Documente Academic
Documente Profesional
Documente Cultură
INTRODUCTION
A lithium-ion battery or Li-ion battery (abbreviated as LIB) is a type of rechargeable
battery in which lithium ions move from the negative electrode to the positive electrode during
discharge and back when charging. Li-ion batteries use an intercalated lithium compound as
one electrode material, compared to the metallic lithium used in a non-rechargeable lithium
battery. The electrolyte, which allows for ionic movement, and the two electrodes are the
constituent components of a lithium-ion battery cell. The use of lithium-ion batteries (LIBs) is
expected to increase in the near future. The main reason for this will be the use of electric cars,
which use LIBs as the power source. LIBs are also widely used in portable electronic devices
(e.g. cellular phones and laptops). The popularity of LIBs is due to their high energy density,
high voltages and low weight to volume ratio (Xu et al., 2008). LIBs have an expected lifespan
of 3-5 years. Over the next few years, an increasingly large waste stream of LIBs is expected.
LIBs contain toxic and flammable components, as well as valuable metals such as Li, Ni, Cu
and Co. For these reasons, there are benefits to recycling used LIBs, instead of disposal in
landfills.
According to the directives published in many countries, the adequate destination of spent
batteries may involve methods such as landfill disposition, stabilization, incineration and/or
recycling processes. Safe disposal in landfills or stabilization of battery residues becomes more
and more expensive due to the increasing amount of waste produced, and also due to the limited
storage capacity of sanitary landfills and/or special waste dumpsites. Incineration of batteries
is an expensive method as well and it can even cause mercury, cadmium and dioxin emissions
into the environment.
Fig 1. Waste management hierarchy is one presentation and recommendation of waste treatment options
In a closer examination, the level of recycling can be specified. When the recycled material can
substitute a large share of virgin material in a new product and has properties close to the
original quality, the level of recycling is considered high. Using the material in a commodity
that has clearly lower quality or functionality than the original one is in turn referred to as
“downcycling”. (Worrell 2014a, p. 499). It is hence thought that more of the original material
value and the energy investments made for it are restored by higher level of recycling.
1|Page
Chemical Project Economics Assignment
LITHIUM-ION BATTERIES
In an LIB, the cathode is an aluminium plate coated with the cathode material, which is a
lithium metal oxide. The typical composition of LIBs is provided in Xu et al (2008).
Polyvinylidene fluoride (PVDF) is used to bind the electrode coating to the plate.
BATTERY RECYCLING
The recycling of LIBs has an enormous potential for economically strategic industrial metals.
However, there is a growing amount of diverse lithium-ion subsystems, operating with
different metals and lithium compounds in the cathode material. The Li-ion battery is named
after the used cathode material such as LCO (lithium cobalt oxide), NCM (lithium nickel
manganese cobalt oxide), NCA (lithium nickel cobalt aluminum oxide) and LFP (lithium iron
phosphate). As a result of missing industrial agreement on standards it is not possible to distinct
these systems visually. This severely complicates the efficient recycling processes. Recycling
processes for LIBs are combinations of different unit operations. Fig 3 summarizes possible
process options for the involved unit operations such as deactivation, mechanical treatment, as
well as the subsequent pyro- and hydrometallurgical treatments. The scheme displayed in Fig3
depicts the advantage of combining different unit operations in order to fulfill the goal of high
recovery rates. Thus, the casing, copper and aluminum foil, and the most valuable components
such as nickel, cobalt, and manganese can be recovered using a combination of mechanical and
hydrometallurgical treatments.
Fig 3. Unit operations in battery recycling and their possible combinations to establish efficient recycling
process routes.
2|Page
Chemical Project Economics Assignment
Fig 4. Flowchart of Toxco’s (Retriev Technologies Inc.) hydrometallurgical recycling process for LIBs.
3. Recupyl
4. Accurec
4|Page
Chemical Project Economics Assignment
RETRIEV
PROCESS/TREATMENT UMICORE RECUPYL ACCUREC
TECHNOLOGIES
CATHODE RECYCLING
CoCl2 MeO + C cake LCO/CO(OH)2/Co Co-alloy
PRODUCT
Cathode
END USE Metal manufacturing unknown As such
material
Ready for
LEVEL VS CATHOD hydrothermal
- - -
PRECURSOR synthesis of
LCO
In furnace,
BINDER but not Not discussed Not discussed In furnace
discussed
5|Page
Chemical Project Economics Assignment
Polymer
Fe partly Steel recovered evaporated,
recovered in with magnetic Fe recovered
Steel, Al and plastics
alloy, separator; Al, Cu with
CASINGS recovered with shaker
Al slagged, and plastics with magnetic
table
Polymer used densimetric separator, Al
as energy separator with air
separator
Recovered with
Al slagged, Recovered
Recovered with densimetric table
AL AND CU FOILS Cu recovered with air
shaker table Impurity Cu also
in alloy separator
precipitated
From
CATHODE MATERIAL cathode to From cathode to raw From cathode
-
LOOP cathode material to alloy
precursor
Processes using mechanical separation methods and the methods used
Shredder and/or Rotary shear,
COMMINUTION - Mill
hammer mill Impact mill
Vibrating
SIZE SEPERATION - Not mentioned Vibrating screen
screen
Zig zag air
GRAVITY SEPERATOR - Densimetric table Densimetric table
separator
Treating of graphite in different technologies
Partly burnt;
partly used in
Used as
carbo-
reducing Recovered in MeO + Filtered off in
GRAPHITE reductive
agent in C filter cake leaching step
melting;
furnace
finally,
slagged
SELECTION OF ROUTE
1. In the case of the Recupyl process, complete dissolution of the metals was very difficult to
achieve. Since recovering the lithium on its own did not satisfy the aim of recovering all the
valuable components (e.g. copper, aluminium) partial dissolution was not acceptable.
