Accepted Manuscript

Recovery of active cathode materials from lithium-ion batteries

using froth flotation

Ruiting Zhan, Zachary Oldenburg, Lei Pan

PII: S2214-9937(18)30024-1
DOI: doi:10.1016/j.susmat.2018.e00062
Article Number: e00062
Reference: SUSMAT 62
To appear in: Sustainable Materials and Technologies
Received date: 27 January 2018
Revised date: 2 April 2018
Accepted date: 8 June 2018

Please cite this article as: Ruiting Zhan, Zachary Oldenburg, Lei Pan , Recovery of
active cathode materials from lithium-ion batteries using froth flotation. Susmat (2017),
doi:10.1016/j.susmat.2018.e00062

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 ACCEPTED MANUSCRIPT

Recovery of Active Cathode Materials from Lithium-ion Batteries using Froth Flotation

Ruiting Zhan, Zachary Oldenburg and Lei Pan

Department of Chemical Engineering, Michigan Technological University

Corresponding author:

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Lei Pan

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Address: 1400 Townsend Drive, Houghton, MI, United States
Email: [email protected]; Phone: +1 (906) 487-2569

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Acknowledgement:

The authors would like to acknowledge funding from the U.S. Environmental Protection Agency,
Michigan Technological University, Pavlis Honor College, and MTU I-Corps Site program for
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their financial support. Thanks to Jennifer Eikenberry at Michigan Technological University for
assistance with the ICP analysis. We would also like to extend my appreciation to Tim Eisele,
Taehee Han, Hosop Shin, Owen Mills for helpful discussions. Special thanks to Angelo Biviano
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for proofreading this manuscript.

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This publication was developed under Assistance Agreement No. SU839299 awarded by the U.S.
Environmental Protection Agency to Michigan Technological University. It has not been formally
reviewed by EPA. The views expressed in this document are solely those of authors of this article and do
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not necessarily reflect those of the agency. EPA does not endorse any products or commercial services
mentioned in this publication.
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Abstract

An ability to separate battery electrode materials while preserving functional integrity is

essential to close the loop of material use in lithium-ion batteries. However, a low-energy and
low-cost separation system that selectively recovers cathode materials has not yet been
established. In this study, froth flotation experiments were carried out with a variety of new and
spent lithium-ion batteries using kerosene as the collector. The products were characterized using
thermogravimetric and chemical analysis. It was found that over 90% of anode materials were
floated in froth layers, while 10-30% of cathode materials were floated. Thermogravimetric
analysis showed that the presence of binders and conductive additives within the cathode

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materials liberated from electrode layers might be responsible for the partial floatability of the

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liberated cathode materials. Separability of mixed electrode materials was evaluated using a
modified procedure based on release analysis. Results showed that the froth flotation process

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using kerosene as the collector produced a tailing product having cathode materials of higher
grade than those obtained without kerosene. For spent lithium-ion batteries, a low purity of
cathode materials in tailings might be improved by fine grinding, at which freshly liberated
hydrophobic surfaces are exposed and consequently anode materials become floatable. The

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present result confirms that the froth flotation technique is a viable and versatile technique in
producing high-purity cathode materials from lithium-ion batteries.
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Keywords: recycling; lithium-ion battery; froth flotation; physical separation.
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1 Introduction

Lithium-ion battery (LIB) technology has become a dominating energy storage solution for
consumer electronics, electric vehicles (EVs), and renewable energy systems such as wind and
solar [1, 2]. Because these batteries are expected to last 2-10 years, they will enter the waste
stream after reaching their useful life cycles [3]. It is estimated that as high as 340,000 t/y of
lithium-ion batteries from EVs are available for recycling by 2040 [4]. Lithium-ion batteries are
classified as a hazardous material under federal regulation. One reason is that lithium-ion battery
is nothing more than a package of chemical energy, and it can catch a fire or cause an explosion
if the battery is short circuited [5]. Another reason is that the disposal of end-of-life LIBs can

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have negative impacts on the environments and human health due to toxic materials that

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potentially release into the environment [6]. To date, many articles have been devoted to the
environmental and life-cycle impacts of battery recycling [7-9].

