid ratio of
150 g L 1, for 100 min. These conditions were effective to dissolve
the metals and the leach liquors had the following average
Fig. 3. Recycling process proposed by Zhang et al. [1].
compositions: 39.6 g/L Ni, 18 g/L La, 4.7 g/L Co, 4.4 g/L Fe, 1.9 g/L Mn
and 1 0.0 g/L of Zn. After leaching and filtration the leach liquor was
sent to solvent extraction step with pure TBP at 25  C and aqueous/
organic phase ratio of 1/1. 100% of Zn and Fe were extracted in the
organic phase. The raffinate was sent another step of extraction
with 10% v/v of Alamine in kerosene, 25  C and aqueous/organic
phase ratio of 1/1 in two stages. 93.6% of Co was extracted with a
coextraction of Ni of 2.8%. Other two stages of extraction with 20%
v/v of PC 88A in kerosene at 25  C, aqueous/organic phase ratio of 1/
1 and pH 1 were carried out to remove almost completely
lanthanum. In the residual raffinate, finally, was added ammonium
oxalate to precipitate Ni under the following conditions 0.3 M of
reagent, 60  C at pH equal to 2 with mixing. The precipitate was rich
in Ni oxalates (>95%) with 1% of Co oxalates and 4% of Mn oxalate.
Fig. 6 reports the block scheme proposed by Fernandes et al. [32].
Larsson et al. [42,49] in their works described solvent extraction
experiments to recover solutions rich of metals. Three block
scheme were proposed based on the experimental results. In the
first cathode material was dissolved using a solution of HCl (8 M).
The leach liquors contained base metals as iron, zinc, manganese,
nickel, cobalt, potassium, aluminum and yttrium. After leaching a
first series of extraction was performed to remove zinc and iron
from solutions. The operational conditions were: 8% v/v Cyanex 923
in kerosene, 10% v/v TBP in kerosene, aqueous/organic phase ratio
of 1/1, 3e4 stages. The organic phase that contained Fe and Zn was
sent to scrubbing section with HCl 3 M O/A phase ratio of 2/1 in two
stages and then it was sent to a stripping section to recover a so-
lution rich in Fe and Zn and regenerate the organic phase for the
recycle. The raffinate coming from the first extraction rich of the
other metals was sent to another liquid eliquid extraction with 70%
Fig. 4. Recycling of spent NiMH batteries, Nayl, 2010 [40].
 V. Innocenzi et al. / Journal of Power Sources 362 (2017) 202e218
Fig. 5. Flow sheet for the recycling of spent NiMH batteries, Li et al. [20].
v/v Cyanex 923, 10% TBP and 20%v/v kerosene and 5 stages. The
raffinate was rich in Ni, Mg and K, instead the organic phase was
rich in Al, Co, Mn, Y, Ni. This last was treated in a stripping section
with 1 M NaNO3 to strip Co and Ni. Then the loaded organic phase
was sent to another stripping phase with 1 M of HCl to separate Al
and Y and regenerated the organic solution for the recycle. The
second flowsheet proposed by the authors included the treatment
of anode material leached using HCl (8 M). The solution contained
Al, Ce, Co, K, La, Mn, Nd, Ni, Pr and Y. The leach liquor was sent to the
solvent extraction section using 70%v/v Cyanex 923, 10% v/v TBP in
kerosene to remove a large amount of the chloride content and
loads the solvent, thereby making the lanthanides extraction
difficult. The raffinate contained aluminum, cobalt, manganese,
lanthanides, yttrium and a nickel impurity; it was sent to a strip-
ping section with nitrate solution (1 M) to strip Co and Mn. The
residual organic phase was sent to another stripping section with
1 M of HCl to recover Al and the lanthanide. The last hydrometal-
lurgical process included the treatment of the mixture constituted
by anode and cathode materials. In all suggested process the
number of the stages for the extraction steps was based on ideal
systems requiring more than 99% purity.
