Von Li-Ionen-Altbatterien zur Produktion neuer Li-Ionen-Batterien –
Lösungsansätze für geschlossene Stoffkreisläufe
Arno Kwade1)2), Wolfgang Haselrieder 1), Stefan Doose 1), Stefan Blume2)
1) Institute for Particle Technology and Battery LabFactory (BLB), TU Braunschweig2) Fraunhofer Center for Energy Storage and Systems, Braunschweig
Arno Kwade | Lösungsansätze für geschlossene Stoffkreisläufe | BLB | Slide 2
Motivation
E-mobility and green energy production
cause extreme increase in battery
demand, especially lithium-ion batteries
Primary raw material reserves are not
sufficient to fulfill mid- and longterm demand
of battery materials and are ecological not
advantageous
Germany must become less dependent on
material delivery from foreign countries
Circular production and closed
material cycles are essential for
ecological friendly e-mobility and
green energy production
Arno Kwade | Lösungsansätze für geschlossene Stoffkreisläufe | BLB | Slide 3
Components and function of Lithium-ion battery
Cath
od
eA
no
de Active material
Anode
Active material
Cathode
Carbon black
Binder
Electrolyte
Arno Kwade | Lösungsansätze für geschlossene Stoffkreisläufe | BLB | Slide 4
Cath
od
eA
no
de
Discharge
Components and function of Lithium-ion battery
A. Kwade et.al. (2018) Nature Energy 3 (4), pp. 290-300
Energy & Power
density
CostsLife
time
SafetySustainability
(e.g. CO2 foot print)
Requirements
Arno Kwade | Lösungsansätze für geschlossene Stoffkreisläufe | BLB | Slide 5
Cost breakdown of cell production costs and material costs
Manufacturing
cost
Material costs
74.9 %
Direct labour
8.2 %
Depreciation
8.5 %
Capital
2.8 %
Energy
3.1 %
Other
2.5 %
Anode
14.3 %
Cathode
49.5 %
Separator
17.5 %
Electrolyte
4.8 %
Housing/parts
13.9 %
Material cost
Accum
ula
ted
valu
e
ES
A
Determination based on C//NMC, PHEV2, 36 Ah
Arno Kwade | Lösungsansätze für geschlossene Stoffkreisläufe | BLB | Slide 5
A. Kwade et.al. (2018) Nature Energy 3 (4), pp. 290-300
Arno Kwade | Lösungsansätze für geschlossene Stoffkreisläufe | BLB | Slide 6
Demand of materials for battery production
Very high demand of
following metals for
battery production
Nickel (cathode)
Graphite (anode)
Cupper (current
collector, pack
wiring)
Aluminium (current
collector, housing,
cathode material)
Arno Kwade | Lösungsansätze für geschlossene Stoffkreisläufe | BLB | Slide 7
High importance of low environmental impact
[Ellingsen et al. (2017), Identifying key assumptions and differences in life cycle assessment studies of lithium-ion traction
batteries with focus on greenhouse gas emissions, Transportation Research Part D: Transport and Environment, 55:82–90.]
Cell materials have high
share with regard to the
environmental impact of
batteries
Car manufacturer force
material supplier and by
that mines to minimize
environmental impact
(e.g. CO2 footprint) and
production cost
We require new environmental
friendly material production
technologies
Arno Kwade | Lösungsansätze für geschlossene Stoffkreisläufe | BLB | Slide 8
Content
Motivation of closed material cycles1
Recycling of spent lithium-ion batteries2
Re-synthesis of active material3
Battery cell production4
Conclusions5
Outlook – Future battery technologies6
20
µm10 µm
Arno Kwade | Lösungsansätze für geschlossene Stoffkreisläufe | BLB | Slide 9
Circular Economy and Production of Batteries
Knowledge based
CircularBattery
Production
System Integration
Raw
materials Material/Component
Production
Manufacturing
of cells
Battery system manufacturing
Battery usage
(primary/secondary)
