Recycling of Lithium-Ion Batteries (from Electric Vehicles)

Abstract

In this webinar, different aspects of recycling of lithium-ion batteries from electric vehicles will be discussed.

Different industrial and research processes are designed to reach different goals in their recycling yields and product purities. So, some processes concentrate on the recycling of the most valuable metals like cobalt, nickel and copper in very stable pyro-metallurgical processes. Whereas, others are designed to avoid down-cycling of valuable battery active materials, but to regain battery grade materials.

Furthermore, safety issues in the field of recycling of lithium-ion batteries and ways how to deal with them will be addressed.

Newest developments of different process chains, and some new process alternatives for recycling of LIB from EVs in research and development will be talked about. And last but not least, the option of an In-Process-Recycling of LIB-Production Rejects will be reviewed, which is a very interesting possibility to reduce material, and thereby production costs.

This webinar will focus on the following key topics:

• Recycling of Lithium Ion Batteries
• Different Industrial and Research Processes and Recycling Yields
• Safety Issues in Battery Recycling and how to address them
• Recent Developments in Recycling of LIB from EVs
• Recycling of LIB-Production Rejects

Full text

Christian Hanisch, Recycling of Lithium-Ion Batteries, June 14, 2014, Slide 1
Recycling of Lithium-Ion Batteries
Christian Hanisch, c.hanisch@lion-eng.de

Christian Hanisch, Recycling of Lithium-Ion Batteries, June 14, 2014, Slide 2
 Recycling of Lithium Ion Batteries
 Different Industrial and Research Processes and Recycling
Yields
 Safety Issues in Battery Recycling and how to deal with them
 Recent Developments in Recycling of LIB from EVs
 Recycling of LIB-Production Rejects
Outline

Christian Hanisch, Recycling of Lithium-Ion Batteries, June 14, 2014, Slide 3
Recycling of Lithium-Ion Batteries

Christian Hanisch, Recycling of Lithium-Ion Batteries, June 14, 2014, Slide 4
Composition of a traction battery
Battery system Battery cells Electrodes Current collector
+
Active material
Reference: TU Braunschweig

Christian Hanisch, Recycling of Lithium-Ion Batteries, June 14, 2014, Slide 5
Composition of a traction battery
Battery system level:
50-70% Battery cells  Further treatment (next slide)
15-45% Casing  Smelting  Steel, aluminum
2-6% Wiring  Separation  Smelting Copper, plastic
2-3% Electronics, PCB  Separation  Iron, copper, aluminum, residual
0-3% Cooling tubes, casing parts  Granulation  Plastic
0-3% Busbars  Separation  Copper, Plastic
1-2% Screws, metal parts  Reuse, remelt  Iron
<1% Rubber, tape, etc.  Waste
Reference: TU Braunschweig

Christian Hanisch, Recycling of Lithium-Ion Batteries, June 14, 2014, Slide 6
Composition of a traction battery
Battery cell level:
ca. 65% Electrodes  Further treatment (next slide)
10-15% Steel / Aluminum casing  Smelting  Aluminum, steel
10-20% Electrolyte  Recovery  Valuable solvents,
electrolytic salt
 Incineration?
2 - 5% Further parts  Smelting  Steel, copper, aluminum
ca. 3% Separator/Foils  Incineration
Reference: TU Braunschweig

Christian Hanisch, Recycling of Lithium-Ion Batteries, June 14, 2014, Slide 7
Composition of a traction battery
Electrode level:
15% Copper foil  Briquetting  Smelting
8% Aluminum foil  Briquetting  Smelting
31% Anode coating  Hydrometallurgy  Lithium, organic residues
46% Cathode coating  Hydrometallurgy  Lithium, Ni/Co/Mn-solution.
New active materials
Reference: TU Braunschweig

Christian Hanisch, Recycling of Lithium-Ion Batteries, June 14, 2014, Slide 8
Current world market prices
1.818
7.125
27.500
13.853
2.100
Aluminum Copper Cobalt Nickel Manganese
Price in USD per ton
Prospective active materials: More and more
spinel and olivine structures (e.g. LFP) without
cobalt and nickel

