Waste Management 172 (2023) 1–10

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Waste Management
journal homepage: www.elsevier.com/locate/wasman

Research Paper

Influence of different discharge levels on the mechanical recycling

efficiency of lithium-ion batteries
Alexandra Kaas a, *, Christian Wilke a, Anna Vanderbruggen b, Urs A. Peuker a
a
TU Bergakademie Freiberg Institute of Mechanical Process Engineering and Mineral Processing, Germany
b
Helmholtz Institute Freiberg for Resource Technology, Germany

A R T I C L E I N F O A B S T R A C T

Keywords: Prior to the mechanical processing, discharging is necessary to prevent hazards. While the discharging process,
Lithium-Ion Batteries different phenomena can occur changing the characteristics of the functional units of LIB. This study reveals the
Recycling influence on the mechanical recycling and the obtained material when different discharge levels are used for
Separation
various cells differing in their cell chemistry. It shows that for different cells, for example, copper deposits
Discharge
happen on the cathode as well as active material deposits on the separator foil. These new properties deteriorate
Overdischarge
Black mass the black mass quality and show contamination of the products with other material streams. It is being tested
whether established sub-processes are suitable. However, it becomes clear that further recycling steps (e.g.
flotation, hydrometallurgy) can be influenced as well as their product quality and element specific yield.

1. Introduction prevent a shortage of materials, new terms are proposed in European

One central opportunity to stop the climate change is to lower carbon
emissions and the transport sector accounts for 23% of the European
greenhouse gas emissions (EU 2020). Therefore, one alternative in the
transportation sector to combustion vehicles are electric vehicles (EV)
(Tian et al. 2014). The functional units of electric vehicles are lithium-
ion batteries (LIB), which are powered by electrical energy.. These
electrochemical storage systems are especially attractive due to their
properties: high voltage, large specific capacity, long lifetime and no
memory effects (Korthauer 2013, Lv et al. 2018). Forecasts show a rapid
increase of EVs from 11 Mio. in 2020 to 145–230 Mio. in 2030 globally
(Bibra et al. 2021).
LIB consist of a succession of cells, each cell is made of two elec­
trodes, cathode and anode, which are separated by a porous membrane,
the separator foil. More detailed information concerning the used ma­
terials for the functional units and their composition can be found in
(Sommerville et al. 2020, Werner et al. 2020, Korthauer 2013, Roth­
ermel et al. 2018).
Most of the raw materials used in the manufacturing of LIBs are
currently obtained from primary resources, with some of them pre­
senting a supply risk (e.g., Al, Cu, Ni, Mn), while others (e.g., Co, Li and
natural graphite) are even categorized as critical raw materials by the
European Commission (Keersemaker and Keersemaker 2020). To
legislation to promote the need for recycling. The minimum recycling
efficiency of the whole battery cell is increasing from 50 wt–% to 70% by
2030. Furthermore, a recycling rate of single components is introduced,
e.g. 95% for Co, Cu and Ni by 2030 (EU 2020). Recycling is a method to
ensure resource sustainability and to reduce mining of resources.
Moreover, recycling is one way to overcome hazards like fire, toxic
chemical release and environmental pollution caused by improper
disposal (Kang et al. 2013, Werner et al. 2020, Werner et al. 2021).
During the last decades different recycling processes were estab­
lished. These can be categorized in three main groups, pyrometallurgi­
cal, hydrometallurgical and mechanical, which can be combined with
each other. These processes and their challenges are reviewed in
numerous articles like (Sommerville et al. 2020, Werner et al. 2020,
Windisch-Kern et al. 2022). The authors agree that each process, even
the combination of them, poses challenges. For example, the sufficient
decoating of the electrodes, sufficient quality of the black mass for hy­
drometallurgy or flotation, but also the deficient crystallisation of the
metal oxides in slags with regard to pyrometallurgy. The first step of
nearly all recycling processes is to discharge the battery to ensure safety
(Rothermel et al. 2018, Werner et al. 2020). The lower the State of
Charge (SoC) becomes, the less temperature increase occurs during
crushing (Wuschke et al. 2019) and therefore the lower the risk of
thermal runaway and the lower the reactions is to happen (Perea et al.

* Corresponding author.
E-mail address: alexandra.kaas@mvtat.tu-freiberg (A. Kaas).

https://doi.org/10.1016/j.wasman.2023.08.042
Received 12 April 2023; Received in revised form 28 July 2023; Accepted 30 August 2023
Available online 11 September 2023
0956-053X/© 2023 The Author(s). Published by Elsevier Ltd. This is an open access article under the CC BY license (http://creativecommons.org/licenses/by/4.0/).
A. Kaas et al. Waste Management 172 (2023) 1–10

