XXXI International Mineral Processing Congress 2024 Proceedings/Washington, DC/Sep 29–Oct 3 3237
commercial standards provided by VWR containing 1000
pm Li, Co, Mn, and Ni in 2% (vol.) HNO3. Standard
compositions were adjusted by adding sulfuric acid (0.35
mol L–1) in order to have the same sulfate concentration as
in the sample to analyse and reduce interference phenom-
ena during elemental analyses.
RESULTS AND DISCUSSION
Lithium-ion battery recycling involves several steps.
Initially, mineral processing is used to create a concentrated
material known as ‘black mass.’ Subsequently, this black
mass undergoes treatment through pyrometallurgy, hydro-
metallurgy, or a combination of both processes (pyromet-
allurgy and hydrometallurgy). The objective is to extract
valuable metals and convert them into reusable salts, which
are then utilized in the production of cathode materials for
new lithium-ion batteries.
Figure 2 shows typical flowsheets implemented to
extract and separate metals contained in the black mass.
In both flowsheets, sulfuric acid is usually used in the pres-
ence of hydrogen peroxide to leach the black mass, but
other reagents such as hydrochloric acid or organic acids
like citric acid could be good alternatives [2–4]. Depending
on the performance of the black mass production process,
the black mass can contain more or less copper, aluminum
and iron beside the valuable metals (cobalt, nickel, manga-
nese and lithium). It is therefore necessary to remove these
impurities. In the hydrometallurgical flowsheet displayed
in Figure 2a, copper can be removed by solvent extraction
[5] or by sulfide precipitation [6] while aluminum and iron
can be precipitated by increasing the pH with hydroxide
ions. Then, in hydrometallurgical processes, impurities are
removed prior to extracting manganese, cobalt, nickel and
lithium. Manganese, cobalt and nickel can be extracted by
solvent extraction by using appropriate extractants, and
then, crystallized as sulfate salts, which can be used further
to resynthesize cathode materials. Lithium precipitation
by sodium carbonate is the last step of the process. The
main disadvantages of this flowsheet are the production of
sodium sulfate effluent and lithium losses throughout the
different process stages.
Figure 2b shows the different steps implemented in a
flowsheet combining thermal treatment and hydrometal-
lurgy. In this flowsheet, the black mass undergoes a thermal
treatment at 500 °C before leaching to release lithium from
the black mass. Thus, lithium losses can be reduced since
it is extracted and converted in lithium carbonate at the
beginning of the process. After removing impurities, man-
ganese, cobalt and nickel can be extracted by solvent extrac-
tion and crystallized as sulfate salts as previously described.
The main advantages of this process are low lithium losses
and it does not produce sodium sulfate effluent.
In order to reduce lithium losses, electrodialysis should
be implemented at the beginning of the process just after the
(a)
(b)
Leaching
Cu
recovery
Impur.
precip.
Mn SX Co SX Ni SX Na
recovery
Na2SO4
Li
precipit.
Ni
Cryst.
Co
Cryst.
Mn
Cryst.
BM
Graphite CuS Al, Fe
P, etc.
MnSO4,H2O CoSO4,6H2O NiSO4,7H2O Li2CO3
Na2CO3
Black mass Leaching
Impur.
precip.
Mn SX Co SX Ni SX
Reductant
500 °C
CO2
Li2CO3 Al, Cu,
etc.
Ni
Cryst.
Co
Cryst.
Mn
Cryst.
MnSO4,H2O CoSO4,6H2O NiSO4,7H2O
Graphite
Figure 2. Typical general flowsheets to extract and separate metals contained in the black mass of spent lithium-ion batteries
by (a) hydrometallurgy and (b) a combination of hydrometallurgy and pyrometallurgy
commercial standards provided by VWR containing 1000
pm Li, Co, Mn, and Ni in 2% (vol.) HNO3. Standard
compositions were adjusted by adding sulfuric acid (0.35
mol L–1) in order to have the same sulfate concentration as
in the sample to analyse and reduce interference phenom-
ena during elemental analyses.
RESULTS AND DISCUSSION
Lithium-ion battery recycling involves several steps.
Initially, mineral processing is used to create a concentrated
material known as ‘black mass.’ Subsequently, this black
mass undergoes treatment through pyrometallurgy, hydro-
metallurgy, or a combination of both processes (pyromet-
allurgy and hydrometallurgy). The objective is to extract
valuable metals and convert them into reusable salts, which
are then utilized in the production of cathode materials for
new lithium-ion batteries.
Figure 2 shows typical flowsheets implemented to
extract and separate metals contained in the black mass.
In both flowsheets, sulfuric acid is usually used in the pres-
ence of hydrogen peroxide to leach the black mass, but
other reagents such as hydrochloric acid or organic acids
like citric acid could be good alternatives [2–4]. Depending
on the performance of the black mass production process,
the black mass can contain more or less copper, aluminum
and iron beside the valuable metals (cobalt, nickel, manga-
nese and lithium). It is therefore necessary to remove these
impurities. In the hydrometallurgical flowsheet displayed
in Figure 2a, copper can be removed by solvent extraction
[5] or by sulfide precipitation [6] while aluminum and iron
can be precipitated by increasing the pH with hydroxide
ions. Then, in hydrometallurgical processes, impurities are
removed prior to extracting manganese, cobalt, nickel and
lithium. Manganese, cobalt and nickel can be extracted by
solvent extraction by using appropriate extractants, and
then, crystallized as sulfate salts, which can be used further
to resynthesize cathode materials. Lithium precipitation
by sodium carbonate is the last step of the process. The
main disadvantages of this flowsheet are the production of
sodium sulfate effluent and lithium losses throughout the
different process stages.
Figure 2b shows the different steps implemented in a
flowsheet combining thermal treatment and hydrometal-
lurgy. In this flowsheet, the black mass undergoes a thermal
treatment at 500 °C before leaching to release lithium from
the black mass. Thus, lithium losses can be reduced since
it is extracted and converted in lithium carbonate at the
beginning of the process. After removing impurities, man-
ganese, cobalt and nickel can be extracted by solvent extrac-
tion and crystallized as sulfate salts as previously described.
The main advantages of this process are low lithium losses
and it does not produce sodium sulfate effluent.
In order to reduce lithium losses, electrodialysis should
be implemented at the beginning of the process just after the
(a)
(b)
Leaching
Cu
recovery
Impur.
precip.
Mn SX Co SX Ni SX Na
recovery
Na2SO4
Li
precipit.
Ni
Cryst.
Co
Cryst.
Mn
Cryst.
BM
Graphite CuS Al, Fe
P, etc.
MnSO4,H2O CoSO4,6H2O NiSO4,7H2O Li2CO3
Na2CO3
Black mass Leaching
Impur.
precip.
Mn SX Co SX Ni SX
Reductant
500 °C
CO2
Li2CO3 Al, Cu,
etc.
Ni
Cryst.
Co
Cryst.
Mn
Cryst.
MnSO4,H2O CoSO4,6H2O NiSO4,7H2O
Graphite
Figure 2. Typical general flowsheets to extract and separate metals contained in the black mass of spent lithium-ion batteries
by (a) hydrometallurgy and (b) a combination of hydrometallurgy and pyrometallurgy