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OPEN Studies on the deposition

of copper in lithium‑ion batteries
during the deep discharge process
Thomas Langner*, Tim Sieber & Jörg Acker

End-of-life lithium-ion batteries represent an important secondary raw material source for nickel,
cobalt, manganese and lithium compounds in order to obtain starting materials for the production of
new cathode material. Each process step in recycling must be performed in such a way contamination
products on the cathode material are avoided or reduced. This paper is dedicated to the first step
of each recycling process, the deep discharge of lithium-ion batteries, as a prerequisite for the safe
opening and disassembling. If pouch cells with different states of charge are connected in series and
deep-discharged together, copper deposition occurs preferably in the cell with the lower charge
capacity. The current forced through the cell with a low charge capacity leads, after lithium depletion
in the anode and the collapse of the solid-electrolyte-interphase (SEI) to a polarity reversal in which
the copper collector of the anode is dissolved and copper is deposited on the cathode surface. Based
on measurements of the temperature, voltage drop and copper concentration in the electrolyte at
the cell with the originally lower charge capacity, the point of dissolution and incipient deposition of
copper could be identified and a model of the processes during deep discharge could be developed.

Lithium-ion batteries (LiBs) are currently the most important technology for storing electrical energy and
increasingly penetrating all areas of human everyday life due to their expanding use in smartphones, laptops,
tools and e-mobility. Commercial cells are usually manufactured in a cylindrical design, whereas LiBs are used
in the automotive industry in large prismatic cells or as so-called pouch cells.
At the end of their lifetime, LiBs represent a valuable secondary raw material source to cover the demand of
the necessary elements (Li, Ni, Mn, Co). Recycling is becoming increasingly important as many such batteries are
at the end of their life cycle and the raw materials are expensive and are mined under critical conditions. There
are currently two basic industrially implemented technologies for the recycling of spent LiBs: the pyrometal-
lurgical and the hydrometallurgical ­process1–11. The pyrometallurgical route is energy-intensive due to the high
temperatures required. After pretreatment, cobalt and manganese nickel are separated pyrometallurgically from
the spent LiBs by melting and refining. The hydrometallurgical route involves leaching disassembled or shredded
LiBs in strong inorganic acids to dissolve metals and battery materials. Similar to the pyrometallurgical method,
the metals are recovered as inorganic salts. Losses typically occur during leaching and precipitation/separation
of the metal salts. In addition, the complete production chain (precipitation, calcination, shaping, tempering)
must then be run through again.
Sieber et al. chose an alternative approach for the recovery of nickel, manganese and cobalt (NMC), which
is carried out while maintaining the chemical, physical and morphological properties of the NMC and with the
minimal use of ­chemicals12. This approach, known as functional recycling, can be applied to the cathodes of
disassembled and separated LiBs at the end of their lifetimes and to residues from cathode production. The target
of functional recycling is the recovery of high quality cathode material which can be reused for the production
of new LiBs, so-called recycled batteries. Functional recycling takes into account the current development that
the performance and, thus, the added value of modern high-performance materials is determined significantly
by their defined composition, the effort and know-how of their synthesis or their defined geometric shape, e.g.
as fibers, hollow fibers, micro- and nanowires, defined layers and stratifications, and particles of a defined size.
Therefore, all process steps of functional recycling must be designed in a way that changes in the chemical com-
position of the materials used or the topographies of the surfaces of the compounds are avoided or minimized.
The first step in recycling is always the deep discharge of the modules, in which the individual battery cells
(e.g. pouch, prismatic) are electrically combined into a single unit, so that the lithium is transferred to the cathode
material as completely as possible to ensure that the cells can be dismantled safely. This is followed by dismantling

Department of Physical Chemistry, Brandenburg University of Technology Cottbus-Senftenberg, 01968 Senftenberg,

Germany. *email: [email protected]