2018, Essl et al. 2020). There are different possibilities to discharge LIB: pole reversal, by positive temperature coefficient resistance) in the
submerging in a salt solution (Zhang et al. 2013, Lv et al. 2018), using recycling process is investigated and compared.
stainless-steel chips in a stainless-steel container (Gratz et al. 2014) or
conventionally with an electric circuit (Krüger et al. 2014). 2. Materials
Depending on the SoC, different levels of discharge are differenti­
ated. The cells can be discharged to a SoC of 0% (Wuschke et al. 2015, To evaluate the influence of overdischarging five different types of
Wuschke et al. 2019), so-called cut-off voltage, which lies around 2.5–3 LIB cells were investigated: C2, C3, P1, P2 and P6 (Table 1). Photos of
V (Rothermel et al. 2018, Petrovic 2021). At the cut-off voltage around the cells can be found in the supplementary information M1. For each
20% capacity are remaining [19]. The cells can therefore be further type, a batch of three individual cells were studied. All of them originate
discharged as low as 0 V, which is defined as overdischarging (He et al. from the automotive sector. They differ in the cathode chemistry (NCA,
2013, Guo et al. 2016, Rothermel et al. 2018, Juarez-Robles et al. 2020). LFP, NMC) and shape (prismatic and cylindric). These cells were chosen
If the cell is discharged further into a negative polarity, pole reversal to investigate whether the effect of overdischarge has in general an
occurs (Wu et al. 2015, Rothermel et al. 2018). impact on the recycling.
Causes for overdischarged LIBs are long storage, internal cell defects, The procedure for different discharge levels (Fig. 1) is explained as
poor battery design or failures in the battery management system follows. The level PTC describes cells which were discharged using a
(Fuentevilla et al. 2015). Additionally, overdischarging can occur for positive temperature coefficient (PTC) resistance (Osram H4 60/55 W,
batteries which are connected in series. Different aging of the batteries 12 V, Osram GmbH, Munich, Germany) with a maximum resistance of
can lead to overdischarge into reversal (Rieger et al. 2016) or capacity 2.4 Ω. The cells with a high capacity (P2 and P6) were discharged to a
degradation and internal short circuit (Guo et al. 2016). According to voltage below 1 V and the cells with a low capacity to a voltage below 2
Rothermel et al. (Rothermel et al. 2018), higher recycling efficiency is V. The voltage was measured 12 h after disconnecting the resistance to
obtained when the LIB are discharged as whole modules instead of single allow the relaxation of the cell. Batteries with IPR level were first dis­
cells. However, this can cause discharge into reversal of individual cells charged like the PTC level batteries and afterwards forced into pole
(Rothermel et al. 2018). For safe mechanical recycling, it is recom­ reversal by connecting them to a charged cell together with the same
mended to overdischarge the LIB before crushing to reduce the energy resistance for 8 h. Afterwards the voltage was measured, if it was above
content, and therefore prevent heat generation and thermal runaway 0.1 V the procedure was repeated for another 8 h. Furthermore, P6 was
(Rothermel et al. 2018, Wuschke et al. 2019, Werner et al. 2021). discharged with an electronic load ESL-1500-USB (ET Instrumente
Overdischarging into reversal has the advantage that no relaxation of GmbH, Hockenheim, Germany) with a constant resistance of 0.05 Ω
the voltage occurs (Rothermel et al. 2018), decreasing further the risk of until it reached 0 V. Afterwards P6 was short-circuited with a wire (tin-
thermal runaway during crushing. On the other hand, the behaviour plated copper 0.25 mm2) for more than 96 h. The short circuit was
during overdischarging of LIB is not predictable. Heat generation is removed and more than 12 h later the voltage was measured prior to
possible (Rothermel et al. 2018) as well as internal short circuits due to crushing.
Cu dendrites (Maleki and Howard 2006) which can lead to explosion For the processing of the batteries the procedure of the TU Berga­
and fire during overdischarge (Fear et al. 2018). kademie Freiberg was used as originally suggested by Wuschke
By discharging over 0% SoC the chemistry of a cell can be changed (Wuschke 2018). In this study, the first part of the process chain is
(Sonoc et al. 2015, Essl et al. 2020). During discharge Li-ions migrate investigated which is shown in Fig. 1. Each flow shows one batch of cells
from anode to cathode. At overdischarge, after all Li-ions are trans­ which was processed. Due to the dimensions of P6, the battery was pre-
ported to the cathode (Rothermel et al. 2018), further forced over­ crushed with a dual-shaft rotary ripper and a dual-shaft rotary shear
discharge leads to the oxidation of Cu from the anode current collector (design of TU Bergakademie Freiberg (Woldt et al. 2004)), whereas P2
to Cu2+ ions. Those migrate through the separator and reduce at the needed to be pre-crushed only in the dual-shaft rotary shear. For the
cathode to metallic copper (He et al. 2013, Kasnatscheew et al. 2017, final liberation of the first part of the process all batteries were subjected
Feng et al. 2018). The starting point for the voltage of this effect varies to a fast rotating, single-shaft rotary shear (Universal Granulator UG300,
due to cell type and occurs independently of the cell chemistry: NCA Andritz MeWa GmbH; Gechingen, Germany) with a 20 mm discharge
(Fuentevilla, Hendricks et al. 2015, Hendricks, Mansour et al. 2018, grid.
Robert and Novák 2018), LNO (Shu et al. 2012, Robert and Novák After the first comminution each batch of cells was dried for 14 days
2018), LFP (Robert and Novák 2018), LCO (Robert and Novák 2018). at 22–25 ◦ C in a fume cupboard to remove the high-volatile electrolyte
Moreover, the Cu foil does corrode which reduces the foils stability components. To separate the first black mass, the crushed battery ma­
(Hashimoto et al. 2015, Rothermel et al. 2018). terial of each batch was screened at 1 mm using an EML 450 sieve ma­
Other effects which can occur for overdischarged batteries are that chine (Haver & Boecker OHG; Oelde, Germany). In general, the black
the separator can be coated with active material of the cathode (Fear mass is the fraction containing the active particles (anode graphite +
et al. 2018, Hendricks, Mansour et al. 2020), that the separator melts cathode active particles) after comminution process. To separate cell
(Wu et al. 2018, Wang et al. 2020) due to heat generation (Mähliß 2012, housing and separator foil from the electrodes and to investigate the
Fear et al. 2018, Rothermel et al. 2018) or that pure aluminium is settling velocity behavior, a zig-zag air classifier (design of TU
formed on the separator (Wu et al. 2018). Degradation of the Solid
Electrolyte Interphase (SEI) layer at the negative electrode is another
Table 1
effect (Hashimoto et al. 2015, Hendricks et al. 2020). In addition, gas
Studied battery cells information, including their active materials and voltage
can be generated (Hendricks et al. 2020). Impurities of hydrogen in the
after overdischarge and relaxation (PTC: positive temperature coefficient; IPR:
cathode material can lead to generation of H2 (Hashimoto et al. 2015, into pole reversal; ESL: using electronic load ESL-1500-USB).
Zheng et al. 2016) and the decomposition of the electrolyte creates
Indication C2 C3 P1 P2 P6
gaseous carbon compounds (CO, CO2, CH4) (Kumai et al. 1999, Mähliß
2012, Zheng, et al. 2016). Format Cylindric Cylindric Prismatic Prismatic Prismatic
As has been shown, overdischarge can lead to changes in the material Capacity 5 Ah 4 Ah n.a. 20 Ah 94 Ah
Chemistry NCA LFP NMC111 NMC111 NMC111
distribution within the battery cells. Therefore, it is important to know PTC 1.31–1.57 1.29–1.63 0.32–0.44 0.76–0.82 0.44–0.49
how this new characteristic and the resulting properties influence the V V V V V
mechanical recycling. However, yet no study exists on how the struc­ IPR 0V 0V 0V 0V 0V
tural changes affect the recyclability of the batteries. In this paper the ESL – – – 0.22–0.31 0.44–0.46
V V
behaviour of differently overdischarged batteries (by electronic load, by

