metals

Article
Early-Stage Recovery of Lithium from Tailored Thermal
Conditioned Black Mass Part I: Mobilizing Lithium via
Supercritical CO2-Carbonation
Lilian Schwich *, Tom Schubert and Bernd Friedrich

IME, Institute for Process Metallurgy and Metal Recycling, RWTH Aachen University, 52056 Aachen, Germany;
[email protected] (T.S.); [email protected] (B.F.)
* Correspondence: [email protected]; Tel.: +49-2418-095-194

Abstract: In the frame of global demand for electrical storage based on lithium-ion batteries (LIBs),
their recycling with a focus on the circular economy is a critical topic. In terms of political incentives,
the European legislative is currently under revision. Most industrial recycling processes target
valuable battery components, such as nickel and cobalt, but do not focus on lithium recovery.
Especially in the context of reduced cobalt shares in the battery cathodes, it is important to investigate
environmentally friendly and economic and robust recycling processes to ensure lithium mobilization.
In this study, the method early-stage lithium recovery (“ESLR”) is studied in detail. Its concept
comprises the shifting of lithium recovery to the beginning of the chemo-metallurgical part of the
recycling process chain in comparison to the state-of-the-art. In detail, full NCM (Lithium Nickel
Manganese Cobalt Oxide)-based electric vehicle cells are thermally treated to recover heat-treated
black mass. Then, the heat-treated black mass is subjected to an H2 O-leaching step to examine the
share of water-soluble lithium phases. This is compared to a carbonation treatment with supercritical





 CO2 , where a higher extent of lithium from the heat-treated black mass can be transferred to an
Citation: Schwich, L.; Schubert, T.;
aqueous solution than just by H2 O-leaching. Key influencing factors on the lithium yield are the filter
Friedrich, B. Early-Stage Recovery of cake purification, the lithium separation method, the solid/liquid ratio, the pyrolysis temperature and
Lithium from Tailored Thermal atmosphere, and the setup of autoclave carbonation, which can be performed in an H2 O-environment
Conditioned Black Mass Part I: or in a dry autoclave environment. The carbonation treatments in this study are reached by an
Mobilizing Lithium via Supercritical autoclave reactor working with CO2 in a supercritical state. This enables selective leaching of lithium
CO2 -Carbonation. Metals 2021, 11, in H2 O followed by a subsequent thermally induced precipitation as lithium carbonate. In this
177. https://doi.org/10.3390/met approach, treatment with supercritical CO2 in an autoclave reactor leads to lithium yields of up
11020177 to 79%.

Received: 19 November 2020

Keywords: battery recycling; lithium-ion batteries; metallurgical recycling; metal recovery; recycling
Accepted: 18 January 2021
efficiency; carbonation; lithium phase transformation; autoclave; supercritical CO2
Published: 20 January 2021

Publisher’s Note: MDPI stays neutral

with regard to jurisdictional claims in
1. Introduction
published maps and institutional affil-
iations. The need for lithium recovery from LIBs is a crucial topic in terms of increased elec-
tromobility since lithium is and will remain a relevant element also in next-generation
batteries. Lithium is currently industrially, not recycled. Hydrometallurgical research
focuses on recovering lithium at the end of the processes; thus, impurities from process
Copyright: © 2021 by the authors.
additives are possible, and moreover, reagents like Na2 CO3 are needed for generating
Licensee MDPI, Basel, Switzerland.
a marketable lithium product. The present study aims to present a method to mobilize
This article is an open access article
lithium without using expensive or environmentally harmful additives: The early-stage
distributed under the terms and lithium recovery (“ESLR”) method. This “ESLR” particularly requires a suitable ther-
conditions of the Creative Commons mal pretreatment, and other elements can then be integrated into existing metal refining
Attribution (CC BY) license (https:// processes. The full “ESLR” process investigated here are shown in Figure 1.
creativecommons.org/licenses/by/ For this research’s purpose, the publication is structured into three parts: first, state-of-
4.0/). the-art processes for LIBs recycling are contrasted to innovative research for lithium phase

Metals 2021, 11, 177. https://doi.org/10.3390/met11020177 https://www.mdpi.com/journal/metals

Metals 2021, 11, 177 2 of 30

transformation. Second, our own research results based on experimental studies are pre-
sented and subsequently evaluated in terms of lithium yield and purity. Concludingly,2 the
Metals 2021, 11, x FOR PEER REVIEW of 30
obtained results are discussed by showing their scientific findings and process technology
relevance in comparison to the state-of-the-art.

LiBs

Thermal Treatment

Crushing

Sieving and Sorting

Heat-treated black mass

Anticipatedbenefits
Anticipated benefitsof
of„ESLR“
“ESLR”

H2O, CO2
• No chemicals required
Early-Stage Li-Recovery Li2CO3
• No carbonation agent impurities like
Na oder K in Li-product
• Comparing to hydrometallurgy: Less
Extractive Hydromet. Pyrometallurgy leaching agents due to reduced mass
• Comparing to direct pyrometallurgy
with purifying hydrometallurgy: Less
Purifying Hydromet.
energy needed

Figure 1. General flowchart of the early stage Li-recovery discussed in this study and the process benefits at a glance.
Figure 1. General flowchart of the early stage Li-recovery discussed in this study and the process benefits at a glance.

1.1. State-of-the-Art in Recycling Li-ion Batteries

For this research’s purpose, the publication is structured into three parts: first, state-
LIBs recycling
of-the-art processescomprises differentare
for LIBs recycling modules
contrastedand sequences,
to innovative leading
researchto alternative
for lithium
process paths. Statements regarding future-dominant process
phase transformation. Second, our own research results based on experimental studies pathways are afflicted withare
uncertainties due to location and know-how aspects and also
presented and subsequently evaluated in terms of lithium yield and purity. Concludingly,because of the heterogeneous
and changingresults
the obtained scrap stream compositions
are discussed by showing[1]. However, the available
their scientific findings processes,
and processuntiltech-
the
point of having generated marketable
nology relevance in comparison to the state-of-the-art. products, can be divided into preconditioning and
metallurgical extraction [2]. The pretreatment steps, in turn, can be asserted to different
sectors: deactivation/discharging
1.1. State-of-the-Art in Recycling Li-ion [3], mechanical
Batteries processing as dismantling of EV modules
and packs to cell level, comminution and sorting by size or physical properties [4] and
LIBs recycling comprises different modules and sequences, leading to alternative
finally a thermal treatment [5]. Within the metallurgical techniques, there are mainly
processand
hydro- paths. Statements regarding
pyrometallurgical processesfuture-dominant
available [6].process
They both pathways
comprise are afflicted
benefits andwith
uncertainties due to location and know-how aspects and
drawbacks; for example, in hydrometallurgy also ignoble elements, like Fe, Al and C, also because of the heterogene-
ousbe
can and changingbut
recovered, scraponstream
the other compositions [1]. However,
hand, the processing goes the available
along with processes,
comparatively until
the point of having generated marketable products, can be
slow kinetics [6]. Depending on individual core objectives, the cells can be charged intodivided into preconditioning
aand metallurgical
smelter without extraction [2]. The pretreatment
any pretreatment [3], but regarding steps,aincircular
turn, can be asserted
economy to differ-
approach, it
isent sectors: to
beneficial deactivation/discharging
consider pretreatment steps [3], mechanical
[7] in orderprocessing
to maximize as resource
dismantling of EV
efficiency.
modules
Besides and packs to
conventional cell level,
industrial comminution
treatments, andstudies
different sortingare byinsize or to
place physical
give anproperties
overview
[4] and finally a thermal treatment [5]. Within the metallurgical
also on innovative emerging recycling paths [8,9] and also approaches to evaluate techniques, there the are
mainly hydro- and pyrometallurgical processes available [6]. They
environmental impacts of different paths [10–12]. First, the available processes for recycling both comprise benefits
and drawbacks;
Li-ion batteries are fordescribed,
example, and in hydrometallurgy
second, innovative alsoprocesses
ignoble elements, like Fe, Allithium
for CO2 -promoted and C,
can betransformations
phase recovered, but on arethe other Therefore,
shown. hand, the processing
first, indirectgoes along withprinciples
carbonation comparativelyand
slow kinetics
studies [6]. Depending
are outlined, on individual
second, literature core objectives,
on direct carbonation theiscells can be and
presented charged
third,into
thea
smelter
role of CO without
2 in a any pretreatment
supercritical state [3],
is but
pointed regarding
out. Goala circular
of this economy
detailed approach,
elaboration it ais
is
beneficial to consider pretreatment steps [7] in order to
monitoring of gaps in literature regarding efficient lithium recovery from LIBs. maximize resource efficiency. Be-
sides conventional industrial treatments, different studies are in place to give an overview
1.1.1.
also onThermal
innovativePreconditioning
emerging recycling paths [8,9] and also approaches to evaluate the en-
vironmental
Thermalimpacts of different
pretreatments can be paths
carried[10–12]. First,
out, for the available
example, processes
as pyrolysis. for recycling
Here, the cells
Li-ion
are batteriesin
deactivated arethe
described,
absence of and second,
oxygen at innovative
temperatures processes for CO
of typically ◦ C [13]. Pyrolysis
6002-promoted lithium
phase
(as welltransformations are shown.
as classical incineration) are Therefore, first, indirect
thermal pretreatments carbonation
allowing for a safeprinciples and
cell deacti-
studiesand
vating arefacilitating
outlined, second,further literature
downstream on direct
recycling carbonation is presented
without risking and third,
a so-called thermal the
role of CO
runaway 2 in a supercritical
[14,15]. Through chemical state iscracking
pointed and out.such
Goalremoval
of this detailed
as organic elaboration
compounds is a
monitoring of gaps in literature regarding efficient lithium recovery from LIBs.
Metals 2021, 11, 177 3 of 30

in gaseous form, which originate primarily from binder, electrolyte, and separator, takes
place [13,16]. A major advantage of thermal treatments comprises a safe cell deactivating,
thus contributing to risk mitigation in the context of fire incidents. This thermal runaway
can occur, for example, during scrap transport, storing, but also by mechanical processing
due to this mechanical, electrical or thermal abuse [17]. Several studies report the second
advantage of thermal pretreatments, namely an improved detaching of black mass from the
cell’s current collector foils [7,16,18–21]. Additionally, suitable mechanical preconditioning
concepts are required for efficient downstream processing, especially for hydrometallurgi-
cal treatments [3]. A mechanical process consists of comminution and sorting for splitting
black mass and other cell components, such as casing and current collector foils. Hence,
by subsequent mechanical postprocessing, aluminum and copper foils, along with the
metallic casing, either aluminum or steel, can be separated as marketable products from
the black mass. Black mass then contains all electrochemical active electrode materials [22].
Due to different battery systems on the market, black mass always has different chemical
compositions [22].
The separation into individual fractions by means of sieving or physical separation
techniques contributes to higher yields of the valuable components and, finally, increases
process recycling efficiency [14]. In this way, copper, aluminum and steel can be integrated
into their specific recycling processes. Regarding the extracted black mass, two processing
alternatives are in place: hydrometallurgical and pyrometallurgical treatments. In the
following, these two methods and their challenges for lithium recycling are compared.

1.1.2. Lithium Behavior in Pyro- and Hydrometallurgical Recycling Steps and Need for
Early-Stage Li-Separation
Smelting of possibly pelletized black mass with the addition of SiO2 as slag additive in
an electric arc furnace has shown that lithium accumulates both in slag and flue dust [23].
Due to its ignoble character, extraction via a metal phase is not possible. As can be seen in
Figure 2, a negligible proportion of approximately 0.35% of lithium is accounted for in the
alloy produced. Depending on the selected slag system and the amount of slag, increased
accumulation in the slag or flying dust can be realized (see Figure 2). Since the slag has a
solubility limit for lithium oxide, according to Vest [24], the evaporation of lithium takes
place when the corresponding concentration is exceeded. Due to re-oxidation processes,
lithium oxide is accumulated in the flue dust (see Figure 2 below, according to Vest [24]).
When operating at the lab-scale, smaller quantities of slag are generated, leading to a larger
proportion of lithium transferred to the flue dust. The two Sankey diagrams in Figure 2
show a broad distribution of lithium between the three phases slag, flue dust and partly
alloy, which is valid for both smelting setups. In order to extract lithium from the produced
slag, energy-intensive crushing, classifying and hydrometallurgical purifying are required,
but the costs for these treatment steps are currently not covered by lithium’s raw material
price [3].
Metals 2021, 11, 177 4 of 30
Metals 2021,
Metals 2021, 11,
11, xx FOR
FOR PEER
PEER REVIEW
REVIEW 44 of
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30

Figure 2.
Figure Lithiumdistribution
2.Lithium
2. Lithium distributionafter
distribution afterthe
after the
the smelting
smelting
smelting ofof
of black
black
black mass
mass
mass in
anan
in an
in electric
electric
electric arcarc
arc furnace.
furnace.
furnace. Above:
Above:
Above:
process design
process design aiming
aiming for for aa lithium
lithium enrichment
enrichmentin influe
fluedust,
flue dust,based
dust, basedon
based on[23,24].
on [23,24].Below:
[23,24]. Below:process
Below: processdesign
process de-
de-
sign
sign aiming
aiming
aiming for
for afor aa lithium
lithiumlithium enrichment
enrichment
enrichment in slag
in slag
in slag [23].
[23]. Reproduced
Reproduced
[23]. Reproduced with
with
with permissionfrom
permission
permission fromStallmeister,
from Stallmeister,C.,
Stallmeister,
C.,
C., Schwich,
Schwich,
Schwich, L. and
L.
L. and and Friedrich,
Friedrich,
Friedrich, B., Early-Stage
B., B., Early-Stage
Early-Stage Li-Removal—Vermeidung
Li-Removal—Vermeidung
Li-Removal—Vermeidung von
vonvon Lithiumverlusten
Lithiumverlusten
Lithiumverlusten im
im
im Zuge
Zuge
Zuge der Thermischen
der Thermischen
der Thermischen und Chemischen
und Chemischen
und Chemischen Recyclingrouten
Recyclingrouten
Recyclingrouten von Batterien;
von Batterien;
von Batterien; published
published
published by Thomé-
by Thomé-
by Thomé-Kozmiensky
Kozmiensky Verlag
Kozmiensky Verlag GmbH,GmbH, 2020.2020.
Verlag GmbH, 2020.