Christian Hanisch, Recycling of Lithium-Ion Batteries, June 14, 2014, Slide 9
Lithium-ion battery cell
Per 200 battery cells:
 ca. 4 kg lithium
 ca. 12 kg nickel
 ca. 12 kg cobalt
 ca. 10 kg manganese
Stoichiometric compostion of the active material
lithium-nickel-cobalt-manganese-oxide Li(NiCoMn)
1/3
O
2
Oxygen
[PROZENTSATZ
]
Lithium
7%
Nickel
20%
Cobalt
[PROZENTSATZ
]
[RUBRIKENNA
ME]ese
[PROZENTSATZ
]
Cobalt
21%
Manganese
19%
Oxygen
33%
Lithium
7%
Nickel
20%

Christian Hanisch, Recycling of Lithium-Ion Batteries, June 14, 2014, Slide 10
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: TU Braunschweig
Further information: 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

Christian Hanisch, Recycling of Lithium-Ion Batteries, June 14, 2014, Slide 11
Process routes
Active material
Co, Ni
Cu, Al
Casing,
electrolyte
Mechanical treatment
Pyrometallurgy
Battery / Battery cells
Reference: TU Braunschweig
Deactivation
Umicore
Cu
Accurec
Further information: Recycling of Lithium-Ion Batteries

Christian Hanisch, Recycling of Lithium-Ion Batteries, June 14, 2014, Slide 12
Process routes
Li
Co, Ni
Mechanical treatment
Hydrometallurgy
Casing,
etc.
Cu, Al
Battery / Battery cells
Pyrometallurgy
Co, Ni,
Mn
Cu
Reference: TU Braunschweig
BatRec
Retriev Technologies
Recupyl
Further information: Recycling of Lithium-Ion Batteries

Christian Hanisch, Recycling of Lithium-Ion Batteries, June 14, 2014, Slide 13
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

Christian Hanisch, Recycling of Lithium-Ion Batteries, June 14, 2014, Slide 14
 Recycling of Lithium Ion Batteries
 Different Industrial and Research Processes and Recycling
Yields
 Safety Issues in Battery Recycling and how to deal with them
 Recent Developments in Recycling of LIB from EVs
 Recycling of LIB-Production Rejects
Outline

Christian Hanisch, Recycling of Lithium-Ion Batteries, June 14, 2014, Slide 15
Retriev Technologies Inc.
Sorted Lithium-Ion Batteries
Crushing in
Brine-Solution
Separation
Mixing, Washing,
Drying
Filtering
H
2
O
Plastic/Steel
(Housing)
Copper, Cobalt,
Aluminum
Cobalt filter
cake
Na
2
CO
3
Li
2
CO
3
Mechanical
Treatment
Hydro-
metallurgy
Further information: Recycling of Lithium-Ion Batteries

Christian Hanisch, Recycling of Lithium-Ion Batteries, June 14, 2014, Slide 16
Basic process chain
Hydrometallurgy
Synthesis of active
material
Separation of foil and
coating
Separated
Coating
Battery cells
Electrode
Intermediates
Separated foils
Li
2
CO
3
/ LiOH
New active
material
Co / Ni / Mn
Cell shredding
Reference: TU Braunschweig

Christian Hanisch, Recycling of Lithium-Ion Batteries, June 14, 2014, Slide 17
Basic process chain
Hydrometallurgy
Synthesis of active
material
Separation of foil and
coating
Separated
Coating
Battery cells
Electrode
Intermediates
Separated foils
Li
2
CO
3
/ LiOH
New active
material
Co / Ni / Mn
Cell shredding
Reference: TU Braunschweig

Christian Hanisch, Recycling of Lithium-Ion Batteries, June 14, 2014, Slide 18
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

Christian Hanisch, Recycling of Lithium-Ion Batteries, June 14, 2014, Slide 19
Air Classification and Sieving
Zigzag-Classifier
Air jet
Heavy fraction
Light fraction

Christian Hanisch, Recycling of Lithium-Ion Batteries, June 14, 2014, Slide 20
Basic process chain
Hydrometallurgy
Synthesis of active
material
Separation of foil and
coating
Separated
Coating
Battery cells
Recycling-
elektrode
Intermediate
products
Separated foils
Li
2
CO
3
/ LiOH
New active
material
Co / Ni / Mn
Cell shredding
Reference: TU Braunschweig

Christian Hanisch, Recycling of Lithium-Ion Batteries, June 14, 2014, Slide 21
Measurements in Recycling of LIB
Coating
Battery
Electrode
Compound
Current
Collector
Foil
CSE = 50% CSE = 100%
Coating
Powder
Coating
Powder
Coating
Powder
Coating
Powder
Foil Scraps Impurities
 important for hydrometallurgical process
 determined via Atomic Absorbtion Spectroscopy
of leach liquor