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Battery recycling is a norm in the United States, when it comes to lead-acid and nickel-
cadmium batteries [10-12]. However, recycling of lithium-ion batteries is much less mature

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compared to lead-acid batteries, since both the recycling network and technology have not yet
been established [3, 13]. As a result, recycling rate of spent lithium-ion battery is much lower
compared to other types of batteries in the United States. Cylinder lithium-ion batteries, used in
laptops and EVs, are constructed by rolling anode layers, separator layers, and cathode layers in
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a steel casing. In contrast to simple chemistry used in lead-acid batteries, components used in
lithium-ion batteries are much more complex. In addition, battery manufactures have their own
proprietary, non-standard chemistry, further complicating the recycling process. Current research
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has been directed towards the extraction of high-value metals from cathode materials using
pyrometallurigcal and hydrometallurgical processes [14-16]. Before being fed into metal
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extraction processes, separation of mixed materials from lithium-ion batteries using low-cost
and energy-efficient methods is critical to lower processing cost, minimize secondary waste, and
increase product values [17].
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Various separation technologies have been studied to sort battery materials by size, specific
gravity, magnetism and electrostatic conductivity [18]. For instance, magnetic components (e.g.
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steel casings) can be sorted by means of dry and wet magnetic separators [19]. One of most
simple methods is sieving by means of a screen. In this process, coarse particles are retained
above the screen while fine materials pass through. Separation by sieving can be operated in both
dry and wet conditions. In lithium-ion batteries, fines materials rich in cobalt and nickel metals
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can be separated from coarse pieces such as copper and aluminum using a sieve [20, 21]. For
particles of similar sizes, components can be separated individually based on differences in
specific gravity (SG). For instance, among all coarse components (+200 μm) in lithium-ion
batteries, plastic pieces can be separated from aluminum and copper pieces using a table [22] or
an air classifier [20]. Such separation equipment have been widely used in the minerals industry,
and includes devices such as jigs, spiral, sluice, shaking table, and etc [23]. Al-Thyabat
introduced a Li-ion battery recycling system based on a combination of mechanical,
pyrometallurgical and hydrometallurgical processes [17].

Chen et al. recently reported a method of reusing valuable cathode materials for the spent
LiFePO4 batteries [24]. In this process, cathode materials were manually removed from cathode
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layers. One benefit of this method is that recovered cathode powders can be regenerated and
reused in new lithium-ion batteries [24-26]. To scale up the cathode regeneration process, it is
requisite to have a scalable separation and purification process that segments cathode materials
from other components in spent batteries while preserving functional integrity.

In lithium-ion batteries, anode and cathode materials are graphite and lithium metal oxide,
respectively. After lithium-ion batteries are shredded and crushed, a fine fraction (-200 μm)
mainly consists of anode and cathode materials. Purification of cathode materials can be
achieved using 1) thermal method, 2) physical separation method, and 3) chemical method. The
first method burns off volatile materials, such as binder, carbon black, and graphite, from a

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mixture of fine battery materials at a temperature of 500-800 oC [27, 28]. The second method

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involves a separation of anode materials from cathode materials by a physical separation method.
The separation of fine particles has been studied using a dense liquid separation, such as

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bromoform [29]. This process might become very difficult to scale up due to environmental
toxicity of those heavy liquids. The chemical method involves a dissolution of cathode materials
in corrosive acids while retaining anode powders as solids [30]. This process is followed by a

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solid-liquid separation, whereby metal-rich filtrate can be processed to precipitate metal
hydroxide [30-32], be synthesized to active cathode materials [33, 34], or a new type of cathode
material by controlling solution chemistry [35, 36]. It is more desirable to have a physical or
physiochemical separation system that separates mixed fine materials in that as those systems are
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much more cost effective and energy efficient.

Froth flotation is a physicochemical separation process that separates fine materials based on
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the differences in surface hydrophobicity. In this process, only hydrophobic particles are attached
on surfaces of air bubbles. The particle-laden air bubbles rise to form a froth layer, and exits into
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a launder, while leaving hydrophilic particles behinds. A key in froth flotation is the control of
particle hydrophobicity [37, 38]. Graphite is naturally hydrophobic, while cathode material such
as LiCoO2 is hydrophilic. Thus, one can separate two materials. For example, naturally
hydrophobic materials, e.g. graphite, can be readily separated from hydrophilic fine materials by
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froth flotation [39]. To increase the hydrophobicity of naturally hydrophobic minerals, a small
amount of kerosene might be used [40]. Due to recent emerging research on lithium-ion battery
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recycling, studies on froth flotation for the separation of anode and cathode materials are very
rare [41, 42]. In one patent, a froth flotation process is integrated in a recycling system to
separate carbon black from cathode powders [42]. In this process, slurries were filtered and
treated at a temperature of 500 oC for an hour to burn off binders. Particles were then mixed with
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water and subjected to froth flotation. However, no detailed experimental results have been
released, and the effects of heat treatment on surface hydrophobicities were not studied. In
addition, it is not clear how binders and conducting additives affect the separation performance
of anode and cathode materials.

