From battery-to-precursor - Recycling of Lithium-Ion Batteries

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, [email protected]

http://www.lion-eng.de/


mailto:[email protected]




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




Composition of a traction battery

Battery system Battery cells Electrodes Current collector

+ Active material

Reference: TU Braunschweig



http://www.ipat.tu-bs.de/en/forschung/arbeitsgruppen/elektrochemische-speichertechnik/recyclingrecycling


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%




World market prices – 06.04.2016

1.498

4.775

22.800

8.270

1.630

Aluminum Copper Cobalt Nickel Manganese

Pri

ce in

USD

per

to

n

Prospective active materials: More and more spinel and olivine structures (e.g. LFP) without cobalt and nickel




Unit operations of battery recycling

Mech. treatment Hydrometallurgy Pyrometallurgy

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



https://www.researchgate.net/publication/277570136_Recycling_of_Lithium-Ion_Batteries?ev=prf_pub









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











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%




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












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






Air Classification and Sieving

Zigzag-Classifier

Air jet

Heavy fraction

Light fraction




Separation results after sifting and sieving

Reference: TU Braunschweig and Lion Engineering GmbH






Separation results after sifting and sieving








Hydrometallurgical process

Leaching / Extraction of active material

Purification through:

- Crystallisation

- Ion-exchange

Salt separation by

electrochemical processes

LiOH / Li2CO3

Co

, N

i, M

n-S

ol.

Li-brin

e

Precipitation

Metal oxide particles

New active materials

Calcination


Referenz

LNCMO V21

LNCMO V5-Z

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.




http://www.erneuerbar-mobil.de/de/projekte/foerderprojekte-aus-dem-konjunkturpaket-ii-2009-2011/batterierecycling/abschlussberichte-recycling/abschlussbericht-lithorec.pdf






https://www.researchgate.net/publication/262641103_Effect_of_Impurities_Caused_by_a_Recycling_Process_on_the_Electrochemical_Performance_of_LiNi0.33Co0.33Mn0.33O2?ev=prf_pub























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



http://www.lion-eng.de/images/pdf/Recycling-of-Lithium-Ion-Batteries-LionEngineering.pdf

















1 metric ton LIB-System

Input and Output

Process Costs vs. Sales Value







Recycling of Production Scraps/Rejects

0 100 200 300 400 500

0

20

40

60

80

100

120

140

Sp

ecific

Ca

pa

city [m

Ah

/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


Further information: In-Production Recycling of Active Materials from Lithium-Ion Battery Scraps in ECS Transactions 64(22): 131-145 · April 2015





https://www.researchgate.net/publication/275823634_In-Production_Recycling_of_Active_Materials_from_Lithium-Ion_Battery_Scraps




















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











http://www.sciencedirect.com/science/article/pii/S0959652615011154






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



https://www.linkedin.com/groups/LithiumIon-Battery-Recycling-8481232/about










… 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

[email protected]

Thank you…. and Thanks to all our partners…