2
A. Kaas et al.
Fig. 1. Process steps for the different cell types including the discharge and comminution procedure (PTC: positive temperature coefficient; IPR: into pole reversal;
ESL: using electronic load ESL-1500-USB).
Bergakademie Freiberg) was used for the first air flow sorting. Manual
sorting was used to determine the composition of the individual settling
velocities. Tweezers were used for this purpose.
The black mass was sieved with an AS200 control (Retsch GmbH;
Haan, Germany). For the metal content an ICP-OES analysis (iCAP 6300,
Thermo Fisher Scientific Inc; Waltham, United States) was conducted.
This was done only for the P6 cells due to the intense sample preparation
required and the availability of the ICP measurement device. In order to
investigate the effects of the overdischarge on the material distribution
in the battery cells, the cells were cut-open and disassembled. This was
done into air atmosphere as the batteries are also comminuted into air
atmosphere. Therefore, this ambient can represent the properties of the
cells in the crusher for its best. Further on, the characteristics of the
cathode and separator foil were visualized by a scanning electron mi­
croscope (SEM, FEI Quanta 600F) equipped with a field emission source
(FEG) and an SSD-EDS X-ray spectrometer (Bruker Quantax X-Flash
5030 EDS-Detectors). The samples were fixed on a tab (PELCO Tabs TM,
6 mm OD from TED PELLA, INC, Redding, CA, USA). Due to cell avail­
ability, no P1 cells were cut-open.
The specific energy consumption wm was calculated according to:The
degree of liberation was determined by:
( )
massofcompounds
degreeofliberation = 1 − × 100% (1)
cellweight
Compounds are particles where different components macroscopy
are still attached to each other e.g. separator foil to electrodes or casing
to plastics. Electrodes with coatings and coated separator foil are not
classified as compounds. The specific energy consumption wm was
calculated according to:
∫ t1
wm = 0
t
P(t)dt − PL
(2)
mF
In Eq. (2) t0 and t1 mark the start and end of crushing, P(t) represents
the power draw during crushing. PL indicates the idle drive power, and
mF is the feed mass for the respective crushing step.
The particle size distribution of the crushing products was generated
using an EML 450 sieve machine (Haver & Boecker OHG; Oelde, Ger­
many) with the mesh sizes (0; 1; 2; 4; 8; 10; 12.5; 16; 20; 25; 30) mm.
3
Waste Management 172 (2023) 1–10
3. Results and discussion
3.1. Observations for cut-open cells
To observe, which phenomena occurs for the different cells by dis­
charging them to PTC, IPR or ESL, they were cut open and the windings
unrolled. The first impression is that the windings of IPR were more
difficult to unroll because the electrodes and separator foil adhere more
firmly to each other.
All cells that were discharged into pole reversal showed visible
copper deposits on the surface of the cathodes as described in the
literature by e.g. (Hendricks, Mansour et al. 2018, Rothermel, Winter
et al. 2018). Via SEM-EDX it was verified that the deposits are copper,
the image of the SEM-EDX analysis of the P6 IPR can be seen in Fig. 2d-f.
The cathodes of the PTC cells and the P6 ESL were also analysed with
SEM-EDX and showed no deposits of copper on the surface. At the
cathodes of P2 and P6 copper deposits are visible over the whole length
and width of the cathode surface as can be seen in Fig. 2a for the P6.
Some parts of the cathodes showed bare aluminium because the coating
had detached completely during unrolling. The detachment of the
cathode coating from the Al-foil derives from an increase in adhesion of
the cathode material to the separator, which is due to the copper
deposition (Fig. 2d-f). This latter acts as a metallic binder. The detached
coating ranged from covering the whole width of the electrode to only
small spots distributed over the whole width of the cathode. The copper
deposition at the cylindrical cells was far less. The main deposition was
on the parts of the cathode that were at the outer part of the jelly roll.
Additional to the copper deposition there are some spots of separator foil
sticking to cathode for C2. In the case of C3, copper deposition occurs
mainly at the cathode sites where this electrode is directly connected to
the poles. Since the strongest current density for discharging occurs at
these points. It is stronger at the top and the bottom than in the middle.
At the parts where the graphite coating was falling off, the anode
copper foil of the P6 IPR (Fig. 2b) showed corrosion caused by the
copper dissolution as described in the literature by (Hashimoto, Yama­
shiro et al. 2015, Rothermel, Winter et al. 2018). The anode of the P6
PTC had very little loss of coating. For the PTC the decoating happened
mostly at the bends of the windings. Underneath the metal foil was shiny
and did not show any visible sign of copper dissolution even though it
A. Kaas et al.
Fig. 2. Unrolled windings of cathode (a), anode, (b) and separator foil (c), (d) – (f) analysis of the Copper plating on the cathode. (d): photo overview of the cathode
electrode; (e): SEM image showing NMC particles and Cu plating. (f): secondary electron (SE) image detail and applied EDX mapping showing Cu plating.
was discharged below the cut-off voltage. At the other cell types there
was no mayor decoating of the anode and therefore there were no visible
signs of copper corrosion.
The cells of P2 and P6 that were discharged into pole reversal
showed a separator that was heavily coated with the coating from the
cathode as can be seen in Fig. 2c for the P6. There was more coating at
those parts that were opposite of the cathode parts that showed blank
aluminium or heavy copper plating. The separator of P2 IPR had more
coating than the P6 IPR because the P2 cell was discharged into pole
reversal by a cell with a proportionally higher capacity (60 Ah to 20 Ah),
whereas the P6 was discharged with a cell with lower capacity (60 Ah to
94 Ah). The C2 and C3 IPR separator had not much coating, only some
parts had a light dark shade. The separator foil is mainly coated on the
outside of the jelly roll. This occurs mainly at the joints of the current
collectors and the copper deposits at the cathode.
The casings of P2, P6 and C3 showed no differences between PTC and
IPR. The cell components of the cells that were discharged with the
electronic load (P6 ESL) looked the same as those of the cells discharged
by the PTC. There was no sign of copper dissolution or plating and no
coating of the separator.
3.2. Crushing and liberation
The energy consumption between the experiments with the same cell
type and discharge method vary already quite much with ± 20%. It is
therefore not possible to say if the differences between PTC and IPR are
caused by the discharge method or whether they lie within the typical
range of variation. Overall, the average specific energy consumption
amounted to between 4.2 kWh/t for the P6 and 7.3 kWh/t for the C3.
For the cells using NMC as cathode active material (P1, P2 and P6)
and having a prismatic shape, the degree of liberation (1) of PTC and IPR
Table 2
Degree of liberation for the different cell types and their discharge level.
Cell type P6 P2 P1 C3
Discharge level Degree of liberation in %
PTC 95.3 98.4 93.5 93.5
IPR 96.9 92.8 91.8 75.4
ESL 93.3 – – – –
Waste Management 172 (2023) 1–10
discharge level is in the same range as can be seen from Table 2. The ESL