The objective of the present work is to study the performance of froth flotation in separating
cathode and anode materials from new and spent lithium-ion batteries. A series of laboratory-
scale froth flotation experiments were conducted with individual anode and cathode materials as
well as mixed materials. The results show that the froth flotation process enables a separation of
fine battery materials efficiently. The recovered powder samples were examined using
thermogravimetric (TGA) and chemical analyses.
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2 Materials and Experiments

2.1 Materials and Chemicals

New lithium-ion batteries were obtained from vendors, and they come in different sizes
and configurations. Used lithium-ion batteries were provided from Michigan Tech’s Information
Technology Department, Marquette County Solid Waste Management Authority, and other
sources. Used battery packs were removed from old working laptops and consumer electronics.

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These were opened by manually removing plastic casings to obtain 18650 cylinder cells. A
fraction of lithium-ion batteries surveyed in this study are of a pouch cell design, which were

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manufactured by stacking layers of electrodes in a foil envelope. Pure graphite flake (>99%) and
lithium cobalt oxide (97%) were obtained from Alfa Ester. The top sizes of graphite and lithium

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cobalt oxide are 44 and 30 μm, respectively.

Lithium-ion batteries were first discharged to 1.0-2.0 V by connecting with a load (a 10W

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– 35W halogen bulb) in a circuit to prevent explosion and fire during disassembly process. The
discharged lithium-ion battery cells were manually disassembled to remove stainless steel casing
using a rotary tool (Proxxon). Lithium-ion battery cores were unfolded to sort anode layers,
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cathode layers, plastic separators, and other components individually. The unfolding process was
performed under a fume hood to evaporate toxic organic solvents (ethylene carbonate and/or
ethyl methyl carbonate). A fraction of the samples were used for single-component flotation tests.
In these tests, samples were prepared by scraping off coatings from either anode or cathode
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conducting layers. The fine materials were dry grinded using a pestle and mortar until all fine
powders passed through a 70-mesh screen (-210 μm). This ensured that flotation experiments
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were performed at an optimum size range. Fine materials were rinsed with distilled water at least
five (5) times to remove excess electrolytes and additional distilled water was added to obtain a
1-2% w/w solid slurry for flotation tests. Kerosene and methyl isobutyl carbinol (MIBC) were
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used as the collector and frother, respectively, except where otherwise specified.

For multi-stage flotation tests, a mixture of anode and cathode layers were shredded into
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micro-cut pieces (5 mm x 12mm) using a heavy-duty paper shredder. The shredded metal foils
were mixed with distilled water for at least five (5) times to rinse off electrolyte and other
soluble organic components. A slurry of shredded metal foils with electrode materials was
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transferred into a 3hp blender (CleanBlend) at a speed of approximately 12000 rpm. The
agitation time was controlled to ensure that active battery materials were liberated from current
conducting layers while the size of current conducting foils remained significantly larger than
that of active battery materials. Liberated active battery materials were separated from metal foils
by wet sieving using a 70 mesh screen (-210 μm). The battery materials were filtered using a
laboratory-scale pressure filter, and fine battery materials retained above the filter were mixed
with distilled water for flotation experiments.

2.2 Froth Flotation

Flotation experiments were carried out in a 2-liter batch cell using a Denver D-12
laboratory flotation machine. In a single-material flotation experiment, a slurry was fed to a
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flotation cell and allowed to condition for five minutes at an impeller speed of 1500 rpm.
Collector was then added, and the slurry conditioned for three minutes. This was followed by
adding frother and conditioning the slurry for two more minutes prior to flotation. Flotation
commenced after the air inlet valve was open. Froth products were collected in collection pans
every 30-60 seconds. The obtained products were dried in an oven at a temperature of 105 oC
overnight and weighed. Froth height was kept at approximately 40 mm throughout the course of
experiments by adding water periodically. Froth products from a batch flotation cell in a series of
timed fractions were collected, dried and weighed.

Separation performance of a mixture of anode and cathode electrode materials was

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evaluated using a modified experimental procedure which was originally developed by Dell [43].

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The original test procedure, also known as “release analysis”, provides a measure of materials’
separability by froth flotation. The result obtained using this method represents the ideal flotation

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response of a given sample [44].