Recycling of
battery systems Production of
electrodes
Arno Kwade | Lösungsansätze für geschlossene Stoffkreisläufe | BLB | Slide 10
Circular Economy and Production of Batteries
Pilot scale battery production facility
Knowledge based
CircularBattery
Production
System Integration
Material/Component
production
Manufacturing
of cells
Battery system manufacturing
Battery usage
(primary/
secondary)
Recycling of
battery systems Electrode
production
Arno Kwade | Lösungsansätze für geschlossene Stoffkreisläufe | BLB | Slide 11
Circular Economy and Production of Batteries
Knowledge based
CircularBattery
Production
System Integration
Material/Component
Production
Manufacturing
of cells
Battery system manufacturing
Battery usage
(primary/secondary)
Recycling of
battery systems Production of
electrodes
Arno Kwade | Lösungsansätze für geschlossene Stoffkreisläufe | BLB | Slide 12
Importance of Battery Recycling
Number of End-of-Life Battery Systems and components
Source: Institute of Automotive Management and Industrial Production
2015 2016 2017 2018 2019 2020 2021 2022 2023 2024 2025
0
50k
100k
150k
200k
250k
300k
350k
Qu
an
tity
of E
oL
Batt
ery
Syste
ms
Year
BEV
PHEV
HEV
Quantity of EoL Battery Systems in EuropeRealistic Scenario
Plastics
3.8%
Volatile
Components
8.3%
Aluminium
5.8%
Graphite
8.2%
Copper
9.2%
Oxygen
4.8% Mn
2.8%Co
3.1%
Ni
3.1%
Li
1.0%
Aluminium
5.5%
Steel
3.3%
Plastics
1.5%
Alumimium
5.3%
Cables
2.3%
Plastics
5.7%
Aluminium
18,0%
Electronics
2.7%Steel
5.7%
Electrolyte,
Separator,
OthersCell
Housing
Anode
Cathode
Module
Periphery
Battery
System
Periphery
Electrolyte,
Separator,
OthersCell
Housing
Anode
Cathode
Module
Periphery
Battery
System
Periphery
Electrolyte,
Separator,
OthersCell
Housing
Anode
Cathode
Module
Periphery
Battery
System
Periphery
Li
1 %Co, Ni
6 %
Copper
9 %
A. Kwade, J. Diekmann (2017) Recycling of Lithium-Ion Batteries:
The LithoRec Way, Springer
Arno Kwade | Lösungsansätze für geschlossene Stoffkreisläufe | BLB | Slide 13
Unit operations of battery recycling
Deassembling
Crushing / Milling
Classifying
(sieving, air
classification)
Sorting
(e.g. magnetic
separation)
Smelting of
Battery Moduls
Electrode Scraps
Active Material
Powder
Regaining of
Co, Ni, Cu
Chemical Processes
Leaching
Extraction
Cristallisation
Precipitation
Regaining of
Metals Co, Ni, Li
from separated
powders or slag
Thermal
Pretreatment
Discharging
Freezing of
Electrolyte
Short circuit
(e.g. in water)
Mechanical
Processing
Hydro-
metallurgy
Pyro-
metallurgyDeactivation
of cells
Arno Kwade | Lösungsansätze für geschlossene Stoffkreisläufe | BLB | Slide 14
Li
Co, Ni
Mechan. Treatment Hydro-Metallurgy Pyro-Metallurgy
Casing,
etc.
Cu, Al
Battery / Battery Cells
Co, Ni,
Mn
Cu
Possible solutions with recovery of lithium
Deactivation
Arno Kwade | Lösungsansätze für geschlossene Stoffkreisläufe | BLB | Slide 15
Lithorec process overview
Hydro-metallurgy
Active Material Synthesis
Separation of housing, foil, coating, electrolyte Separated
Coating
Module
Electrode
Intermediates
Separated
Foils
Li2CO3 / LiOH
Battery Active
Material
Co / Ni / Mn
Discharge andDisassembling
Battery Module Crushing
C. Hanisch, T. Loellhoeffel, J. Diekmann, K.J. Markley, W. Haselrieder,
A. Kwade (2015). Journal of Cleaner Production 108, pp. 1-11
Arno Kwade | Lösungsansätze für geschlossene Stoffkreisläufe | BLB | Slide 16
Process Chain for
Demonstration Plant
Discharge Disassembly Crushing Drying Sieving1st Classification 2nd
Classification
2nd Crushing
Arno Kwade | Lösungsansätze für geschlossene Stoffkreisläufe | BLB | Slide 17