In our previous work [9], concentrated on the recycling of spent
NiMH batteries, a hydrometallurgical process was proposed. The
powder, used for the experimental tests, was collected by industrial
plant of recycling of the spent batteries (Seval, Colico, Italy). The
initial material was washed to dissolve potassium hydroxide and
other soluble compounds, after a leaching with sulfuric acid was
performed to dissolve rare earths. The most suitable conditions for
leaching process were: 2 M of H2SO4, 80  C, 1.5/10 g/mL of pulp
density and three hours. The yields were about >94% for nickel and
211
zinc, 65% for aluminum, 100% for manganese and 35% for
lanthanum and cerium. A second leaching at the following condi-
tions was proposed to completely dissolve the rare earths:
1 M H2SO4, room temperature, 15% pulp density for 1 h.
Rare earths were recovered after precipitation, as double sul-
fates, by selective precipitation adding sodium hydroxide. The
precipitate of REE sulfates, after leaching and selective precipitation
contained 64% w/w of lanthanum sulfate and 28% w/w of cerium
sulfate. The major impurities were manganese and aluminum
(2e3.5% each other) and traces of nickel and zinc. The total recovery
for La and Ce was 99%. Finally, the experimental tests showed that
precipitation was not efficient to recover selectively the other
metals content in leach liquor, so another process was studied
described in the following work [31]. The separation of nickel, zinc
and manganese contained in the leach liquors after rare earth
precipitation was investigated using solvent extraction. Two
extractants were considered for the experiments D2EHPA and
Cyanex 272 in n-dodecane. The preliminary tests showed that the
first extractant was more efficient to separate manganese and zinc
from the solutions. 100% of Zn and 95% of Mn were extracted with
two cross-flow liquideliquid extraction steps. The raffinate con-
tained 80% of initial Ni. The metals in the organic phase were
stripped using 4 M of sulfuric acid, obtained yields greater than 98%
for Mn and Zn. In the paper a complete hydrometallurgical process
was proposed; it included the recovery of rare earths by selective
precipitation and the base metals by solvent extraction. The solvent
extraction circuit had two stages of extraction with 20% v/v of
D2EHPA in n-dodecane (organic/aqueous ratio of 1/1, room tem-
perature, 30 min of contact, pH  2.5) and one stage of stripping
with 4 M of H2SO4 (organic/aqueous ratio of 1/0.5, room
212 V. Innocenzi et al. / Journal of Power Sources 362 (2017) 202e218
Fig. 6. Flow sheet for the recycling of spent NiMH batteries, Fernandes et al. [32].
temperature, 15 min of contact). The raffinate rich in Ni could be
treated to recover Ni, instead the aqueous liquid from the stripping
step rich in Zn, Mn and Ni could be recycled in electrolytic section
to recover metallic zinc and manganese oxide. Fig. 7 reports the
processes just described.
More recently Tanong et al. [37] described in their work the
efficiency of several technologies for the recovery of metals from
leach liquors coming from the dissolution of unsorted spent bat-
teries. The solutions contained Zn, Mn, Cd, Ni and Co. Zn metallic
was recovered by solvent extraction using Cyanex 272 and by
electrodeposition. D2EHPA was used to extract cadmium and
manganese. After Cd was stripped using sulfuric acid and recovered
by electrodeposition. The residual Mn was recovered as carbonate
by adding sodium carbonate. Another step of extraction with Cya-
nex 272 could be performed to remove cobalt from residual solu-
tion rich in nickel. Ni was finally recovered by precipitation adding
sodium carbonate.
Petranikova et al. [50] described the optimization of the hy-
drometallurgical process in the pilot scale, including a series of
mixer settler, using as raw material spent NiMH car batteries that
were dismantled manually or mechanically. The treatment had
been designed to recover metals from cathodic and anodic material
or from a mixed of them. The dissolutions were performed using
high concentration of HCl (8 M) at 30  C. After leaching and
filtration the solvent extraction operations were carried out using
Cyanex 923 and TBP diluted in kerosene. The process included
several stages of extraction: a preliminary step (8%v/v Cyanex 923,
10%v/v TBP, 82%v/v kerosene; four stages of extraction) for the
removal from leach liquors iron and zinc from cathode and mixed
material solutions. A scrubbing with three stages were performed
to remove co-extracted metals followed by four stripping stages to
recover Zn and Fe. Another circuit of extraction included the sep-
aration of Al and REEs from Ni, K and Mg (70%v/v Cyanex 923, 10%v/
v TBP, 10%v/v kerosene, 10%v/v 1-Decanol; three stages). The raffi-
nate contained nickel with high purity, greater than 99.9%, instead
the organic phase was stripped with a mixture of sodium nitrate
(0.9 M) and nitric acid (0.1 M) to remove the metals as cobalt,
manganese and nickel. Finally, aluminium and REEs were recovered
by scrubbing with sodium nitrate (1 M) with the aim to remove the
residual traces of cobalt and manganese and stripping with hy-
drochloric acid (1 M).