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the batteries, opening the cells and separating the anode, cathode and separator foils. All further steps of the
chemical–mechanical separation of the cathode material from the aluminum foil must also be designed in such
a way that any degradation of the particles, for example, due to breakage, deposits on the surface, contamination
with other battery components (e.g. particles of the aluminum or copper foils) or direct chemical attack on the
material is prevented or minimized.
The subject of this study is the first step of recycling, the deep discharge of the battery, which has an enormous
impact on the functional recycling and reusability of the cathode material recovered.
An unwanted side reaction that can occur during deep discharge is the deposition of copper on the cathode
foil. Jo et al. found out in their investigations that an increasing copper content in the NMC leads to a loss of
capacity of the b ­ attery13. They found a slightly lower discharge capacity at a copper content of 0.5…1.5 mol%.
After 50 cycles, the capacity of the pure active material was 135.64 mAh ­g−1. By comparison, the discharge
capacity of the active material contaminated with 0.5, 1.5 and 2.5 mol% was 131.81, 129.17 and 85.2 mAh ­g−1,
respectively. The material contaminated with 2.5 mol% copper showed a slightly lower capacity than the pure
active material only at low discharge rates (0.1 C). At high discharge rates (5 C), the capacity decreases by about
85% compared to cells with copper-free cathode material.
Guo et al. connected four fully charged NMC-based batteries (state of charge: SOC = 100%) in series with a
fully discharged battery (SOC = 0%)14. The current flow generated when the full battery is discharged forces a
charge transport on the discharged cell, which, due to the absence of L ­ i+, must be ensured by other charge carri-
ers as an unwanted side reaction. They found that the voltage curve of the initially deeply discharged cell passes
through a minimum at a SOC = − 11% (relative to the initially fully charged batteries) during further “discharg-
ing.” The time the voltage reaches the minimum was declared as the point at which the dissolution of the copper
foil of the anode begins. According to Guo, copper is deposited on the cathode at the interface to the separator
and leads to local short circuits from a SOC = − 13% onward, which increase in frequency up to SOC = − 20%,
and the internal resistance of the cell asymptotically approaches a limit value. The process can be reversed as
long as the dissolved copper (SOC > − 12%) has not yet been deposited on the cathode. These cells can be almost
fully recharged and show only slight power losses. Cells that were discharged to a SOC ≤ − 14.5% and deposited
copper could be charged but showed a significant self-discharge and depleting open-circuit voltage.
Zheng et al. investigated the degradation mechanisms of ­LiFePO4 cells as a function of ­overdischarge15. They
found a correlation between the capacity loss of the cell and the value of the end-of-discharge voltage. They found
that overdischarge to 0.5 V and 0 V lead to lower cycle performance in addition to serious capacity loss. Electrode
impedance trends showed that the impedance of both electrodes increased, with the cell at 0 V exhibiting the
highest values. Based on half-cell tests, the capacity loss could be related to the anode.
Experiments on overdischarge were carried out by Fear et al. with NCA (nickel–cobalt-aluminum oxide) as
the cathode ­material16. They divided the discharge into different phases using the first and second derivation
of the voltage curve. They concluded that the oxidation of the copper of the carrier foil begins at the minimum
voltage curve at − 1.5 V, where the first derivative is 0, and is followed by the dissolution of the copper after the
NCA breakdown. Furthermore, they described the voltage rise after the minimum by the increasing potential of
the cathode, since the overpotential for copper reduction is reduced and copper ions compete with the lithium
ions to be reduced at the electrode surface, as already described by ­Kasnatscheew17. The internal resistance of the
cell decreases due to internal short circuits and the voltage approaches − 0.23 V asymptotically. At this point, the
copper bridges across the cell have grown sufficiently so that the cell behaves like a resistor in the circuit rather
than an electrochemical system.
Robles et al. performed long-term cycling to investigate the degradation mechanisms as a function of
­overdischarge18. Cells whose discharge voltage was 2.7 V exhibited a 20% capacity loss after 287 cycles. The
capacity loss was attributed to the thickening of the SEI. If the discharge voltage is set to of 1.5 V, the capacity
loss of 20% is reached after 120 cycles. In addition to SEI thickening, increased li-plating is responsible for this.
If the final discharge voltage is set to 0 V or − 0.5 V, Li-plating, particle cracking, copper dissolution and the
formation of copper bridges occur. Cells that were overdischarged to this − 0.5 V failed after only 14 cycles due
to internal short circuits.
The deep discharge of ­LiCoO2 cells to 0 V leads to an increase of the anode potential to about 3.5 V, so that the
copper of the anode foil is oxidized and, as a result, is deposited on the cathode foil. The investigations of Li et al.
showed that the SEI decomposes to gaseous products (CO, ­CO2, ­CH4) and the cells swell during deep discharge
to 0 ­V19. Kasnatscheew et al. analyzed the interactions between the electrodes in a three-electrode Swagelok cell
during overdischarge by determining the single-electrode potentials of anode and cathode to a reference electrode
located in the ­system17. A characteristic potential plateau at about 3.56 V was found at the graphite electrode
due to the oxidation of the copper. The constant anode potential after the beginning of the copper oxidation
was interpreted to mean that this process continues during the entire remaining discharge phase. The time-
delayed potential drop observed at the positive electrode was attributed to the competitive reaction between the
conventional lithium plating reaction and the parasitic Cu plating reaction. He et al. cyclized different L ­ iFePO4
cells under overdischarge conditions (5, 10, 15 and 20% overdischarge)20. Under these conditions, for example,
the cell cyclized to 120% depth of discharge failed on the second cycle. The oxidation and reduction potentials
of Cu/Cu+ and ­Cu+/Cu2+ were determined vs. Li/Li+. They showed that there is a gradual formation of copper
bridges, which lead to internal short circuits and result in considerable self-discharge.
Hendricks et al. performed deep discharges to 0.5 V, 0.25 V and 0 ­V21. The electrodes were subsequently
examined with XPS and XAFS. Copper was detected in all cells discharged below 0.5 V, which was attributed
to the dissolution of the anode current collector. They suggested that the dissolution of the copper foil leads to
a poorer adhesion of the anode material, which justifies a capacity loss, during 40 cycles, of 10%. Furthermore,
they found that the deposition of copper species leads to a blockage of intercalation sites and thus also contrib-
utes to a capacity loss. The deposited copper species were identified as ­Cu2O and Cu(OH)2. These species are