When
When
Whentreatingtreating
treatingthe the extracted
theextracted
extractedblack black mass
blackmass massby byby hydrometallurgical
hydrometallurgical
hydrometallurgical processing,
processing,
processing, lithium
lithium
lithium is
is
not
not always
always
is not always enriched
enriched
enriched in one
in one single
in single product
product
one single fraction,
fraction,
product neither,
neither,
fraction, but can
but
neither, can but be can
be distributed
distributed
be distributed during
during
the
the multi-step
multi-step precipitation
precipitation series
series in
in all
all filter
filter cakes
cakes [25].
[25]. Firstly,
Firstly,
during the multi-step precipitation series in all filter cakes [25]. Firstly, a black mass is aa black
black mass
mass is
is typically
typically
leached
leached
typicallyin inleached
mineralinacid.
mineral acid. For this
For
mineral this purpose,
For this itit
acid.purpose, is beneficial
is beneficial
purpose, to conduct
to conduct
it is beneficial the
tothe thermal
thermal
conduct pretreat-
thepretreat-
thermal
ment
ment as
pretreatment described
as described easing
easing the
as described the dissolution
dissolution
easing process
process [26].
the dissolution [26].
processHere,
Here, [26]. Shin
Shin et al.
et al.Shin
Here, report
reportet al. the binder´s
thereport
binder´s the
(polyvinylidene
(polyvinylidene
binder’s (polyvinylidene fluoride, fluoride,
fluoride, PVDF) property
PVDF) property of not
of
PVDF) property not dissolving
dissolving in acidic
in
of not dissolving acidic solution
solution
in acidic and and disturb-
solution disturb-
and
ing
ing the filtration
the
disturbing filtration process after
process
the filtration after
process leaching
leaching [27]. Yang
after [27].
leachingYang[27].et al.
et al.Yang
haveet
have shown
shown
al. have aa strategy
strategy
shownto to separately
separately
a strategy to
incinerate
separatelyand
incinerate and then hydrometallurgically
incinerate
then hydrometallurgically
and then hydrometallurgically treat spent
treat spenttreat anode
anode spentmaterial
materialanode inmaterial
in order to
order toin purify
orderthe
purify the
to
C-fraction
purify the from
C-fractionlithiumfrom impurities,
lithium recovering
impurities, lithium
recovering
C-fraction from lithium impurities, recovering lithium by means of Na2CO3 [28]. by
lithiummeans by of
meansNa 2 CO
of Na
3 [28].
CO
2 When When
3 [28].
treating
When treating
treating the black
the black mass
themass
black from
mass
from both
from
both cathode and anode,
both cathode
cathode and anode,
andthe the
anode,target
target products
theproducts
target productssuch as
such as copper,
copper,
such as
iron
iron andiron
copper,
and aluminum,
and aluminum,
aluminum, cobalt, nickel
cobalt, nickel and
cobalt, and
nickelmanganese
and manganese
manganese are cemented
are cemented
are cemented or precipitated
or precipitated
or precipitated one after
one after
one
the
after
the other.
the other.
other. Lithium
Lithium salt recovery,
Lithium
salt recovery,
salt recovery, e.g., e.g.,
e.g., as carbonate
as carbonate
as carbonate (Li22CO
(Li CO ),is
(Li323),CO is3the
the last
), islast process
the process
last process stepstep
step in the
in the
in
hydrometallurgical
the hydrometallurgical
hydrometallurgical process
processprocess chain,
chain,
chain, as suggested
as suggested
as suggested by by
by Wang
WangWang etet
et al.al.[25].
al. [25]. Wang
[25].WangWanget et al. have
et al. have
proven aa lithium
proven lithium leaching efficiency of
leaching efficiency of 98.5%
98.5% [25].
[25]. For
For obtaining
obtaining Li Li22CO333 in in the
the last
last process
process
step, aa carbonation
carbonation additive
additive likelike sodium
sodium carbonate
carbonate is
step, a carbonation additive like sodium carbonate is used. During the precipitation is
used. used.
During During
the the precipitation
precipitation stages,
as can
stages, be
as seen
can befrom
seen the
fromdata thein Figure
data in 3, approx.
Figure 3, 27%
approx.
stages, as can be seen from the data in Figure 3, approx. 27% of lithium remains in other of27%lithium
of remains
lithium in
remains other in filter
other
cakes. Thus,
filter cakes.
filter cakes. Thus, the purity
Thus, the of
the purity the
purity of obtained
of the
the obtainedcopper,
obtained copper, Fe/Al
copper, Fe/Al and
Fe/Al and Ni-Co
and Ni-Co products
Ni-Co products is
products is reduced,
is reduced,
reduced, and
the yield
and
and the yield
the of recovered
yield of lithiumlithium
of recovered
recovered suffers. suffers.
lithium Moreover,
suffers. a share ofaalithium
Moreover,
Moreover, share of
share remains
of lithium
lithium in remains
wastewater
remains in in
leading
wastewater to a complex
leading circuit
to a with
complex continuous
circuit neutralization
with continuous
wastewater leading to a complex circuit with continuous neutralization salt removal, salt removal,
neutralization again
salt including
removal,
lithium
again
again losses. This
including
including complex
lithium
lithium losses.processing
losses. This complex
This is up toprocessing
complex now industrially
processing is up
is up to only
to now
now viable by recovering
industrially
industrially only
only
the
viablevaluable
by metals
recovering nickel,
the copper
valuable and
metals cobalt
nickel,
viable by recovering the valuable metals nickel, copper and cobalt [3]. [3].copper and cobalt [3].

Figure 3.
Figure 3. Lithium distribution
distribution after leaching
leaching trials of
of extracted
extracted black
black mass
mass (current
(current trials
trials at
at IME),
Figure 3.Lithium
Lithium distributionafter
after leachingtrials
trials of extracted black mass (current trials IME),
at IME),
based on
based on [23]
[23] (data
(data used
used in
in [23]
[23] was
was based
based on
on experiments
experiments byby Wang
Wang et et al.
al. [25]).
[25]). Reproduced
Reproduced withwith
based on [23] (data used in [23] was based on experiments by Wang et al. [25]). Reproduced with
permission from
permission from Stallmeister,
Stallmeister, C.,
C., Schwich,
Schwich, L.
L. and
and Friedrich,
Friedrich, B.,
B., Early-Stage
Early-Stage Li-Removal—
Li-Removal—
permission from
Vermeidung vonStallmeister, C., Schwich,
Lithiumverlusten L. and
im Zuge
Zuge Friedrich,
der Thermischen
ThermischenB., Early-Stage Li-Removal—Vermeidung
und Chemischen
Chemischen Recyclingrouten
Vermeidung von Lithiumverlusten im der und Recyclingrouten
von Batterien;
von Lithiumverlusten
publishedimbyZuge der ThermischenVerlag
Thomé-Kozmiensky und Chemischen
GmbH, Recyclingrouten von Batterien;
2020.
von Batterien; published by Thomé-Kozmiensky Verlag GmbH, 2020.
published by Thomé-Kozmiensky Verlag GmbH, 2020.
Hence, the
Hence, the process´s
process´s bottleneck
bottleneck lies
lies in
in lithium
lithium extraction
extraction as
as aa solid
solid product
product instead
instead
Hence, the process’s bottleneck lies in lithium extraction as a solid product instead
of lithium
of lithium leachability
leachability (leaching
(leaching efficiency).
efficiency). A A wide
wide range
range of
of hydrometallurgical
hydrometallurgical studies
studies
of lithium leachability (leaching efficiency). A wide range of hydrometallurgical studies
shows high
shows high leaching
leaching efficiencies
efficiencies using
using different
different solvents
solvents [29–34],
[29–34], for
for example,
example, by by using
using
shows high leaching efficiencies using different solvents [29–34], for example, by using
H SO a lithium leaching efficiency of 96.7% [35], and by HCl 99.2% [36]. In
H2SO4, a lithium leaching efficiency of 96.7% [35], and by HCl 99.2% [36]. In [37], leaching
2 4, [37], leaching
Metals 2021, 11, 177 5 of 30

H2 SO4, a lithium leaching efficiency of 96.7% [35], and by HCl 99.2% [36]. In [37], leaching
in citric acid and precipitating lithium by sodium phosphate leads to a leaching efficiency
of 99% Li and a recovery as Li3 PO4 of 89%. In [38–41] also a lithium precipitation of solid
Li2 CO3 by Na2 CO3 is reported, reaching yields of 80% [38], 90% [39] and 99% [40]. In [38],
a corresponding purity of 96.97% is reached; in [39], no purity is given; in [40], the lithium
filter cake consists of 10.13 wt.% Li. With a molar ratio of Li/Li2 CO3 = 18.79%, this would
mean a Li2 CO3 content of 53.91%, assuming 10.31 wt.% exists as pure Li2 CO3 . When using
cathode black mass only, a recovery of Li as Li2 CO3 of 98.22% with a purity of 99.9% is
reported [41]. This means that reaching both a high Li2 CO3 purity with a high yield is not
straightforward but achievable. Nonetheless, lithium recovery always requires additives,
which can be avoided by direct H2 O-leaching. Moreover, the volume of required leaching
agents can be lowered by H2 O-leaching before entering conventional hydrometallurgy due
to a mass reduction. In this study, H2 O-leaching and using supercritical CO2 are assessed
for environmentally friendly and additive-free lithium recovery.

1.1.3. Liquid–Gas Carbonation (Indirect Carbonation)

The hypothesis of this work is a mobilizing of lithium by an “Early-Stage Li-Recovery”.
Different methods may be applied for this phase transformation to Li-carbonate, which are
addressed in the following paragraphs. The use of CO2 for carbonation purposes has been
examined for non-lithium materials in numerous studies, e.g., [42–45], and even treating of
battery materials with CO2 is possible, as shown above by Hu et al. and Zhang et al. [46,47].
Generally, Kunzler et al. investigated the parameters influencing indirect carbonation,
which is understood as a reaction between dissolved elements and CO2 . In contrast to
that, direct carbonation is defined as a gas–solid reaction for generating carbonates [48].
Kunzler et al. found a correlation between extraction efficiency and grain size of the target
metals, solid to liquid ratio, concentration and hence pH value of the leaching agent, and
temperature [48].
When aiming for indirect CO2 -driven reactions, Hu et al. have conducted a combina-
tion of a reductive thermal treatment and H2 O-leaching in combination with CO2 -gas [46].
Here, only cathode material from NMC (Lithium Nickel Manganese Cobalt Oxide)-cells
was mixed with lignite as a reducing agent. According to the maximum reported leaching
efficiency of 85% for Li, the optimal thermal-treatment temperature is at 650 ◦ C, and the
optimal s/l ratio is 10 mL/g (1:10 (g/mL)). Zhang et al. have developed this study further
using the same parameters but also investigating optimal CO2 flow rate and leaching time,
leading to a Li-recovery of 85% [47]. In summary, when treating the cathode mass only and
adding reducing agents like lignite or carbon black to the thermal treatment, lithium yields
of 85% [46,47]. However, if not applying CO2 during leaching, the leaching efficiency of
lithium is 40% [46,47]. This indicates that the mechanism of indirect carbonation is decisive,
but in [46,47], no CO2 atmosphere was used during the thermal treatment; instead, a solid
C-carrier was added.
A similar approach is pursued by Jandová et al., where a lithium-containing solution,
not stemming from batteries, is treated with CO2 [49]. Then, the solution is heated until
the lithium concentration reaches 12–13 g/L, and afterward treated with CO2 -gas at a
temperature of 40 ◦ C for 2 h to generate LiHCO3 . Lithium hydrogen carbonate provides a
higher solubility in comparison to the first, formed Li2 CO3 . Finally, the lithium solution
is boiled to produce Li2 CO3 [46,47,49]. Moreover, an indirect carbonation approach for
non-battery materials gives insights into general mechanisms when purging CO2 into
aqueous solutions [45]. Within these aqueous treatments, CO2 dissolves as [45,50]:

CO2 + H2 O ↔ H2 CO3 ↔ H+ + HCO3− ↔ CO23− + 2 H+ (1)

The more H-cations are released, the stronger is the resulting acidification [50]. These
reactions are to be understood as a function of temperature, pressure and pH [45]. With
increasing pH, the dominantly existing phases alternate in the following sequence: H2 CO3 ,
HCO3− and CO23− , hence the higher the pH-value, the more H+ -ions are released, contribut-
Metals 2021, 11, 177 6 of 30
Metals 2021, 11, x FOR PEER REVIEW 6 of 30

ing to a lowered
contributing to apH. Especially,
lowered CO23− is dominant
pH. Especially, in a pH-area
CO23 is dominant in aofpH-area
10 onwards, whereas
of 10 onwards,
−
HCO
whereas
3 is dominant
- in an area from 6 to 9, as can be seen in Figure 4:
HCO is dominant in an area from 6 to 9, as can be seen in Figure 4:
3

Figure4.4.Available
Figure AvailableCO
CO 2-based
2 -based phasesininaqueous
phases aqueous solution
solution over
over thethe
pHpH [45].
[45]. Reproduced
Reproduced with
with per-
permis-
mission
sion fromfrom
Haug,Haug,
T. A.,T.Dissolution
A., Dissolution and carbonation
and carbonation of mechanically
of mechanically activated
activated olivine—Investi-
olivine—Investigating
gating
CO CO2 sequestration
sequestration possibilities;
possibilities; published published byT.A.,
by Haug, Haug, T.A., 2010.
2010.
2

AA reaction
reaction between
between HCOHCO3−3/CO
/CO2323− and
andlithium
lithiumrequires
requiresthe
thepresence
presenceofof + in
Li+Liin thethe
so-
solution.
lution. InInTable
Table1,1,possible
possiblelithium
lithiumphases
phasesand
andtheir
theirsolubility
solubilityisispresented.
presented.Connected
Connectedto
to that,the
that, thechemical
chemicalreaction
reactionformula
formulaisis presented
presented describing the dissolution
dissolution of
oflithium
lithium
phases
phasesin inan
anaqueous
aqueoussolution,
solution,without
withoutand andwith
withCOCO22-gas
-gaspurging.
purging.

Table1.1.Solubility
Table Solubilityofofselected
selectedlithium
lithiumphases
phasesatat20
20and 100◦ C.
and100 °C.

Phase
Phase Solubility
Solubility atat2020◦ C
°C Solubilityatat100
Solubility ◦ C°C
100
LiOH
LiOH 110 g/L
110 g/L 11 161g/L
161 g/L1 1

LiF g/L11
1.2g/L
1.2 g/L1 1
1.34g/L
1.34
LiHCO33
LiHCO 55 g/L22
55g/L 57.4 g/L1 1
57.4g/L
Li22CO
CO33 13.3 1 1
Li 13.3g/L
g/L 1 7.2
7.2g/L
g/L 1
1 1[51], 2 2[52] at 18 ◦ C.
[51], [52] at 18 °C.

Yi
Yietetal.al. have
have also
alsoreported
reportedthe theconversion
conversionfrom
fromLiLi
2 CO
2CO33 in
in aqueous
aqueoussolution
solutioninto
into
LiHCO
LiHCO33 by by CO
CO22-based carbonation,
carbonation, followed
followed byby aa chemical
chemical purification
purification ofofthethesolution
solution
and
andsubsequent
subsequentcrystallization
crystallizationof ofLi
Li22CO
CO33 from
from aa LiHCO
LiHCO33 solution
solution byby boiling
boiling [53].
[53].
IfIflithium
lithiumisispresent
presentasasLi
Li22CO
CO33,, it
it decomposes
decomposes according
according to
to Equation
Equation (2)
(2) [54]:
[54]:
3 ↔+ Li+(aq) + CO23−
Li2 COLi3 2CO
↔ Li 2−
(aq) + CO3 ((aq) aq) (2)
(2)
The carbonate ion (CO232− (aq)) is the conjugate base of a weak acid (carbonic acid) [55].
The carbonate ion (CO3 − (aq) ) is the conjugate base of a weak acid (carbonic acid) [55].
Hence, H++-ions are attracted at neutral or acidic areas and consumed from H2O, which
Hence, H -ions are attracted at neutral or acidic areas and consumed from H2 O, which
generally is present in the ionic form [55–57]. This chemical behavior equals the property
generally is present in the ionic form [55–57]. This chemical behavior equals the property
of Li2CO3 to be alkaline (see Equation (7)) [58]. In combination with CO2-gas, Yi et al. also
of Li2 CO3 to be alkaline (see Equation (7)) [58]. In combination with CO2 -gas, Yi et al.
report the chemical steps between Li2CO3 dissolution consuming H+-ions from the H2CO3-
also report the chemical steps between Li2 CO3 dissolution consuming H+ -ions from the
decomposition (see Equation (3)) [53] and precipitation of solid Li2CO3 according to Equa-
H2 CO3 -decomposition (see Equation (3)) [53] and precipitation of solid Li2 CO3 according
tion (4) to Equation (7) [53]:
to Equation (4) to Equation (7) [53]:
CO2 + H2O + Li2CO3 ↔ 2 LiHCO3 (3)
CO2 + H2 O + Li2 CO3 ↔ 2 LiHCO3 (3)
LiHCO3 ↔ HCO3 + Li+ (4)
− +
LiHCO3 ↔ HCO + Li (4)
HCO-3 ↔ CO3 23 + H+ (5)
− + 2− + H+
2- ↔ CO
HCO
HCO3 + H ↔ 3 H2O + CO2 (5)
(6)
3

HCO23−Li H+3
+2CO ↔
↔ Li + CO
H+2 O + 3CO
2−
2 (7)
(6)
Metals 2021, 11, 177 7 of 30

Li2 CO3 ↔ Li+ + CO3 2− (7)

Hereby, the possible recombinations between aqueous CO2 -phases and lithium ions in
aqueous phases are shown. These combinations can be transferred to other lithium phases,
liberating lithium cations in aqueous solution, too:
If lithium is present as LiF is a black mass, it dissolves in aqueous media according to
Equation (8) [59]:
LiF + H2 O ↔ HF + LiOH (8)
According to the definition of strong acids and bases [60], HF (pKS = 3.17 [61]) is a
strong acid, whereas LiOH (pKb = −0.36 [62]) is very strong base. As a resulting pH-value
for dissolving 0.26 g/L at 25 ◦ C pH = 7–8.5 is reported [63].
If lithium is formed as LiOH in a black mass, it dissociates in an aqueous solution
according to Equation (9) [64–66]:

LiOH + H2 O ↔ Li+ + OH− + H2 O ↔ LiOH·H2 O (9)

the following reaction can take place if CO2 is applied to the system [67]:

2 LiOH· H2 O + CO2 ↔ Li2 CO3 + 3 H2 O (10)

If lithium is present as Li2 O in a black mass, it dissociates to LiOH in aqueous solu-

tions according to Equation (11) [68]. LiOH(aq) is generally stable as lithium hydroxide
octahydrate (LiOH · 8H2 O) [61].