2.2.4. Combination of acid leaching, chemical precipitation and
electrochemical process
Tzanetakis and Scott [31] reported the results of their study
about the recycling of spent NiMH batteries. The accumulators
were mechanical processing to separate steel case from the elec-
trodes. These last were leached using HCl adopting the best
leaching conditions found during the experiments: 4 M HC1 at
95  C, S/L of 1/10 g/mL and a leaching time of 3 h. 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 leaching and filtration, the solvent extraction with 25%v/v
D2EHPA in kerosene was carried out and REEs, Mn, Fe, Al and Zn
were extracted at pH 2.5. REEs were stripped and recovered by
 V. Innocenzi et al. / Journal of Power Sources 362 (2017) 202e218
precipitation. Nickel and cobalt contained in the raffinate were sent
to electro winning. Galvanostatic tests investigated the effect of
current density, pH, and temperature. Experiments at low current
densities gave a deposit of Co with a crystalline structure; while
higher current densities gave amorphous materials and relevant
reduction in current efficiencies.
Bertuol et al. [25] studied a process to treat spent NiMH batte-
ries. The electrodes were dissolved using sulfuric acid with a con-
centration of 2 M at 90  C for 4 h, solid/liquid ratio of 1/20 under
mixing. The results of the leaching experiments showed good ex-
tractions for the metals, in fact yields greater than 90% were ob-
tained for cobalt, zinc and manganese, exceeding of 80% for
lanthanides and iron. After filtration the rare earths were precipi-
tated, after filtration, as sulfates increasing the pH up to 1.3. Total
recovery was estimated to be 98% with sulfates rich in rare earths
and having zinc as the main impurity. The pH of the residual so-
lution was increasing using sodium hydroxide until pH up to 6, in
this manner iron, zinc and manganese were precipitated after 18 h
under mixing. Then, electro winning tests were carried out to
recover nickel and cobalt. The experiments were performed gal-
vanostatically in a two-compartment cell separated by an anionic
membrane. A platinum/iridium-coated titanium anode and a
stainless-steel cathode were used. A sodium sulfate solution served
as anolyte. The optimum conditions for Ni deposition were: 30 g/L
of boric acid, 50  C, 250A me2, and pH 4. The compositions of the
deposit were 53.9% of Ni, 8.77% of Zn, 13.63% Co, 3.04% Fe, 1.15% Mn.
Santos et al. [36] studied a method to recover metals, mainly Co,
Ni, Zn and Mn, from the positives electrodes of spent NiMH bat-
teries by chemical and electrochemical processes. The leaching was
Fig. 7. Hydrometallurgical process for the recovery rare earths and base metals from spent NiMH batteries, Innocenzi and Veglio
213
performed using 0.5 M of nitric acid with a pulp density of 0.5/10 g/
mL. After dissolution the suspension was filtered to remove
graphite and plastics. A solution of NaOH (5 M) was added to in-
crease the pH until 9 at 5  C. The aim of this operation was to
precipitated materials that were electrodeposited from a bath
prepared by dissolving 5% of the positive electrode in 0.5 M of
sulfuric acid. NaOH was added until the pH was 1.5; additionally,
0.4 M of H3 BO3 (as a buffering agent) and 0.3 M of ammonium
sulfamate (as a complexing agent) were added. The analysis on the
recovered solid samples showed that the compounds present were
b-Ni(OH)2, Co(OH)2, Zn(OH)2 and Mn3 O4. The powder retained
sulfate, nitrate and carbonate anions from the mother solution as
well as adsorbed water. Studies using cyclic voltammetry showed
that the current density decreased for scan rates greater than
10 mV s1 because of the formation of hydroxide films. The amount
of deposited nickel ions was related to the composition of the
sulfamate bath. The electrodeposited material contains Ni, Co, CoO,
Co(OH)2, and Mn3 O4. 83.7% of charge efficiency was achieved for
the electrodeposits formed by the application of 1.1 V vs. Ag/AgCl
at a charge density of 90 C cm2. The experimental results
showed that the dissolution of the electrodeposits depended on the
applied potential.
2.2.5. Combination of acid leaching, precipitation and adsorption
A process of selective precipitation followed by adsorption was
described by Gasser and Aly [26], Fig. 8. The process included two
leaching step 2 M, 25  C with a solid/liquid ratio equal to 1/10
(g mL1) for two hours. The leaching yields for cobalt and nickel
were 98% and 85%, respectively. Two stages of leaching were
 [39].
