The use of lithium-ion batteries has grown since the market entry of portable power tools and consumer electronic devices. Soon, the need for lithium-ion batteries (LIB) will rise, when they are used in hybrid and full electric vehicles as well as in energy storage systems to enable the use of renewable energies. To prevent a future shortage of cobalt, nickel and lithium and to enable a sustainable life cycle of these technologies, new recycling processes for LIBs are needed. These new processes have to regain not only cobalt, nickel, copper and aluminum from spent battery cells, but also a significant share of lithium. Therefore, this presentation approaches unit operations and their combination to set up for efficient LIB recycling processes, especially considering the task to recover high rates of valuable materials with regard to involved safety issues. Further discussed unit operations are: • Deactivation / Discharging of the battery • Disassembly of battery systems (specifically for EV-Battery Systems) • Mechanical Processes (inert crushing, sorting, sieving and thermo-mechanical separation) • Hydro-metallurgical processes • Pyro-metallurgical processes

1. Christian Hanisch, Recycling of Lithium-Ion Batteries, April 7, 2016, Slide 1
From Battery to Precursor and back again
- Recycling of Lithium-Ion Batteries -
Christian Hanisch, Lion Engineering GmbH, c.hanisch@lion-eng.de

2. Christian Hanisch, Recycling of Lithium-Ion Batteries, April 7, 2016, Slide 2
 Loss of ressources
 Energy consuming
 Recycling fees
 Impurities from recycling interfere with
re-synthesis of new battery active
materials
Recycling of Lithium-Ion Batteries - Problems
transportation of hazardous
waste > 500 €/t
Disposal:
~ 1.000 €/t

3. Christian Hanisch, Recycling of Lithium-Ion Batteries, April 7, 2016, Slide 3
Composition of a traction battery
Battery system Battery cells Electrodes Current collector
+
Active material
Reference: TU Braunschweig

4. Christian Hanisch, Recycling of Lithium-Ion Batteries, April 7, 2016, Slide 4
Battery Cell Composition
Separator
4% Rod
2% Case
11%
Lithium
2%
Cobalt
7%
Nickel
6%
Manganese
6%
Oxygen
11%
Al Foil
5%
Anode Coating
19%
Cu Foil
11%
Electrolyte
16%

5. Christian Hanisch, Recycling of Lithium-Ion Batteries, April 7, 2016, Slide 5
World market prices – 06.04.2016
1.498
4.775
22.800
8.270
1.630
Aluminum Copper Cobalt Nickel Manganese
PriceinUSDperton
Prospective active materials: More and more
spinel and olivine structures (e.g. LFP) without
cobalt and nickel

6. Christian Hanisch, Recycling of Lithium-Ion Batteries, April 7, 2016, Slide 6
Unit operations of battery recycling
Mech. treatment HydrometallurgyPyrometallurgy
 Shredding
 Classifying
(e.g. sieving, separating)
 Sorting
(e.g. magnetic separation)
Smelting of the
 whole battery
 cells
 electrodes
 active materials
 Recovery of
transition metals Co,
Ni
Chemical processes
 Leaching
 Extraction
 Crystallization
 Precipitation
 Recovery of
pure metals from
 Active materials
 Slag
Deactivation
 Thermal
pretreatment
 Discharge
 Freezing of the
electrolyte
Reference: Recycling of Lithium-Ion Batteries
Christian Hanisch, Jan Diekmann, Alexander Stieger, Wolfgang Haselrieder, Arno Kwade
Handbook of Clean Energy Systems - Volume 5 Energy Storage, 2015 edited by Jinyue Yan, Luisa F. Cabeza, Ramteen
Sioshansi, 01/2015: chapter 27: pages 2865-2888; John Wiley & Sons, Ltd.., ISBN: 978-1-118-38858-7

7. Christian Hanisch, Recycling of Lithium-Ion Batteries, April 7, 2016, Slide 7
Process routes
Li
Co, Ni
Mechanical treatment Hydrometallurgy
Casing,
etc.
Cu, Al
Battery / Battery cells
Pyrometallurgy
Co, Ni,
Mn
Cu
Reference : Recycling of Lithium-Ion Batteries
Deactivation

8. Christian Hanisch, Recycling of Lithium-Ion Batteries, April 7, 2016, Slide 8
State of the art: Technically possible:
on battery cell level
Green: material recycling
Red: other recycling or disposal
Recycling Efficiency
Separator
4%
Rod
2%
Case
11%
Lithium
2%
Cobalt
7%
Nickel
6%
Manganese
6%
Oxygen
11%
Al Foil
5%
Anode Coating
19%
Cu Foil
11%
Electrolyte
16%
Separator
4%
Rod
2%
Case
11%
Lithium
2%
Cobalt
7%
Nickel
6%
Manganese
6%
Oxygen
11%
Al Foil
5%
Anode
Coating
19%
Cu Foil
11%
Electrolyte
16%

