Resource Recovery Technologies

Metals recovery
from spent Li-ion batteries
by pyrometallurgy
Belen Rosas – Felipe Guerrero – Ernest Kyei

1
 LIB: Markets
Refined Cobalt Supply and Demand Forecast Nickel Supply and Demand Forecast

“Global Cobalt (Co) supply entered a deficit in “The global Nickel market is now in a supply shortfall”
2016 and this is expected to continue to drive
prices up until its new supply”.
2
 LIB: Markets
Global LIB market size and forecast 2015-2024 (US$ Billion)

Source: Variant Market Research.

3
 LIB: Environmental Hazards
Component Materials Hazard
     
LiNiO, LiMnO, LiCoO, Heavy metals such as Ni and Co pose a threat
Cathode LiFePO, LiNiCoMnO to the environment and to human health.

Corrosive, produces hazardous gas such as HF,

Electrolyte LiClO, LiPF, LiBF, DMSO, chlorine , carbon dioxide and Carbon
PC, and DEC Monoxide when burnt.

                                                                              Polyvinylidene
                                    fluoride
          
(PVDF),
Binder polytetrafluoroethylene Produces Hydrogen Fluoride when burnt.
(PTFE)

4
 LIB: Applications
Depends on the type of LIB’s;
Lithium Cobalt Oxide Lithium Nickel Manganese Cobalt Oxide
(LiCoO2) (LiNiMnCoO2 )

5
 LIB: Applications
Depends on the type of LIB’s;
Lithium Manganese Oxide (LiMn2O4)

Vehicles   

Medical

6
From LIB to Spent-LIB: Functioning

7
Spent-LIB: Thermodynamics on Pyrometallurgy

Crude metal production.

“Liquifying LIBs under controlled atmosphere for separating produced phases by their
densities”.
Off-gas
O2
Slag (oxidized metals)
Reductive Smelting
Spent LIB
Furnace Alloy (reduced metals)

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Spent-LIB: Thermodynamics on Pyrometallurgy

Metal intermediate production.

Roasting: Chemical reaction for remotion without involving smelting.

Off-gas CO

Reductive
Spent LIB
Roasting Reduced metals.

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Recycling process: UMICORE’s VAL’EAS

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Spent-LIB: Thermodynamics on Pyrometallurgy
LIB

LiCoO2 LiMn2O4 LiFePO4 LiNi0,8Co0,15Al0,05O2

pO2 Controlling oxidation and/or

reduction.

CO/CO2 Efficiency when using C

CO2
Use of C

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 Spent-LIB: Thermodynamics on Pyrometallurgy
LIB
CO/CO2 ≈ 1/10 LiCoO2 LiMn2O4 LiFePO4 LiNi0,8Co0,15Al0,05O2
Reducing agent

O2 = 2NiO Carbon 2C + O2 = 2CO Oxidized

+
2N i
To-be alloyed
elements oO pO2 ≈ 10-9,5 atm Lithium Li + O2 = LiO2
O2 = 2C 2C +
O Slagged
+ = 2C CO/CO2 ≈ 103
2Co 2
O
2M nO Aluminum 4/3 Al + O2 = 2/3 Al2O3
+ O2 =
2Mn Slagged

3 Al 2O 3 pO2 ≈ 10-18 atm

Manganese 2Mn + O2 = 2MnO Slagged
To-be slagged =2/
A l + O2
elements 4/3
Li O 2 2Co + O2 = 2CoO
O2
= Cobalt
Li + Alloyed

Nickel 2Ni + O2 = 2NiO

Alloyed
1200 °C 12
Recycling process: INMETCO

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 Spent-LIB: Thermodynamics on Pyrometallurgy
LIB
CO/CO2 ≈ 1/101,4 LiCoO2 LiMn2O4 LiFePO4 LiNi0,8Co0,15Al0,05O2

iO Carbon 2C + O2 = 2CO Oxidized

= 2N
+ O2
2N i pO2 ≈ 10-9,5 atm
To-be alloyed
elements oO
Lithium Li + O2 = LiO2
= 2C 2C + Slagged
+ O2 O
2Co 2 =2
CO CO/CO2 ≈ 103,5
2M nO Aluminum 4/3 Al + O2 = 2/3 Al2O3
+ O2 =
2Mn Slagged

