HYDROMETALLURGICAL RECOVERY OF COBALT METAL FROM SPENT LITHIUM-ION BATTERIES

ABSTRACT

This study assesses the recovery of cobalt present in spent or waste lithium-ion batteries through
hydrometallurgical process as a measure of prevention towards environmental and health problems
resulting from improper disposal of these batteries. Spent lithium-ion batteries of three different
mobile phone brands (Samsung, Nokia and Blackberry) were collected and separated/dismantled into
four components (Inner roll, casing, plastic and paper). Six samples labeled 1 to 6 were analyzed in all.
These components were initially weighed before leaching the inner roll in a shaker water bath. The
leaching temperatures used were 70, 80 and 90oC and the leaching time, 60 and 120 minutes. The
quantities of hydrochloric acid used were 123, 246 and 344 ml with varying quantities of distilled water.
The pregnant solutions obtained from leaching were filtered in order to remove impurities. A mass of
5 g of sodium hydroxide mixed with 60 ml of water was then added to 40 ml of the filtered pregnant
solution to precipitate cobalt and the precipitated solution was filtered. Atomic Absorption
Spectrophotometer (AAS) was finally used to analyze 2 ml of the leaching solution, filtered-pregnant
solution and filtrate obtained after precipitation were all mixed separately with 98 ml of distilled water
in order to determine the quantities of cobalt present in the solutions. The results of the analyses
showed that cobalt leached was between 95.00 – 409.00 PPM with equivalent percentage recovery of
98.02 – 99.98% which signifies abundant availability of the metal in spent lithium-ion batteries. This
recovery process of heavy metals can therefore serve as an effective means of preventing
environmental and health problems associated with waste batteries.

1. INTRODUCTION
The utilization of batteries in many domestic and industrial applications is on the increase since 1990s.
This has improved and rapidly shaped the economy and social landscape of humans. A battery is one of
the electrochemical devices that convert stored chemical energy into electrical energy and have turned
out to be a frequent power source for diverse household and industrial applications. Usually, battery
can be classified as primary and rechargeable batteries; which include, lead-acid, nickel-cadmium (Ni-
Cd), nickel-metal hydride (NiMH), and lithium-ion batteries (LIBs) (Zheng et al., 2014). In contrast with
other rechargeable batteries, lithium ion batteries (LIBs) have become the main power supply for
communication and portable instruments, like mall, PDAs, watches, camcorders, digital cameras,
thermometers, calculators, laptop BIOS, communication equipment, and remote car locks. Their high
energy density, high cell voltage, less memory effect, low self-discharge, good cycle life and easy to
charge and maintain property makes them better choices for users (Wakihara, 2001; Armand and
Tarascon 2008; Zheng et al., 2014). This has brought about an increased consumption of LIBs in recent
years. LIBs contain various components such as a cathode plate, an anode plate, an electrolyte, and a
polymer separator. Among these components, cathode materials that contain Li and other metals are
the most valuable for recycling (Cai et al., 2014). LIBs are also considered as the preferable battery for
powering the next generation of hybrid electric vehicles (HEVs) as well as plug-in hybrids (PHEVs),
(Wakihara, 2001) given that enhancements can be achieved in terms of functionality, cost, and safety
(Dunn et al., 2011).

The world population has continued to grow at a very fast rate. With this incessant growth in
population, comes an increasing demand and use for the products. A rise in battery consumption results
into a proportionate increase in the waste produced. Waste is produced at different stages including
when products are being manufactured, during the use of the products and eventually when the
product has come to the end of its life. World Bank, (2012) reported that a total estimate of 1.1 billion
tonnes per year of waste is being produced and that by the year 2025 the amount of waste produced
will increase to about 2.2 billion tonnes per year. This has therefore, raised public concern about how
the environment can be safe guarded. Waste management agencies especially in developed countries
have set stricter regulations with some priorities given to the destination of hazardous wastes
containing heavy metals like cobalt and nickel from spent batteries (Gabriel, 2016).

LIBs have an average life-span of 1 - 3 years. Combustible and toxic elements or compounds in waste or
spent LIBs may lead to serious risks to the environment and human health if discarded LIBs are
improperly treated (Zheng et al.,2016). Recycling of valuable components from LIBs will not only relieve
the pressure of environmental contamination, but also generate remarkable economic and social
benefits as reported by Fan et al. (2016) and Joo et al. (2016). Sonoc et al. (2015) however asserted that,
only about 3% of the spent lithium ion batteries are recycled and lithium recovery is still very limited as
more focus is placed on other metal components such as cobalt, copper and nickel which have higher
economic value.