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Figure 1.  (a) Voltage and temperature behavior during a deep discharge of a single cell at 41 mΩ; (b) current
behavior at different resistors.

non-conductive and thus do not lead to internal short circuits. However, it was not been excluded that overdis-
charge into reversal could result in deposition of metallic copper.
It is necessary for the best possible performance of the recyclate that the material for recycling is copper-free;
this applies to both the active material and the electrolyte. It is, therefore, crucial to determine the point on the
voltage curve during discharge where copper is present in the electrolyte and the point where copper is deposited.

Results
Discharge of individual cells. Deep discharges of single cells with different load resistors and, conse-
quently, different discharge currents (0.5 … 200 A) to a final clamp voltage of ≈ 0 V were performed. Apart
from temperature influences, the resistor over the discharge process can be regarded as almost constant (∆R ≈ 0
… 10%). The voltage drop across the internal resistance of the cell increases due to the low load resistors and
the resulting high load currents, resulting in a lower clamp voltage under load. With a resistor of 41 mΩ, for
example, an initial current of 80…90 A flows (Fig. 1a,b). Figure 1b shows the corresponding current behaviors
at selected resistors (30…74 mΩ).
The voltage plateau in Fig. 1a is explained by the fact that the cathode potential is nearly constant and the
anode potential increases only slightly in the range up to approx. 20 ­Ah19. The height of the plateau results from
the discharge current. The collapse of the clamp voltage at a discharged charge quantity of about 20 Ah results
from the rapid increase of the anode potential (> 3 V vs. Li/Li+) with a simultaneous decrease of the cathode
potential (≈ 3.5 V vs. Li/Li+). When both potentials have reached the same value, the cell is potential-free
­(UCV = 0 V).
Figure 1a shows that the temperature increases continuously during the discharge at the load resistor of
41 mΩ. The greatest increase is at the point where the clamping voltage collapses rapidly. This rapid tempera-
ture rise is associated with the collapse of the S­ EI22. The maximum temperature reached is ≈ 44 °C (Fig. 1a).
By contrast, a maximum temperature of about 67 °C was measured when discharging at 13 mΩ. The discharge
currents show the same curve as the clamp voltage during discharging. The current is dependent on the value
of the resistor (Fig. 1b).

Opening the cells. The batteries were then opened and the cathode foils analyzed for degradation and
copper deposition. The most visually striking finding is that the plastic separator degrades massively during
discharge with load resistors ≤ 10 mΩ. In some places, the aluminum oxide coating of the separator adheres so
firmly to the cathode that the separator carrier foil can be removed from the aluminum oxide coating. In other
places, the separator adheres so firmly to the cathode that it breaks when the separator is pulled off. The gas
development during discharging can be followed by inflating the battery. The collapse of the SEI and the result-
ing gaseous reaction ­products22 cause gas bubbles to form between the foils, which remain between the separator
and the cathode foil. No degradation of the separator occurs only at these, typically round or oval places, so that
no buildup can be detected there. After opening the cells, none of the foils showed visually recognizable copper
deposits on the cathode foil. No deposition of copper independent of the discharge current can be detected by
means of REM-EDX analysis. It should be noted that the chemical analysis shows no cobalt, manganese, nickel
or copper could be detected in the electrolyte. The EDX analysis of the NMC also shows no measurable influence
of the discharge current on the chemical composition of the NMC.