Christian Hanisch, Recycling of Lithium-Ion Batteries, June 14, 2014, Slide 22
First Solution: Cutting Mill and Sieving
Electrodes/
Production Rejects
Coating Powder
(NMC, Graphite, Carbon Black)
Copper and
Aluminum Foil
CSE 80 - 95 % of Active Material
Al/Cu Impurities 1 - 5 wt.-%
 Simple
 Low Investments

Christian Hanisch, Recycling of Lithium-Ion Batteries, June 14, 2014, Slide 23
Separation results after sifting and sieving
Reference: TU Braunschweig and Lion Engineering GmbH

Christian Hanisch, Recycling of Lithium-Ion Batteries, June 14, 2014, Slide 24
Separation results after sifting and sieving
Reference: TU Braunschweig and Lion Engineering GmbH

Christian Hanisch, Recycling of Lithium-Ion Batteries, June 14, 2014, Slide 25
Basic process chain
Hydrometallurgy
Synthesis of active
material
Separation of foil and
coating
Separated
Coating
Battery cells
Recycling-
elektrode
Intermediate
products
Separated foils
Li
2
CO
3
/ LiOH
New active
material
Co / Ni / Mn
Cell shredding
Reference: TU Braunschweig

Christian Hanisch, Recycling of Lithium-Ion Batteries, June 14, 2014, Slide 26
Hydrometallurgical process
Hydrometallurgical lithium extraction
recycling yield:
 85 % of lithium from LiFePO
4
 95 % of lithium from LiNi
1/3
Mn
1/3
Co
1/3
O
2
Source: Rockwood Lithium
Pilot plant for hydrometallurgical process
Leaching / Extraction of
active material
Purification through:
- Crystallisation
- Ion-exchange
Salt separation by
electrochemical processes
LiOH / Li
2
CO
3
Co, Ni, Mn-Sol.
Li-brine
Precipitation
Metal oxide particles
New active materials
Calcination
Reference: TU Braunschweig

Christian Hanisch, Recycling of Lithium-Ion Batteries, June 14, 2014, Slide 28
Influence of Impurities on the Re-Synthesis
Further information: Krüger, S.; Hanisch, C.; Nowak, S., Kwade, A.; Winter, M.:
Effect of Impurities Caused by a Recycling Process on the Electrochemical
Performance of Li[Ni
0.33
Co
0.33
Mn
0.33
]O
2
, Journal of Electroanalytical Chemistry, 2014
0 100 200 300 400 500
0,000
0,005
0,010
0,015
0,020
0,025
0,030
0,035
0,040
0,045
0,050
Electrochemical Performance (3C, 21°C)
Capacity [Ah]
Cycles [-]
Reference: Commercial Activ Material NMC
(Al < 20 ppm)
Low Recycling-Impurities (Al = 0,2 g/L )
Higher Recycling-Impurities (Al = 1,2 g/L )
Reference: TU Braunschweig

Christian Hanisch, Recycling of Lithium-Ion Batteries, June 14, 2014, Slide 29
 Recycling of Lithium Ion Batteries
 Different Industrial and Research Processes and Recycling
Yields
 Safety Issues in Battery Recycling and how to deal with them
 Recent Developments in Recycling of LIB from EVs
 Recycling of LIB-Production Rejects
Outline

Christian Hanisch, Recycling of Lithium-Ion Batteries, June 14, 2014, Slide 30
Dangers
 Decomposition of the binder polyvinylidene fluoride in case
of fire
 Hydrogen Fluoride (HF)
 Cathodic Active Materials contain nickel oxide  carcinogenic
 Risk of dust explosion
 Electrolyte solvents are inflammable
 Exothermic decomposition of conducting salt LiPF
6
to
hydrogen fluoride
 Electrical hazard and reaction activation by short circuits
Reference: TU Braunschweig

Christian Hanisch, Recycling of Lithium-Ion Batteries, June 14, 2014, Slide 31
Ba.Z.U.Ka. (BatterieZellen-UntersuchungsKammer
Battery-Security-Test-Object-to Operate-Gas-Analytics): system to analyze
gases resulting from abuse tests quantitatively and qualitatively
Ba.Z.U.Ka.
Resulting gases during a nail-penetration-test with a NMC pouch cell in Ba.Z.U.Ka.
before penetration after penetration a few moments later