The activity of recycling spent lithium-ion batteries is usually by physical separation process, leaching
process and thermal treatment which is referred to as hydrometallurgical process. Figure 1 shows a
comprehensive summary of the hydrometallurgical process, which mainly includes leaching, solvent
extraction, precipitation, and the electrochemical method. Owing to their operational ease, the first
two processes (i.e. the physical separation and leaching processes) are the most commonly used
methods because of their simplicity. Thermal treatment is most often geared towards the complete
meltdown of the entire process that results in the recovery of alloys containing mainly cobalt and nickel-
lithium and aluminum, however, they are often lost because, a complete separation of the metal
components from the batteries is usually avoided (Wang and Friedrich, 2015).

In addition, during the cycle life period, Li tends to deposit on the anode due to overcharging or other
inappropriate usage. The deposited Li can react with water to generate hydrogen gas (H2) and yield
lithium hydroxide (LiOH) (Lv et al., 2017). The residual electric power has a tendency to result in
explosions or fire accidents (Zheng et al., 2014). Consequently, effective recycling of spent LIBs in light
of the environmental and safety challenges is crucial to make certain sustainable development in this
field. Therefore, this paper aims at recovering cobalt present in three different brands spent lithium-
ion batteries and the method employed is the hydrometallurgical recycling process. The specific
objectives are to first determine the material composition of the spent lithium-ion batteries; identify
the presence of cobalt available in pregnant solution after leaching; and conduct a recovery test of
cobalt from the spent batteries by precipitation method

2. MATERIALS AND METHODS

2.1 Materials and Equipment Used

The major material used this study is the spent lithium-ion batteries. Other materials and equipment
used are, plier, saw, screw driver, atomic absorption spectrophotometer (AAS Buck Scientific 210 VGP
AAS Buck Scientific Model) and shaker water bath (DKZ series) while the reagents used are Hydrochloric
acid (HCI) and sodium hydroxide(NaOH).

2.2 Methodology
The methods employed in this research sequentially follow the stages shown in Figure 2.
a. Collection, Sorting and Component Separation: Waste lithium-ion batteries were collected from
mobile phone repairer’s workshops at Olukayode Shopping Complex in Oja-Oba, Akure in Ondo
State, Nigeria. The batteries collected were then sorted and classified according to brand
separated/dismantled manually into various components of casing paper, plastic and inner roll.
Each component was weighed and measured. During this stage, precautionary measures like
the use of hand gloves and nose cover were taken.
b. Leaching Process: The leaching experiment the atomic absorption spectrophotometer (AAS)
analysis were carried out. Leaching was done in the shaking water bath (DKZ series model
while Atomic absorption Spectrophotometer was used for and HCl are the most us
hydrochloric acid (HCl) w samples labeled 1 – 6. The inner roll of sample 1 was divided into
two equal parts and labeled as 1A and 1B; 123 ml of hydrochloric acid was mixed with 377 ml
of distilled water to leach sample 1A while 246 ml of hydrochloric acid was mixed with th 254
ml of distilled water to leach sample 1B by placing the inner roll of the battery into the
mixture. These ratios were in agreement with work, which discovered that the best leaching
process is achieved with a mix ratio of 1:2 of leaching reagents to distilled water respectively.
These beaker containing mixture of HCl distilled water and the inner rolls were placed in the
shaking water bath at varying temperatures usually between 50 and 90oC as suggested by
Wenxuan et al. (2018) as best leaching results are achieved at these temperatures. The
temperatures selected for the experiments were 70, 80 and 90oC, and the duration for each
leaching experiment for the different samples were 60 and 120 minutes. At the expiration of
the period of time chosen for each leaching experiment, the water bath was switched off and
the solutions obtained after leaching (which are termed the pregnant solutions) in the water
bath were left to cool down. In the process of cooling down, clear solutions were formed
which afterward were subjected to filtration process in order to remove impurities in the
pregnant solutions.
c. Filtration Process: Pregnant solutions obtained from the leaching process were filtered. A
mixture of 2 ml filtrate and 98 ml distilled water was analyzed using atomic absorption
spectrophotometer to determine the amount of cobalt present in the filtrate.
d. Precipitation Process: Precipitation process was used to recover the cobalt present in the
filtered-pregnant solution. Following the procedures established by Chen and Zhou (2014), 5g
of sodium hydroxide (NaOH) was mixed thoroughly with 60 ml of distilled water, the mixture
was added to 40 ml of the filtered-pregnant solution to precipitate the cobalt in the solution.
The precipitated solution was filtered, and the precipitate was dried in the sun. To validate
further presence of cobalt in the solution, 2 ml of the filtrate was added to 98 ml of distilled
water and further analyzed.
3. RESULTS
The weight of the different components of the batteries were determined and presented in
Table 1. Also, the leaching conditions (which include the temperature, time, quantity of reagent
and distilled water) are as shown in Table 2.The leaching of the inner roll of each of the battery
was carried out and the result after analysis with AAS was presented in Table 3. Table 4 shows
the percentages of cobalt and copper leached. Comparison were made between cobalt and
copper present in pregnant solution so as to establish whether there is variation in the elements
produced by different battery producers. Table 5 presents the results of AAS analysis after
precipitation. Comparisons were also made between the quantities of cobalt in pregnant
solution and cobalt in filtrate obtained after precipitation so as to determine the amount of
cobalt recovered.