3 Al 2O 3 pO2 ≈ 10-17,8 atm

2Mn + O2 = 2MnO Slagged
To-be slagged =2/
Al + O2
elements 4/3 Li O 2
O2
=
Cobalt 2Co + O2 = 2CoO
Li + Alloyed

Nickel 2Ni + O2 = 2NiO

Alloyed
1260 °C 14
Recycling process: Accurec (technical scale)

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 Spent-LIB: Thermodynamics on Pyrometallurgy
LIB

LiCoO2 LiMn2O4 LiFePO4 LiNi0,8Co0,15Al0,05O2

Reducing agent
2N i O
Carbon 2C + O2 = 2CO Oxidized
=
2N i
+ O2
O = 2CoO
2Co +
2
Lithium Li + O2 = LiO2
CO/CO2 ≈ 10 3,4
To-be alloyed 2C +
O
Slagged
elements 2 = 2C
O
= 2M
nO
pO2 ≈ 10-13 atm Aluminum 4/3 Al + O2 = 2/3 Al2O3
CO/CO2 ≈ 10 4,8

2M n + O2 Slagged
pO2 ≈ 10-16 atm
Al 2O 3
Manganese 2Mn + O2 = 2MnO Alloyed
/3
To-be slagged O2 =2
elements /3 Al +
4 iO 2
=L Cobalt 2Co + O2 = 2CoO
O 2
Li + Alloyed

Nickel 2Ni + O2 = 2NiO

Alloyed
1750 °C
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 Recycling process: Lab scale tests

Reduction roasting is used to break

LiNixCoyMnzO2 into Li2CO3, Ni, Co and MnO

12LiNi1/3Co1/3Mn1/3O2 + 7C = 6Li2CO3 + 4Ni + 4Co + 4MnO2 + CO2 (g)

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 Spent-LIB: Thermodynamics on Pyrometallurgy
LIB
CO/CO2 ≈ 1/101,5

LiCoO2 LiMn2O4 LiFePO4 LiNi0,8Co0,15Al0,05O2

Reducing agent
Carbon 2C + O2 = 2CO Oxidized
= 2N i O
+ O2 CO/CO2 ≈ 10
To-be alloyed 2C + 2N i
elements
O2 = 2C Lithium Li + O2 = LiO2
Co O O Oxidized
O = 2
2Co + 2
2M nO Aluminum 4/3 Al + O2 = 2/3 Al2O3
+ O2 =
2Mn Oxidized
pO2 ≈ 10-15 atm

3 Al 2O 3 Manganese 2Mn + O2 = 2MnO Oxidized

To-be slagged =2/
O2
elements /3 Al + pO2 ≈ 10-20 atm
4 Li O 2
+ O2
=
Cobalt 2Co + O2 = 2CoO
Li Reduced

Nickel 2Ni + O2 = 2NiO

Reduced
650 °C 18
 Conclusions
When recovering/recycling metals from Spent LIB’s:
• Driving forces: Critical supply of metals Co, Mn & Ni, increasing demand of LIBs, Spent-
LIB environmental impact.
• 100 % pyrometallurgical process is generally not possible.
• Need to purify alloy and slag phases through hydrometallurgy before re-using.
• Remarks:
• High production capacity and simple operation.
• Required off-gas treatment to decrease environmental impact.
• Higher-energy consumption compared to hydrometallurgical processes.
• Besides technical aspects to be improved.
• Proper collection system is a key issue to achieve high-recycling rates.

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 References
T. Georgi-Maschler, B. Friedrich, R. Weyhe, H. Heegn and M. Rutz, “Development of a recycling process for Li-ion
batteries,” Journal of Power Sources, pp. 173-182, 2012.

Hu, J., Zhang, J., Li, H., Chen, Y., & Wang, C. (2017). A promising approach for the recovery of high value-added metals
from spent lithium-ion batteries. Journal of Power Sources, 351, 192-199.

Zheng, X., Zhu, Z., Lin, X., Zhang, Y., He, Y., Cao, H., & Sun, Z. (2018). A mini-review on metal recycling from spent lithium
ion batteries. Engineering.

Väyrynen, A., & Salminen, J. (2012). Lithium ion battery production. The Journal of Chemical Thermodynamics, 46, 80-85.

Meshram, P., Pandey, B. D., & Mankhand, T. R. (2014). Extraction of lithium from primary and secondary sources by pre-
treatment, leaching and separation: A comprehensive review. Hydrometallurgy, 150, 192-208.

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