Christian Hanisch, Recycling of Lithium-Ion Batteries, June 14, 2014, Slide 32
Nail-Penetration-Test of a Lithium-Ion Battery Cell
0 5 10 15 20 25 30
0
5
10
15
20
25
30
Hydrogen fluoride (HF) in Gas Phase of a Nail-Penetration-Test
Battery Cell: 1,8 Ah; 4,1 V
Atmosphere: Air
Measurement: FT-IR
Gasflow
FT-IR
: 1 l/min
T
Tubes and Chamber
: 180 °C
Hydrogen fluoride
c
HF
(mg/L)
Time after Penetration t [min]
(with continuous Gasflow N
2
(1 L/min))
Reference: TU Braunschweig and Lion Engineering GmbH
Queries: info@lion-eng.de

Christian Hanisch, Recycling of Lithium-Ion Batteries, June 14, 2014, Slide 33
0,0187
2,75862
0,06739
0,02039
0,00752
14,05127
7,75E-04
0,01666
0,01566
1,00486
0,00234
0,3199
0,00
0,05
0,10
0,15
0,20
0,25
2
4
6
8
10
12
14
16
18
20
Freigesetzte Gesamtmassen [mg/g Anodenverbund] der
Abgaskomponenten
einer thermischen Behandlung
von Anodenverbund
Messprinzip: FTIR-Spektrometrie
behandelte Masse Anodenverbund: 2g
T
Ofen
: 500°C
Volumenstrom
Probenahmesystem
: 1l/min
T
Probenahmesystem
: 180°C
COF
2
feigesetzte Gesamtmasse [mg/g Anodenverbund]
Abgaskomponenten
CO
2
CO
NO
N
2
O
HCN
HF
CH
4
C
16
H
34
HCHO
SiF
4
COF
2
HNCO
CH
4
0,320
C
n
H
m
*
If an electrode burns: Infrared Spectroscopy
Gas Emission [mg/g Anode Compound]
Components
Only infrared active
components –
Queries: info@lion-eng.de
Reference: TU Braunschweig and Lion Engineering GmbH

Christian Hanisch, Recycling of Lithium-Ion Batteries, June 14, 2014, Slide 34
 Recycling of Lithium Ion Batteries
 Different Industrial and Research Processes and Recycling
Yields
 Safety Issues in Battery Recycling and how to deal with them
 Recent Developments in Recycling of LIB from EVs
 Recycling of LIB-Production Rejects
Outline

Christian Hanisch, Recycling of Lithium-Ion Batteries, June 14, 2014, Slide 35
Separation of Active Materials from LIB Cells
Hydro-metallurgy
Active Material Synthesis
Separation of Foil and
Coating
Separated
Coating
Battery
Cells
Electrode
Intermediates
Separated
Foils
Li
2
CO
3
/ LiOH
Battery Active
Material
Co / Ni / Mn
Cell Crushing

Christian Hanisch, Recycling of Lithium-Ion Batteries, June 14, 2014, Slide 36
First Solution: Cutting Mill and Sieving
Electrodes/
Production Rejects
Coating Powder
(NMC, Graphite, Carbon Black)
Copper and
Aluminum Foil
CSE 80 - 95 % of Active Material
Al/Cu Impurities 1 - 5 wt.-%
 Simple
 Low Investments

Christian Hanisch, Recycling of Lithium-Ion Batteries, June 14, 2014, Slide 37
Facts, which led to a new process
1. Binder polyvinylidene fluoride (PVDF)
a) adhesion between coating and current collector foil
b) cohesion between electrode coating particles
c) lower decomposition temperature than other components

Christian Hanisch, Recycling of Lithium-Ion Batteries, June 14, 2014, Slide 40
Facts, which led to a new process
1. Binder polyvinylidene fluoride (PVDF)
a) adhesion between coating and current collector foil
b) cohesion between electrode coating particles
c) lower decomposition temperature than other components
2. High educt purity for synthesis battery grade active material
0 100 200 300 400 500
0,00
0,01
0,02
0,03
0,04
0,05
Electrochemical Performance (3C, 21°C)
Capacity [Ah]
Cycles [-]
Reference: Commercial Active Material NMC
(Al < 20 ppm)
Low Recycling-Impurities (Al = 0,2 g/L )
Higher Recycling-Impurities (Al = 1,2 g/L )
Referenz
LNCMO V21
LNCMO V5-Z
Reference
Material
Al < 20 ppm
Low
Impurities
Al = 0.2 g/L
Higher
Impurities
Al = 1.2 g/L