2. Lab-scales tests at the high temperatures required for the Umicore process were also
difficult to achieve. Smelting at the lower ranges quoted for the Umicore process did not
produce a clean separation of metal and slag. It does not aim at the recovery of lithium which
is the main disadvantage. Furthermore, ignoble metals are slagged and organic materials as
well as carbon are lost. Ultimately the failure of these tests led to a re-evaluation of other
approach.
3. Therefore, an alternative competing recycling process based on pyro- and
hydrometallurgical process steps should also consider an appropriate pre-treatment to recover
as many battery components as possible.
4. In the case of the Toxco’s process recycle efficiency was better for primary lithium
batteries and not for LiB.
5. In Accurec process high recovery rate of Co alloy and Li2CO3 is pursued by a combination
of physical separation, hydrometallurgical and pyrometallurgical methods (Vezzini 2014, p.
542), although it is also mentioned that the target is to recover as many battery components as
possible (Georgi-Maschler et al. 2012).
6|Page
Chemical Project Economics Assignment
The criteria used to select a process for the recycling of LIBs are listed below:
➢ The process must recover lithium and cobalt from the batteries treated.
➢ It must be possible to test the process steps at a lab scale within the budget of this
project.
➢ The process should be made up of steps which have been demonstrated at a
commercial scale.
➢ The product should be of a battery grade, so that it can be used in production of new
batteries.
➢ The process should be simple to design and operate.
➢ The process should be scalable.
➢ All products can be fed into another industry (zero waste).
PROCESS DESCRIPTION
(recently modified in south Africa)
Step 3: Leaching
The first stage of leaching was done on the roasted product. The purpose of this leach was to
selectively dissolve lithium, with minimal dissolution of other metals. Leaching was done at
7|Page
Chemical Project Economics Assignment
60°C in 1 M hydrochloric acid (HCl). The solid to liquid ratio was 1:10. Agitation was achieved
by swirling every 10 minutes. Leaching was done for varying lengths of time. It was found that
40 mins of leaching resulted in the highest lithium extraction, with the lowest copper
dissolution.
Element Leach Extent
Al 85.8%
Ca 27.7%
Co 17.0%
Cu 4.2%
Fe 40.2%
Li 76.0%
Mg 71.0%
Mn 83.2%
Na 42.5%
Ni 6.4%
Zn 90.0%
Table 2: Leaching extents in the low acid concentration leach (1 M HCl, 60°C, 40 mins)
After filtration, the residue from the low concentration leach was then re-leached in 2M HCl,
with hydrogen peroxide (50%) added to oxidise the copper.
Table 3: Leaching extents in the high concentration leach (2 M HCl, 60°C, 60 mins with H 2O2)
The scoping tests indicated the technical viability of the two-stage leach process.
Step 4: PH Adjustment
Solution from the first leaching stage is fed to the pH adjustment step. The pH of the leach
solution is increased prior to the lithium precipitation step. This is achieved by adding lithium
hydroxide. The target pH is 9. As a result of the increase in pH, copper, aluminum, iron,
magnesium and manganese precipitate from solution. These precipitates are removed by
filtration. The filtrate solution is fed to lithium precipitation.
8|Page
Chemical Project Economics Assignment
9|Page
Chemical Project Economics Assignment
Basis: - 1 year
H20 Low
concentration L pH L
HCl Leaching S adjustment S
LiOH Li Lithium
precipitation product
CO2
L
S
Vent
H202 High
L Mixed
concentration
L
precipitation Hydroxide
Leaching
S S
H20 Product
Leach
HCl
Residue
Lime
Gypsum L Gypsum
Removal S Precipitate
H2SO4
Recycling
10 | P a g e
Chemical Project Economics Assignment
If we compare other process/treatment there the recycling efficiency was less compare to this
selected route and plus they not focus on recovery of each and every element. So, we can say
that this selected route is economically feasible.
References: -
1. Shin, S.M., Kim, N.H., Sohn, J.S., Yang, D.H. & Kim, Y.H., 2005. Development of a metal
recovery process form Li-ion battery wastes, Hydrometallurgy, 79, p. 172 – 181.
2. Zhang, P. Yokoyama, T., Itabashi, O. Suzuki, T.M. & Inoue, K., 1998. Hydrometallurgical
process for recovery of metal values from spent lithium-ion secondary batteries,
Hydrometallurgy, 47, p. 259 – 271.
3. Xu, J., Thomas, H.R., Francis, R.W., Lum, K.R., Wang, J. & Liang, B. (2008) A review of
processes and technologies for the recycling of lithium-ion secondary batteries, Journal of
Power Sources, 177, p. 512 – 527.
4. Kondas, J., Jandova, J. & Nemeckova, M., 2006. Technical note: Processing of spent
Li/MnO2 batteries to obtain Li2CO3, Hydrometallurgy, 84, p. 247 – 249.
5. Contestabile, M., Panero, S. & Scrosati, B., 1999. A laboratory-scale lithium battery
recycling process, Journal of Power Sources, 83, p. 75 – 78.
6. Castillo, S., Ansart, F., Laberty-Robert, C. & Portal, J., 2002. Advances in the recovering of
spent lithium battery compounds, Journal of Power Sources, 112, p. 247 – 254.
11 | P a g e