214 V. Innocenzi et al. / Journal of Power Sources 362 (2017) 202e218

necessary to dissolve almost completely rare earths, nickel and

cobalt. After leaching with sulfuric acid, the suspension was filtered
and the rare earths double salts were recovered after addition of
sodium hydroxide (pH ¼ 2.5). The residual solid after filtration
contained around 16 g/L di Co and Ni. The solid that contained the
rare earths was dissolved using hydrochloric acid (2 M). Synthetic
adsorbent was used for separation of lanthanum and neodymium
from the leach liquors. The adsorption process was carried out by
using 0.1 g adsorbent/10 mL solution at 25  C for 2 h to adsorb
lanthanum ions. The results of the experiments showed that the
adsorption yields were 98% and 1% for lanthanum and neodymium,
respectively. The solid absorbed solid was filtered and after treated
with a solution of hydrochloric acid (0.01 M) at 25  C. The solution
contained mainly lanthanum. Instead the solution rich in neo-
dymium was sent to precipitation step in which oxalic acid was
added to precipitate Nd oxalates. The precipitation yields were 97%
for neodymium and 0.8% for lanthanum.

2.3. Other scientific works: bio-metallurgical processes

In the last years, the bio-metallurgical processes have been

developed and represent an alternative to the hydrometallurgical
processes. They have higher efficiency, lower cost and fewer in-
dustrial requirements [51e53]. The advantages of the bio-
treatments are the long period of the processes and different
types of bacteria are required. Among the different types of
microorganism and inorganic chemical solutions, the acid-
ithiobacillus ferroxidans are extensively investigated for the treat-
ment of the spent batteries. Bajestani et al. [54] studied the effect of
these bacteria on the bioleaching of the metals from exhausted
NiCd and NiMH accumulators. The effect of the initial pH, power
size and initial Fe3þ on metals recovery (Cd, Ni and Co) was studied
according to a Box-Behnken design. Under optimal conditions 99%
of metals recovery was obtained, confirming that the acid-
ithiobacillus ferroxidans are an effective toxin resistant microor-
ganism for bio-recovery of heavy metals. The extraction of Ni and
Co increased decreasing the initial pH and particle size and
increasing the initial Fe3þ concentration. Cd had a different Fig. 8. Recovering of REEs from NiMH spent batteries, Gasser and Aly [26].
extraction trend and to maximize simultaneous bioleaching of
three metals, the optimum value for initial pH, particle size and
stripping and precipitation is necessary to selective recover metals
initial Fe3þ concentration were 1,62 mm and 9.7 g/L, respectively.
and REES with high grade of purity. Various types of organic phases
Under these conditions, the experimental recoveries were 87%,
were tested (as Cyanex 272, 525, 923 and D2EHPA); these com-
67%, and 93.7% for Ni, Cd and Co, respectively.
pounds are mixture of organic substances having high purchase
However, even if the bioleaching process shows good results
and disposal costs. From an industrial point of view, their use must
with respect to the recovery efficiencies, the methods needs to be
be optimized to reduce the amount of the exhausted solutions and
implemented with the aim to reduce the costs for culturing the
to avoid their dispersion.
bacteria. In order to bring the process to an industrial scale, the bio-
After all, the scientific works described in the previous sections
metallurgy process remains challenging.
are mainly developed in the laboratory scale, other implementa-
tions must be necessary: a) to reduce the use of the dangerous
2.4. Overview and discussions
materials; b) to increase the use of the environmental friendly
leaching reagents; and c) to reduce the wastewater produced
There are many scientific works that described possible recy-
during the hydrometallurgical treatments with the main goal to
cling processes for recovering of metals from spent NiMH batteries.
develop a zero liquid discharge processes.
At the first the batteries must be mechanically treated in order to
An alternative to the hydrometallurgical processes is repre-
separate the various fractions of the batteries and to produce a fine
sented by bioleaching treatments that show good results with
powder for the next steps of dissolution and recovery. The most
respect to the recovery efficiencies. However, these methods need
commonly used leaching acids are sulfuric and hydrochloric acid at
to be implemented with the aim to reduce the costs for culturing
different concentrations. H2SO4 is preferred from an environmental
the bacteria. In order to bring the process to an industrial scale, the
reason. Anyway, the environmental impact of these substances
bio-metallurgy process remains challenging.
should not be underestimated and it is important to improve the
research to find effective conditions to dissolve metals using
environmental friendly leaching reagents as the organic acid (for 3. Industrial recycling processes of spent NiMH batteries
example citric acid).