Fig. 1 shows a schematic representation of a modified experimental procedure used in this

study, which consists of two stages of separation experiments. The first stage is to separate

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floatable materials from non-floatable materials by minimizing the amount of entrained materials
in froth layers. The first flotation experiment was carried out using 30 μL collector and 30 μL
frother. Flotation continued until no visible particles appeared on the froth layers. The froth
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concentrate was re-pulped in the next experiment to clean non-floatable hydrophilic particles
entrained in the froth layers. A small amount of frother (20 μL) was added to maintain a stable
froth. All tailings were combined for the second-stage experiment. This procedure was repeated
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for one or two additional times for fine or ultrafine particle samples when necessary to minimize
the amount of entrained materials in froth concentrates.
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Fig. 1. A schematics of a modified froth flotation procedure for separation of mixed fine
materials from lithium-ion batteries.

The second stage of the modified procedure involves a segmentation of fine materials into
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components having various degrees of floatability. In this stage, froth product from the first stage
of this procedure was re-pulped to obtain a 2L slurry as the feed. Flotation was initialized at an
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impeller speed of 1200 rpm and an aeration rate of approximately 50% of full range for 2
minutes. Flotation continued by increasing impeller speeds and/or aeration rates. Froth
concentrates obtained at different operating conditions were collected, dried and sampled, and
the remaining tailing was combined with those obtained in the first stage.
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The same experimental procedure was applied to the tailings. In this experiment, flotation
was initialized at an impeller speed of 1200 rpm and an aeration rate of full range for 2 minutes.
Flotation continued by increasing the aeration rate to 1350 rpm and 1500 rpm for 2 minutes,
respectively. A constant froth height was kept over the course of the experiments by adding
water periodically. A total of three (3) froth concentrates combined with tailings were collected,
dried and weighed. The chemical analysis of the samples was performed using the inductively
coupled plasma optical emission spectrometry (ICP-OES) technique, which will be described in
detail in the following paragraph.
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2.3 Sample Characterization

Chemical analysis was performed using a Perkin Elmer Optima 7000DV ICP-OES system.
Samples were prepared by digesting 10-100 mg solids in a mixture of hydrochloric acid (HCl)
and hydrogen peroxide (H2O2) solution (HCl:H2O2 = 7:3 by volume) at a temperature of 80 oC
for 15 minutes. The pregnant solutions were diluted with deionized (DI) water to obtain solutions
having concentrations of the metal elements of interest in the range of 0.5–25.0 mg/L. Prior to
the ICP analysis, sample solution was filtered using a membrane filter when necessary to remove
suspended particles in liquids. The DI water was supplied from a Barnstead water purification
system (Thermo Scientific). TGA studies were performed using a LECO TGA 701 instrument at

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a scanning rate of 1 oC min-1 at a temperature range of 25-800 oC. The measurements were

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conducted at an air flowrate of 7 L/min. The TGA results were used to determine active material
contents in samples. Both morphology and particle size of recycled fine battery powders were

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examined using a JEOL JSM-6400 Scanning Electron Microscope (SEM).

3 Results and Discussion

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3.1 Single-material Flotation AN
Fig. 2 presents the froth flotation results of pure graphite and lithium cobalt oxide powders
in distilled water using 30 μL kerosene and 30 μL MIBC. Kerosene was added to increase
hydrophobicity of graphite particles. In this testing, 20 grams of particles were added to 2L
distilled water to obtain a slurry of 1% w/w solid concentration. The result is shown as recovery
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versus flotation time. As shown, over 98% of graphite particles were floated in 4 minutes after
flotation commenced, while only 8% of lithium cobalt oxide particles were recovered in the froth
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concentrate. This result is not surprising in that graphite is naturally hydrophobic having a water
contact angle of approximately 80o [40]. On the contrary, the lithium cobalt oxide (LiCoO2)
structure consists of CoO2 slabs with layers of lithium in between [45]. When immersed in water,
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LiCoO2 is easily hydrated, rendering the surface hydrophilic. Note that a tiny fraction of
hydrophilic LiCoO2 particles recovered in froth concentrates is attributed to particle entrainment
[46]. The entrainment is proportional to water recovery, and entrainment is more pronounced
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with ultrafine particles [46, 47].

It has been assumed that the separation of particles in froth layers from the suspension
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can be described using a first-order kinetic model as [48],

R  R max 1  exp(  kt )  (1)

where Rmax is maximum recovery and k is rate constant. Both Rmax and k values can be
determined from experimental R versus t data using a linear least-squares regression. As shown
in Figure 1, the experimental data can be well represented by a model fit. The coefficient of
determination, denoted R-squared, for two sets of experimental data are above 0.95, confirming
that the experimental results are replicated by the first-order kinetic model. The Rmax and k values
obtained for graphite are 97.7% and 1.68min-1, respectively, while those obtained for lithium
cobalt oxide are 10.9% and 0.32 min-1, respectively. As can be seen from Fig. 2 and reflected by
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the Rmax and k values, graphite powders were recovered by air bubbles in froth products, while
cathode materials were selectively concentrated in tailings.
Fig. 2. Laboratory froth flotation results of pure graphite and lithium cobalt oxide (LiCoO2) at 1%
w/w solid concentration.