Discharge of cells connected in series. Pouch cells with different state-of-charge (­ SOC1 >  > ­SOC2, see
Fig. 2) were connected in series and discharged in a further series of experiments. The aim is to simplify the
simulation of a battery stack containing batteries with different charge capacities, which can be caused, for exam-
ple, by production differences (layer quality, capacity differences) or by uneven aging or the failure of individual
cells. As a result, the cell with a lower charge capacity is already completely discharged after a shorter discharge
time, while the cell with a higher charge capacity still supplies voltage, thus, forcing a current flow in the cell

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Figure 2.  (a) Schematic layout of the series connection (SOC Cell 2 <  < SOC Cell 1), (b) discharge curve of
a single cell at 41 mΩ, red marking, point at which the pre-discharge was stopped for the experiments with a
series connection.

Figure 3.  (a) Complete discharge curve of a cell during overdischarge at 58 mΩ; markers show the points
at which the discharge was stopped and the electrolyte was removed; (b) voltage curve of the cells during
overdischarge; red dots show the copper concentration in the electrolyte; (c) cathode foil with copper deposition
(Q = 31.5 Ah).

already discharged. The forced current flow causes complex chemical side reactions, such as the almost complete
de-intercalation of the anode material, a collapse of the SEI at the anode and, in another process, the dissolution
of the copper carrier foil at the carbon anode and the deposition of copper on the c­ athode16,20.
Figure 3a shows the complete discharge curve and its derivative of a cell during overdischarge. The course of
the discharge voltage curves is in very good agreement with the discharge voltage curves determined by Fear et al.
The latter concluded from the voltage curves and their 1st and 2nd derivations that the oxidation of the copper
­ inimum16. In order to provide analytical evidence of
foil does not begin until the voltage curve has reached its m
which point of the voltage curve marks the dissolution of the copper foil, one cell at a time was discharged to a
defined voltage value, the electrolyte was removed and the cell was opened. The copper content in the electrolyte
was quantitatively determined by a high-resolution continuum source atomic absorption spectrometer (Table 1).

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Cell 1 2 3 4 5 6 7
UEnd/V 0 − 0.8 − 1.2 − 1.5 − 1.77 − 1.91 − 1 a.M
Q/Ah 24.3 24.9 25.3 25.7 26.1 26.8 31.5
wCu/mg ­kg−1 < LOD < LOD 0.11 ± 0.01 1.08 ± 0.07 4.33 ± 0.15 6.53 ± 0.20 7.96 ± 0.24
wNi,Mn,Co/mg ­kg−1 n.d n.d n.d n.d n.d n.d n.d
Cu on AF x x x x ✓ x x
Cu on CF x x x x ✓ ✓ ✓

Table 1.  Analysis of electrolyte ­(wCu, ­wNi,Mn,Co) and visual inspection of anode (AF) and cathode (CF) foils,
x → not present, ✓→ present; ­UEnd is the voltage drop across the battery at electrolyte withdrawal, Q is the
amount of charge withdrawn from the circuit, cell 7 a.M. after the minimum, L ­ ODCu = 0.01 mg ­kg−1, n.d. →
not detectable.

Figure 4.  (a) Anode foil with copper deposits; (b) SEM image with EDX mapping superimposed on the cross-
section of the anode foil, A: superficial copper layer, B: graphite layer, C: Cu carrier foil; U = − 1.77 V, Q = 26.1
Ah.