Li2 O + H2 O ↔ 2 LiOH (11)

This passage has shown that no study on indirect carbonation by CO2 using whole
LIBs black mass, meaning anode and cathode material, is in place. In contrast to that, in the
study, real industrial heat-treated black mass from anode and cathode was used without
adding a reducing agent. Moreover, this gives the first-time overview of all possible lithium
reactions when considering battery materials, which is crucial to extract hypotheses on
ongoing mechanisms.

1.1.4. Solid–Gas Carbonation (Direct Thermal Carbonation)

Direct carbonation describes solid–gas reactions for generating a carbonate phase [48].
In this study, it will be investigated by using SCO2 . There are different studies in literature
optimizing a reductive thermal treatment of black mass for mobilizing lithium via subse-
quent H2 O-leaching [46,47,69–74]. It should be recalled that in [46,47], which were already
discussed in chapter 1.1.3, a combination of direct carbonation and indirect carbonation was
performed: On one hand, a reductive thermal treatment with adding a carbon-reducing
agent like lignite or carbon black contributes to the formation of Li2 CO3 , hence direct
carbonation. On the other hand, CO2 was added during leaching or Na2 CO3 was used
after a first filtration, both representing indirect carbonation. Therefore, a classification into
studies with direct and indirect carbonation is not always straightforward.
However, in all reported studies [46,47,69–74], first, the battery cells are shredded, and,
after extracting, a black mass is thermally treated. Battery systems used are LCO-cathode
based [69,72,74], LMO-cathode based [71,74], or NMC-cathode based [73,74]. In [73], the
only cathode material is used. Most studies focus on a thermal treatment in an inert
atmosphere, like a vacuum, Ar or N2 [69,71,72,74,75] or in the air [70] instead of CO2 . CO2
was only used in [73]. The performed reductive roasting reportedly also contributes to the
carbonation of lithium by precipitating it from the black mass matrix [19,70,72,74,76].
Since the focus of this study is the use of NMC-cathode based black mass, the matching
studies are reported in detail: CO2 -gas purging at 600, 700 and 800 ◦ C (direct carbonation)
of NMC-cathode material was performed by Wang et al. for 120 min., but lithium yields
are not given. Instead, it is stated that 1.735 g lithium of 1.95 g lithium was transferred to
Metals 2021, 11, 177 8 of 30

a solution after water leaching [73]. However, no optimal temperature for carbonation is
given; instead, a spectrum of 650–800 ◦ C is reported, and no discussion on lithium purity
is in place. Xiao et al. treated black mass from NMC-cathode based cells. According to the
best-case scenario for pyrolysis and H2 O-leaching, 66% of the lithium is recovered. The best-
case scenario here implies vacuum pyrolysis at 700 ◦ C for 30 min. in combination with H2 O-
leaching for 30 min. and an s/l ratio of 1:40 (g/mL) (25 g/L) [74]. Nevertheless, no details
on the procedure of NCM-black mass are given, especially regarding lithium recovery.
Since [73] is the only study in place using CO2 for direct carbonation, no detailed
yields are quoted from the literature.
In terms of chemical reactions involving lithium phases, only a few data are given,
mostly based on thermodynamic simulations [76–78]. Nonetheless, gas–solid reactions are
known, e.g., from CO2 absorbing for air purification. Here, a reaction between LiOH and
CO2 for generating lithium carbonate is targeted [67].

2 LiOH + CO2 → Li2 CO3 + H2 O (12)

A similar reaction is possible if Li2 O is present [79]:

Li2 O + CO2 → Li2 CO3 (13)

The reaction is rather a surface reaction, after which CO2 diffuses into the inner part of
the Li2 O particles. This diffusive process is temperature-supported. For example, at 600 ◦ C,
the diffusion takes place 10 times faster than at 500 ◦ C [79]. In addition, once lithium
carbonate is formed, it remains stable in the CO2 atmosphere, even though being in a
liquid state, until 1611 ◦ C, before decomposing into Li2 O [80]. This passage has shown that
there is a lack of process details in terms of direct carbonation LIBs black mass by CO2 -gas
purging. Moreover, the available studies focus on shredding before thermal treatment. In
this study, the thermal treatment is performed before a mechanical treatment.
Finally, at this point, no study has reported investigating the influence of solid/gas
mechanisms (direct thermal carbonation) in contrast to liquid/gas mechanisms (indirect
carbonation) in terms of carbonation either by using supercritical or ambient pressure CO2
and by keeping the process parameters equal. The present research aims to give answers
to this question.

1.1.5. The Role of Supercritical CO2 (SCCO2 )

When using CO2 for phase transformations, the combination of the liquid and gaseous
phase properties is advantageous. For CO2 , the supercritical state is reached at a tempera-
ture of at least 31 ◦ C and a pressure of 73.8 bar [81]. Here, the physical properties of CO2
can be described by a density according to the liquid state and as viscosity equally to the
gaseous state, enabling a high efficiency [82]. Chen et al. report on using supercritical
CO2 (SCCO2 ) for carbonating spodumene-based lithium; thus, this study refers to primary
lithium production [83]. In their study, also sodium carbonate (Na2 CO3 ) is used as a car-
bonation agent, and CO2 is added, aiming for a higher carbonate dissolution. It is reported
to precipitate as Li2 CO3 when reducing the liquid volume, according to Equation (14) [83]:

2 LiHCO3(aq) ↔ Li2 CO3(s) + {CO2 } + H2 O(aq) (14)

Bertau et al. have dealt with a similar research topic: They suggested a treatment of
Zinnwaldite, a lithium ore located in Germany, with SCCO2 . It is a promising solution
for primary lithium recovery as carbonate [84]. Specific benefits comprise the avoidance
of additional chemicals, such as Na2 CO3 , and significant lithium losses, the economic
viability due to the low CO2 price, and the high selectivity by transforming only alkali
metal compounds [84]. Moreover, Liu et al. investigated the possibilities of recover-
ing LIB-electrolyte components by means of SCCO2 [85]. Grützke et al. also aimed for
LIB-electrolyte recycling using SCCO2 , but in contrast to Liu et al., who used synthetic
Metals 2021, 11, 177 9 of 30

electrolyte components, whole end-of-life NMC-cells were discharged, deep-frozen and

manually opened to extract the electrolyte by supercritical CO2 [86,87]. SCCO2 , at, e.g.,
40 ◦ C and 80 bar in flow-through mode, is used for extracting the electrolyte along with
the CO2 -stream in a cryogenic trap. A patented technique by Sloop describes a treatment
of full batteries with SCCO2 , where lithium carbonate from the electrolyte is recovered in
the frame of electrolyte removal. The electrolyte removal is reached by dissolving it in the
stream of CO2 [81,88].
Rothermel et al. rather focused on graphite recycling options and the achievable
graphite purity by making use of supercritical CO2-supported electrolyte recovery (SCCO2) [89].
In 2019, Bertau et al. also reported options to recover lithium from battery black mass [90].
The so-called COOL process, consisting of discharging, mechanical extraction of black
mass and a SCCO2 treatment, obtained lithium carbonate with a purity of >99.5% and yield
of 60%, but the yield is referring to primary ore treatments, so no information on lithium
from black mass is in place [90]. In this context, another benefit is highlighted: consuming
CO2 instead of producing CO2 in the context of rising industrial, environmentally harmful
CO2 -emissions [90]. However, no details about the best-case treatment parameters and the
resulting lithium yields in terms of black mass carbonation are given. An earlier patent by
Bertau et al. describes lithium recovery from so-called lithium-containing battery residues
by SCCO2 for obtaining lithium carbonate [91]. For this material, lithium yields of >90%
are reported by using electrodialysis and subsequent addition of carbonates like Na2 CO3 or
K2 CO3 , but facts on the corresponding treatment details and parameters are not given. An
exemplary process with s/l = 1:40 (g/mL) (50 g/2 L), 4 h at 230 ◦ C and 100 bar is described,
reporting on a leaching efficiency of 95%. The lithium extraction via electrodialysis takes
place in a Li2 SO4 -solution recovering 98% of the lithium in solution [91]. A lithium yield
based on the final, solid product is not given.
This passage has shown that supercritical CO2 plays a role in lithium recovery from
different materials, but for LIB-black mass, there is a lack of knowledge regarding decisive
process details. This article focuses on lithium carbonation from black mass by means of
supercritical CO2 .

2. Materials and Methods

2.1. Recycling Concept with Integrated Early-Stage Li-Recovery
Under the view of the current process-related drawbacks in conventional recycling
processes, and especially in terms of the need for lithium recovery, this study suggests
the strategy of an early-stage Li-recovery (“ESLR”) process. The method “early-stage” is
studied here, describing lithium carbonation before entering acidic leaching or smelting,
hence at an earlier position in the recycling chain. This treatment prevents lithium distri-
bution, the further use of additives needed for hydrometallurgical treatments, and costly
refining from a slag. The “ESLR” process comprises the following steps, as presented in
Figure 5b: After the cells have been deactivated by means of a thermal treatment followed
by mechanical processing (shredding and sieving to <1 mm), lithium is enriched in the
heat-treated black mass, along with other electrode elements, such as Co, Ni, Mn, and
C and partly Al- and Cu foil fragments. This heat-treated black mass is then leached in
H2 O- to transform and extract the lithium phases and, thus, separated them from the other
electrode elements.
Metals 2021, 11, 177 10 of 30
Metals 2021, 11, x FOR PEER REVIEW 10 of 30

Heat-treated black mass

CO2 Leaching in H2O

Filtration Black mass

without Li
Li-bearing solution

Boiling

Full boiling
Filtration (drying in beaker)

Li2CO3

(a) (b)
Figure5.5.(a)
Figure (a)Recycling
Recyclingstrategy
strategyfor
forlithium-ion
lithium-ionbatteries
batteries(LIBs)
(LIBs)atatIME
IMEwith
witha afocus
focuson
onalternative
alternativeprocessing
processingusing
using“ESLR”,
“ESLR”,
(b) detailed process steps of the “ESLR” process by autoclave/ supercritical CO2-carbonation.
(b) detailed process steps of the “ESLR” process by autoclave/supercritical CO2 -carbonation.

Asmentioned
As mentionedininSectionSection1,1,this
thisphase
phasetransformation
transformationcancanbeberealized
realizedbybytreatment
treatment
withsupercritical
with supercriticalCO CO 2
as
2as indirect
indirect or
or direct
direct carbonation.
carbonation. Lithium
Lithium in
in the
the heat-treated
heat-treated black
black
mass is converted into water-soluble lithium hydrogen carbonate
mass is converted into water-soluble lithium hydrogen carbonate (LiHCO3 ) and lithium(LiHCO 3 ) and lithium
carbonate(Li
carbonate (Li 2CO3). Indirect carbonation and H2O-leaching occur simultaneously because
2 CO3 ). Indirect carbonation and H2 O-leaching occur simultaneously because
the heat-treated
the heat-treated black black mass
mass is fed in in the
thereactor
reactoralong
alongwith
withdeionized
deionized water.
water. In In
direct car-
direct
bonation, the
carbonation, theheat-treated
heat-treatedblackblack mass
mass is subjected to to neutral
neutralleaching
leachinginindeionized
deionizedHH 2O2O

afterthe
after thephase
phasetransformation
transformationofoflithium
lithiumcompounds.
compounds.InInboth
bothcases,
cases,lithium
lithiumdissolves
dissolvesinto into
ananaqueous
aqueoussolution,
solution,and andthe
theLi-reduced,
Li-reduced,heat-treated
heat-treatedblack
blackmass
massisisseparated
separatedby bya afirst
first
filtration.The
filtration. Thefirst
firstfiltration’s
filtration´sproducts
productscomprise:
comprise:
1.1. AAfilter
filtercake
cakewith
withmainly
mainlycarbon,
carbon,nickel,
nickel,cobalt,
cobalt,manganese,
manganese,aluminum
aluminumand
andcopper
copper
fragmentsand
fragments andaashare lithium(→
shareofoflithium (→C-filter
C-filtercake);
cake);
2.2. AAlithium-bearing
lithium-bearingfiltrate
filtrate(solution)
(solution)
The
TheLi-containing
Li-containingfiltrate
filtratemust
mustfinally
finallybebeboiled
boiledsince
sincelithium’s
lithium´ssolubility
solubilitydecreases
decreases
from ◦ ◦
from13.313.3g/L
g/Latat20
20 C °Ctoto7.2
7.2g/L
g/Lby
byheating
heatingto to100 C [25].
100 °C [25].Moreover,
Moreover,thus,
thus,the
thecarbonate
carbonate
precipitation
precipitationisissupported.
supported.EitherEitheraasecond
secondfiltration
filtrationstep
stepseparates
separatesthe
thesolid
solidcarbonate
carbonate
(filter
(filtercake)
cake)from
from thetheresidual
residual solution, or the
solution, solution
or the is further
solution boiled
is further and and
boiled is left
is in the
left inair
the
toair
dryto the
drycarbonate.
the carbonate.

2.2.
2.2.Material
MaterialCharacterization
Characterization
The
Theblack
blackmass
massused
usedininthe
thepresent
presentstudy
studytotovalidate
validatethe
the“ESLR”
“ESLR”process
processhas
hasbeen
been
generated by thermal treatment of whole NCM-traction cells. Therefore, a real
generated by thermal treatment of whole NCM-traction cells. Therefore, a real industrialindustrial
heat-treated
heat-treatedblack
blackmass
masswas
wasobtained
obtainedby bythermal
thermaltreatment
treatmentatatdifferent
differentatmospheres:
atmospheres:Ar,Ar,
95% Ar + 5% O2 and CO2 . For Ar-pyrolysis, the temperatures targeted are 509 ◦ C and
95% Ar + 5% O 2 and CO2. For Ar-pyrolysis, the temperatures targeted are 509 °C and 603
603 ◦ C. For Ar + O2 -pyrolysis, the temperature targeted is 501 ◦ C. For CO2 -pyrolysis,
°C. For Ar + O2-pyrolysis, the temperature targeted is 501 °C. For CO2-pyrolysis, the tar-
the targeted temperature is 466 ◦ C. These atmospheres have been generated by dynamic
geted temperature is 466 °C. These atmospheres have been generated by dynamic pyrol-
pyrolysis in a sealed reactor. It should be noted that due to the experimental setup, not all
ysis in a sealed reactor. It should be noted that due to the experimental setup, not all ther-
thermal treatment temperatures have been identical. The thermally treated cells were then
mal treatment temperatures have been identical. The thermally treated cells were then
subjected to a shredding and sieving process for extracting the heat-treated black mass.
subjected to a shredding and sieving process for extracting the heat-treated black mass.
The composition of the heat-treated black mass is shown below (see Table 2):
The composition of the heat-treated black mass is shown below (see Table 2):
Table 2. Chemical composition of the heat-treated black mass used for the autoclave trials pyrolyzed
in Ar-atmosphere.

Al Co Cu F Fe Li Mn P C Ni
wt.%
2.10 11.7 0.88 4.10 0.00 3.69 8.91 0.44 33.9 11.5
 Table 2. Chemical composition of the heat-treated black mass used for the autoclave trials pyrolyzed in Ar-atmosphere.