Christian Hanisch, Recycling of Lithium-Ion Batteries, June 14, 2014, Slide 41
Facts, which led to a new process
1. Binder polyvinylidene fluoride (PVDF)
a) adhesion between coating and current collector foil
b) cohesion between electrode coating particles
c) lower decomposition temperature than other components
2. High educt purity for synthesis battery grade active material
3. Mechanical separation of electrodes
 a) coating agglomerate diameters up to 250 µm
 b) foil scraps of 50-200 µm

Christian Hanisch, Recycling of Lithium-Ion Batteries, June 14, 2014, Slide 43
Facts, which led to a new process
1. Binder polyvinylidene fluoride (PVDF)
a) adhesion between coating and current collector foil
b) cohesion between electrode coating particles
c) lower decomposition temperature than other components
2. High educt purity for synthesis battery grade active material
3. Mechanical separation of electrodes
 a) coating agglomerate diameters up to 250 µm
 b) foil scraps of 50-200 µm
4. Fine sieving reduces impurities
5. Impact stress transforms kinetic energy into dispersing energy
 a) loosen coatings from their substrate
 b) break agglomerates

Christian Hanisch, Recycling of Lithium-Ion Batteries, June 14, 2014, Slide 44
Adhesion Neutralization via Incineration
and Impact Liberation (ANVIIL)
T = 500 °C
HF,…
Gas Scrubber
Coating
Powder
Incineration
Impact Liberation
Nozzle
Fine
Sieve
Lid
Electrode
Compounds

Christian Hanisch, Recycling of Lithium-Ion Batteries, June 14, 2014, Slide 45
Adhesion Neutralization via Incineration
and Impact Liberation (ANVIIL)
T = 500 °C
HF,…
Gas Scrubber
Coating
Powder
Incineration
Impact Liberation

Christian Hanisch, Recycling of Lithium-Ion Batteries, June 14, 2014, Slide 47
Conclusion
 High Compound Separation Efficiency > 99%
 Aluminum Impurities < 0.1 wt.-%
 Incineration Gases have to be dealt with
 Results of the LCA of the Öko-Institut e.V. are published
HF,…

Christian Hanisch, Recycling of Lithium-Ion Batteries, June 14, 2014, Slide 48
 Oracle based database and logistics solution for
lithium-ion battery systems:
 Tracking of the systems and its components within the recycling path
 Generation of dispatch notes with characteristics
 Condition validation according to VDA standards
 Materials management
 Where is which amount?
 Verification of disposal
 Monitoring of materials behaviour in the process
 Recycling quotas
 Consistent and enforced data entry for process steps by different stakeholders
 Easy tracing of products and samples
 Better analysis/comprehension of the process steps
 Replicable process evaluation on reliable data base
 Good overview
TRUSD (The Reliable Universal Secure Database)

Christian Hanisch, Recycling of Lithium-Ion Batteries, June 14, 2014, Slide 49
 Recycling of Lithium Ion Batteries
 Different Industrial and Research Processes and Recycling
Yields
 Safety Issues in Battery Recycling and how to deal with them
 Recent Developments in Recycling of LIB from EVs
 Recycling of LIB-Production Rejects
Outline

Christian Hanisch, Recycling of Lithium-Ion Batteries, June 14, 2014, Slide 50
Recycling of Production Rejects
Maybe some simple, still
effective tricks
Re-Coating
Separation of foil and
coating
Shredding
Separated
Coating
Production
Rejects
Recycling
Electrode
Intermediate
products
Separated
foils

Christian Hanisch, Recycling of Lithium-Ion Batteries, June 14, 2014, Slide 51
Recycling of Production Scraps/Rejects
0 100 200 300 400 500
0
20
40
60
80
100
120
140
Specific Capacity [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

Christian Hanisch, Recycling of Lithium-Ion Batteries, June 14, 2014, Slide 52
Conclusion
 Metallurgical Recycling of spent batteries is feasible
to regain Co and Ni
 Future battery materials will be an economical
challenge for the recycling process (reduction of
Co/Ni in Battery Active Materials)
 Increasing of Recycling Yield possible by
Combination of different unit operations  payoff of
higher process costs? info@lion-eng.de !
 Challenges:
 Hydrogen fluoride and other components
 Purity of regained materials
Further information: 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

Christian Hanisch, Recycling of Lithium-Ion Batteries, June 14, 2014, Slide 53
Further questions?
Christian Hanisch
c.hanisch@lion-eng.de
Thank You!