Moreover the literature showed that after dissolution, to recover The main sections are “3.1” and “3.2” in which the industrial
metals from leach liquors a complex series of solvent extraction, processes and the patents regarding the recycling of spent NiMH
 V. Innocenzi et al. / Journal of Power Sources 362 (2017) 202e218 215

batteries were reported, respectively. Table 4 summarizes these
processes and patents described below.
3.1. Industrial applications
NiMH batteries are complex systems and they require specific
processes that result relatively expensive. For this reasons, from an
industrial point of view the technologies to recycle of these types of
accumulators are continuously developing with the aim to reduce
the costs and improve the efficiency of the treatments. Inmetco and
Snam‘s processes, developed for recovering dusts from electric arc
furnaces and for recycling of spent NiCd spent batteries, can be
applied to treat spent NiMH batteries by pyrometallurgical
methods and to recover a fraction rich in nickel.
Umicore developed another important process for the treat-
ment of spent NiMH batteries with the aim to recover base metals
and rare earths. Following the description of these industrial pro-
cesses have been reported.
3.1.1. Inmetco process
Inmetco was developed and implemented by Inco (International
Nickel Company, Pennyslvania). The treatment was initially applied
to recover zinc, iron and lead from powders coming from electric
arc furnaces. After it was applied for recycling of Ni-Cd batteries to
recover cadmium and also for other type of accumulator: nickel-
iron, nickel metal hydride, lithium ion and mercury-free zinc car-
bon [55]. From the process, base metals were recovered instead the
rare earths remained in the slag [56]. Since 1978 the feed of the
Inmetco High Temperature Metals Recovery (HTMR) process was
wastes (cake, liquids, catalysts and batteries) containing mainly
nickel. A rotary Hearth Furnace (RHT) was used to reduce oxidized
metals waste to their metallic form. The main steps of the process
were: feed preparation, reduction, smelting and casting. Liotta et al.
[57] in their paper deepened the process for NiCd spent batteries
and described the various phases of the treatment. In the feed
preparation the batteries were drained; the electrolyte (KOH so-
lution) was recovered and subsequently used as a reagent for the
wastewater treatment. The batteries were shredded and mixed
with green pellets produced in this phase after addition of additives
to other solid and liquid wastes contained nickel. The material was
fed to a furnace at high temperature, 1260  C. The gas output was
sent to wet scrubber, water from scrubber was treated and reuse,
pressed into a cake with Cd, Zn and Pb. The cake was mixed with
dust from the system's baghouse which also contains Zn, Pb and Cd
and after sent to another facility. The hot reduced feed was sent to
Submerged Electric Arc Furnace (SEAF) where was smelted and a
slag/metal containing Ni, Cr, Fe and others, was produced. Metal
and slag were discharged periodically from the furnace. Metals was
sent to the last step, casting, producing a product containing about
10% Ni, 14% Cr and 68% Fe, instead the slag is further processed and
sold for use in building roads, parking lots and commercial
driveways.
3.1.2. Snam process
Snam is a French company whose main activity is the recycling
of Nickel-Cadmium, Nickel-Metal-Hydride and Lithium-Ion from
spent batteries. The spent batteries come from commercial uses
(from computers, cell phones), industrial uses and waste (from
electrical vehicles, aviation, …) [58]. The batteries were cut to
separate the plastic cases, the electrolyte was recovered and treated
to separate Cd and then sold to the manufactures. The main steps
were: automatic separation of batteries, distillation to product Cd
vapor with 99.99% of purity and a Fe-Ni alloy. Vapor cadmium was
cooled, melted and sold to NiCd batteries manufactures or to the
coating industry. Fe-Ni residue was smelted with other material
that contains Ni and a Fe-Ni alloy was produced and sold to steel-
making plants [56,59].
3.1.3. Umicore process
Umicore and Rhodia have developed a process for the treatment
of spent NiMH batteries with the aim to recover base metals and
rare earths [60]. Around 7000 tons/year of this waste was treated in
a pilot plant in Hoboken (Belgium): the batteries were fed in a
vertical furnace with coke and air and a slag former [61]. The metals
were converted into an alloy containing base metals as nickel, co-
balt, copper and iron. Moreover a slag of a mixture of oxides (cal-
cium, aluminum, silicon, iron, lithium and rare earth) was
recovered [62]. The slag was treated to product a concentrate of
REEs that could be sent to solvent extraction plant of Rhodia in La
Rochelle (Francia). The details of the process are not disseminated

Table 4
List of the main industrial processes and patents relative to the recycling of NiMH spent batteries.