Al Co Cu F Fe Li Mn P C Ni
wt.%
2.10
Metals 2021, 11, 17711.7 0.88 4.10 0.00 3.69 8.91 0.44 33.9 11.5
11 of 30

Dynamic particle analysis with QICPIC/L02 (Sympatec GmbH, Clausthal-Zellerfeld,

Germany) of the heat-treated black mass reveals that according to the distribution sum
Dynamic particle analysis with QICPIC/L02 (Sympatec GmbH, Clausthal-Zellerfeld,
(Q3), the d99.3 -value is 101.74 µm. This means that 99.3% of the heat-treated black mass has
Germany) of the heat-treated black mass reveals that according to the distribution sum
a grain size smaller than 101.74 µm (see Figure 6). Here, the material´s distribution density
(Q3 ), the d99.3 -value is 101.74 µm. This means that 99.3% of the heat-treated black mass has
(q3*), see Equation (15), can also be extracted, reaching a global maximum at ~95 µm. Ac-
a grain size smaller than 101.74 µm (see Figure 6). Here, the material’s distribution density
cording to DIN ISO 9276-1, the distribution density is defined as the first derivation of the
(q3 *), see Equation (15), can also be extracted, reaching a global maximum at ~95 µm.
distribution sum:
According to DIN ISO 9276-1, the distribution density is defined as the first derivation of
the distribution sum: dQ ( ) (15)
q3* = qr (x) = dQr (dx )
q3 ∗ = qr ( x ) = (15)
Furthermore, the distribution sum of the particles dxrepresents the number of all parti-
cles andFurthermore, the distribution
not their volume share in sum of the particles
the powder. Hence,represents
there arethe number
many smallofparticles
all particles
in
andheat-treated
the not their volume share in
black mass, butthe
in powder.
contrast toHence,
that, there are many
the volume small
of big particles
particles in the
(>101.74
heat-treated
µm) could takeblack mass, than
up more but in contrast
99.3%. to that, the largest
Moreover, volumeparticle
of big particles
detected(>101.74
in the heat-µm)
could take up more than 99.3%. Moreover, the largest particle detected
treated black mass comprises a diameter (EQPC) of 653.74 µm with a FERET_MAX value in the heat-treated
black
of evenmass comprises
748.13 µm. EQPC a diameter
is defined(EQPC)
as of 653.74 µm with a FERET_MAX value of even
748.13 µm. EQPC is defined as r
xEQPC = 2A A (16)
xEQPC = π (16)
π
Hence,
Hence,ititdescribes
describes thethe
diameter
diameter of aof
circle whose
a circle projection
whose surface
projection (shadow)
surface is iden-is
(shadow)
tical to the particle. FERET_MAX, on the other hand, detects the maximum
identical to the particle. FERET_MAX, on the other hand, detects the maximum diameter diameter of a
particle by analyzing
of a particle it fromit20from
by analyzing different perspectives
20 different betweenbetween
perspectives 0 and 180°. This180
0 and value
◦ de-
. This
viates from thefrom
value deviates EQPC, especially
the EQPC, in terms
especially of irregularly
in terms of irregularly shaped
shapedparticles;
particles;hence,
hence,
FERET_MAX
FERET_MAXtakes takesbigger
biggervalues,
values,especially
especiallywhen
whenbeing
beingdistinct
distinctfrom
fromaacircular
circularform.
form.The The
maximum detectable particle size with this method comprises
maximum detectable particle size with this method comprises 1252 µm. 1252 µm.

2.5

densityqq3*3*
2.0
Distribution sum Q3 / %

Distribution density
1.5

Distribution
1.0

0.5

0.0

Particle size x / µm
Distribution sum Q3 / %
Distribution density q3*

Dynamicparticle
Figure6.6.Dynamic
Figure particleanalysis
analysisofofCO
CO 2 -pyrolyzed
2-pyrolyzed black
black mass.
mass. AA total
total of of 32,650
32,650 particles
particles werewere
counted and hence considered for the evaluation. The distribution sum and distribution
counted and hence considered for the evaluation. The distribution sum and distribution density in density
in this
this diagram
diagram is based
is based on heat-treated
on the the heat-treated
blackblack
massmass comprises
comprises a diameter
a diameter (EQPC)-value
(EQPC)-value of theof the
particles,
particles,which
whichisisindicated
indicatedasasparticle
particlesize
sizex.x.

Moredetails
More detailson
onthe
thequantitative
quantitative grain
grain size
size detected
detected areare shown
shown in Figure
in Figure 7 and
7 and cancan
be
be extracted
extracted fromfrom the chemical
the chemical composition
composition of particles.
of the the particles.
EDS EDS analyses
analyses werewere carried
carried out
outelemental
for for elemental mapping,
mapping, as well
as well as for
as for point
point analysis
analysis onon theblack
the blackpowder,
powder,using
using aa
ZeissGemini-FE-SEM,equipped
ZeissGemini-FE-SEM, equippedwith
withan anOxford
OxfordUltimMax170
UltimMax170detector
detector(Carl
(CarlZeiss
ZeissAG,
AG,
Oberkochen,Germany).
Oberkochen, Germany).In InFigure
Figure7a,b,
7a,b,the
theresults
resultsofofthe
theelemental
elementalmapping
mapping(EDX-layered
(EDX-layered
image) are depicted. Here, the appearance of metallic Al-flakes is shown in Figure 7a;
second, a heat-treated black mass particle and a graphite particle are shown in Figure 7b.
Moreover, third, Figure 7c is a 1 mm-scale distance shot showing the heterogeneity of the
heat-treated black mass in terms of metallic aluminum fragments, heat-treated black mass
particles and graphite powder. It should be noted that lithium cannot be displayed by this
method. In addition, Figure 7c reveals that the liberation of heat-treated black mass from
 image) are depicted. Here, the appearance of metallic Al-flakes is shown in Figure 7a;
second, a heat-treated black mass particle and a graphite particle are shown in Figure 7b.
Metals 2021, 11, 177
Moreover, third, Figure 7c is a 1 mm-scale distance shot showing the heterogeneity 12of ofthe
30
heat-treated black mass in terms of metallic aluminum fragments, heat-treated black mass
particles and graphite powder. It should be noted that lithium cannot be displayed by this
method. In addition, Figure 7c reveals that the liberation of heat-treated black mass from
the aluminum
the aluminum current
current collectors
collectors could
could be
be realized
realized since
since the
the particles
particles do
do not
not show
show direct
physical contact.
physical contact.

Spectrum 33

Spectrum 16
Spectrum 38

250 µm
1 mm

S Fe O P F Cu Al Mn Co C Ni O P F Al C 250 µm O Al C

(a) (b) (c)

Figure
Figure 7.
7. EDS
EDSanalysis
analysisofofCO
CO22-pyrolyzed
-pyrolyzedEV-battery
EV-batteryblack
blackmass.
mass.(a)
(a)results
resultsof
ofthe
theelemental
elementalmapping
mapping(EDX-layered
(EDX-layeredimage)
image)
of an aluminum particle, (b) results of the elemental mapping (EDX-layered image) of both an NMC-and-graphite particle,
of an aluminum particle, (b) results of the elemental mapping (EDX-layered image) of both an NMC-and-graphite particle,
(c)
(c) Distance
Distance shot
shot of
of the
the heat-treated
heat-treated black mass from
black mass from elemental
elemental mapping
mapping (EDX-layered
(EDX-layered image).
image).

The
Thefollowing
followingTable
Table33shows
showsthe chemical
the chemicalcomposition
composition of the taken
of the spectra.
taken Here,
spectra. the
Here,
chemical composition
the chemical compositionof the Al-flake
of the cancan
Al-flake bebeseen
seenbybySpectrum
Spectrum38.38.However,
However,therethere are
are
some
some oxide-graphite-mix
oxide-graphite-mix particles
particles visible,
visible, which
which results
results in
in the
the chemical
chemical composition
composition of
just
just 58.28
58.28wt.%.
wt.%.Moreover,
Moreover,spectrum
spectrum1616shows
showsthat
thatthe
thedominant
dominant particle composition
particle composition is
aisNi-Mn-Co-Oxide,
a Ni-Mn-Co-Oxide, hence,
hence, heat-treated
heat-treated blackblack
massmass particles.
particles. Spectrum
Spectrum 33 reflects
33 reflects a graph-a
graphite
ite particle
particle (C = 46.46
(C = 46.46 wt.%),
wt.%), whichwhich
alsoalso shows
shows a high
a high amount
amount ofofoxygen.
oxygen.This
Thismaymay be
be
explained by
explained by lithium
lithium oxides,
oxides, hydroxides
hydroxides or carbonates,
carbonates, which cannot be shown here. This This
theory can be supported
theory supported by by the
thelithium
lithiumintercalation
intercalationininthe
thegraphite
graphitematrix
matrixdue
dueto to
charging.
charg-
ing.
Table 3. Chemical composition of the heat-treated black mass spectra taken by EDS-analysis. Only
Table 3. Chemical composition of the>1
elements heat-treated black mass
wt.% are shown spectra taken by EDS-analysis. Only elements > 1 wt.% are
quantitatively.
shown quantitatively.
Element C O F P Mn Co Ni Al
Element C O F P
Mn Co Ni Al
Unit wt.%
Unit wt.%
Spectrum 38 31.9 7.35 <1 wt.% <1 wt.% <1 wt.% <1 wt.% <1 wt.% 58.28
Spectrum 38 31.9 7.35 <1 wt.% <1 wt.% <1 wt.% <1 wt.% <1 wt.% 58.28
Spectrum 16 32.83 12.1 21.9 1.81 8.59 11.38 10.62 <1 wt.%
Spectrum 16 32.83 12.1 21.9 1.81 8.59 11.38 10.62 <1 wt.%
Spectrum 33 46.46 Spectrum
33.51 33 46.46
1.47 33.51<1 wt.%
1.47 <1
<1 wt.%
wt.% <1 wt.%
<1 wt.%<1 wt.% <1 wt.% 17.95
<1 wt.% 17.95

These
These findings
findings are
are essential
essential toto understand
understand the the properties
properties ofof NCM-heat-treated
NCM-heat-treated blackblack
mass:
mass: AnAn important
importantresult
result is
is the
the revelation
revelation of
of the
the material´s
material’s heterogeneity. Hence,
Hence, each
each
sample
sample taken
taken shows
shows different
different chemical
chemical compositions.
compositions. Considering
Considering thethe colorful
colorful mixture
mixture of
of
relatively
relatively big
big Al-particles,
Al-particles, cathode
cathode material particles and smaller graphite/soot
graphite/soot particles,
particles,
this statement is supported.
this supported. Moreover,
Moreover,ititcancanbebeseen
seenthat thethe
that Al-foils areare
Al-foils liberated from
liberated the
from
cathode
the material.
cathode Hence,
material. Hence,a thermal
a thermalpretreatment
pretreatment removes
removes binders and
binders therefore
and loosens
therefore loos-
adhesions.
ens This This
adhesions. enhances the subsequent
enhances leaching
the subsequent efficiency,
leaching as indicated
efficiency, before. Moreover,
as indicated before.
it is shown that fluorine enriches the cathode material particles.
Moreover, it is shown that fluorine enriches the cathode material particles.

2.3. Neutral
2.3. NeutralLeaching
Leaching Reference
Reference Tests
Tests in
in Deionized
Deionized H
H22OO
Neutral leaching
Neutral leaching comprises
comprises reference
reference trials
trials to
to evaluate
evaluate the
the carbonation
carbonation success. It
success. It
was performed in a 1 L glassware beaker filled with deionized water. Here, 20
was performed in a 1 L glassware beaker filled with deionized water. Here, 20 g of the g of the
heat-treated black mass is inserted and magnetically stirred at 350 rpm for the defined
leaching time. After H2 O-leaching, a first filtration obtains a C-filter cake and a Li-bearing
solution, then boiled to recover lithium as Li2 CO3 (→ Li-filter cake). Neutral leaching is
performed at room temperature to increase lithium dissolution. Lithium contents in both
filter cakes and solutions are measured by ICP-OES (inductively coupled plasma optical
 Metals 2021, 11, x FOR PEER REVIEW 13 of 30

heat-treated black mass is inserted and magnetically stirred at 350 rpm for the defined
Metals 2021, 11, 177 leaching time. After H2O-leaching, a first filtration obtains a C-filter cake and a Li-bearing
13 of 30
solution, then boiled to recover lithium as Li2CO3 (→ Li-filter cake). Neutral leaching is
performed at room temperature to increase lithium dissolution. Lithium contents in both
filter cakes and solutions are measured by ICP-OES (inductively coupled plasma optical
emission
emissionspectrometry). Liisisthe
spectrometry). Li thecrucial
crucialindicator
indicator
forfor carbonation
carbonation success,
success, andand hence,
hence, lith-
lithium yields are calculated as follows:
ium yields are calculated as follows:
LiLi Li Li2 CO3 -(fcg(g)
)
nLi = ƞLi = 2 Li3total
CO − fc (17)
(g) (17)
Litotal (g)
where Litotal is the lithium mass in the input, and Li-Li2CO3-fc is the lithium mass in the lith-
where Litotal is the
ium carbonate lithium
filter mass the
cake. Since in the
inputinput, and Li-
material shows is the lithium
deviations
Li2CO3-fc in termsmass
of itsinchem-
the
lithium carbonate filter cake. Since the input material shows deviations
ical composition, the Litotal value does not equal the share of the original input analysis. in terms of its
chemical composition, the Li total value does not equal
For this reason, the lithium values in the input are calculated as follows: the share of the original input
analysis. For this reason, the lithium values in the input are calculated as follows:
Litotal (g) = LiC-fc (g) + Lisolution (g) (18)
Litotal (g) = LiC−fc (g) + Lisolution (g) (18)
Here, C-fc represents the carbon filter cake, also indicated as “heat-treated black mass
without
Here,lithium,” and “Lithe
C-fc represents solution” corresponds to “Li-bearing solution”. This calculation is
carbon filter cake, also indicated as “heat-treated black mass
without lithium,” and “Lisolutionefficiency
to be contrasted to the leaching ” corresponds (LE).to When calculating
“Li-bearing ƞLi based
solution”. Thisoncalculation
Lisolution [g],
the yields in this study were ~10% higher. For example, in one trial
is to be contrasted to the leaching efficiency (LE). When calculating nLi based on Lisolution with a yield of 79%
based on Equation (17), the LE was 88%. The reason for this
[g], the yields in this study were ~10% higher. For example, in one trial with a yield inaccuracy cannot be deter-
of
mined
79% at this
based on point,
Equation but (17),
sincethe the LEdeviation
was 88%. wasThe systematic,
reason for thethis
authors decidedcannot
inaccuracy to use be the
lower values
determined atfor
thisconservative
point, but since result theinterpretation.
deviation was systematic, the authors decided to
use the lower values for conservative result interpretation.
2.4. Carbonation by Supercritical CO2
2.4. Carbonation by Supercritical
The unit operation used isCO 2
a batch 1 l Büchi autoclave reactor operated with deionized
waterThe(indirect
unit operation used isor
carbonation) a batch
without1 l Büchi autoclave
any liquid reactor
(direct operated with
carbonation). The deionized
maximum
water (indirect
operating carbonation)
temperature is 250or°C,
without
and the any liquid (direct
maximum carbonation).
applicable pressure Theis 200 maximum
bar. After
operating temperature is 250 ◦ C, and the maximum applicable pressure is 200 bar. After
sealing, a stirrer constantly mixes the powder (50 g heat-treated black mass per trial (T0–
sealing,
T9) anda 20stirrer constantly mixes
g heat-treated the powder
black mass (50(T10–T22)
per trial g heat-treated
or theblack mass perintrial
suspension the(T0–T9)
reactor.
and 20 g heat-treated black mass per trial (T10–T22) or the suspension
The gas flows into the reactor occurs via a valve into H2O if the trial is conducted within the reactor. The
an
gas flows into the reactor occurs via a valve
aqueous medium. As soon as the supercritical conditions into H 2 O if the trial is conducted with
are reached, a processing time an
aqueous
of 120 minmedium. As soon
is started. as the supercritical
The defined holding time conditions
of 120 min arecanreached, a processing
be attributed time of
to preliminary
120 min is started. The defined holding time of 120 min can be attributed
studies using autoclave-induced carbonation [92]. The general parameters for the auto- to preliminary
studies usingcan
clave trials autoclave-induced
be seen in Figure carbonation
8a. Moreover,[92].Figure
The general
8b shows parameters
picturesforof the
theautoclave
unit oper-
trials
ation.can be seen in Figure 8a. Moreover, Figure 8b shows pictures of the unit operation.

Pressurestart 50 bar

Heating rate 10 °C/min.

Tmax 230 °C

Pmax (spectrum of 95.4–138.3 bar

trials)
Holding time 120 min.