Use of inert gas
to avoid
hazardeous
reactions and fire
Lithorec process overview
Module
Intermediates
Discharge andDisassembling
Battery Module Crushing
Arno Kwade | Lösungsansätze für geschlossene Stoffkreisläufe | BLB | Slide 18
Lithorec process overview
Separation of Foil andCoating Separated
Coating
Module
Intermediates
Separated
Foils
Discharge andDisassembling
Battery Module Crushing
Arno Kwade | Lösungsansätze für geschlossene Stoffkreisläufe | BLB | Slide 19
Al module
26.6 %
Copper
5.0 %
Al housing
47.7 %
Steel
13.8 %
Plastics
4.0 %
Inclusions
2.9 %
heavy parts
Cu-, Al- Foil, Separator,
Plastics, Black Mass
vS 3,34 m s-1
µS 190 g kg-1
36 %
1st Air-Classification
Arno Kwade | Lösungsansätze für geschlossene Stoffkreisläufe | BLB | Slide 20
2nd Air-Classification
vS 1,10 m s-1
µS 25 g kg-1
89 %
Separator (+ Al foil)
Cu foil
29.8 %
Al foil
16.6 %
Plastics
5.9 %
Black Mass
44.8 %
Separator
2.9 %
Arno Kwade | Lösungsansätze für geschlossene Stoffkreisläufe | BLB | Slide 21
0
2
4
60
80
100
120
with
2nd
crushing step
mass o
upu
t [%
]
Black Mass
Fe impurities
Al impurities
Cu impurities
without
2nd
crushing step
Mass ouput and impurities of black mass fraction
Battery Type: EV
Battery cells: 6 PHEV1, LiNiCoMnO2 / Graphite
Fraction: < 500 µm
Fine sieving of fine/light fraction
Yield and purity black mass
97.6 %
0.6 %
1.7 %
97.7 %
0.5 %
1.6 %
mass o
utp
ut
[%] Black mass
recovery rate
> 75% at this point
Black mass recoverd by sieving at 200 µm
Arno Kwade | Lösungsansätze für geschlossene Stoffkreisläufe | BLB | Slide 22
Lithorec process overview
Hydro-metallurgy
Separation of housing, foil, coating, electrolyte Separated
Coating
Module
Intermediates
Separated
Foils
Li2CO3 / LiOH Co / Ni / Mn
Discharge andDisassembling
Battery Module Crushing
A. Kwade et.al. (2018) Nature Energy 3 (4), pp. 290-300
Arno Kwade | Lösungsansätze für geschlossene Stoffkreisläufe | BLB | Slide 23
Active material
Cathode
Residual cross contamination (Al, Fe, Cu)
Acidic desintegration of active material
Dissolution of metal components
Solid separation
Metal salt solution
Solids remaining
Precipitation
of transition metal salts
Preservation of a Lithium-Salt-Solution Rockwood Lithium
Recycling
Hydrometallurgical treatment
Arno Kwade | Lösungsansätze für geschlossene Stoffkreisläufe | BLB | Slide 24
Recycling Efficiency
based on material recycling
Separator4%
Rod2%
Case11%
Lithium2%
Cobalt7%
Nickel6%
Manganese6%
Oxygen11%
Al Foil5%
Anode Coating19%
Cu Foil11%
Electrolyte16%
Separator4%
Rod2%
Case11%
Lithium2%
Cobalt7%
Nickel6%
Manganese6%
Oxygen11%
Al Foil5%
Anode Coating19%
Cu Foil11%
Electrolyte16%
Separator4%
Rod2%
Case11%
Lithium2%
Cobalt7%
Nickel6%
Manganese6%
Oxygen11%
Al Foil5%
Anode Coating
19%
Cu Foil11%
Electrolyte16%
State of the art(mainly pyrometallurgy)
≈ 30%
Available technology(Mechanical treatment,
hydrometallurgy)
≈ 80% *
Advanced technology
(Mechanical treatment,
hydrometallurgy)
> 95%*
Material recyclingOther recycling or disposal
* on battery cell level, normalized after substraction of oxygen
Arno Kwade | Lösungsansätze für geschlossene Stoffkreisläufe | BLB | Slide 25
76204
-2600
448
-1874
1481
-460
-2725
Transp
ort
Dis
asse
mbly
Dis
asse
mbly
Mec
h. Sep
arat
ion
Mec
h. Sep
arat
ion
Hyd
rom
. Tre
atm
ent
Hyd
rom
. Tre
atm
ent
Sum
-3000
-2000
-1000
0
1000
2000
GW
P [
kg
CO
2-
eq
.*t
batt
ery
sy
ste
ms
-1]
Ecobalance LithoRec-ProcessÖko-Institut e.V.
Source: Abschlussbericht zur Ökobilanz des LithoRec II –Verfahrens, Öko-Institut e.V.