3.1 Comparison of Different Components of Spent Lithium-Ion Battery

The percentage by weight of the waste lithium-ion of Nokia, Samsung and Blackberry
batteries components which include the inner roll, casing, plastic and paper ranges from
67.08 – 80.09 %, 15.00 - 28.94 %, 3.97 – 8.33 % and 3.68 %, respectively. The inner roll in all
the dismantled batteries has the largest percentage by weight as it represents the main
functional parts of the battery make up. Most of the paper component of the batteries
could not be recovered as some were already torn during battery usage life while others
got peeled off in the process of separating the components.From Table 4, samples 1A and
1B used in Samsung mobile phone had percentage of copper and cobalt leached between
0.07 – 0.15 % and 99.85 - 99.93 %, respectively while samples 2, 3 and 5 used in Nokia mobile
phone had percentage of copper and cobalt leached between 15.91 – 20.46 % and 79.54 –
84.09 %, respectively. Samples 4 and 6 used in Blackberry mobile phone had percentage
copper and cobalt leached between 24.52 – 24.65 % and 75.35 – 75.48 %, respectively.
Obvious variation was observed between the quantities of cobalt leached and copper
leached from the batteries manufactured by the various brand used. This clearly established
the dominant composition of cobalt metal present in all the brand of spent lithium-ion
batteries.

4. DISCUSSIONS The effects of the leaching conditions presented in Table 2 on the leaching
efficiency were observed from the results of AAS analysis recorded in Tables 3 and 4, and
the findings were presented as follows.
4.1 Effect of Leaching Solution
The effect of leaching solution (i.e. quantity of hydrochloric acid mixed with distilled water)
on leaching efficiency was done using the inner roll of sample 1. This sample was divided
into two equal parts of 6.15g each and recorded as samples 1A and 1B. The same leaching
temperature and time duration of 80oC and 60 minutes were used while the leaching
solution was varied. 123 ml of hydrochloric acid was mixed with 377 ml of distilled water to
leach sample 1A, and 246 ml of hydrochloric acid was mixed with 254 ml of distilled water
to leach sample 1B. These results show that little hydrochloric acid or other similar reagent
is needed to leach. This observation implies that the leaching process is economical.

4.2 Effect of Leaching Temperature

For samples 2, 3 and 5, the same leaching time (1 hour), quantity of hydrochloric acid (344
ml) and distilled water (656 ml) were used whereas the temperatures were varied at 70oC,
80oC and 90oC for the three samples. From the result of the analysis presented in Table 3,
the leaching temperature of sample 3 was observed to have the highest output while
leaching temperature for sample 5 had the lowest output.
4.3 Effect of Leaching Time
For samples 4 and 6, all other leaching conditions apart from leaching time were
maintained. Temperature used was 80oC while quantities of hydrochloric acid and distilled
water used were 344 ml and 656 ml respectively. The leaching time for samples 4 and 6 are
120 and 60 minutes hour respectively. It could be observed that sample 6 has higher
leaching efficiency than sample 4.This observation is in line with Gabriel (2016) in his work
recovering lithium from spent lithium-ion batteries made similar claim that longer leaching
time determine the leaching efficiency rate.

4.4 Recovery of Cobalt

Comparison was made between the quantity of cobalt leached and the quantity of cobalt
in the filtered solution after precipitation to determine the quantity of cobalt recovered.
The analysis by AAS gave percentage cobalt recovery between 98.02% - 99.98%

5. CONCLUSION
Batteries are used in varieties of devices that bring comfort to its users. However, if they
are not properly managed after their life span, they could cause several environmental and
health problems like headaches, cancer and so on which emanates from frequent exposure
to some of their metals like lead, cobalt, cadmium, etc. Waste/Spent batteries could be
managed and recycled through the recovery of these metals. This study has demonstrated
recovery of cobalt metals present in spent batteries as a means of managing batteries after
their life span on a laboratory scale. The following are therefore concluded: (i) There are
significant variations in quantity of both cobalt and copper leached from spent batteries
produced by different brands. (ii) About 98.02 – 99.98% of cobalt metal was recovered
which signifies a commendable result.

It can be infer from this study that, hydrometallurgical recovery of metals involving leaching
process under certain conditions of 80oC, 1 hour leaching duration, low quantity of
hydrochloric acid, proper filtration and precipitation of pregnant solution can serve as an
effective means of managing spent batteries, thereby preventing or reducing the
occurrence of environmental and health problems caused by improper disposal of these
spent/waste batteries in landfills and incinerators.