These defined voltage values, each point corresponding to a single cell, are shown as red circles in Fig. 3a and in
Table 1. The red squares in Fig. 3b show the copper concentration determined in the electrolyte during overdis-
charge. The voltage curve (blue line) was drawn in again for illustration. Figure 3c shows a cathode foil (tab. 2,
cell 7) with a large area of deposits of copper with the typical “leopard skin” pattern and separator components
(white deposits).
Figure 3a clearly shows that copper is already detectable in the electrolyte at − 1.2 V and, thus, before the
voltage minimum is reached. This is remarkable since, according to Fear et al., the electrochemical dissolution
of the copper foil should only begin at the voltage minimum (here − 1.91 V)16. The amount of charge transferred
at − 1.2 V of Q = 25.3 Ah corresponds approximately to the amount of charge that can be withdrawn from a cell
that has been individually discharged to 0 V (Fig. 2). Since, from this point on, practically no Lithium-ions are
available in the working cell as a charge carrier, the charge flow in the working cell forced by the driving cell
leads to the dissolution of the copper of the anode carrier foil and the transport of copper ions to the cathode.
At this point, no copper is yet detectable on the cathodes of the opened cell.
Copper deposits are found both on the cathode and on the anode only at a potential of − 1.77 V (Q = 25.7 Ah)
at the working cell. At the same time, an increased concentration of copper ions is detectable in the electrolyte.
Copper deposits could also be detected on the surface of the graphite anode (Fig. 4a) only in the cell discharged to
− 1.77 V (Q = 26.1 Ah), but not inside the graphite layer (Fig. 4b). Since there is no electron conduction between
cathode and anode at this stage, this leads to the assumption that the first copper ions reaching the surface of the
graphite are possibly reduced to metallic copper by reactive, reducing decomposition products from the collapse
of the SEI. Once these are consumed, the copper deposited on the graphite, which is electronically connected
to the copper carrier foil by the graphite, dissolves again in the further course of the discharge of the driver cell.
After the collapse of the SEI, a further reduction of copper ions at the anode surface is no longer observed. In the
further course of the overdischarge, the deposition of copper only takes place on the cathode surface.
As the discharge proceeds to the voltage minimum, the amount of copper deposited on the cathode foil and
the copper concentration in the electrolyte continue to increase. At Q ≈ 27 Ah, the clamping voltage of the work
cell rises sharply from − 1.91 V to about − 1.5 V. The cause, according to other a­ uthors14,16,18, is assumed to be
the first copper dendrites growing through the separator and leading to internal short circuits. The first copper
dendrites, which grow through the separator and lead to internal short circuits, are suspected of being the cause.
Apparently their initial conductivity is very limited, so that although the internal resistance of the cell decreases,
further dissolution of the copper foil and further copper deposition on the cathode foil occurs. Thus, at this

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Figure 5.  SEM–EDX analysis of cell 7. (a) The graphite layer remains on the separator; (b) SEM image with
EDX mapping superimposed on a cross-section of a cathode foil (red circle on the left) which is connected to
the separator and the graphite layer (from left to right) D: Al carrier foil, E: NMC layer, F: A
­ l2O3 coating of the
separator foil (red), G: separator foil penetrated by copper (green), H: graphite layer; (c) EDX mapping of a
copper dendrite, upper image: copper highlighted in green, lower image: oxygen highlighted in light blue.

stage, two conduction mechanisms are present coexisting in parallel. Part of the charge transport takes place
through internal short circuits via the first copper dendrites, while parallel charges are transported as a result of
the dissolution and deposition of copper. This effect is confirmed by the fact that, despite the decreasing internal
resistance, the deposition of copper on the cathode continues to spread and cover it more and more. Finally, as
already described by Guo et al., the voltage drop asymptotically approaches 0 ­V14. It follows that the current flow
almost completely passes over copper dendrites, which have led to a cell short circuit from the cathode surface
across the separator to the graphite layer. The increase in the voltage drop across the working cell at the end of the
discharge then corresponds to a decrease in the internal cell resistance due to the electron conduction through
the copper dendrites. In their studies, Hendricks et al. found that the deposited copper was non-conductive
­species21. However, they considered it possible that further overdischarge into reversal, as described in this and
other ­work14,16,18, could result in deposition of metallic copper.
Figure 5 shows an example of the top view and cross-section of a cathode foil taken from cell no. 7 after open-
ing. It can be seen that the separator is very firmly attached to the graphite layer in places (Fig. 5a). Figure 5b
shows the cross-section of the area marked in Fig. 5a, consisting of an Al carrier foil (D) coated on both sides
with NMC (E), plastic separator foil (G) coated on both sides with A ­ l2O3, and the graphite layer (H). The sharp
boundary between the copper layer and the NMC layer shows that the copper is deposited on both sides and flat
on the NMC surface of the cathode (Fig. 5b, layer “G”). Furthermore, the plastic membrane of the separator (G)
and the ­Al2O3 coating of the separator foil (F) are completely penetrated by deposited copper. The original ­Al2O3
coating of the separator foil (in red) is still present but seems to be completely penetrated by copper. Figure 5b
also shows that copper has grown dendritically from the surface of the NMC coating through the separator and
into the carbon coating of the anode (H). In addition, no oxygen is detectable in the deposited copper by EDX
(Fig. 5c), which supporting the theory that further overdischarge into reversal results in the deposition of metallic
and thus conductive ­copper14,16,18,21.
Finally, it should be noted that the chemical analysis shows that the cathode material is not affected by the
discharge processes and no cobalt, manganese or nickel could be detected in the electrolyte (Table 1).