References Industrial process/patent Type of batteries Type of Main final products

process

[55e57] Inmetco NiMH Pyro Metallic product (10% Ni, 14% Cr and 68% Fe) and slag further processed and sold
NiCd for use in building roads, parking lots and commercial driveways.
[58,59] Snam NiCd Pyro Final products: Cd metallic and Fe-Ni alloy
NiMH Li-ion
[60,61] Umicore NiMH Pyro/Hydro Alloy containing base metals (Ni, Co, Cu, Fe).
Rhodia Li-ion Slag of a mixture of oxides (Ca, REEs,.)
[63] Japan Metals & Chemical Co. NiMH Hydro REE oxides
and Honda Motor Co. Ltd
[64] Mond Process Several types of wastes that Pyro
contain nickel as NiMH scraps
[65] TNO Cd and Ni as metals
ferric hydroxide sludge
[65] NIFE Pyro Cd as metal
Residual materials sold to a steel maker
[66] Patent 2011/113860A1 Mechanical Powders containing Co, Ni, Fe, Al, Cd and REEs
process
[67] Patent US 8246717 B1 NiMH Mechanical Ni(OH)2and the AB2 and/or AB5
process
[68] Patent US8696788 NiMH Hydro Ni as metal
[69] Patent EP2444507 A1 NiMH Hydro REEs as sulfates
[70] EP2788517 A2 NiMH batteries and zirconia Hydro REEs as oxides
waste Zr as oxide
[71] WO201414144463 NiMH Hydro REEs as oxides
216 V. Innocenzi et al. / Journal of Power Sources 362 (2017) 202e218
but behind the treatment there is patent of Umicore [61]. The plant
can be treated also Li-ion spent batteries.
3.1.4. Japan metals & chemical and Honda Motor
In 2012 the Japan Metals & Chemical Co. and Honda Motor Co.
Ltd presented their new hydrometallurgical process to recover REEs
from exhausted NiMH batteries of Honda HEV. The recycling circuit
included acid leaching and recovery of REEs as oxides. By applying
molten salt electrolysis to these oxides, Honda has succeeded in
extracting metallized rare earth that can be used directly as
negative-electrode materials for nickel-metal hydride batteries.
The rare earth metals extracted in the Honda process had a purity of
more than 99% which was as high as that of ordinary traded, newly
mined rare earth metals. In addition, the new process enabled the
extraction of as much as above 80% of rare earth metals contained
in nickel-metal hydride battery [63].
3.1.5. Others processes
In addition, to the listed treatments, in literature it is possible to
find a list of other processes used to treat all batteries and Ni based
batteries including spent NiMH ones [64]. These treatments are
mainly applied for recoveries of Cd for Ni-Cd batteries by vapor-
ization (i.e. Accurec, Toho Zinc). Metals with high concentration of
cadmium and zinc were fumed off and captured in the flue dust for
reprocessing and the remaining metals were sent to convention
secondary Ni smelters to recover nickel values. The Mond Process
was applied for several types of wastes that contain nickel as NiMH
scraps. Nickel oxide reacted with syngas at 200  C to remove O2 and
leaving the metal with some impurities as Fe, Co. The impure nickel
reacted with CO and Ni-tetra-Carbonyl is produced, this mixture is
headed to 220e250  C and Ni and CO are formed. Non Ni-materials
were sent to the secondary recovery or to hydrometallurgical steps
to recover other non ferrous metals.
Other processes that treat NiCd batteries are TNO and NIFE.
Recently, there have been discussed the possibility to utilize these
plants to recover metals from spent NiMH batteries. The plants are
not designed to recover the hydride alloy components. The pro-
cesses will need to be modified to treat NiMH accumulators.
The TNO process (Netherlands) is a hydrometallurgical process
to recover metallic Ni and Cd. The batteries were shredded in a
knife mill and separated into three fractions by magnetic separation
and screening. The first fraction was ferrous residue, the second
was plastics and paper and the third one was fine materials (1% of
the initial feed). These fractions were dissolved and after sent to
solvent extraction circuit with TBP in kerosene. Cd was extracted,
stripped with HCl and after sent to electrowinning step in order to
recover Cd as metal. In the raffinate sodium hypochlorite and so-
dium hydroxide was added to precipitate iron as ferric hydroxide
sludge. Hence the solution was sent to electrowinning operation for
recovering nickel as metal.