discharged cells of P6 show a bit lower degree of around 3.7% to the PTC
which can be neglected. Summing up that for the NMC based cells the
discharge level has no great impact on the liberation and maybe the
prismatic shape influences the result too. Focusing on the cylindrical
cells C2 and C3, which have a different cell chemistry and shape
compared to the other cells, more deviations in the liberation were
evaluated. For C2 a degree of liberation of 89% for IPR to 98% (Sup­
plementary R1.2) for PTC was determined. The same range of deviations
showed C3 with 75% for IPR and to 93% (Supplementary R1.2) for PTC
of liberated material. This already indicates that some components still
stick together for the IPR and cannot be properly sorted in the following
process steps. One explanation can be that the coating is transferred to
the separator foil but still strongly bound to the cathode and thus forms
larger compounds, which consists of three layers. Another reason can be
the formation of the dendrites (Hendricks et al. 2018, Flügel et al. 2021)
which could lead to the cohesion. Also, the influence of the electrolyte
could not be determined. The reasons for the different behaviour of the
cell chemistries NCA and LFP cannot be sufficiently explored in this
work. Therefore, further investigations are necessary to clarify the
comparatively increased compound formation and reduced coating of
the separator. Hence, it is necessary to process further these products
using a second stage comminution stage in order to reach a higher
liberation degree of the components and a higher yield in black mass.
After the first comminution a first black mass is obtained by dry
screening at 1 mm. The amount of black mass output between the
different discharge levels of the cells does not show a great variation as
can be seen in Table 3. Only exemption is the P2 cell which had with
18.9 % a slightly lower black mass yield for the IPR in comparison to the
PTC (24.6 %). A possible reason is a stronger coating of the separator foil
Table 3
Black mass yield related to the original cell weight for the different cell types and
their discharge level.
C2 Cell type P6 P2 P1 C3 C2
Discharge level Black mass yield related to cell weight in %
97.8 PTC 36.7 24.6 13.0 5.8 36.4
89.5 IPR 36.8 18.9 14.7 7.9 34.4
ESL 35.8 – – – –
4
A. Kaas et al.
in comparison to the other IPR cells. This way more less active material
from the cathode could end up in the black mass. However, earlier in­
vestigations using the same process observed that the anode is more
subjected to delamination than the cathode (Wuschke, Jäckel et al.
2019, Lyon et al., 2022a). This is due to the difference of binder
chemistry, the anode is made of water soluble binder, whereas the
cathode uses PVDF (Vanderbruggen et al., 2022). Therefore, the black
mass yield is more affected by the decoating of the anode than of the
cathode. As the anodes of the cut-open cells did not show a huge vari­
ation for IPR and PTC, they probably have a similar delamination
behaviour and therefore the difference of the black mass yield is not
significant. The decoating of the cathode foil happens mostly at the
secondary comminution step (Wuschke 2018, Lyon et al., 2022a). As
shown in Fig. 2c, the active material of the cathode is for IPR transferred
to the separator foil. Therefore, the second comminution step needs to
investigated as well to decoate the cathode foil and the coated separator
foil and then subsequently, it can be quantified if the coated separator
has an impact on the total black mass yield.
The particle size distribution of the black mass showed no mayor
differences between IPR and PTC as showed in Fig. 3. In general, the IPR
material seemed to be slightly finer than the PTC material (Fig. 3b). Only
deviation is for the P2 cell, here the distribution of the IPR black mass
was finer than of the PTC. The x50 decreased for this material from 288
to 202 µm. This might have been caused by the stronger discharge into
reversal of the P2 in comparison to the other cells, but it could also come
from the cell itself, e.g. due to a different composition.
The elemental composition was analysed by ICP-OES of the P6 black
mass and is displayed in Fig. 4. The main difference between PTC and
IPR is the copper content. The IPR had a three times higher copper
content (1.8 to 0.6%) than the PTC cell. A higher copper content is able
to decrease the efficiency of the hydrometallurgical process, as copper
tends to coprecipitate with metals of the cathode active material (Or
et al., 2020). The reason for the higher copper content are the copper
deposits on the cathode active particles which got liberated together
with the coating. For P6, the cathode active particles are made of NMC,
Fig. 4 shows that the content of Li, Ni, Mn and Co is more than 10%
lower for IPR than for the IPR black mass. This difference can be
explained by the loss of cathode active particles which are coated to the
separator, and therefore in this process stage do not end up in the black
mass product after sieving. The conclusion is that the composition of the
black mass is affected by the separator coating when the cells are dis­
charged into pole reversal. This could lead to cathode active particles
losses in the non-black mass fraction and therefore do not end up in the
hydrometallurgical process. The consequence is a decrease in the overall
recovery of Co and Ni which could be problematic regarding the future
European battery regulations (EU 2020) where 95% of these elements
have to be recovered. Al was not influenced by the discharge method.
Fig. 3. Particle size distribution of the first black mass for the investigated cell types (P1, P2, P6, C2, C3) and their discharge.
5
Waste Management 172 (2023) 1–10
3.3. Separation
To evaluate how the discharge level influences the sorting behaviour
for density separation, the settling velocity distributions of each elec­
trode, casing material, coated and no coated separator foil were inves­
tigated. This settling velocities were investigated using a Zig-zag air
classifier. As the observations of the cut-open cells revealed the casing
material of the different discharge levels showed no difference in its
settling velocity. Unlike the casing the functional unit of electrodes and
separator foil can be influenced by the different discharge levels as the
literature (Hendricks, Mansour et al. 2020) and prior observations in
Fig. 2 revealed. However, the settling velocity of the electrodes shows no
clear influence of the discharge level. For all batteries the settling ve­
locity of IPR and PTC cells for anode and cathode is in the same range.
For P1, P6, C2 and C3 the behaviour of anode and cathode are identical
for the two discharge levels. Larger deviations are only visible for P2.
The reason for that is the greater detachment of the active material from
the cathode to the separator foil. Consequently, the settling velocity of
the cathode is lower for IPR than for PTC. However, P2 shows for the
anode the same settling velocities for IPR and PTC and thus joins the
other investigated battery cells. Evaluating ESL, IPR and PTC for P6
shows that no significant deviations occur. Hence, the electronic load
discharge also does not influence the settling velocity behaviour.
Independent of the cell design or chemistry, the settling velocity of
the non-coated separator foil of the IPR cells showed the same behaviour