(a) (b)
Figure8.8.(a).
Figure (a).Fixed
Fixed process
process parameters
parameters andand reached
reached pressures
pressures forautoclave
for an an autoclave trial (combination
trial (combination of heat-treated
of heat-treated black
black mass
mass
with with deionized
deionized H 2O
H2 O and CO and
2
CO
gas) 2 gas)
in casein
ofcase of
trials trials
T1–T9. T1–T9.
After After
the the starting
starting pressurepressure
of 50 of
bar,50 bar,
the the
reactorreactor
is is
heated heated
until
until reaching
reaching 230 ◦ C,230 °C, resulting
resulting in different
in different P PmaxUsed
. (b): . (b): Used autoclave
autoclave reactor
reactor at RWTH
at IME, IME, RWTH AachenAachen University.
University.
max

Afterleaching,
After leaching,either
eitherduring
duringautoclave
autoclavetreatment,
treatment,ififHH 2Ois
2O isused
usedininthetheautoclave
autoclaveoror
afterthe
after theautoclave,
autoclave,ififno
noHH2 O
2Ois
isused
usedininthe
theautoclave,
autoclave,aafirst
firstfiltration
filtrationisisperformed.
performed.The
The
experimental procedure is identical to the procedure described in Section 2.3: Boiling is
performed to reduce the volume of liquid and to precipitate Li from the solution. Lithium
is obtained in the form of solid Li2 CO3 in a subsequent (second) filtration step or by full
boiling until obtaining a solid Li2 CO3 product within the beaker. The (second) filtration
Metals 2021, 11, 177 14 of 30

step is performed as follows: The Li-bearing solution is boiled until reaching 100 mL and
then is filtrated, obtaining Li2 CO3 . The Li2 CO3 -filter cake is then washed with pure ethanol
since lithium carbonate does not show solubility in ethanol. It is dried for at least 24 h
and then weighed. The full boiling (indicated as “drying in a beaker”) is performed as
follows: The Li-bearing solution is boiled until no liquid is left, why the weight of the
empty beaker is to be measured before and after performing full boiling. In addition,
weighing is done after a drying time of at least 24 h, too. The difference in weight equals
the solid carbonate obtained.
An overview of the experimental series described in Sections 2.3 and 2.4 is given in
Table 4. Parameter set 1.A, 1.O and 1.C (reference trials) represents H2 O-leaching without
CO2 addition. Hereby, insights into the mass of water-soluble Li-phases already present in
the heat-treated black mass are provided. Enhanced leaching efficiencies are obtained by
combining neutral leaching with CO2 -carbonation. (see experimental series 2.A, 2.O and
2.C). Moreover, carbonation trials were conducted in the autoclave as well by using argon
(Ar) as process gas aiming for the same excess pressures as needed for the supercritical
state (73.8 bar) (see Table 4, Parameter set 3.A). Ar as inert gas can deliver knowledge
on the main mechanism for ongoing phase transformations: Either the presence of CO2
or the extreme pressure. Parameter set 4.A detects the influence of an autoclave setup
without H2 O and with CO2 to find out whether gas–solid or gas–liquid reactions dominate
in carbonation.

Table 4. Parameter matrix for combining pyrolysis conditions with autoclave conditions in this study.
Reference trials represent H2 O-leaching without autoclave or CO2 -incorporation.

Pyrolysis Conditions
Ar- 95 % Ar + 5 % CO2 -
Atmosphere O2 -Atmosphere Atmosphere
H2 O-leaching 1.A 1.O 1.C
(reference trials)
Autoclave
SCCO2 + H2 O 2.A 2.O 2.C
conditions
Ar + H2 O 3.A n/a n/a
CO2 + dry autoclave 4.A n/a n/a

The labels of the trials are to be understood as follows: “number.letter”, where the
number stands for an experimental series: 1 = neutral leaching in H2 O without an auto-
clave, 2 = autoclave operated with SCCO2 + H2 O, 3 = autoclave operated with Ar + H2 O,
4 = autoclave operated with SCCO2 and without H2 O. The letter stands for the pyrolysis
atmosphere: A = Ar-pyrolysis, O = 95 vol % Ar + 5 vol % O2 -pyrolysis, C = CO2 -pyrolysis.
In this study, only experimental series 1 and 2 take different pyrolysis atmospheres into ac-
count. Hence, the fields of experimental series 3.O/3.C and 4.O/4.C are not experimentally
conducted yet (n/a).

3. Results
In this Section, the results of the trial series 1.A—4.A, 1.O/2.O and 1.C/2.C are
discussed by lithium yields. Moreover, Sankey diagrams of the lithium distribution and
bar charts on the impurities of the lithium filter cake are shown for trials 1.A.1 and T2 (2.A).
The evaluation calculations are performed, as described in Section 2.3.

3.1. Neutral Leaching in Deionized H2 O

For a profound understanding of water-soluble lithium phases already present in the
heat-treated black mass, the following results can be obtained. In total, 40 experiments
were conducted in experimental series 1.A, 1.O, and 1.C. The amount per parameter set
comprises one trial, except for trials 1.A.2-1.A.4, 1.A.5-1.A.7, 1.A.28 and 1.A.40. Since the
results are in good accordance, the other trials have not been repeated. All trials have in
 3.1. Neutral Leaching in Deionized H2O
For a profound understanding of water-soluble lithium phases already present in the
heat-treated black mass, the following results can be obtained. In total, 40 experiments
Metals 2021, 11, 177 were conducted in experimental series 1.A, 1.O, and 1.C. The amount per parameter set
15 of 30
comprises one trial, except for trials 1.A.2-1.A.4, 1.A.5-1.A.7, 1.A.28 and 1.A.40. Since the
results are in good accordance, the other trials have not been repeated. All trials have in
common that when charging heat-treated black mass in H2O, the pH value of the solution
common
has become that when charging
alkaline heat-treated black mass in H2 O, the pH value of the solution
(pH = 11–12).
has become alkaline (pH = 11–12).
Figure 9 accordingly reveals how lithium yields from leaching heat-treated black
mass Figure
in H2O9(neutral
accordingly reveals
leaching) how lithium
depend yieldsparameters:
on six main from leaching heat-treated black mass
in H2 O (neutral leaching) depend on six main parameters:
1. Washing of C-filter cake with deionized water: if this parameter is performed, it is
1. important
Washing of to C-filter
keep thecake with deionized
washing water: if
volume constant. Inthis
thisparameter
study, 200ismL performed,
of deionized it is
important
water are used;to keep the washing volume constant. In this study, 200 mL of deionized
water areof
2. Filtration used;
Li-filter cake or full boiling: full boiling describes the removal of H2O
2. inFiltration of
the laboratory Li-filter cake
beaker. or full boiling:
Filtration fullfiltering
stands for boiling describes the removal
the precipitating Li2CO of3 H
at2 O
a
in the laboratory beaker. Filtration stands for filtering the precipitating
minimum liquid volume. Hence, there are losses in the residual filtrate. Filtration3 is Li 2 CO at
a minimum liquid
conventionally used volume. Hence,
after acidic there
leaching to are
avoidlosses in the residualoffiltrate.
a co-precipitation Filtra-
acid compo-
tion is conventionally
nents and chemical additives; used after acidic leaching to avoid a co-precipitation of acid
components and chemical additives;
3. Leaching time: 5, 30, 90 and 120 min;
3. Leaching time: 5, 30, 90 and 120 min;
4. Particle size of heat-treated black mass: <1 mm vs. <90 µm. The particles <90 µm are
4. Particle size of heat-treated black mass: <1 mm vs. <90 µm. The particles <90 µm
obtained by additional grinding of the heat-treated black mass;
are obtained by additional grinding of the heat-treated black mass;
5. Solid/liquid ratio (g/mL): 1:10, 1:15, 1:22.5 and 1:30;
5. Solid/liquid ratio (g/mL): 1:10, 1:15, 1:22.5 and 1:30;
6. Pyrolysis temperature: 501 vs. 603 °C in Ar-pyrolysis
6. Pyrolysis temperature: 501 vs. 603 ◦ C in Ar-pyrolysis
Neutral leaching trials and Li-recovery
100%

90%

80%

70% 57% 64%

61% 55%
57% 54% 52% 55% 53%
60%
Li-yield [%]

53% 54% 54% 54% 53%

53% 45% 52% 46% 52% 52%
49%
50% 44% 46% 45% 47%
45% 44% 45%
37% 38% 39% 37%
40% 36%
32%
23% 27% 29% 29%
30%
19%
20%
10%
10%

0%
1.O.1
1.C.1
1.A.1
1.A.2
1.A.3
1.A.4
1.A.5
1.A.6
1.A.7
1.A.8
1.A.9
1.A.10
1.A.11
1.A.12
1.A.13
1.A.14
1.A.15
1.A.16
1.A.17
1.A.18
1.A.19
1.A.20
1.A.21
1.A.22
1.A.23
1.A.24
1.A.25
1.A.27
1.A.28
1.C.29

1.A.31
1.A.32
1.A.33
1.A.35
1.A.36
1.O.30

1.O.37
1.C.38
1.A.39
1.A.40

Trial label

Figure 9. Lithium yields when applying no carbonation (neutral leaching) dependent on the parameters used. Trials 1.A.26
Figure 9. Lithium yields when applying no carbonation (neutral leaching) dependent on the parameters used. Trials 1.A.26
and 1.A.34
and 1.A.34 are
are left
left out
out of
of this
this overview
overview since
since they
theycomprise
comprisekinetic
kinetictrials,
trials,for
forwhich
whicha ayield
yieldcalculation
calculationisisnot
notpossible
possibledue
dueto
heat-treated
to black
heat-treated blackmass
masslosses during
losses sampling.
during sampling.

Here, a variation of the selected parameters has an impact on the lithium yield. To
Here, a variation of the selected parameters has an impact on the lithium yield. To
evaluate the key influencing factors, representative trials are extracted and shown in detail.
evaluate the key influencing factors, representative trials are extracted and shown in de-
For efficiency reasons, only the results of experimental series 1.A are depicted for the
tail. For efficiency reasons, only the results of experimental series 1.A are depicted for the
evaluation according to the parameters selected. In terms of these influencing factors, the
evaluation according to the parameters selected. In terms of these influencing factors, the
following conclusions are possible:
following conclusions are possible:
1. Washing of C-filter cake with deionized water:
The detailed observation of trials whose parameter combination was equal apart
from the washing of the C-filter cake shows that washing is highly beneficial. During the
filtration of the C-filter cake, there are physical depositions of the Li-bearing solution left
in the C-filter cake. Hence, washing with deionized water liberates the C-filter cake from
remaining lithium ions (see Figure 10a).
 in the C-filter cake. Hence, washing with deionized water liberates the C-filter cake from
remaining
1. Washing lithium ions (see
of C-filter Figure
cake with10a).
deionized water:
The detailed
2. Filtration observation
of Li-filter cake of trialsboiling:
or full whose parameter combination was equal apart
fromFiltration
the washing of the C-filter
is, according cake shows
to Figure thatanwashing
10b, not is highly
adequate beneficial.
tool when During
applying the
neutral
Metals 2021, 11, 177 16 of 30
filtration in
leaching of H
the C-filter
2O. cake,this
However, there are physical
analysis depositions
only focuses of the distribution.
on lithium Li-bearing solution
Hence, left
no
in the C-filteroncake.
information filterHence, washing with
cake impurities, e.g., deionized
F is given water
here. liberates the C-filter cake from
remaining lithium ions (see Figure 10a).
Parameter 2: Filtration of Li-filter cake
2. Filtration
Parameter 1: Washing of C-FC of Li-filter cake or full boiling: (after 30 Minutes)
(after 30 Minutes)
100%
Filtration is, according to Figure
100% 10b, not an adequate tool when applying neutral

80% leaching in H2O. However, this analysis80% only focuses on lithium distribution. Hence, no
60% information
47% on46% filter
54% cake impurities,
60%e.g., F is given here.
46% 47%
54%
36% 37%
40% 29% 37%
23% 40%
19%
20% Parameter 2: Filtration of Li-filter cake
Parameter 1: Washing of C-FC 20%
0% (after 30 Minutes) (after 30 Minutes)
1.O.1 1.O.37 1.C.1 1.C.38 1.A.1 1.A.39 1.A.17 1.A.32 0%
100%
100% 1.A.1 1.A.17 1.A.39 1.A.32
80% 1:10, <1mm 1:10, <1mm 1:10, <1mm 1:10, <1mm 80%
1:10, <1mm 1:10, <1mm
filtrated filtrated filtrated 47% Not 54%
60% 46%filtrated 60%
Not washed
46% 47%Washed
54%
36% 37%
40% 29% 37%
23% 40%
19%
20% Not washed Filtrated
20%
0% Not filtrated (full
1.O.1 1.O.37 1.C.1 1.C.38 1.A.1 Washed
1.A.39 1.A.17 1.A.32 0% boiling)
1.A.1 1.A.17 1.A.39 1.A.32
1:10, <1mm 1:10, <1mm 1:10, <1mm 1:10, <1mm
(a) 1:10, <1mm (b) 1:10, <1mm
filtrated filtrated filtrated Not filtrated
Not washed Washed
Figure 10. Detailed
Detailedobservation
observationon onachievable
achievablelithium
lithiumyields
yieldsbyby neutral
neutralleaching
leaching(H(H
2O)2 O)
of heat-treated black
of heat-treated mass.
black (a)
mass.
Parameter 1: washing of C-filter cake. (b) Parameter
(a) Parameter 1: washing of C-filter cake. (b)
NotParameter
washed
2: filtration of Li-filter cake or full boiling.
2: filtration of Li-filter cake or full boiling. Filtrated
Not filtrated (full
Washed boiling)
3.
2. Leaching
Filtrationtime:
of Li-filter cake or full boiling:
(a) The optimal leaching time cannot be extracted from(b) the performed trials, as can be
seen Filtration
in the range is, between
according to Figure
5 and 90 min10b,
(seenot an adequate
Figure tool when
11a) and between 30applying
and 120 min neutral
(see
Figure 10. Detailed observation on achievable
leaching in H O. lithium yields
However, this by neutralonly
analysis leaching
focuses(H2O)onoflithium
heat-treated black mass.
distribution. (a) no
Hence,
Figure 11b). Here,
2 no significant improvement of dissolved
Parameter 1: washing of C-filter cake. (b) Parameter 2: filtration of Li-filter cake or full boiling. lithium is achieved when com-
information
paring trials on
withfilter cake impurities,
constant parameterse.g., F is for
except giventhehere.
leaching time.
3. Leaching
Leaching time:
time:
The
Parameter 3: Leaching optimal
time leaching time
time cannot
cannot be
be extractedParameter
extracted from3:the
Leaching
the time
performed trials, as
as can
can be
be
The optimal leaching from performed trials,
100% seen in 100%
seen in the
the range
rangebetween
between5 5and and9090min
min(see Figure
(see Figure 11a) andand
11a) between
between 30 and 120 120
30 and min min
(see
80% Figure
(see 11b).11b).
Figure Here,Here,
no significant improvement
no significant 80%
improvement of dissolved lithium
of dissolved is achieved
lithium whenwhen
is achieved com-
60% paring trialstrials
comparing withwithconstant parameters
constant except
60%
parameters for55%
except the
for leaching 54%
the leachingtime.time. 52%
46% 45%
38% 40%
40%
Parameter 3: Leaching time 20% Parameter 3: Leaching time
20%
100% 100%
0% 0%
80% 1.A.11 1.A.17 1.A.15 80% 1.A.33 1.A.35 1.A.27
60% 55% 54% 52%
60% 5 min. 30 min. 90 min. 30 min. 90 min. 120 min.
46% 45%
38% 40%
40% 1:10, <1mm, not filtrated, not washed 1:15, <1mm, not filtrated, washed
20% 20%
(a) (b)
0% 0%
Figure 11. Detailed
1.A.11 observation
1.A.17on achievable 1.A.33
1.A.15 lithium yields by neutral leaching 1.A.35 mass. The
(H2O) of black 1.A.27
considered
parameter is parameter
5 min. 3: leaching
30 min. time. (a) Dissolution
90 min. and lithium recovery by comparing
30 min.
trials
90 min.
with a leaching
120 min.
time
between 5 and 90 min. (b) Dissolution and lithium recovery by comparing trials with a leaching time between 30 and 120
1:10, <1mm, not filtrated, not washed 1:15, <1mm, not filtrated, washed
min.
(a) (b)
Figure 11.
Figure 11. Detailed
Detailed observation
observation onon achievable
achievable lithium
lithium yields
yields by
by neutral
neutral leaching
leaching (H (H22O)
O) of
of black
black mass.
mass. The
The considered
considered
parameter is
parameter is parameter
parameter 3:3: leaching
leaching time.
time. (a) Dissolution and lithium recovery by comparing
comparing trials with
with aa leaching
leaching time
time
between 55 and
between and 90
90 min.
min. (b)
(b)Dissolution
Dissolutionand
andlithium
lithiumrecovery byby
recovery comparing
comparing trials with
trials a leaching
with time
a leaching between
time between 30 and 120
30 and
min.min.
120