NIFE process (Sweden and North Caroline) is similar to SNAM
process. The accumulators were dismantled, the electrolyte was
neutralized and the battery plates were separated. The cells were
head heated in a pyrolysis furnace to drive off the water and to burn
the plastics. The residue and the negative plates were calcined to
900  C to volatize and recover Cd as metal. The remaining material
and the positive plates were sold to a steel maker [65].
3.2. Patents
In this section the main relevant patents for the treatment of
spent NiMH batteries are reported.
The works described mechanical, physical, pyro and hydro-
metallurgical processes for the recovery of base metals and rare
earths. An example of mechanical process of different batteries
(NiMH, Ni-Cd, alkaline) was described by Pudas et al. [66]. The
spent batteries were sorting according to composition and type.
NiMH batteries were crushed and the powder was sent to a mag-
netic separator to remove Fe. The powder, after crushing, contained
cobalt, nickel, iron, aluminum, cadmium and rare earths that could
be recovered by refining.
The process described by Smith and Swoffer [67], (Assigne
TOXCO, Inc.) included: 1) grinding in a hammer-mill in presence of
water spray to produce a slurry; 2) screening the solids using one or
more screens to separate large pieces and plastic; 3) screening the
filtrate coming from the step 2) using a screen which is þ20 mesh
to remove nickel plated steel and nickel metal; 4) screening the
filtrate from step 3) through a 140 mesh screen and 20 mesh
screen to separate Ni alloys; 5) the filtrate from step 4) is sent
through a magnetic stripping to recover Ni and Fe; 6) the filtrate
coming from the step 5) is sent to a foam or froth flotation equip-
ment whereby the froth that contains residual light matter and
metallic powder of AB2 or AB5 drops to the bottom; and the last
step 7) that include the recovery of AB2 or AB5 powder after
filtration.
The outputs of interest are the nickel hydroxide and the AB2
and/or AB5 coming from the step 6) and 7), respectively.
Regarding the hydrometallurgical processes in the scientific
database the following patents were found. The same authors [68]
in the patent US8696788 (Assignee Retriev Technologies incorpo-
rated) described another treatment included crushed of the steel
cased batteries in a hammer mill under an inert atmosphere and in
presence of water. From this step metals and slurry were recovered
after a screening. The slurry contained 85% of the initial electrode
material (including AB5 anode and Ni(OH)2 cathode materials). The
slurry was neutralized until pH of 5 using the non-oxidizing acid
and glycol acid to leach Ni(OH)2. The dissolution conditions were:
4 h, 18e25  C with mixing and inert atmosphere. Ni(OH)2 was
recovered, after filtration, adding sodium hydroxide solution (50%)
to pH 10e11. The glycolic acid was recovered by acidifying the
filtrate with sulfuric acid to pH 1e2, distilling off the water and then
the glycolic acid azeotrope. AB5 metal powders, recovered after the
first step (milling), were washed several times to remove the re-
sidual binder. After washing the solid was filtered and dried at
100  C under vacuum, cooled and screened. The assay was 25% with
oxygen less than 1%. The rare earths add up to about 6% with a few
percent cobalt and aluminum. The nickel metal was 65%. The
estimated total recovery from the electrode was about 50e80% of
the contained AB5 metal in the electrode mix.
Luidold and Luidold and Antrekowitsch [69] in their patent
described a hydrometallurgical process for the recovery of rare
earths from spent NiMH batteries. -The process included dissolu-
tion using a non-oxidizing acid (as HCl) for the leaching of the
metals, the non emetallic fraction remained in the solid residue.
The solution was filtered and rare earths were selectively precipi-
tated as sulfates salts after adding of alkaline solution to increase
the pH-value.
In the EP2788517 A2 [70] the authors reported a method for
recovery of rare earths from several types of waste including the
spent NiMH batteries and zirconia waste. A pulverized mixture of
oxide materials and ammonium sulfate was fired in microwave or
in boats at 300e600  C. The residue was leached in aqueous so-
lution to obtain a solution containing salts of the rare earth min-
erals and zirconium. The REEs could be separated from the
solution by several methods (ion eexchange, solvent extraction
and fractional crystallization) and precipitation as oxalates. The
solid was calcined at 1000  C to form the rare earth oxides. The
zirconia, instead was recovered from the filtrate adding ammo-
nium hydroxide. The precipitated solid was washed and calcined
at 1000  C to obtain zirconium oxide.