Froth flotation technique was extended to separate anode and cathode materials liberated
from new lithium-ion batteries, and the results are shown in Fig. 3. All new batteries surveyed in
this study use graphite as anode material and lithium metal oxide (e.g., LCO, LMO, NCA) or
lithium iron phosphate (LFP) as cathode material. The top size of the feed was 210 μm, which is
within the particle size range for effective separation process [49, 50]. As shown, anode

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materials liberated from all four samples floated well, with a total recovery of 92.7% or above in

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4 minutes of flotation after aeration. On the contrary, cathode materials exhibited a low
floatability, with the amount of floatable materials in the range of 8.1-31.0% for all four samples

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in 4 minutes of flotation. Also shown in Fig. 3 is the theoretical fit to the experimental data using
Eq. (1) with the model parameters listed in Table 1. In general, the first-order kinetic model
gave a reasonably good fit to the experimental data for all four samples surveyed. The present

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result shows that a separation of anode and cathode materials from a mixture of fine battery
materials can be achieved using the froth flotation process. Furthermore, there appears to be no
discernible difference to the response of froth flotation for all four lithium-ion batteries surveyed
in this study. This indicates that the froth flotation process might be versatile for any types of
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lithium-ion battery as long as graphite and lithium metal oxide are used as the anode and cathode
materials, respectively.
Table 1. Fitting parameters obtained from the model fit to the froth flotation result obtained with
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four new lithium-ion battery samples (A-D) as shown in Fig. 3.

A B C D
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Samples
Anode Cathode Anode Cathode Anode Cathode Anode Cathode

Rmax (%) 96.18 30.51 97.56 8.842 98.61 22.56 90.25 18.80
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k (min-1) 3.01 1.29 0.88 0.58 5.19 0.57 1.53 0.31

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Fig. 3. Froth flotation results of individual anode and cathode electrode materials liberated from
four new lithium-ion batteries samples.
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It is worthy to mention that the recovery of “real” cathode materials is higher than that of
“hypothetical” cathode materials. Fig. 3a, for example, shows that the recovery of cathode
materials after 4 minutes of flotation was 27.1%, which was substantially higher than that
obtained with pure LiCoO2. It is unlikely that a significant amount of cathode materials
recovered by froth flotation was due to the entrainments in the froth layer, but instead originated
from the hydrophobicity of liberated cathode materials. Cathode electrode is manufactured by
coating a mixture of active cathode materials, conductive additives and binders on aluminum
foils. Upon liberation, some cathode materials are covered by binders and conductive additives
such as carbon blacks, rendering a fraction of electrode materials hydrophobic, resulting in a
high recovery in froth concentrates. It should also be mentioned that the recovery of cathode
materials was not consistent for all four batteries surveyed in this study, despite great care being
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taken to ensure the experimental procedures were exactly followed for all experiments. Such a
discrepancy might be attributed to the types and composition of binders and conductive additives
in battery chemistry as well as manufacturing process.
Fig. 4. Froth flotation results of individual anode and cathode electrode materials liberated from
four spent lithium-ion battery samples.
Table 2. Fitting parameters obtained from the model fit to the flotation results of spent lithium-
ion batteries samples (E-H) as shown in Fig. 4.
E F G H
Samples
Anode Cathode Anode Cathode Anode Cathode Anode Cathode

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Rmax (%) 82.05 20.11 85.73 8.21 97.33 21.44 90.77 35.99

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k (min-1) 2.31 0.75 2.05 2.06 3.10 0.79 2.65 0.78

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Fig. 5. Thermogravtimetric analysis of a froth concentrate after 30 seconds of flotation and a
tailing product after 4 minutes of floatation.