Temperature characteristics. Figure 6a shows the voltage curve of the discharge of a working cell at a
resistor of 58 mΩ and the temperature curves of the working cell and driver cell. The temperature in the work-
ing cell increases only slightly until the end of the capacity expected but very significantly as soon as the voltage
drop occurs. This effect becomes obvious because, as shown in Fig. 6b, the strongest increase of the temperature
corrected by the waste heat (Newton’s cooling law) takes place at the point where the 1st derivative of the voltage
function has the local minimum. The maximum temperature of about 50 °C is reached at the voltage minimum
of the working cell. The temperature difference between the work cell and the driver cell is, therefore, consid-
erable since the same current flows through both cells. Only when the voltage in the working cell rises again
(Fig. 6b, dU/dQ = max), the 1st derivative of the corrected temperature drops to about 0 and the temperature
of the cell decreases continuously. It is plausible to assume that the maximum temperatures inside the cell are
significantly higher and initiate the degradations there that cause the separator foil to adhere to the surfaces of
the electrodes in a virtually non-detachable manner. High temperatures inside the cell are also likely to cause the
viscosity of the electrolyte to decrease and the resulting gas bubbles to displace the electrolyte.

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Figure 6.  (a) Voltage curve and temperature curves during overdischarge of a series connection of the driving
cell and the working cell at 58 mΩ. (b) Derivation of the voltage curve (black) and derivation of the corrected
temperature curve (working cell, red).

Discussion
Interpretation of the voltage curve. It has been shown that the deep discharge of a single cell does not
lead to the dissolution and deposition of copper. If, on the other hand, at least two cells are connected in series
in which one cell has a lower charge capacity than the other, deep discharge in this cell causes the copper carrier
foil to dissolve and copper to be deposited on the surface of the NMC cathode. If the anode is completely delithi-
ated, no lithium is available for further charge transport. The potential of the series-connected cells of higher
charge capacity (SOC > 0) is the driving force to trigger the parasitic process of dissolving the copper in the cell
with lower charge capacity, which is discharged earlier (SOC = 0) with further current flow (SOC < 0). Based on
the present results, the following interpretation of the discharge curve is suggested (Fig. 7). The black area marks
the area of delithiation and breakdown of the SEI, the green area, the copper dissolution and the red area, the
internal short circuit through copper dendrites.
The point at which the delithiation is finished as a dominant process is shown as a minimum in the deriva-
tive of the voltage curve. This is also the point where the temperature increase is greatest (Fig. 6b). It is assumed
that the further, smaller drop in voltage or the subsequent increase in discharge (dV/dQ) is possibly due to the
discharge of protic species or the residual water in the electrolyte at the ­anode23,24. This is accompanied by the gas
formation, which leads to cell bloating. This process is determinant up to the point where the derivative forms a
small plateau (Fig. 7, transition black–green). Following this plateau, the derivative increases more strongly again
and the voltage drop proceeds with a smaller increase, which means that the charge transport is less inhibited.
In this region, charge transport is carried out by copper ions, although it is still unclear whether this is C­ u+16 or
­Cu2+14. The section marked in red is introduced with a steep rise and a subsequent maximum of the derivative
function. From this point on, a large number of copper dendrites cause internal short circuits (see Fig. 5) and
connect the surfaces of anode and cathode in an electrically conductive manner. Electrochemical processes take
on a subordinate role from this moment. As shown in Fig. 6, no further significant heat generation is observed
after this stage, which suggests that the electrical work performed is low and the cell behaves approximately as
an ohmic resistor.