Recycling of 1 ton of NMC based
batteries results in a reduction of
approximately 2.7 ton of CO2
Arno Kwade | Lösungsansätze für geschlossene Stoffkreisläufe | BLB | Slide 26
Circular Economy and Production of Batteries
Knowledge based
CircularBattery
Production
System Integration
Material/Component
Production
Manufacturing
of cells
Battery system manufacturing
Battery usage
(primary/secondary)
Recycling of
battery systems Production of
electrodes
Arno Kwade | Lösungsansätze für geschlossene Stoffkreisläufe | BLB | Slide 27
Active materials of Lithium-ion battery
Cath
od
eA
no
de Active material
Anode
Active material
Cathode
Carbon black
Binder
Electrolyte
Arno Kwade | Lösungsansätze für geschlossene Stoffkreisläufe | BLB | Slide 28
Active materials for the cathode
• Lithium metal oxides with morphology of layered oxide
• LiCoO2
• LiNMO2 (N, M = Ni, Co, Mn in different amounts N + M = 1)
- e.g. LiNiMnCoO2 (NMC 111, NMC 622, NMC 811)
- e.g. LiNiCoAlO2 (NCA)
• Lithium metal oxides with morphology of spinels
- LiM2O4 (M = Mn, Ni, Co)
• Lithium metal phosphates
- LiMPO4 (M = Fe, Co, Ni, Mn) e.g. LiFePO4
VAss. Dr. Kai-C. Möller, Primäre und wiederaufladbare Lithium-Batterien
Arno Kwade | Milling in Energy Storage Industry | BLB | Slide 29
Synthesis of cathode material
Calcination
Dispersion
GrindingPyrolysis
Precipitation
Pre
-tre
ate
dre
agant
Mate
rial w
ith
defined
part
icle
siz
e
NMC Precursor after precipitationNMC after calcination
Arno Kwade | Milling in Energy Storage Industry | BLB | Slide 30
Production and preparation of cathode active materials
Continuous Stirred Tank ReactorTaylor Vortex Reactor
Source: www.anl.gov
Arno Kwade | Lösungsansätze für geschlossene Stoffkreisläufe | BLB | Slide 31
SEM-Images of Re-Synthesized NCM
Source: S. Krueger, C. Hanisch, A. Kwade, M. Winter, S. Nowak, Effect of Impurities Caused by
a Recycling Process on the Electrochemical Performance of Li[Ni0.33Co0.33Mn0.33]O2, Journal of Electroanalytical
Chemistry (2014), doi: http://dx.doi.org/10.1016/j.jelechem.2014.05.017
/ g·L-1 Referen
ce
Rejects Cycled
Li - 0.56 6.46
Ni 34.00 39.00 39.00
Co 34.00 38.00 37.70
Mn 32.00 32.00 33.60
Al < 0.02 0.24 1.48
Cu < 0.01 <0.01 0.10
Fe < 0.01 <0.01 0.03
Mg - 0.01 0.03
Si < 0.01 0.01 0.11
Reference
From pure
metal salts
Rejects
From electrode
production
rejects
Cycled
From resynthe-
sized spent
cells
Increase of BET-surface area
Reference 0.23 m2 g-1
Rejects 0.28 m2 g-1
Cycled 0.60 m2 g-1
Reference and Rejects are closer in BET-
surface area
Reason is secondary particle shape as a result
of particle conditioning
Aluminium content increases as main impurity
Arno Kwade | Lösungsansätze für geschlossene Stoffkreisläufe | BLB | Slide 32
Electrochemical Performance of Re-Synthesized NCM - Material
Source: S. Krueger, C. Hanisch, A. Kwade, M. Winter, S. Nowak, Effect of Impurities Caused by
a Recycling Process on the Electrochemical Performance of Li[Ni0.33Co0.33Mn0.33]O2, Journal of Electroanalytical
Chemistry (2014), doi: http://dx.doi.org/10.1016/j.jelechem.2014.05.017
Reference
From pure
metal salts
Rejects
From electrode
production
rejects
Cycled
From resynthe-
sized spent
cells
Arno Kwade | Lösungsansätze für geschlossene Stoffkreisläufe | BLB | Slide 33
Re-Synthesized Graphite – Recycling Strategies
Graphite
recycling
strategies
Electrolyte extraction with
subcritical CO2 in combination
with acetonitrile
Thermal evaporation of volatile
electrolyte compounds
Washing steps,
removal of SEI and
binder
Source: Rothermel S, Evertz M, Kasnatscheew J, Qi X, Grützke M, Winter M, Nowak S (2016) Graphite recycling from Spent
Lithium Ion Batteries. ChemSusChem [accepted]. doi:10.1002/cssc.201601062
Thermal evaporation of volatile
electrolyte compounds
Arno Kwade | Lösungsansätze für geschlossene Stoffkreisläufe | BLB | Slide 34
Production of Battery cells – German competency cluster on
battery cell production ProZell
Knowledge based
CircularBattery
Production
System Integration
Material/Component
production
Manufacturing
of cells
Battery system manufacturing
Battery usage
(primary/secondary)
Recycling of
battery systems
Electrode
production
(5 Institute)
(4 Institute)
(5 Institute)
(2 Institute)
(2 Institute)
Arno Kwade | Lösungsansätze für geschlossene Stoffkreisläufe | BLB | Slide 35
New german wide academic recycling platform „INNOREC“
within German competency cluster ProZell
Arno Kwade | Lösungsansätze für geschlossene Stoffkreisläufe | BLB | Slide 36
Conclusions
Closed material circuits within circular battery production
Demand of battery cells and consequently required raw materials and
synthesized active materials rise tremendously in the future
Sustainable processes especially for materials are very important to
fulfill environmental goals of car manufacturer (e.g. CO2 footprint)
In the future recycling of spent batteries and re-synthesis of active
materials from spent lithium battery systems are decisive
to close material cycle,
to decrease dependency on primary raw materials and
to minimize ecological impact of battery production.