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Froth flotation experiments were extended to spent lithium-ion batteries, and the results
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are shown in Fig. 4 and Table 2. Note that a fraction of electrode materials in spent batteries
appeared to be less adhered on current conductors, which might be due to a weaker coating-to-
foil adhesion by mechanical degradation [24]. In general, 80%-97% of anode materials were
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floated in 4 minutes after aeration commenced, while the fraction of floated cathode materials
varied from 8.8% to 35.0% for all four samples surveyed. The present work seems to indicate
that the hydrophobicity of anode materials weakens slightly after having reached their useful life
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cycle. While the hydrophobicity of those electrode materials weakened slightly, the extent of
their material degradation is not clear and will be discussed in future.
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To illustrate the role of binder and conducting additives, thermogravimetric analysis

(TGA) were performed on both froth and tailing products. Fig. 5 shows the results of a froth
product after 30 seconds of flotation and a tailing using cathode materials liberated from spent
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lithium-ion battery cells as sample. The result is shown as weight and derivative weight loss as a
function of temperature. The TGA curve of the tailing product shows a loss of weight started at a
temperature of approximately 300 oC, signifying an onset of decomposition of binder and carbon
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additives under an air atmosphere [51]. The peak of binder’s decomposition occurred at a
temperature of 498 oC, which is consistent with the literature data [52, 53]. The total weight loss
of the sample reached 4.5% at a temperature of 800 oC.

The TGA curve of the froth concentrate exhibits a distinct response in weight loss to the
temperature rise compared to the tailing product. As shown, the derivative weight loss curve of
the froth product has a secondary peak at a temperature of 558 oC, which might be indicative of
conductive additives’ decomposition. Clearly, those additives are hydrophobic and consequently
they are floatable. The total weight loss of the froth product reached 13.1% at a temperature of
800 oC.
Table. 3. Weight and active material content of froth concentrates and tailing product.
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Weight (%) Recovery of

Active
Products Individual Cumulative Active
Material (%)
Material (%)
Froth (0-0.5 min) 9.40 9.40 86.9 8.7
Froth (0.5-1.5 min) 8.02 17.42 89.9 7.7
Froth (1.5-4.0 min) 7.27 24.69 94.4 7.3
Tailing 75.31 100.00 95.4 76.3
Feed - - 94.1 100

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Table 3 shows both froth flotation and TGA results obtained using the cathode materials

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liberated from spent lithium-ion battery cells. The active material content was determined from
the total weight loss at a temperature of 800 oC, at which both binders and additives were

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decomposed. As shown, the active material content in tailing and 30-second froth concentrate is
reach 95.4% and 86.9%, respectively. The result confirms that both conductive additives and
binders in liberated cathode materials are hydrophobic, causing liberated cathode materials being
floated in froth products. It should also be mentioned that a majority of binders might be

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engulfed in coarse cathode materials [54], which explained that the active material content in
tailing product remained at 95.4%.
Table. 4. A comparison of cobalt (Co) and lithium (Li) concentrations and active material
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content of tailing product obtained at fine grinding and coarse grinding.

Grinding Co (%) Li (%) Active Material (%)

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coarse 36.10 4.47 69.9

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fine 46.73 5.70 90.8

3.2 Flotation of mixed materials

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The previous paragraphs verified that a froth flotation process can be used to separate
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cathode materials from anode materials in the fine fractions of shredded lithium-ion battery
based on the difference in the surface hydrophobicity of the two constituents to be separated.
Assuming 100% of anode materials are floatable while 20% of cathode materials are floatable,
one can obtain a high purity of cathode materials in the final tailing using the froth flotation
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process. To verify the hypothesis, a modified procedure was used to evaluate the separability of
anode and cathode electrode material mixtures via froth flotation. The modified procedure has
been described in the experimental section.

Fig. 6 shows the recovery versus active material content with and without excessive
grinding. The result was obtained using 12 identical spent cylinder lithium-ion battery cells. A
fine grinding was carried out by agitating slurries in a blender at a speed of 36000 rpm for 10
minutes. The mean particle sizes at coarse and fine grinding were estimated to be 60 and 18 μm,
respectively, as determined from SEM images. As shown, the recovery vs. active material
content curves at fine grinding exhibits a sharper inflection point and is significantly shifted to
the right as compared to those obtained at coarse grinding. The result clearly suggests that a fine
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grinding can produce a purer product than coarse grinding at the same recovery. For instance, at
fine grinding, the active material content in tailings reaches 87.2% at a recovery of 51.6%. The
coarse grinding, on the contrary, produces a tailing product with the active materials content of
69.9% at a recovery of 70.9%. Also shown in Fig. 6 are a hypothetical “no” separation curve and
a near “perfect” separation curves for comparison. Both curves assume that composition of
liberated cathode materials does not change upon the liberation. Table 4 shows the content of
metal elements in tailings at fine and coarse grinding. Clearly, the chemical analysis result is in
good agreement with the active material content data.
Fig. 6. Recovery versus active material content curves at fine and coarse grinding obtained with
spent lithium-ion batteries.

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Fig. 7. Thermogravtimetric analysis of tailing products obtained at fine and coarse grindings as

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well as the 1st froth concentrate at coarse grinding.