Reduced lithium shares over time can be explained by slight deviations in the chemical
composition. Hence, deviations in lithium yields are also possible, also due to different
lithium phases in the heat-treated black mass. Therefore, a kinetic trial can be found in
Figure 12. It can be seen that lithium compounds in the heat-treated black mass of the
Ar-pyrolyzed battery cells dissolve as ions instantly. Although the lithium yield can be
found below Figure 12, it cannot be directly transferred to the other neutral leaching trials
since the amount of heat-treated black mass, and therefore the lithium-bearing input is
reduced each time a sample is taken. Samples were taken from the leaching liquor by
 ical composition. Hence, deviations in lithium yields are also possible, also due to differ-
ical
entcomposition.
lithium phases Hence,
in thedeviations in lithium
heat-treated yieldsTherefore,
black mass. are also possible,
a kineticalso trialdue
cantobediffer-
found
ent lithium phases in the heat-treated black mass. Therefore, a
in Figure 12. It can be seen that lithium compounds in the heat-treated black mass kinetic trial can be found
of the
inAr-pyrolyzed
Figure 12. It can be seen
battery cellsthat lithium
dissolve as compounds
ions instantly. in the heat-treated
Although black mass
the lithium yield of
canthebe
Ar-pyrolyzed battery cells dissolve as ions instantly. Although the lithium
found below Figure 12, it cannot be directly transferred to the other neutral leaching17trials yield can be
Metals 2021, 11, 177 of 30
found
since below Figureof12,heat-treated
the amount it cannot beblack
directly transferred
mass, to the other
and therefore neutral leaching
the lithium-bearing trials
input is
since the amount
reduced each time of aheat-treated black mass,
sample is taken. Samples andweretherefore
takenthe
from lithium-bearing input is
the leaching liquor by
reduced each time
using a particle a sample
filter, is taken. Samples
why redirecting were taken
the lost particles from
to the the was
liquid leaching liquor byIn
not possible.
using
using
an a particle
a particle
upscale filter,
setup,filter, why redirecting
why redirecting
this mass the
reduction would lost
the lost particles
particles
show to the
to the
a lower liquid
liquid
impact. was
Thewas not possible.
not possible.
calculation InIn
of lith-
an upscale
an upscale
ium setup,
yields issetup, this
basedthis mass
on mass reduction
reduction
a reduced would
leaching show
would a
show
liquor lower impact.
a lower
volume by impact. The calculation of
The calculation
sample extraction. lith-
The last of
ium yields
lithium is based
yields is on
based a reduced
on a leaching
reduced liquor
leaching volume
liquor by
volume sample
sample is taken, at 125 min, shows increased lithium mass, which can be explained byby extraction.
sample The
extraction. last
The
sample is taken,
last sample
analytical at 125
is taken,
deviations. at min, shows
125 min, increased
shows increasedlithium
lithiummass, which
mass, which cancanbebeexplained
explainedby by
analytical
analyticaldeviations.
deviations.
1.A.26
0.5 1.A.26
0.5
Li in solution [g]

0.4
Li in solution [g]

0.4
0.3
0.3
0.2
0.2
0.1
0.1
0.0
0.0 0 10 20 30 40 50 60 70 80 90 100 110 120 130
0 10 20 30 40 50 Time
60 70 80 90 100 110 120 130
[min.]
Time [min.]
120 min., 1:30, < 1mm, no filtration, flushed
120 min., 1:30, < 1mm, no filtration, flushed
Li in input: 0.52 g, Li-yield=70%
Li in input: 0.52 g, Li-yield=70%

Figure 12. Kinetic trial for lithium dissolution in deionized H2O at an s/l ratio of 1:30.
Figure
Figure12.
12.Kinetic
Kinetictrial
trialfor
forlithium
lithiumdissolution
dissolutioninindeionized
deionizedHH
2O
2Oatatanans/ls/l
ratio of of
ratio 1:30.
1:30.
4. Particle size of heat-treated black mass:
4.4. Particle
Particlesizesizeofofheat-treated
heat-treatedblackblackmass:
mass:
As already reported, 99.3% of black mass particles have a grain size below 101.74 µm.
AsAsalready
alreadyreported,
reported,99.3%99.3%ofofblack
blackmass
massparticles
particleshave
havea agrain
grainsize
sizebelow
below101.74
101.74µm.µm.
In order to reduce the grain size of the few particles above this threshold, the heat-treated
In order
Inblack
ordermassto reduce
to reduce the grain
the grain size size of the
of the fewfew particles
particles above
above thisthis threshold,
this approach
threshold,was the heat-treated
the heat-treated
blackmass
masswas was ground
groundinin
wasground inaaaplanetary
planetary
planetary mill. The
mill.The aim
aimofof
Theaim ofthis
thisapproach
approachwas wastoto detect
todetect
detectthe the
the
black
correlation between smaller grain size mill.
and an eased liberation of lithium
correlationbetween
correlation betweensmaller
smallergrain
grainsize
sizeandandananeased
easedliberation
liberationofoflithium compoundsinin
compounds
lithiumcompounds in
neutral
neutral leaching.
leaching. InInFigure
Figure 13a, nono
13a, difference with
difference or without
with or withoutgrinding
grindingis detected.
is In Fig-
detected. In
neutral
ure leaching.
13b, thisthis In Figure
trend shows 13a, no difference
slightly irregular with or without
behavior when grinding istrial
comparing detected.
1.A.19 In Fig-
Figure
ure 13b, 13b,
this trendtrend
showsshows slightly
slightly irregular
irregular behavior
behavior when
when comparing
comparing trial 1.A.19toto
trial1.A.19 trial
totrial
trial
1.A.20.
1.A.20. However,
However, in
in no
no parameter
parameter combination
combination and
and hence,
hence, trial
trial pair
pair compared,
compared, grinding
grinding
1.A.20.
to <90 However,
µm has in noan
shown parameter
improved combination
lithium andThis
yield. hence,
can trial
be pair compared,
explained by the grinding
grain size
to<90
<90µmµmhas
todistribution hasshown
shownan animproved
improvedlithium
lithiumyield.
yield.This
Thiscancanbebeexplained
explainedby bythethegrain
grainsizesize
shown
distributionshown before:
shownbefore: The
before:The majority
Themajority of
majorityofofthethe particles
theparticles shows
particlesshows grain
showsgrain sizes
grainsizes below
sizesbelow
below100100
100µm.µm.
µm.
distribution
Parameter 4: Particle size
Parameter 4: Particle size
(1:15)
Parameter 4: Particle size
Parameter(1:22.5)
4: Particle size 100% (1:15)

100% (1:22.5) 100%

80%
100% 80%
80%
60% 46%
80% 57% 54% 53% 52% 57% 53% 45% 45%
60% 60% 39% 46%
57% 54% 53% 52% 57% 53% 40% 45% 45%
60% 39%
40% 40%
40% 20%
20% 20%
20% 0%
0%
0% 0% 1.A.8 1.A.9 1.A.19 1.A.20
1.A.2 1.A.3 1.A.4 1.A.5 1.A.6 1.A.7
1.A.2 1.A.3 1.A.4 1.A.5 1.A.6 1.A.7 1.A.8 1.A.9 1.A.19 1.A.20
90 min., 1:15, no 30 min., 1:15, no
30 min., 1:22.5, no filtration, not washed
90 min., 1:15,not
filtration, no 30 min., 1:15,
filtration, no
washed
30 min., 1:22.5, no filtration, not washed
<90µm <1mm filtration,
washednot filtration, washed
<90µm <1mm washed
<90µm <1mm <90µm <1mm
<90µm <1mm <90µm <1mm
(a) (b)
(a) (b)
Figure 13. Detailed observation on achievable lithium yields by neutral leaching (H2 O) of heat-treated black mass. The
considered parameter is parameter 4: particle size. (a) Dissolution and lithium recovery by comparing trials with a
solid/liquid ratio of 1:22.5. (b) Dissolution and lithium recovery by comparing trials with solid/liquid ratio of 1:15.

Comparing trials 1.A.2-1.A.4 with trials 1.A.5-1.A.7 and trial 1.A.8 with trial 1.A.20
reveals that the grain size of the heat-treated black mass does not influence lithium yields.
This is particularly interesting for residual lithiation in the anode. It proves that the degree
of liberation of lithium is not enhanced by grain size reduction to <90 µm.
 considered parameter is parameter 4: particle size. (a) Dissolution and lithium recovery by comparing trials with a
solid/liquid ratio of 1:22.5. (b) Dissolution and lithium recovery by comparing trials with solid/liquid ratio of 1:15.

Comparing trials 1.A.2-1.A.4 with trials 1.A.5-1.A.7 and trial 1.A.8 with trial 1.A.20
Metals 2021, 11, 177 reveals that the grain size of the heat-treated black mass does not influence lithium yields.
18 of 30
This is particularly interesting for residual lithiation in the anode. It proves that the degree
of liberation of lithium is not enhanced by grain size reduction to <90 µm.
5.5. Solid/liquid
Solid/liquidratio
ratio(g/mL):
(g/mL):
At a constant grain size and leaching time, higher lithium yields are obtained at a
At a constant grain size and leaching time, higher lithium yields are obtained at a
solid/liquid ratio of 1:30 in comparison to 1:10 and 1:15 (see Figure 14a). In addition, an
solid/liquid ratio of 1:30 in comparison to 1:10 and 1:15 (see Figure 14a). In addition, an
improved lithium recovery is possible when comparing a solid/liquid ratio of 1:30 and
improved lithium recovery is possible when comparing a solid/liquid ratio of 1:30 and
1:22.5 (see Figure 14b). Although the leaching time has not shown an impact, the highest
1:22.5 (see Figure 14b). Although the leaching time has not shown an impact, the highest
yield is reached with a solid/liquid ratio of 1:30 for 120 min. (see trial 1.A.25). When con-
yield is reached with a solid/liquid ratio of 1:30 for 120 min. (see trial 1.A.25). When
sidering the solubility product of lithium carbonate in the water at 20 °C (13.3 g/L), and a
considering the solubility product of lithium carbonate in the water at 20 ◦ C (13.3 g/L),
lithium share of 3.7 wt%, a liquid volume of 294 mL is required for full
and a lithium share of 3.7 wt%, a liquid volume of 294 mL is required for full dissolution, dissolution, as-
suming an inserted heat-treated black mass weight of 20 g. Thus, if all
assuming an inserted heat-treated black mass weight of 20 g. Thus, if all lithium is presentlithium is present
as
aslithium
lithiumcarbonate,
carbonate, aa solid/liquid
solid/liquidratioratioof
of1:15
1:15g/mL
g/mLisisneeded.
needed.SinceSincethe theinput
inputmaterial
material
(heat-treated black mass) shows deviations in lithium shares and phases,
(heat-treated black mass) shows deviations in lithium shares and phases, the findings the findingsofofa
a1:30
1:30solid/liquid
solid/liquid ratio
ratio are
are supported.
supported. ThisThis means
means thatthat an
an excess
excess of of H
H22O
Oisisneeded
neededfor forhigh
high
lithium dissolution. In Figure 14, examples of the solid/liquid ratio´s
lithium dissolution. In Figure 14, examples of the solid/liquid ratio’s impact on lithium impact on lithium
yields
yieldsare
aregiven.
given.More
Moretrialtrialcomparisons
comparisons would
would bebe
1.A.11
1.A.11withwitha yield of 38%
a yield at aatratio
of 38% of
a ratio
1:10, and 1.A.10 with a yield of 44% at a ratio of 1:15. There are also trial
of 1:10, and 1.A.10 with a yield of 44% at a ratio of 1:15. There are also trial combinations combinations
where
wherean anincrease
increaseofof the
the solid/liquid
solid/liquidratioratioleads
leadstotoequal
equallithium
lithiumyields
yields(e.g.,
(e.g.,1.A.15
1.A.15with
with
1.A.9,
1.A.9,leading
leadingtoto45%
45%lithium
lithiumyield),
yield),but
butgenerally,
generally, yields
yields of of >60%
>60%can canbe bereached
reachedonlyonly
when
whenhaving
having2020g/600
g/600mL mL(1:30).
(1:30).

Parameter 5: s/l Parameter 5: s/l

(120 minutes) (30 minutes)
100% 100%

80% 80%
64% 61%
60% 53% 52% 60% 54% 55% 54%

40% 40%
20% 20%
0% 0%
1.A.28 1.A.27 1.A.25 1.A.32 1.A.33 1.A.23 1.A.24
1:10 1:15 1:30 1:10 1:15 1:22.5 1:30
<1mm, not filtrated, washed <1mm, not filtrated, washed

(a) (b)
Figure14.
Figure Detailedobservation
14. Detailed observationon onachievable
achievablelithium
lithiumyields
yieldsby
by neutral
neutral leaching
leaching (H(H22O)
O)of
ofheat-treated
heat-treatedblack
black mass.
mass. The
The
considered
considered parameter
parameter isis parameter
parameter 5:
5: particle
particle size.
size. (a)
(a)Dissolution
Dissolutionand
andlithium
lithiumrecovery
recoverybybycomparing
comparingtrials
trialswith
with aa
solid/liquid
solid/liquidratio
ratioofof1:22.5.
1:22.5.(b)
(b)Dissolution
Dissolutionand
andlithium
lithiumrecovery
recoveryby
bycomparing
comparingtrials
trialswith
withsolid/liquid
solid/liquidratio ofof
ratio 1:15.
1:15.

6.6. Pyrolysistemperature:
Pyrolysis temperature:
The
The pyrolysistemperature
pyrolysis temperatureplays
playsananimportant
importantrole
rolein
inlithium
lithiumrecovery,
recovery,asascan
canbebeseen
seen
in
inFigure
Figure15.
15.Here,
Here,the
thedifference
differencebetween
betweenaa501 501and
andaa603
603°C◦ Cpyrolyzed
pyrolyzedmaterial
materialisispointed
pointed
out.
out.Reaching
Reachinghigher
highertemperatures
temperaturesleadsleadstotodifferent
differentphase
phase transformations
transformationswithin
within the
the
battery
battery cells. The impact on lithium leaching efficiency and lithium yield as solidlithium
cells. The impact on lithium leaching efficiency and lithium yield as solid lithium
carbonate
carbonateisisproven
provenbybydifferent
differentscenarios:
scenarios:
Here, both grain size and leaching time do not show a significant impact on the yield.
The solid/liquid ratio, along with the washing of the C-filter cake and the solid–liquid-
separation method (filtration vs. full boiling), seems to play an important role in this
context. Up to 64% of lithium can be recovered as lithium carbonate. In addition, the
parameter pyrolysis temperature has an impact on the lithium yield. Lithium yields by
leaching heat-treated black mass without preliminary pyrolysis were not satisfying; hence,
these first trials are not shown in this manuscript. It must be recalled that the pyrolysis
trials at Ar-atmosphere were operated at higher temperatures than the CO2 and Ar + O2
pyrolysis trials.
Metals
Metals2021, 11,11,
2021, 177x FOR PEER REVIEW 1919
ofof
3030

Parameter 6: Pyrolysis
Parameter 6: Pyrolysis temperature temperature
(30 minutes) (120 minutes)
100%
100%
80%
54% 80%
60% 47% 52%
46% 53%
60% 45%
40% 32%
27%
40%
20%
20%
0%
1.A.21 1.A.39 1.A.22 1.A.17 1.A.36 1.A.32 0%
1.A.31 1.A.40
Not filtrated, not
Filtrated, washed Not filtrated, washed
washed
1:10, <1mm Filtrated, washed, 1:10, <1mm

501 °C 501 °C

603 °C 603 °C

(a) (b)
Figure15.15.Detailed
Figure Detailedobservation
observationononachievable
achievablelithium
lithiumyields
yieldsbyby neutral
neutral leaching
leaching (H(H 2O)
2 O) ofofheat-treated
heat-treatedblack
blackmass.
mass.The
The
consideredparameter
considered parameterisisparameter
parameter6: 6:particle
particlesize.
size.(a)
(a)Dissolution
Dissolutionand
andlithium
lithiumrecovery
recoveryby bycomparing
comparingtrials
trialswith
witha a
solid/liquidratio
solid/liquid ratioofof1:22.5.
1:22.5.(b)
(b)Dissolution
Dissolutionand
andlithium
lithiumrecovery
recoveryby bycomparing
comparingtrials
trialswith
withsolid/liquid
solid/liquidratio
ratioof
of1:15.
1:15.