Mechanical-hydrometallurgical recycling process developed in
Niedersachsen is advantageous compared to other processes
Recycling and Re-Synthesis of battery materials should be future key
technology of Niedersachsen
Battery
system
20
µm10 µm
Arno Kwade | Lösungsansätze für geschlossene Stoffkreisläufe | BLB | Slide 37
Challenges of future recycling processes –
Diversity of battery materials and technologies
Substrat
Substrat
cath
od
e co
atin
g
Separator
ano
de
coat
ing
Li+
Li+
Li+ Li+
Li+
Li+
Li+
Li+
Li+
Li+
Li+
e-
e-
Li+
e-
Lithium-Ion
Sodium-Ion
Separator
Anode: Lithium
Kathode: C/S
Li +
2Li +
Li2 S8
Li2 S6
Li2 S4
Li2 S2
Li2 S
V
e-
Lithium-Sulfur
Metal-Air
Batteries
Anode: porous Zinc-Structure
Cathode: Gasdiffusionelectrode
Zn(O
H)4
2-
Ve
-
Zn2
+
OH
-O
2
ZnO
O2
Lithium/Sodium-Metaloxide vs. Graphit/Si
Solvent based electrolyte
Sulfur-Carbon-Composite vs. Li
Solvent based or solid state electrolyte
Gasdiffusion electrode vs. metal (z.B. Lithium, Zinc)
Solvent based electrolyte
All-Solid-State Lithiummetaloxide vs. Li
Solid state electrolyte
+
Li AlCu+
A
l
Li+ Li+
Li+Li+
Li+
Li+
Li+
Li+
Li+
Arno Kwade | Lösungsansätze für geschlossene Stoffkreisläufe | BLB | Slide 38
Challenges in Recycling of All Solid State Batteries
Challenges in Process Technology:
Shredding of the systems / cells only possible
under protective atmosphere
Li-metal is very reactive
Dissolving the Li-metal in water
In aqueous systems formation of LiOH with
release of H2
Polymer-based solid electrolytes: Removal of
valuable cathode active materials (NCM) e.g.
by swelling or dissolving polymers (PEO)
Sulfidic solid electrolytes: Danger of release of
H2S and other sulphur compounds
Anode Composit-Cathode
Oxidic
Polymer-based
Sulfidic
Li
+
AlCu
Charge / Discharge
e-
-
+
Li+
Al
+
Separator
Li+
Li+
Li+
Li+
Li+
Li+
Li+
Li+
Li+
Arno Kwade | Lösungsansätze für geschlossene Stoffkreisläufe | BLB | Slide 39
Thank you very much
.... for the support by
….for the great work of my
PhD-students and co-workers,
especially
Sabrina Zellmer
Julian Mayer
… for your attention
Arno Kwade | Lösungsansätze für geschlossene Stoffkreisläufe | BLB | Slide 40
International Battery Production Conference, IBPC 2019
Visit us in Braunschweig, Steigenberger Parkhotel www.ibpc2019.de
Arno Kwade | Lösungsansätze für geschlossene Stoffkreisläufe | BLB | Slide 41
Estimation of recycling burdens remains a challenge
Source: Ciez R E, Whitacre J F (2019) Examining different recycling processes for lithium-ion batteries. Nature Sustainability.
2(2):148–156.
GW
P (
cra
dle
-to-g
rave
) thro
ug
hre
cyclin
g
Arno Kwade | Lösungsansätze für geschlossene Stoffkreisläufe | BLB | Slide 58
Recycling burdens of battery recycling
Methodology | Step 3: Impacts
Source: Cerdas et al. (2018) Environmental Aspects of the Recycling of Lithium-Ion Traction Batteries, in Recycling of
Lithium-Ion Batteries : the LithoRec Way, pp. 267–288.
Product
Analysis
Target
Materials
Net Env.
ImpactsAllocation
1 2 3 4