 V. Innocenzi et al. / Journal of Power Sources 362 (2017) 202e218
Jacobson and Samarasekere [71] described a process for the
recovery of rare earth elements from several types of materials
including NiMH batteries. The hydrometallurgical treatment con-
sisted a leaching with an organic/inorganic substance followed by a
crystallization of rare earths under solvothermal conditions. The
crystallization medium comprised 80e100% (volume) of at least
one amide, 0e10% volume of at least one organic acid, and 0e10%
(volume) of water. Finally the systems could include a purifying of
the rare earth and a calcination to obtain rare earths oxides.
3.3. Overview and discussions
In the last years some industrial companies have decided to
invest in recycling of spent NiMH batteries. The plants treat several
types of industrial wastes, metallic scraps and other exhausted
accumulator in order to recover mainly base metals. Hydrometal-
lurgical treatments should be preferred to pyrometallurgical ones
for recovering other valuable materials (as REEs) with high eco-
nomic value. The development of the processes from laboratory to
industrial scale must be continued in the future to reduce the cost
of processes, mainly due to costs of the reagents and of the
wastewater treatments, and to meet the industrial requirements.
4. Conclusions
Based on discussion of this review, the following conclusions
can be drawn:
1) Production of the NiMH batteries will rapidly increase as
consequences of their applications in the HV and electronic
devices.
2) Safe disposal of NiMH accumulators at their end life is an
environmental necessity in order to avoid the dispersion of
dangerous materials difficult to degrade.
3) The main metals in NiMH batteries scraps are nickel, cobalt,
manganese, zinc and rare earths elements (lanthanum,
cerium, praseodymium, neodymium). Therefore, the devel-
opment of an efficient recycling process to recover these
metals and safe dispose of is a necessity.
4) Although there are a lot of scientific works that describe
recycling technologies of spent NiMH accumulators, most of
them are still in laboratory and pilot scale.
5) Most of the proposed treatments are based on hydrometal-
lurgical chemistry. The recycling circuits start with me-
chanical pretreatments such as dismantling, grinding,
crushing and screening. The aims of the pretreatments are to
reduce the volume of the accumulators, separate the mate-
rials as plastics and paper and finally produce a fine fraction
rich in metals to treat in the hydrometallurgical section.
6) Hydrometallurgical processes include the dissolution of the
fine fraction in order to dissolve the valuable materials and
after recover them by several chemical operations.
7) Concerning recovery steps, many combined processes
related to selective precipitation, solvent extraction, elec-
trowinning and crystallization have been performed to
obtain final products with high purity.
8) Generally, the industrial plants that recycle these exhausted
batteries treat also other types of accumulators or industrial
wastes rich in nickel. From an industrial point of view the
pyrometallurgical processes were preferred respect to the
hydrometallurgical ones.
9) The advantages of the hydrometallurgical treatments are
that the metals can be selectively recovered with high grade
and recovery yields. The main disadvantages are: accurate
mechanical pretreatment are necessary to reduce the
217
fraction size of the initial materials; large consumption of
chemicals and large amount of wastewater to treat before to
dispose of.
10) As opposed the technology of pyrometallurgical processes is
well known as also demonstrated by the cited industrial
treatments. This route allows recovering energy from plastic
materials and other organic components of the spent batte-
ries. The main disadvantages are the high investment costs
for the equipments (furnaces) and the final products are
fractions rich in nickel and cobalt. Rare earths are recovered
as slag and must be further refined by hydrometallurgical
route.
11) The main processes developed in the laboratory scale are
extremely complex to recover the valuable metals in a long
process with high costs and energy consuming. Therefore, in
the future, new implementations on the recycling methods
will be needed in order to exceed the problems related to the
industrial scale up of the hydrometallurgical processes in
order to meet the recycling limits imposed by European
legislation on disposal of spent batteries, recover critical
metals and benefit of the economic advantages.
12) Future implementations of the processes can be covered
each step: a) increase of the collection rate; b) development
of new pretreatments technologies to improve the efficiency
of the actual industrial sorting and mechanical equipment; c)
use of organic acid and green reagents rather than the most
common mineral acids for hydrometallurgical processes; d)
develop a close loop recycling circuit with zero liquid
discharge.
13) Hence, the key success parameters of the contemporary and
future industrial treatments for the recycling processes, are
no longer based solely on profit margin, but include envi-
ronmental, social, and ethical measures. Therefore, future
recycling process of spent accumulators, such as NiMH bat-
teries, should aim at high eco-efficiency in the life cycle
management of them.
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