as the separator foil of the PTC cells. Therefore, the foils can be sepa­
rated as shown in the process in Fig. 1. However, when the separator is
coated, it has higher settling velocities as shown in Fig. 5a. This is a
result of the active cathode material attaching to the separator foil for
IPR cells (Fig. 2c). Consequently, the separator is transferred to
following process steps with the electrode product and cannot be sepa­
rated at 2.0 m/s like the non-coated separator foil (Wuschke 2018). This
affects the composition of the separator product too (Fig. 5b). Overall,
the separator product of IPR cells consists of less purified separator foil
and to a larger proportion of other components e.g. coating or coated
separator foil (Fig. 5b). Therefore, the overall amount of separator foil in
the separator product is minor to the PTC cells. Moreover, the overall
mass output in the separator fraction varies for the discharge levels
(Table 4). As a result, the composition also differs, as other components
than the separator foil, e.g. aluminium foil or coating, take up a larger
share.
For P6 the composition does not differ for the discharge levels ESL,
PTC and IPR (Fig. 5b). Here the separator foil makes up more than 80%
of the product. Other components of the fraction are coating, small
pieces of cathode and anode, light plastic foils originating from the
casing and small compounds. However, as seen in Fig. 5b, for other cells
the composition of the other investigated cell types differs a lot
depending on the discharge level.
A. Kaas et al.
Fig. 4. Black mass composition of P6 cell with PTC and IPR, measured by ICP-OES. The results are an average of three individual crushing and sieving experiments
and the error bars represent the minimum and maximum.
For P2 and C3, the share of separator foil for PTC to IPR is 60% less in
the separator fraction. In case of the P2 IPR the product mainly consists
of the blank current collector foil of the cathode. Due to the lower
separator recovery the mass output in the separator fraction decreases
from 5.1% for PTC to 2.2% for IPR cells (Table 4). Therefore, the cathode
current collector foil makes up a great share of the whole fraction. The
aluminium foil occurs in this fraction as thin and small pieces, resulting
in low settling velocities, which is why the material is transferred to the
separator fraction. The huge differences for C3 (Fig. 5b) are a result of
the high amount of coating in the separator fraction. As coating has a
greater density than separator foil, for these cells the mass output in­
creases for IPR cells compared to PTC. The coating material of IPR forms
more flakes compared to the PTC cells coating which forms mostly
powder and only a low amount of flaky material. Therefore, the small
pieces of active material are not regained by the sieving and are trans­
ferred into the separator fraction due to their small settling velocity.
For the P1 and C2 cells the difference of the proportion of the
separator for PTC to IPR level in the fraction is varying in a range of
20–50%. The reason for that is the amount of coated separator foil. As
the particle size of the coated separator foil is quite small, the coated
foils were partially transferred to the separator fraction as well.
In a recycling plant the processed batteries could be a mixture of IPR
and PTC cells. Summarizing the results shown, it can be seen that the
discharge level has for the majority of the investigated cells an impact on
the quality of the separator fraction. Therefore, it is questionable if the
formation of a separator fraction is still technical and economical
feasible as too many worthful components (e.g. coating or aluminium
foil) would be subjected in the next process steps to thermal treatment of
the separator fraction. This results in a loss of the components to the
pyrolysis coke or incineration ash. As a conclusion the established pro­
cess in Fig. 1 is not of interest anymore. A new process has to be
developed.
In the established process design, the electrodes and casing are
separated from each other at 6.4 m/s. In Fig. 5a, the settling velocities of
the separator foils of P6 are shown. Here, the worst separation scenario
of the investigated cells is revealed. Around 20% of the mass of the
coated separator is taken to the casing fraction. For the P2 around 8% of
coated separator are collected in the casing fraction. Downstream this
fraction can be subjected to eddy current separation (Lyon et al., 2022b)
where the coated separator is then collected together with other plastic
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Waste Management 172 (2023) 1–10
components. Here further treatment should be considered again to
regain the cathode active material. For the other cell types (P1, C2 and
C3) almost all coated separator is transferred to the electrode fraction.
Therefore, the worthful cathode active material is not lost and can be
regained together with other coating when the electrode fraction is
subjected to further process steps.
As described in Wuschke et al. (Wuschke et al. 2019) the first air flow
separation consists of two sorting steps. After generating the separator
fraction, the remaining material is subjected to an air stream velocity of
6.4 m/s to gain an electrode fraction (2–6.4 m/s) and a housing fraction
(>6.4 m/s). As the electrode fraction is further processed to recover
copper, aluminium and coating, it is important to determine the influ­
ence of the level of discharge and the resulting impurities. Anode,
cathode and coating make up 76–90% of the fractions of the PTC cells
whereas the IPR differ to the PTC cells (Fig. 6). P1 and P6 show around
4–7% less electrodes and coating for the IPR compared to the PTC. This
moderate difference can be even less when adding the coated separator
foil with the valuable black mass to the calculation. As a result, the mass
of cathode, anode, coating and coated separator would be the same for
PTC and IPR. Lager differences of IPR to PTC of 34–54% were revealed
for P2, C2 and C3, especially P2 shows huge differences with 54% less
electrodes and coating for IPR to PTC. The main reason for this is the
significant amount of coated separator. This was already clear by eval­
uating of the cut-open cells in Section 3.1 that this cell forms the biggest
amount of cathode active material on the separator foil for IPR discharge
level.
In general, the cathode active material, which is now bound to
separator product is normally liberated in electrode fraction or already
transferred to BM1. Thus, it is possible that the composition of black
mass changes regarding the cathode active material. More of the active
material is transferred to second black mass fraction, which is generated
in a second downstream separation step as presented in (Wuschke
2018). This can lead to problems in subsequent hydrometallurgical steps
as a greater need for chemicals evolves to separate metals.
For C2 and C3 the main difference of IPR to PTC occurs due to the
formation of compounds (Fig. 6d-e) making up 26.6% for the C2 and
36.5% for the C3. Here the special interest is on the different cell
chemistry to the other investigated cells as NCA and LFP are used as
cathode active material. As already described in Section 3.2 for these
cells a minor degree of liberation is achieved due to the formation of
A. Kaas et al. Waste Management 172 (2023) 1–10