Here,
For both grain
evaluating size andtrials
autoclave leaching time do
in terms not showmobilization,
of lithium a significant impact
the lithiumon the yield.
yields
The neutral
from solid/liquid
leachingratio,
arealongto be with the washing
contrasted of the C-filter
to the lithium yields from cakeautoclave
and the solid–liquid-
trials using
separation
the method (filtration
same parameters (see Figure vs.16).
fullSince
boiling), seems to play
the autoclave trialsan wereimportant
operated role
at in this con-
a holding
time
text.ofUp
120tomin,
64%the following
of lithium candiagram
be recoveredpointsas out the achievable
lithium carbonate. maximum
In addition,lithium
the yields
param-
dependent on the
eter pyrolysis pyrolysishas
temperature temperature/atmosphere
an impact on the lithium andyield.
solid/liquid
Lithiumratio yields examined
by leachingin
Metals 2021, 11, x FOR PEER REVIEWthe autoclave trials.
heat-treated Hereby,
black mass a direct
without comparison
preliminary betweenwere
pyrolysis neutral notleaching
satisfying; 20 of
(experimental
hence, 30
these
series 1.A, 1.O and 1.C) and autoclave carbonation (2.A) can be
first trials are not shown in this manuscript. It must be recalled that the pyrolysis trials at performed.
Ar-atmosphere were operated at higher temperatures than the CO2 and Ar + O2 pyrolysis
Atmosphere trials. Ar Ar 95 % Ar + 5 % O2 CO2
For evaluating autoclave trials in terms of lithium mobilization, the lithium yields
Targeted temperatures on cell
from neutral leaching are to be contrasted to the lithium yields from autoclave trials using
surface during thermalthe pre-
same 509 °C
parameters (see603 °C
Figure 16). Since the501 °C
autoclave trials were 466 operated
°C at a holding
treatment time of 120 min, the following diagram points out the achievable maximum lithium yields
dependent on the pyrolysis temperature/atmosphere and solid/liquid ratio examined in
Parameter 2: Best of Pyrolysis atmosphere
the
100%
autoclave trials. Hereby, a direct comparison between neutral leaching (experimental
series
80%
1.A, 1.O and 1.C) and autoclave carbonation (2.A) can be performed.
the focus of64%
Li-yield [%]

60%
Since52% this study 53% was the Ar-pyrolyzed material since showing the best
neutral
40%
leaching results, only for this material 37% the solid/liquid 29%
ratios were29%
examined in the
autoclave
20%
trials (1:10, 1:15, 1:30) (series 2.A, 2.O and 2.C). The CO 2- and Ar + O2 -the pyro-

lyzed
0%
black mass was only treated in the autoclave carbonation set up with a solid/liquid
ratio of 1:10
1.A.36(2.O and 2.C).
1.A.25 Hence, 1.A.28 Figure 17 sums 1.A.30up the maximum
1.A.38 yields
1.A.29of neutral leach-

ing dependent on the pyrolysis parameters examined so far:

Not filtrated, Not filtrated, Not filtrated, Filtrated, Filtrated, Filtrated,
washed, 1:10, washed, 1:30, washed, 1:10, washed, 1:10, washed, 1:10, washed, 1:10,
30 min. 120 min. 120 min. 120 min. 30 min. 120 min.

Figure 16. Best of lithium

lithium yields
yieldsdependent
dependenton
onthe
thepyrolysis
pyrolysisatmospheres and
atmospheres temperatures.
and 1.A.36
temperatures. hashas
1.A.36 notnot
been leached
been for
leached
for 120
120 min,min,
yet.yet.

Since the focus

3.2. Carbonation of this study
by Supercritical COwas2 the Ar-pyrolyzed material since showing the best
neutral leaching results, only for this
Finally, the obtained lithium yields when using material the solid/liquid ratios were
autoclave treatments examined
with in
an s/l ratio
the1:10
of autoclave trials
for lithium (1:10, 1:15,can
carbonation 1:30) (series 2.A,
be derived from2.O and 17.
Figure 2.C). The CO2 - and Ar + O2
-the pyrolyzed black mass was only treated in the autoclave carbonation set up with a
solid/liquid ratio of 1:10 (2.O and 2.C). Hence, Figure 17 sums up the maximum yields of
Li-yields 2.A, s/l =1:10, with filtration
neutral
100%
leaching dependent on the pyrolysis parameters examined so far:

74% 77%
80%
64% 65% 64% 63% 66% 64%
59% 60%
60%

40%

20%

0%
 30 min. 120 min. 120 min. 120 min. 30 min. 120 min.

Figure 16. Best of lithium yields dependent on the pyrolysis atmospheres and temperatures. 1.A.36 has not been leached
for 120 min, yet.

Metals 2021, 11, 177 3.2. Carbonation by Supercritical CO2 20 of 30

Finally, the obtained lithium yields when using autoclave treatments with an s/l ratio
of 1:10 for lithium carbonation can be derived from Figure 17.

Li-yields 2.A, s/l =1:10, with filtration

100%

74% 77%
80%
64% 65% 64% 63% 66% 64%
59% 60%
60%

40%

20%

0%
T0 2.A T1 2.A T2 2.A T3 2.A T4 2.O T5 2.O T6 2.O T7 2.C T8 2.C T9 2.C

Ar-pyrolysis Ar+O2-thermolysis CO2-thermolysis

Figure 17.
Figure 17.Lithium
Lithiumyields obtained
yields by autoclave
obtained carbonation
by autoclave with a solid/liquid
carbonation ratio of 1:10 ratio
with a solid/liquid for of 1:10 for
trials series 2.A (T0–T3, blue), 2.O (T4–T6, orange) and 2.C (T7-9, violet). Trial T0 2.A stands for an
trials series 2.A (T0–T3, blue), 2.O (T4–T6, orange) and 2.C (T7-9, violet). Trial T0 2.A stands for an
Ar-pyrolysis at 509 °C, whereas T1–T3 2.A stands for an Ar-pyrolysis at 603 °C.
Ar-pyrolysis at 509 ◦ C, whereas T1–T3 2.A stands for an Ar-pyrolysis at 603 ◦ C.
Hence, a direct comparison between the atmospheres of the thermal treatments
3.2. Carbonation by Supercritical CO2
shows the following results: The 509 °C Ar-pyrolysis, that the autoclave can make a 12%
Finally,
difference the obtained
in lithium lithium
yield. In yieldstowhen
comparison the 603using autoclave treatments
°C Ar-pyrolysis, withcan
this difference an s/l ratio
of 1:10upfor
reach tolithium
24% with carbonation can be derived
the correct parameter from Figure
combination 17. For the Ar + O2-py-
(120 min.).
Hence,
rolysis, whichaisdirect comparison
here indicated between the
as thermolysis sinceatmospheres
comprising of O2 the thermal
in the treatments
atmosphere, the shows
the following
increased results:
lithium yieldThe 509 ◦ Cup
comprises Ar-pyrolysis,
to 27%. For the thatCOthe2-pyrolysis,
autoclavethe canobtained
make a 12% difference
differ-
ence
in in lithium
lithium yield
yield. In comprises
comparison up to 37%. This◦ C
the 603 indicates higher lithium
Ar-pyrolysis, yields forcan
this difference reduc-
reach up to
tive pyrolysis
24% with the atmosphere (CO2 vs.combination
correct parameter Ar-atmosphere (120atmin.).
~500 °C)Forand
the aArstronger impact of which is
+ O2 -pyrolysis,
autoclave
here carbonation
indicated when dealing
as thermolysis sincewith a not fullyO
comprising decomposed
in the heat-treated
atmosphere, black
the mass. lithium
increased
2
This correlation needs further investigations in the future.
yield comprises up to 27%. For the CO2 -pyrolysis, the obtained difference in lithium
The elemental lithium distribution and the lithium carbonate impurities are shown
yield comprises up to 37%. This indicates higher lithium yields for reductive pyrolysis
exemplarily for the trial series 1.A with a solid/liquid ratio of 1:10. In Figure 18, the largest
atmosphere (CO2 vs. Ar-atmosphere at ~500 ◦ C) and a stronger impact of autoclave
part of lithium remains in the heat-treated black mass after leaching. Moreover, the main
carbonation
impurity of the when dealing
recovered withcarbonate
lithium a not fully decomposed
is fluorine, followed heat-treated blackThis
by phosphorous. mass. This
correlation needs further investigations in the future.
can be explained by the presence of LiF in the heat-treated black mass. It should be noted
The elemental lithium distribution and the lithium carbonate impurities are shown
exemplarily for the trial series 1.A with a solid/liquid ratio of 1:10. In Figure 18, the largest
Metals 2021, 11, x FOR PEER REVIEW 21 of 30
part of lithium remains in the heat-treated black mass after leaching. Moreover, the main
impurity of the recovered lithium carbonate is fluorine, followed by phosphorous. This
can be explained by the presence of LiF in the heat-treated black mass. It should be noted
that thethe
that value “Li “Li
value in filtrate” does does
in filtrate” only occur
only within neutral neutral
occur within leachingleaching
and autoclave trials
and autoclave trials
T0–T9 and T21 and T22, which have conducted a filtration.
T0–T9 and T21 and T22, which have conducted a filtration.

Li-distribution (reference trials, without carbonation) 1.05 g

Li in input
0.08 g
Li in filtrate
1.79 g
Li in C-filter cake

Li in Li-filter cake
0.664 g
Impurities Li-filter cake
4.0 160
3.5 140
3.0 120
2.5 100
[wt.%]

[mg]

2.0 80
1.5 60
1.0 40
0.5 20
0.0 0
total F P Ni Co Mn Fe Cu Al
wt.% 3.73 3.62 0.11 0.00714 0 0 0 0 0
mass [mg] 140.48 136.14 4.07 0.27 0.00 0.00 0.00 0.00 0.00

Figure
Figure 18.18.
Lithium distribution
Lithium without
distribution autoclave
without carbonation
autoclave as exemplary
carbonation data fromdata
as exemplary the from
param-
the parameter
eter set 1.A.1 by ICP-OES. (Above): Ar-pyrolysis in combination with neutral leaching at a
set 1.A.1 by ICP-OES. (Above): Ar-pyrolysis in combination with neutral leaching at a solid/liquid
solid/liquid ratio of 1:10. (Below): Matching impurities within the lithium filter cake by ICP-OES
ratio
and of 1:10.
lithium (Below):
carbonate Matching impurities within the lithium filter cake by ICP-OES and lithium
impurities.
carbonate impurities.
Figure 19 shows the improvement in Li distribution when applying autoclave car-
bonation. Trials series 2.A was selected since the neutral leaching trials of Ar-pyrolyzed
active mass at 600 °C has shown the best yields. Trial series 2.A represents Ar-pyrolysis,
with a CO2 + H2O autoclave-reaction, and also a solid/liquid ratio of 1:10 in the autoclave.
In this case, the share in the residual heat-treated black mass filter cake is significantly
lower, which is a proof-of-concept of the carbonation mechanism within the autoclave.
 total F P Ni Co Mn Fe Cu Al
wt.% 3.73 3.62 0.11 0.00714 0 0 0 0 0
mass [mg] 140.48 136.14 4.07 0.27 0.00 0.00 0.00 0.00 0.00

Figure 18. Lithium distribution without autoclave carbonation as exemplary data from the param-
eter set 1.A.1 by ICP-OES. (Above): Ar-pyrolysis in combination with neutral leaching at a
Metals 2021, 11, 177 21 of 30
solid/liquid ratio of 1:10. (Below): Matching impurities within the lithium filter cake by ICP-OES
and lithium carbonate impurities.

Figure 19 shows the improvement in Li distribution when applying autoclave car-

Figure 19 shows the improvement in Li distribution when applying autoclave carbon-
bonation. Trials series 2.A was selected since the neutral leaching trials of Ar-pyrolyzed
ation. Trials series 2.A was selected since the neutral leaching trials of Ar-pyrolyzed active
active mass at◦600 °C has shown the best yields. Trial series 2.A represents Ar-pyrolysis,
mass at 600 C has shown the best yields. Trial series 2.A represents Ar-pyrolysis, with a
with a CO2 + H2O autoclave-reaction, and also a solid/liquid ratio of 1:10 in the autoclave.
CO + H O autoclave-reaction, and also a solid/liquid ratio of 1:10 in the autoclave. In
In this2 case,2 the share in the residual heat-treated black mass filter cake is significantly
this case, the share in the residual heat-treated black mass filter cake is significantly lower,
lower, which is a proof-of-concept of the carbonation mechanism within the autoclave.
which is a proof-of-concept of the carbonation mechanism within the autoclave.

Figure 19.19.
Figure Lithium
Lithium distribution with
distribution autoclave
with carbonation
autoclave as exemplary
carbonation data
as exemplary from
data fromthethe
parameter
parameter
setset
2.A2.A
(T2(T2
2.A)2.A)
by ICP-OES. (Above):
by ICP-OES. Ar-pyrolysis
(Above): in combination
Ar-pyrolysis with neutral
in combination leaching
with neutral with with
leaching
carbonation
carbonation by by
supercritical CO2CO
supercritical + aqueous medium at a solid/liquid ratio of 1:10). (Below):
2 + aqueous medium at a solid/liquid ratio of 1:10). (Below):
matching impurities within the lithium filter cake.
matching impurities within the lithium filter cake.

Hence,
Hence,impurities
impurities inin
the range
the rangeofof
2–4 wt.%
2–4 wt.%can bebe
can derived.
derived. AnAn XRD-evaluation
XRD-evaluationgives
gives
more information on the arising phases within the heat-treated black mass, the
more information on the arising phases within the heat-treated black mass, the C-filter cakeC-filter
cake
andand
thethe lithium
lithium carbonate
carbonate filter
filter cakecake
(see(see Figure
Figure 20). 20).
ThisThis is represented
is represented herehere exem-
exemplarily
by the 603 ◦ C-Ar-pyrolyzed samples, thus for trial series 2.A, also with a solid/liquid ratio
of 1:10. One main finding is the removal of Li2 CO3 , present in the heat-treated black mass,
from the C-filter cake. This is an indicator for the removal of water-soluble compounds. In
contrast to Figure 20, XRD-evaluations of CO2 -pyrolyzed black mass at 466 ◦ C and Ar +
O2 -pyrolyzed black mass at 501 ◦ C also detect LiNiMnO- and the NiO, which stands for an
incomplete decomposition of transition metal oxides.
Small amounts of fluorine can be found in the Li-filter cake in the form of LiF. It can
be seen that especially fluorine removal is crucial for reaching high lithium carbonate
purities fluorine. Figure 20 shows the diffractogram of the heat-treated black mass and
the C-and Li-filter cakes (T3 2.A.). X-ray diffraction was performed at room temperature
using a STADI P (STOE Darmstadt) powder diffractometer using an IPPSD detector and
monochromatic Cu-Kα1 radiation (λ = 1.54059 Å; flat sample; 1.5 ≤ 2θ ≤ 116◦ step rate
0.015◦ in 2θ) with a measuring time of 2 h.
LiF was still present in the C-filter cake; hence, the solid/liquid ratio was optimized.
In order to prove influencing factors on the lithium yield by an adjusted solid/liquid ratio,
the parameter 1:15 (solubility of 13.3 g/L lithium carbonate at 20 ◦ C) and 1:30 (solubility of
7.2 g/L lithium carbonate at 100 ◦ C) were tested. Moreover, to prove the mechanism of
autoclave carbonation, two parameters were examined additionally: autoclave carbonation
by Ar-excess pressure (3.A) and direct and dry autoclave carbonation by CO2 -excess
pressure (4.A). Again, since the Ar-pyrolyzed black mass has shown the highest yields in
terms of neutral leaching and in terms of autoclave carbonation, only Ar-pyrolyzed black
mass is chosen for the parameter improvements.
Table 5 sums up the parameters for the second autoclave carbonation with solid/liquid
ratios of 1:15 and 1:30.
 Small amounts of fluorine can be found in the Li-filter cake in the form of LiF. It can
be seen that especially fluorine removal is crucial for reaching high lithium carbonate pu-
rities fluorine. Figure 20 shows the diffractogram of the heat-treated black mass and the
C-and Li-filter cakes (T3 2.A.). X-ray diffraction was performed at room temperature using
Metals 2021, 11, 177 a STADI P (STOE Darmstadt) powder diffractometer using an IPPSD detector and 22 of 30
mono-
chromatic Cu-Kα1 radiation (λ = 1.54059 Å; flat sample; 1.5 ≤ 2θ ≤ 116° step rate 0.015° in
2θ) with a measuring time of 2 h.