9. Christian Hanisch, Recycling of Lithium-Ion Batteries, April 7, 2016, Slide 9
Basic structure of the process chain
Casing,
BMU, wires,
busbars,
screws
Disassembly
battery system
Disassembly
battery modules
Wires,
busbars,
screws…
cooling units
Battery system
Discharge/
Deactivation
Electric
energy
Cell
processing
Material
processing
Electrolyte,
copper/aluminum
Transition metals
Lithiumsalt with
high purity
Reference: TU Braunschweig Further information: Recycling of Lithium-Ion Batteries

10. Christian Hanisch, Recycling of Lithium-Ion Batteries, April 7, 2016, Slide 10
Example: Cell shredding and sorting
Pre
shredding
Magnetic
separation
Cross flow
sifter
Pneumatic
table
Cells / Modules
Electrode
fragments
Separator foil
Heavy fraction:
Steel-/Al-Casing
Fe
Reference: TU Braunschweig

11. Christian Hanisch, Recycling of Lithium-Ion Batteries, April 7, 2016, Slide 11
Air Classification and Sieving
Zigzag-Classifier
Air jet
Heavy fraction
Light fraction

12. Christian Hanisch, Recycling of Lithium-Ion Batteries, April 7, 2016, Slide 12
Separation results after sifting and sieving
Reference: TU Braunschweig and Lion Engineering GmbH

13. Christian Hanisch, Recycling of Lithium-Ion Batteries, April 7, 2016, Slide 13
Separation results after sifting and sieving
Reference: TU Braunschweig and Lion Engineering GmbH

14. Christian Hanisch, Recycling of Lithium-Ion Batteries, April 7, 2016, Slide 14
Hydrometallurgical process
Leaching / Extraction of
active material
Purification through:
- Crystallisation
- Ion-exchange
Salt separation by
electrochemical processes
LiOH / Li2CO3
Co,Ni,Mn-Sol.
Li-brine
Precipitation
Metal oxide particles
New active materials
Calcination
Reference: TU Braunschweig
Special thanks to
H.C. Starck and
Rockwood Lithium
Further information:
LithoRec project report,
2011
and
Effect of Impurities
Caused by a Recycling
Process on the
Electrochemical
Performance of
Li[Ni0.33Co0.33Mn0.33]O2
S. Krueger et al.,
Journal of Electroanalytical
Chemistry 07/2014; 726:
91-96.

15. Christian Hanisch, Recycling of Lithium-Ion Batteries, April 7, 2016, Slide 15
Pilot Plant LithoRec II
• Realized in Research Project
LithoRec II funded by the Federal
Ministry for the Environment with
project partners TU Braunschweig,
Volkswagen
• Discharging, Dismantling, Crushing,
Electrolyte Removal, Sifting and
Sieving
• Material Recycling of 75% of a BEV
system
• Lion Engineering GmbH tested its
patent pending process

16. Christian Hanisch, Recycling of Lithium-Ion Batteries, April 7, 2016, Slide 16
1 metric ton
LIB-System
Input and Output
Process Costs vs. Sales Value

17. Christian Hanisch, Recycling of Lithium-Ion Batteries, April 7, 2016, Slide 17
Recycling of Production Scraps/Rejects
0 100 200 300 400 500
0
20
40
60
80
100
120
140
SpecificCapacity[mAh/g]
Cycle [-]
Material / Separation method
Reference
Rejects / Mechanical
Rejects / Chemical
Electrochemical Cycling of Directly Recoated Reject Materials
Charge / Discharge Rate 3C/3C
25 cm² Pouch Cell, C = 44 mAh, T = 21 °C
(Re-)Coating
Solvent
Dispersing
A
n
t
r
i
e
b
ω
Separated
Coating
Reference: TU Braunschweig and Lion Engineering GmbH
Further information:
In-Production Recycling of Active Materials from
Lithium-Ion Battery Scraps
in ECS Transactions 64(22): 131-145 · April 2015

18. Christian Hanisch, Recycling of Lithium-Ion Batteries, April 7, 2016, Slide 18
Conclusion
 Metallurgical recycling of spent batteries is feasible
to regain Co and Ni
 Future battery materials challenge battery
recyclers even more economically
 Increasing of recycling yield possible by
Combination of different unit operations
 Challenges:
 Safety
 Purity
 Process costs
Further information: Recycling of Lithium-Ion Batteries & Recycling of Lithium-Ion Batteries: A Novel Method to
Separate Coating and Foil of Electrodes

19. Christian Hanisch, Recycling of Lithium-Ion Batteries, April 7, 2016, Slide 19
To Do: Further R&D
Tasks in proposed process chain:
 Providing Batteries
 Extraction of battery active material
 Re-synthesizing battery active material
 Equipping EV with recycled battery material
 Analytics, LCA, Battery Test Cells
Join LinkedIn Group Lithium-Ion
Battery Recycling

20. Christian Hanisch, Recycling of Lithium-Ion Batteries, April 7, 2016, Slide 20
… especially from both LithoRec projects and at
BLB and TU Braunschweig.
Thanks to the Federal Ministry of the
Environment, Nature Conservation, Building and
Nuclear Safety
Further questions?
Christian Hanisch
c.hanisch@lion-eng.de
Thank you…. and Thanks to all our partners…