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It should be mentioned that the low active material content in tailings obtained at a coarse
grinding is attributed to the fact that a fraction (~20%) of anode materials were reported to the
tailings. In this regard, a small fraction of anode powders is non-floatable, which may be
attributed to surface oxidization in water. Using a fine grinding process, surface oxidized groups

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might be removed and new hydrophobic surfaces would be exposed so that graphite can be
readily floatable again. Fig. 7 shows the TGA curves of final tailing products at coarse and fine
grinding, respectively. For tailing products at the fine grinding, there are two peaks occurred at
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temperatures of 380 oC and 558 oC, which might be associated with the thermal decomposition
of poly(methyl methacrylate) (PMMA) binders and conductive additives [53] For tailings at the
coarse grinding, however, there is an additional peak occurred at a temperature of 582 oC. This
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represents the decomposition of anode materials used in these lithium-ion battery cells. At a
temperature of 800 oC, the total weight loss of the tailings at coarse and fine grinding reached 9.2%
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and 30.1%, respectively.

Fig. 8. SEM photos of froth and tailing products at fine grinding.

Also shown in Fig.7 is the TGA curve of the first froth product at coarse grinding for
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comparison. The TGA curve shows that the peak temperature occurred at 582 oC, confirming the
presence of anode materials. The total mass loss reached 82.1% at 800 oC. We anticipated that
the froth product contains roughly 82% anode materials and 18% cathode materials.
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Fig. 8 shows a SEM photo of froth product and tailings at a fine grinding, respectively. The
froth product is mainly graphite, with particle sizes of 16-25 μm. The tailing consists of pure
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lithium metal oxide particles of uniform size, in the range of 6-25 μm.

It is also notable to mention that the active material content in the tailing at the fine
grinding reaches 90.8% (Table 4), which is greater than the theoretical value of pure cathode
material (88.1%). This is attributed to the rejection of all anode materials in froth products as
well as some of carbon blacks and hydrophobic binder [55]. In addition, graphite recovered from
spent lithium-ion batteries might become a commodity for downstream applications [56]. In
terms of graphite particle purity, froth concentrates contain 16% and 22% of active cathode
materials at 60 μm and 18 μm grinding sizes, respectively. Since it is difficult to liberate binders
from cathode materials mechanically, a further upgrading of the purity of graphite materials in
the froth products would be very difficult. Therefore, we conclude based on this work that a froth
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flotation process is better suited for a production of pure cathode materials rather than a
purification of anode materials.

To ensure that tailings are free of anode materials (i.e. graphite), attention should be paid
to ensure that graphite particles are rejected to froth concentrates. Fig. 9 shows the recovery
versus active material content with and without kerosene. The kerosene dosage is 100 μL, which
is equivalent to 1 kg per metric tonne of fine battery materials. As shown, the recovery versus
active material content curve exhibits a sharp inflection point regardless of the kerosene dosage.
The recovery vs. active materials content data obtained without kerosene shows a comparable
separation performance with those obtained at an excess kerosene dosage (100 μL). In terms of

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active material contents in final tailing product, the use of kerosene increases the amount of

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active materials in tailings at an expense of the recovery. Fig. 10 compares the TGA curves for
the tailing products obtained with and without kerosene. As shown, the two curves split at a

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starting temperature of approximately 550 oC, suggesting that there might be a small amount of
anode materials left in tailing without kerosene. In addition, the overlaps of decomposition’s
peaks confirm that the two samples with and without kerosene contain same amount of binders

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and carbon additives. It is worthy to mention that both binders and conducting additives might be
different between samples investigated in this study. Active material content in tailings at 100 μL
kerosene dosage reaches 88.39% while that obtained without kerosene is 87.27%. The active
material content in the tailing with kerosene was found to be identical with the cathode materials
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coated on electrodes, indicating that all anode materials were removed. Thus, a control of
collector dosage is critical if the objective of the flotation separation process is to recycle and
purify cathode materials for making new batteries.
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3.3 Direct-Recycle-Reuse (DR2) Process

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Fig. 9. Recovery versus active material content curves obtained with and without the use of
kerosene.
Fig. 10. Thermogravtimetric analysis for tailing products obtained with and without the use of
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kerosene as the collector.

Fig. 11. A schematic drawing of the Direct-Recycle-Reuse (DR2) Process. It is designed to
produce cathode materials from spent lithium-ion batteries to close the loop of material use in
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new lithium-ion batteries.