(a) (b)

(c)
Figure20.
Figure 20.Graphic
Graphicpattern
patternofof the
the Ar-pyrolyzed
Ar-pyrolyzed black
black mass
mass at 603
at 603 °C (a),
◦ C (a), andand the corresponding
the corresponding C-filter
C-filter cakeand
cake (b) (b)Li-filter
and Li-
filter cake (c) from trial T3 2.A. The XRD-evaluation was performed using the “match!” Software and the COD
cake (c) from trial T3 2.A. The XRD-evaluation was performed using the “match!” Software and the COD Inorganics database. Inorganics
database.
Table 5. Detailed list of parameters examined for autoclave trials T10–T13 (3.A), T14–T16, T18, T19, T21 and T22 (2.A), and
T17 and T20 (4.A) with a solid/liquid LiFratio
was of
still
1:15present inIn
and 1:30. the C-filter
T17/20 s/l cake; hence,
ratio refers to the solid/liquid
leaching ratio was
after autoclave optimized.
treatment.
In order to prove influencing factors on the lithium yield by an adjusted solid/liquid ratio,
Solid/Liquid Ratio (s/l) (g/mL) H2 O in Autoclave Autoclave Gas Washing C-Filter Cake with H2 O
the parameter 1:15 (solubility of 13.3 g/L lithium carbonate at 20 °C) and 1:30 (solubility
T10 1:15 yes
of 7.2 g/L lithium carbonate Ar tested. Moreover, to prove
at 100 °C) were nothe mechanism of
T11 1:15 autoclave carbonation, two parameters were examined additionally: no
yes Ar autoclave carbona-
T12 1:15 yes Ar no
tion by Ar-excess pressure (3.A) and direct and dry autoclave carbonation by CO2-excess
T13 1:15 yes Ar no
T14 1:15 pressure (4.A). Again,
yes since the Ar-pyrolyzed
CO black mass has shown the
no highest yields in
2
T15 1:15 yes CO2 yes
T16 1:15 yes CO2 no
T17 1:30 no CO2 no
T18 1:30 yes CO2 yes
T19 1:30 yes CO2 yes
T20 1:30 no CO2 yes
T21 1:15 yes CO2 no
T22 1:30 yes CO2 no

The following illustration (see Figure 21) shows the results of autoclave carbonation
with solid/liquid ratios of 1:15 and 1:30:
 T19 1:30 yes CO2 yes
T20 1:30 no CO2 yes
T21 1:15 yes CO2 no
T22 1:30 yes CO2 no

Metals 2021, 11, 177 23 of 30

The following illustration (see Figure 21) shows the results of autoclave carbonation
with solid/liquid ratios of 1:15 and 1:30:

Li-yields by autoclave carbonation

100%
3.A 1:15
90% (Ar + H2O)
79%
80%
70% 70% 4.A 1:30
68% 68%
70% (CO2 dry)
60% 57% 57%
53% 2.A 1:15
48%
50% (CO2 + H2O)
40% 42%
40%
2.A 1:30
30% 27%
(CO2 + H2O)
20% 15%

10%

0%
T10 T11 T12 T13 T14 T15 T16 T17 T18 T19 T20 T21 T22

Figure
Figure21.
21. Lithium
Lithiumyields
yields obtained
obtainedby by autoclave
autoclave carbonation
carbonationwith
with aa solid/liquid
solid/liquidratio
ratioofof1:15
1:15(T10–T16,
(T10–T16,and
andT21)
T21)or
or1:30
1:30
(T17–T20,
(T17–T20, and T22). The C-filter-cakes of T15, T18 and T19 were washed, T17 was leached for 5 min and T20 for 90 min.min.
and T22). The C-filter-cakes of T15, T18 and T19 were washed, T17 was leached for 5 min and T20 for 90 T21
T21
andand
T22T22
werewere filtrated
filtrated instead
instead of fully
of fully boiled.
boiled.

Thus,
Thus,the
the only process
process window
windowleading
leadingtotosatisfying
satisfying yields
yields of 79%
of 79% is s/l
is an an ratio
s/l ratio of
of 1:30
1:30 in combination
in combination withwith
CO2CO 2 carbonation
carbonation inaquatic
in an an aquatic medium.
medium. TheThe underlying
underlying mecha-
mechanism
nism
seems seems
to beto be indirect
indirect carbonation.
carbonation.
This
Thiscan
canbebesupported
supportedby bythe
thedetected
detectedpHpHvalue
valueofofall
alltrials.
trials.Whereas
Whereas1.A.1—1.A.40,
1.A.1—1.A.40,
T10–T13,
T10–T13,and andT20
T20(without
(withoutCO CO2 2purging
purgingininthe
theliquid)
liquid)showed
showedaapH pHvalue
valueof of11–12
11–12after
after
charging
chargingheat-treated
heat-treated black
black mass in H22O, O, the trials T0–T9. T14–T16, T18/T19
T18/T19 and T21/T22
T21/T22
(withCO
(with CO2 2purging
purgingininthe theliquid)
liquid)showed
showedaapH pHvalue
valueofof 7–8
7–8 after
after charging
charging heat-treated
heat-treated
blackmass
black massin inHH22O.
O.Hence,
Hence,CO CO2 2was
wasdissolved
dissolvedininthe
theliquid.
liquid.The
Thegenerally
generallyhigher
higheryields
yieldsinin
T10–T20can
T10–T20 canalso
alsobe beattributed
attributedto tothe
theavoidance
avoidanceof ofaasecond
secondfiltration
filtrationstep
stepfor
forrecovering
recovering
lithium.Instead,
lithium. Instead,the thesolution
solutionwaswasboiled
boileduntil
untilreaching
reachingaaslurry-state
slurry-stateandandthen
thenwaswasdried
dried
in a beaker. Hereby, lithium losses in the residual filtrate are avoided. In addition, when
comparing T17 to T20, the advantage of a longer leaching time and washing of the carbon
filter cake with deionized H2 O is shown. The washing of the carbon filter cake generally
leads to higher yields since dissolved lithium remaining in the filter cakes in the solution
can leave the system just by washing. However, comparing T15 to T14 and T16 in terms of
C-filter cake washing reveals a rather small impact on the lithium yields (max. 2%). When
comparing T21 to T14 and to T16, it can be seen that filtrating of the lithium solution is not
expedient. This can be explained by the residual lithium dissolution in the filtrate. The
comparison between T22 and T18–T19 confirms this relation. T21 and T22 show very low
yields. Although the lithium filter cake was filtrated instead of full boiling and the C-filter
cake was not washed, their lithium yield shows disproportionally low yields, which can
only be explained by heterogeneity in the heat-treated black mass.

4. Discussion
This study proves the concept of indirect carbonation for treating lithium-ion battery
heat-treated black mass with supercritical CO2 . The involvement of supercritical CO2
in terms of lithium carbonate generation is supported by yields comparing Ar-excess
pressure and CO2 -excess pressure. Moreover, indirect carbonation is shown by comparing
a dry autoclave process to a liquid-based autoclave process. The lower pH-value of
pH = 7–8 when applying CO2 in comparison to H2 O-leaching (pH = 11–12) can lead to the
following statements:
1. When leaching heat-treated black mass in H2 O, the solution is basic. This can be
attributed to the dissolution of basic phases in the liquid. → LiF and Li2 CO3 could be
detected in the heat-treated black mass by XRD; both phases are slightly soluble and
therefore are responsible for the elevated pH-value. Although LiOH and Li2 O could
not be detected via XRD-analysis in the heat-treated black mass, they may be present
Metals 2021, 11, 177 24 of 30

in small amounts since the SEI-layers consist of Li2 CO3 , LiF, LiOH and Li2 O [93].
However, it was shown that LiF decomposes to HF and LiOH in aqueous solutions,
which indicates Li+ + OH− in the solution.
2. When leaching heat-treated black mass in H2 O and adding CO2 -gas, the pH value of
the solution decreases to 7–8. Mechanisms are in place, which can be attributed to
CO2 and which are leading to a higher lithium leaching efficiency. In the following,
hypotheses for the underlying mechanisms are stated:
a. The formation of carbonic acid and thus the formation of CO3 2− and HCO3 −
as acidic leaching agents. CO2 is added to a basic solution; it reacts acidic
by the release of H+ ions. This pH-value decrease can be responsible for a
higher leaching efficiency by creating quasi-acidic leaching conditions similar
to conventional hydrometallurgy.
b. Recombination of Li+ , stemming from non-lithium carbonate phases like LiF,
with present CO3 2− or HCO3 − . This would entail the following suggested
equations (see Equations (19) and (20), schematically shown in Figure 22):

Li+ + CO3 2− → Li2 CO3 (19)

Li+ + HCO3 − → LiHCO3 (20)

c. A combination of both mentioned mechanisms. In this way, the dissolution
of lithium phases in the heat-treated black mass is promoted by CO2 , more
Metals 2021, 11, x FOR PEER REVIEW lithium ions can be formed to Li2 CO3 , and this effect is also promoted25
byofthe
30
increased operating temperatures and arising excess pressure.

(a) (b)
Figure
Figure22.
22.Schematic
Schematicprocess visualization
process of of
visualization indirect carbonation
indirect promoted
carbonation by by
promoted supercritical COCO
supercritical 2 based on CO32− (a)2and
− (a)
2 based on CO3
HCO3− (b) in− terms of leaching lithium-ion battery heat-treated black mass in deionized water. When increasing the solu-
and HCO3 (b) in terms of leaching lithium-ion battery heat-treated black mass in deionized water. When increasing the
tion´s temperature, lithium carbonate is precipitated as a solid lithium salt.
solution’s temperature, lithium carbonate is precipitated as a solid lithium salt.

5. Conclusions
5. Conclusions
The presented “ESLR” process, consisting of thermal treatment, mechanical commi-
The presented “ESLR” process, consisting of thermal treatment, mechanical com-
nution and a sorting step, followed by a subsequent carbonation process, results in the
minution and a sorting step, followed by a subsequent carbonation process, results in the
following scientific findings:
following scientific findings:
Carbonation by supercritical CO2 shows an increased lithium yield of around 15%.
Carbonation by supercritical CO2 shows an increased lithium yield of around 15%.
This value stems from the difference between a maximum lithium yield in neutral leach-
This value stems from the difference between a maximum lithium yield in neutral leaching
ing of 64% and a maximum lithium yield in autoclave carbonation of 79%. When express-
of 64% and a maximum lithium yield in autoclave carbonation of 79%. When expressing
ing the yield as leaching efficiency, 88% were reached. The different pyrolysis atmos-
the yield as leaching efficiency, 88% were reached. The different pyrolysis atmospheres and
pheres and temperatures show a direct influence on the lithium yield. Further key influ-
temperatures show a direct influence on the lithium yield. Further key influencing factors
encing factors for both H2O-leaching with and without CO2 are solid/liquid ratio, filter
for both H2 O-leaching with and without CO2 are solid/liquid ratio, filter cake washing
cake washing and the lithium extraction method (filtration vs. full boiling). It can be con-
cluded that the “ESLR” process shows benefits in comparison to simple H2O-leaching and
that the mechanism for indirect carbonation is beneficial. Moreover, the “ESLR” process
is a separate step to ease Ni/Co/Mn recovery and to enhance the degree of lithium mobi-
lization. Hence, the resulting lithium-reduced filter cake (C-filter cake) can be integrated
Metals 2021, 11, 177 25 of 30

and the lithium extraction method (filtration vs. full boiling). It can be concluded that the
“ESLR” process shows benefits in comparison to simple H2 O-leaching and that the mecha-
nism for indirect carbonation is beneficial. Moreover, the “ESLR” process is a separate step
to ease Ni/Co/Mn recovery and to enhance the degree of lithium mobilization. Hence, the
resulting lithium-reduced filter cake (C-filter cake) can be integrated into existing hydro-
or pyrometallurgical steps.
The process of technology relevance is shown by the following specific benefits in
contrast to the state-of-the-art:
• Conventional lithium carbonation, e.g., by Na2 CO3 , is avoided, and no further chemi-
cals are required, making lithium recovery more environmentally friendly;
• Subsequent treating the C-filter cake hydrometallurgically for metal extraction (Ni,
Co, . . . ) requires fewer leaching agents because the input mass is reduced, and hence,
fewer additives for pH-adjustments are needed;
• Moreover, in comparison to conventional hydrometallurgical lithium recovery, the
liquid volume can be fully evaporated (filtration vs. full boiling). Hereby, no lithium
remains in the solution. This is possible since no enhancement of salinity is caused
in “ESLR”;
• Lithium losses in various byproducts of chemical solution purification and metal
winning steps are avoided;
• Costly lithium extraction from a pyrometallurgy treatment and hydrometallurgical
purifying of slags is also avoided.
In contrast to other studies, the sequence of thermal and mechanical treatment is
inverted. In this study, battery cells are first thermally treated and then shredded to
extract heat-treated black mass. This procedure is safer due to the avoidance of ignition
during shredding.
Comparing lithium yields by H2 O-leaching in this study to literature, the following
statements can be given: In [74], 66% of lithium from NMC black mass are obtained by
shredding, then thermal treating and H2 O-leaching. Here, the authors rather focus on
LMO-cells and report on one trial, only reaching 66% [74]. However, in this paper, 64%
could be recovered by thermal treatment with subsequent shredding and H2 O-leaching at
a thermal treatment by 100 ◦ C lower than Xiao et al. and without costly vacuum operations.
In comparison to [46,47], where 40% of lithium could be recovered by shredding, thermal
treatment and H2 O-leaching of cathode black mass, the yield in this study are up to
24% higher.
A comparison of lithium yields by H2 O-leaching in combination with CO2 (indirect
carbonation) is not straightforward since there is no study in place using the whole black
mass from NMC-cells for this process. However, by using cathode black mass with
lignite, 85% is reached, whereas, in this study, 79% are reached. This difference might be
attributable to the neglection of anode material and/or the use of lignite instead in [46,47].
In comparison to [90], the yields in this study are 19% higher (60% vs. 79%), but yield and
matching parameters are given based on a lithium ore treatment. Only the transferability to
black mass is mentioned. However, this study also uses heat-treated black mass in contrast
to [90]. In comparison to [91], and avoidance of electrodialysis in a Li2 SO4 -solution and of
carbonation reagents could be reached.
A comparison of lithium yields by a thermal CO2 -treatment with subsequent H2 O-
leaching (direct carbonation) is hardly possible since the autoclave process in this study
worked at Tmax = 230 ◦ C, whereas literature focuses on elevated temperatures (~650–800 ◦ C [73])
with CO2 as purging instead of excess pressure; moreover, no yield calculation is given [73].
In this study, a proof-of-concept regarding the indirect carbonation using supercritical
CO2 in an autoclave could be shown.
The most important follow-up research comprises a further enhancement of lithium
yields to a value of >90%, which is necessary to make the “ESLR” a competitive process
option. Then, CO2 -driven carbonation without supercritical CO2, but by CO2 -gas purging
instead. This is crucial because the combination of thermal pretreatment and an autoclave
Metals 2021, 11, 177 26 of 30

treatment comprise high energy requirements. However, as reported in Section 1.1.1, ther-
mal conditioning is also beneficial for hydrometallurgical treatment. Hence, the connected
energy demands cannot particularly and only be counted for the “ESLR” process. First
trials with CO2 -gas instead of SCCO2 have shown lithium yields around 70%. Hereby,
insights into the role of excess pressure (73.8 bar) and high temperatures (150 ◦ C) are
possible. Moreover, this setup would imply economic benefits due to the avoidance of
high-pressure operations. This will be one topic of “Early-Stage Recovery of Lithium
from Tailored Thermal Conditioned Black Mass Part II: Mobilizing Lithium via gaseous
CO2 -Carbonation”. Moreover, a refining of the C-filter cake by flotation or acidic leaching
should be tested. Upscaling is planned for future research to test possible scale effects
due to losses on equipment surfaces, for example, on beakers after boiling the lithium
filtrate. In addition, a suitable development for removing fluorine from the heat-treated
black mass, filtrates and filter cakes would be an important tool for hazardous-free pro-
cessing, which would not harm the used equipment by developing HF-gas. Moreover,
experimental series 3.O/3.C and 4.O/4.C are to be performed. Moreover, the heat-treated
black mass-producing pyrolysis was conducted with a holding time of 60 min. This may
be optimized as well to find the perfect match in terms of temperature and holding time.

Author Contributions: Conceptualization, L.S. and B.F.; methodology, L.S.; validation, L.S., T.S.
and B.F.; formal analysis, L.S. and T.S.; investigation, L.S. and T.S.; resources, L.S. and T.S.; data
curation, L.S. and T.S.; writing—original draft preparation, L.S.; writing—review and editing, L.S.;
visualization, L.S.; supervision, B.F. All authors have read and agreed to the published version of
the manuscript.
Funding: This research was partly funded by the Research Council of Norway in the frame of the
LIBRES project (project number 282328).
Institutional Review Board Statement: Not applicable.
Data Availability Statement: The data presented in this study are available on request from the
corresponding author. The data are not publicly available since being part of active research.
Acknowledgments: In cooperation with Access e.V. EDS-analyses were enabled, and in cooperation
with the Institute of Inorganic Chemistry (IAC) at RWTH Aachen, XRD-measurements were possible.
We are grateful for the support of both partners.
Conflicts of Interest: The authors declare no conflict of interest.

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