Fig. 5. Characteristics of separator foil a) settling velocity according to for the different discharge levels and b) mass distribution of the battery components in the
separator fraction.

Table 4
Mass output in separator fraction for the different cell types and their discharge level.
Cell type P6 P2 P1 C3 C2
Discharge level PTC IPR ESL PTC IPR PTC IPR PTC IPR PTC IPR

Mass output in% 6,0 5,1 5,1 5,1 2,2 4,5 4,6 4,7 6,7 3,5 2,4

compounds. However, most of the active material containing com­
pounds for these cells are in the electrode fraction, meaning they will be
transferred to further comminution and additional liberation is probable
and no dissipation or loss of active material to other streams occurs.
Further on, the liberated coating should be transferred to the black
mass during the first classification. However, the composition analysis
shows that up to 28% of the electrode product consists of coating. Hence,
this part of the coating could not be transferred to the black mass frac­
tion. The greatest amounts of coating are revealed for P2 and P6 (Fig. 6b-
c). A possible reason for that can be the cell chemistry of NMC and the
binders used. NMC forms flaky particles for PTC and IPR in liberation
whose particle size is greater than 1 mm, which questions the selected
cut of the sieve in the process chain. LFP based batteries (C3) also
formed flaky particles for both discharge levels. However, the particle