The froth flotation technique exhibits many superior features over competing technologies
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in recycling valuable components and constituents from spent lithium-ion batteries. First, froth
flotation is a physiochemical separation process that effectively preserves functional integrity of
electrode materials during the recycling process [57]. As a result, active battery materials might
be regenerated through a relithilization process and re-used in new batteries [24, 26]. Second,
froth flotation serves as a benefication process, which has the potential to sort fine electrode
materials by chemistry. Doing so increases energy efficiency in the downstream process while
minimizing secondary waste to a great extent. For instance, the froth flotation process provides a
metal-rich product that can be used as high-value feedstock for the hydrometallurical and
pyrometallurigical processes. Lastly, beneficiation of fine battery materials using froth flotation
is economically viable at a full-scale production. It was estimated that the operating cost is $4.40
per dry metric ton of fine battery materials based on industrial fine coal cleaning data [58]. This
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represents a remarkably low operating cost compared to the contained value in fine battery
materials. In this regard, battery recycling via froth flotation is economically viable.

On the basis of encouraging experimental result, a new Direct-Recycle-Reuse (DR2)

process is proposed. Fig. 11 shows a schematic representation of the DR2 process for producing
pure cathode materials from spent lithium-ion batteries. In this process, lithium-ion batteries are
shredded and crushed to pieces in inert gas. Upon a full liberation, solid components are sorted
into a coarse fraction and a fine fraction by a screen. Coarse components, including casing,
copper, aluminum, and plastic separator, are separated by a magnetic separator, a spiral classifier,
and a gravity separator. In the fine fraction, active cathode materials can be recovered from fine

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fraction of shredded lithium-ion batteries using the froth flotation technique. The active cathode

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materials can be regenerated through re-lithithization and then used directly in manufacturing
new lithium-ion batteries. The graphite particles leached from the metal cathode materials might

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be re-used in new batteries. The concept of the DR2 process follows the closed-loop model for
lead-acid batteries, in which nearly all battery components are recycled and reused [3].

One major benefit of the DR2 process is that this process is applicable to any types of

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lithium-ion battery as long as they use graphite and lithium metal oxide as the anode and cathode
electrode materials, respectively. Conventional hydrodrometallurigical and pyrotemllurgy
processes will not be economically viable for lithium ion batteries using LiMn2O4 or LiFePO4 as
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the cathode chemistry, since the contained value in those cathode materials is very low [4]. The
DR2 process, however, preserves functional integrity of active electrode materials and
consequently maximizes product values during the recycling process.
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A possible concern with the DR2 process is the purity of cathode materials that might vary
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with feed samples and grinding conditions. There are three major sources of impurities,
including ultrafine aluminum metal pieces, binders, and anode materials. Fine aluminum pieces
can be dissolved in the alkaline solutions. The binder might be re-dissolved in organic solvents
during new cell manufacturing. Future research should be directed towards the removal of a
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small amount of fine anode materials from the spent lithium-ion battery. One solution might be
the development of novel chemical collectors for cycled graphite particles from the spent
lithium-ion battery. It should be also noted that the densities of graphite particles and lithium
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cobalt oxide are 2.26 g/cm3 and 4.9 g/cm3, respectively. Thus, a gravity separation method based
on differences in specific gravity between these particles has the potential to separate anode
materials from cathode materials.
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4 Summary and Conclusions

The separability of active anode and cathode materials from lithium-ion batteries was studied
using the froth flotation technique. It was found that over 90% of anode materials were floatable
after rinsing off electrolytes, while only 10-30% of liberated cathode materials were floatable
using 2 kg/t kerosene as collector. The floatability of electrode materials exhibits comparable
performance between brand new batteries and spent batteries with the exception that a few of
spent batteries exhibit a slightly lower recovery (75-90%) for anode materials. The mechanism of
partial floatability of cathode materials was examined using the thermogravimetric and chemical
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analysis. It was found that the partial floatability of cathode materials might be attributed to the
coverage of hydrophobic binders and carbon additives on surfaces.

Experiments with mixed materials were performed using a modified release analysis procedure.
The results were shown as recovery versus active material contents. It was found that for spent
lithium-ion batteries, a fraction of graphite particles might be non-floatable, resulting in a tailing
product having a lower active material content. A finer grinding enables an exposure of fresh
hydrophobic surfaces in water, resulting in an increase in purity of cathode materials in tailings.
Kerosene was found to be an effective collector for anode materials. The present result showed
that a tailing product having 88.2% active materials can be obtained at a total recovery of 74.3%,

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demonstrating the effectiveness of the froth flotation process in producing pure cathode materials

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from spent batteries. Based on the present result, a novel Direct-Recycle-Reuse (DR2) system
was proposed that has the potential to close the loop of material use in lithium-ion batteries.

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Graphical Abstract

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