Summary. It has been shown that the deep discharge of a single cell does not lead to the dissolution and
deposition of copper. If, on the other hand, at least two cells are connected in series in which one cell has a lower
charge capacity than the other, deep discharge in this cell causes the copper carrier foil to dissolve and copper to
be deposited on the surface of the NMC cathode. If the anode is completely delithiated, no lithium is available
for further charge transport. The potential of the series-connected cells of higher charge capacity (SOC > 0) is the
driving force to trigger the parasitic process of dissolving the copper in the cell with lower charge capacity, which
is discharged earlier (SOC = 0) with further current flow (SOC < 0). By measuring the copper concentration at
various points of the discharge curve, analytical proof was provided of the point at which the dissolution of the
current collector of the anode begins. Furthermore, it could be shown that the copper concentration in the elec-
trolyte increases rapidly afterwards and converges towards a limit value of about 8 ppm in the investigated inter-
val. Using SEM–EDX mappings, the penetration of the separator and thus the electrical contact between anode
and cathode by the copper growing on the cathode surface could be shown. There is no effect on the functional
recycling as long as copper ions are present in low concentrations (≤ 1 ppm) in the electrolyte. On the other
hand, the deposition of copper on the cathode material over the entire surface leads to significant damage to the
NMC recovered since the resulting loss of capacity does not allow for the economic reuse in recycled batteries.

Methods
Discharge tests. Pouch cells with cathodes mainly consisting of NMC 622 and a remaining capacity of 20
Ah were used for the experiments. The deep discharge of individual cells was performed with the help of con-
stant resistors (8 mΩ … 5.9 Ω); cell voltage and discharge current were recorded via a data log system (Arduino
Uno, time interval of the measuring points = 2 s). The temperature was recorded with a temperature sensor

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Figure 7.  Color coding of the voltage curve and its derivation according to the ongoing processes.

TF-500 type K (PCE Instruments) and with a data logger PCE-T 390 (PCE Instruments) at intervals of 5 s during
the deep discharge. Figure 1a shows the test arrangement for the deep discharge of two pouch cells connected
in series. Both cells were previously charged to 100% capacity; cell 2 was then discharged via a resistor of 41 mΩ
to a clamp voltage (­ UCV) of 3 V, which corresponds to a capacity of 15%. A new pair of pouch cells was used for
each deep discharge test in a series connection. If the voltage of the working cell in the deep discharge reached
a defined value ­(UCV = -0.8, -1.2, -1.5, -1.77, -1.91, -1.0 V after the minimum), the test was stopped and the elec-
trolyte was taken from the working cell immediately. The temperature of the working cell was recorded during
deep discharge, as described above.

Electrolyte analysis. The analysis of the electrolyte extracted was carried out using graphite furnace tech-
nology with a high-resolution continuum source atomic absorption spectrometer ContrAA 700 (Analytik Jena
AG, Jena, Germany). Argon 99.999% (Westfalen AG, Münster, Germany) was used as the inert and purge gas.
Characteristic absorption wavelengths were used for the evaluation of the elements nickel (232.0030 nm), cobalt
(240.7254 nm), manganese (279.4817 nm) and copper (324.7540 nm).
An equidistant 11-point calibration (0…0.067 mg ­kg−1) in triple determination was carried out regarding
the quantification of the copper. The electrolyte sample was manually diluted by a factor of 42…43 (by mass)
with deionized water (MilliPore, 18 MΩ cm) and subsequently diluted by a ContrAA 700 autodilution proce-
dure. A calibration was not necessary for Ni, Co and Mn since no element signal could be detected in any of the
electrolyte solutions.

SEM–EDX analysis. All deeply discharged pouch cells were then opened. The morphological and elemen-
tal analysis of the dismounted cathode foils were performed using a scanning electron microscope (SEM, Zeiss
EVO MA15) equipped with an energy dispersive X-ray analysis (EDX, AMETEK, 20 kV).

Received: 4 December 2020; Accepted: 26 February 2021

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Author contributions
J.A. and T.L. wrote the main manuscript text. T.L. done all experiments and analysis. T.S. done SEM–EDX and
AAS measurements. All authors reviewed the manuscript.

Funding
Open Access funding enabled and organized by Projekt DEAL. This research has been funded by the German
Federal Ministry of Education and Research (BMBF) in the project "ReAlBatt" (project number 03XP0194D).

Competing interests
The authors declare no competing interests.

Additional information
Correspondence and requests for materials should be addressed to T.L.
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