7
A. Kaas et al.
Fig. 6. Composition of the electrode product for the investigated cells and their discharge level.
size of the flakes of the IPR cell were greater leading to a higher amount
of coating in the electrode fraction. Thus, further comminution is needed
to mill the coating flakes to transfer them to the black mass fraction. In
addition, it is possible for all cells that a further liberation takes place in
the air classifier due to collisions between particle–particle or parti­
cle–wall (Kaas et al. 2022).
With the formation of coated separator, a possible loss of active
material occurs In addition, less active material can be recovered, as the
active materials are no longer only in powder form but also in flake
form. The future EU regulations are not possible to meet. As a conse­
quence, the mechanical process has to be re-designed or at least the
operation parameters have to be re-checked and adopted in order to
enable following processes e.g. hydrometallurgy to achieve especially
the element specific recovery goals.
4. Conclusion and outlook
This study aims to investigate the influence of different discharge
levels on the recycling process efficiency for different battery types.
Therefore, batteries with different shapes and cell chemistry were
overdischarged (PTC) and discharged into pole reversal (IPR) and then
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Waste Management 172 (2023) 1–10
these batteries went through the crushing and liberation process. The
output fractions were further separated using sieving and air classifi­
cation, leading to three products: separator product, electrode product
and black mass.
By investigating the functional units (electrodes and separator foil)
using cut-open cells, a clear difference between PTC and IPR was
observed. The assumption of plating of metallic copper due to the pole
reversal was confirmed by EDX analysis. Furthermore, when the cells
were discharged into pole reversal, the cathode active material was
coated to the separator foil, leading therefore to bare aluminium foil
area. In order to understand how the discharge step affects the recycling
efficiency process, the particle size distribution, the settling velocity of
each material and the composition of the three products after the air
flow sorting were analysed.
This study shows that the different discharge levels have no signifi­
cant impact on the energy consumption of the comminution process,
particle size distribution of the different fractions or the first obtained
black mass (1st comminution) and the black mass yield. Nevertheless,
the black mass composition reveals that the Cu content is higher for IPR
cells than PTC cells, which can be explained by copper plating on the
cathode electrode.
A. Kaas et al.
The separator product of PTC and IPR obtained by air flow sorting
showed deviations to the known behaviour for most of the investigated
batteries. When the separator particles are coated with cathode active
particles, the air flow process leads to more heterogeneous products due
to the large variance in the density and therefore of the settling velocity.
Indeed, in that case most of the coated separator particles were trans­
ferred into the electrode fraction rather than the separator fraction.
Furthermore, the cathode active particles coated on the separator result
in loss of valuable materials such as Co.
As this study revealed the discharge level has an impact on the
properties and material composition of the functional units of the bat­
teries and thus the characteristics of the recycling products. This work
highlights the need of further research on the impact of discharge on the
recycling. Additional to the mechanical recycling, safety aspects of
overdischarging have to be clarified. The characterization of potential
hazards during the recycling process which result from the discharge
should be explored. Focussing on the mechanical recycling it has to be
investigated if additional comminution processes are able to delaminate
the coated separator and further liberate the formed compounds.
Additionally, a more detailed investigation of the black mass is advis­
able. Here especially the challenge of the higher Cu content and the
influence for further recycling steps needs to be evaluated. As this study
is focussing on a sub-process the recyclability of the different discharge
levels after the whole mechanical process is to be evaluated. This further
research is essential in order to estimate if the recycling rates can be met
or if the mechanical process has to be partly or fully new designed.
Funding
This research was funded by the German Federal Ministry for Edu­
cation and Research (BMBF), as well as the Projektträger Jülich (PTJ),
with the projects DIGISORT (Digitalisation of mechanical sorting pro­
cesses in mechanical battery recycling) 03XP0337 and LOWVOLMON
(Monitoring of low-volatile electrolytes in the mechanical recycling
process chain) 03XP0354 within the competence cluster for battery
recycling (greenBatt).
Declaration of Competing Interest
The authors declare that they have no known competing financial
interests or personal relationships that could have appeared to influence
the work reported in this paper.
Data availability
Data will be made available on request.
Acknowledgments
The authors would like to thank Yvonne Volkmar for conducting the
ICP analysis as well as the technical and scientific staff of the Institute of
Mechanical Process Engineering and Mineral Processing. The authors
would like to thank Nkwenti Giresse, Madhura Kaskhedikar, Saquib
Anjum, Jyotisman Kotoky, Hariharan Piramanayagam and Lakshman­
rao Pentela for the sieving, air classification and manual sorting of the
LIB components. Thanks to the Liofit GmbH for providing the electric
load ESL-1500-USB to discharge the ESL batteries.
Author contributions
A.K. and C.W. developed the idea and the content of the report; A.K.
and C.W conducted the experiments, analyzed the resulting data and
results, and wrote the article; A.V. made the SEM-EDX pictures and
discussed the results with A.K and C.W.; U.A.P. and A.V. revised the
article and improved both the presentation of the results and the
structure of the sections; everything took place under the supervision of
9
Waste Management 172 (2023) 1–10
U.A.P. All authors have read and agreed to the published version of the
manuscript.
Appendix A. Supplementary material
Supplementary data to this article can be found online at https://doi.
org/10.1016/j.wasman.2023.08.042.
References
Bibra, E.M., et al. Global EV Outlook 2021: Accelerating Ambitions Despite the Pandemic
Transportation Research Board 2021 https://trid.trb.org/view/1925380.
Essl, C., et al., 2020. Comprehensive hazard analysis of failing automotive Lithium-ion
batteries in overtemperature experiments. Batteries 6 (2), 30.
Eu, Proposal for a REGULATION OF THE EUROPEAN PARLIAMENT AND OF THE
COUNCIL concerning batteries and waste batteries repealing Directive 2006/66/EC
and amending Regulation (EU) No 2019/1020 2020 Brussels.
Fear, C., et al., 2018. Elucidating copper dissolution phenomenon in Li-ion cells under
overdischarge extremes. J. Electrochem. Soc. 165 (9), A1639.
Feng, X., et al., 2018. Thermal runaway mechanism of lithium ion battery for electric
vehicles: A review. Energy Storage Mater. 10, 246–267.
Flügel, M., et al., 2021. Cu dissolution during over-discharge of Li-ion cells to 0 V: a post-
mortem study. J. Electrochem. Soc. 168 (2), 020506.
Fuentevilla, D., et al., 2015. Quantifying the impact of overdischarge on large format
lithium-ion cells. ECS Trans. 69 (20), 1.
Gratz, E., et al., 2014. A closed loop process for recycling spent lithium ion batteries.
J. Power Sources 262, 255–262.
Guo, R., et al., 2016. Mechanism of the entire overdischarge process and overdischarge-
induced internal short circuit in lithium-ion batteries. Sci. Rep. 6 (1), 1–9.
Hashimoto, M., et al., 2015. Mechanism of gas generation in lithium ion batteries by
overdischarge. ECS Trans. 69 (20), 17.
He, H., et al., 2013. Failure investigation of LiFePO4 cells in over-discharge conditions.
J. Electrochem. Soc. 160 (6), A793.
Hendricks, C.E., et al., 2020. Copper dissolution in overdischarged lithium-ion cells: X-
ray photoelectron spectroscopy and X-ray absorption fine structure analysis.
J. Electrochem. Soc. 167 (9), 090501.
C. Hendricks et al. Copper dissolution investigations in large-format lithium-ion cells
48th Power Sources Conf 2018 Denver CO.
Juarez-Robles, D., et al., 2020. Degradation-safety analytics in lithium-ion cells: Part I.
Aging under charge/discharge cycling. J. Electrochem. Soc. 167 (16), 160510.
Kaas, A., et al., 2022. Review on Zigzag Air Classifier. Processes 10 (4), 764.
Kang, D.H.P., et al., 2013. Potential environmental and human health impacts of
rechargeable lithium batteries in electronic waste. Environ. Sci. Tech. 47 (10),
5495–5503.
Kasnatscheew, J., et al., 2017. Lithium ion battery cells under abusive discharge
conditions: Electrode potential development and interactions between positive and
negative electrode. J. Power Sources 362, 278–282.
Keersemaker, M., Keersemaker, M., 2020. “Critical raw materials.” Suriname Revisited:
Economic Potential of its Mineral. Resources 69–82.
Korthauer, R., 2013. Handbuch lithium-ionen-batterien. Springer.
Krüger, S., et al., 2014. Effect of impurities caused by a recycling process on the
electrochemical performance of Li [Ni0. 33Co0. 33Mn0. 33] O2. J. Electroanal.
Chem. 726, 91–96.
Kumai, K., et al., 1999. Gas generation mechanism due to electrolyte decomposition in
commercial lithium-ion cell. J. Power Sources 81, 715–719.
Lv, W., et al., 2018. A critical review and analysis on the recycling of spent lithium-ion
batteries. ACS Sustain. Chem. Eng. 6 (2), 1504–1521.
Lyon, T., et al., 2022a. Decoating of Electrode Foils from EOL Lithium-Ion Batteries by
Electrohydraulic Fragmentation. Metals 12 (2), 209.
Lyon, T., et al., 2022b. Recycling battery casing materials. In: Nano Technology for
Battery Recycling, Remanufacturing, and Reusing. Elsevier, pp. 349–370.
Mähliß, J., 2012. Aufbau, Funktionsweise und Gefährdungspotenzial von Li-Ionen-
Zellen. Elektronik ecodesign 3.
Maleki, H., Howard, J.N., 2006. Effects of overdischarge on performance and thermal
stability of a Li-ion cell. J. Power Sources 160 (2), 1395–1402.
Or, T., et al., 2020. Recycling of mixed cathode lithium-ion batteries for electric vehicles:
Current status and future outlook. Carbon Energy 2 (1), 6–43.
Perea, A., et al., 2018. State of charge influence on thermal reactions and abuse tests in
commercial lithium-ion cells. J. Power Sources 399, 392–397.
Petrovic, S., 2021. Battery technology crash course. Springer International Publishing,
Cham.
Rieger, B., et al., 2016. A new method to model the thickness change of a commercial
pouch cell during discharge. J. Electrochem. Soc. 163 (8), A1566.
Robert, R., Novák, P., 2018. Switch of the charge storage mechanism of Li x Ni0. 80Co0.
15Al0. 05O2 at overdischarge conditions. Chem. Mater. 30 (6), 1907–1911.
Rothermel, S., et al., 2018. In: Recycling of Lithium-Ion Batteries: The LithoRec Way.
Recycling of Lithium-Ion Batteries: The LithoRec Way. Springer:, New York,
pp. 1–31.
Shu, J., et al., 2012. A comparative study of overdischarge behaviors of cathode
materials for lithium-ion batteries. J. Solid State Electrochem. 16, 819–824.
Sommerville, R., et al., 2020. A review of physical processes used in the safe recycling of
lithium ion batteries. Sustain. Mater. Technol. 25, e00197.
A. Kaas et al.
Sonoc, A., et al., 2015. Opportunities to improve recycling of automotive lithium ion
batteries. Procedia Cirp 29, 752–757.
Tian, Y., et al., 2014. Analysis of greenhouse gas emissions of freight transport sector in
China. J. Transp. Geogr. 40, 43–52.
Vanderbruggen, A., et al., 2022. Lithium-Ion Battery Recycling─ Influence of Recycling
Processes on Component Liberation and Flotation Separation Efficiency. ACS ES&T
Eng. 2 (11), 2130–2141.
Wang, D., et al., 2020. Effects of overdischarge rate on thermal runaway of NCM811 Li-
ion batteries. Energies 13 (15), 3885.
Werner, D., et al., 2020. Recycling chain for spent lithium-ion batteries. Metals 10 (3),
316.
Werner, D.M., et al., 2021. Influence of cell opening methods on organic solvent removal
during pretreatment in lithium-ion battery recycling. Waste Manag. Res.
0734242X211053459.
Windisch-Kern, S., et al., 2022. Recycling chains for lithium-ion batteries: A critical
examination of current challenges, opportunities and process dependencies. Waste
Manag. 138, 125–139.
10
Waste Management 172 (2023) 1–10
Woldt, D., et al., 2004. Size reduction by means of low-speed rotary shears. Int. J. Miner.
Process. 74. S405-S415.
Wu, L., et al., 2018. In situ temperature evolution and failure mechanisms of LiNi0.
33Mn0. 33Co0. 33O2 cell under over-discharge conditions. J. Electrochem. Soc. 165
(10), A2162.
Wu, C., et al., 2015. Research on overcharge and overdischarge effect on lithium-ion
batteries. 2015 IEEE Vehicle Power and Propulsion Conference (VPPC), IEEE.
Wuschke, L., et al., 2015. Recycling of Li-ion batteries—A challenge. Recovery 4, 48–59.
Wuschke, L., 2018. Mechanische Aufbereitung von Lithium-Ionen-Batteriezellen.
Technische Universität Bergakademie Freiberg, Freiberg.
Wuschke, L., et al., 2019. Crushing of large Li-ion battery cells. Waste Manag. 85,
317–326.
Wuschke, L., et al., 2019. Comminution Of Li-Ion Traction Batteries. Proceedings of
European Symposium on Comminution and Classification, Gothenborg, Sweden.
Zhang, T., et al., 2013. Characteristics of wet and dry crushing methods in the recycling
process of spent lithium-ion batteries. J. Power Sources 240, 766–771.
Zheng, F., et al., 2016. Influence of different open circuit voltage tests on state of charge
online estimation for lithium-ion batteries. Appl. Energy 183, 513–525.