Sustainable Materials and Technologies 25 (2020) e00152

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Sustainable Materials and Technologies

journal homepage: www.elsevier.com/locate/susmat

A direct recycling case study from a lithium-ion battery recall

Steve Sloop a,⁎, Lauren Crandon a, Marshall Allen a,f, Kara Koetje a,1, Lori Reed b, Linda Gaines c,
Weekit Sirisaksoontorn d, Michael Lerner e
a
OnTo Technology LLC, 63221 Service Road Suite F, Bend, OR 97703, United States
b
VR Analytical, 63020 NE Lower Meadow Drive, Suite 3, Bend, OR 97701, United States
c
Transportation Systems Analyst, Energy Systems Division, Argonne National Laboratory, 9700 South Cass Avenue, Bldg. 362, Argonne, IL 60439-4815, United States
d
Department of Chemistry and Centre of Excellence for Innovation in Chemistry, Faculty of Science, Kasetsart University, Bangkok 10900, Thailand
e
Department of Chemistry, Oregon State University, 153 Gilbert Hall, Corvallis, OR 97331, United States
f
McKetta Department of Chemical Engineering, 200 E Dean Keeton St., University of Texas at Austin, Austin, TX, United States

a r t i c l e i n f o a b s t r a c t

Article history: Direct recycling of lithium-ion is a promising method for manufacturing sustainability. It is more efficient than
Received 1 April 2018 classical methods because it recovers the functional cathode particle without decomposition into substituent el-
Received in revised form 4 December 2019 ements or dissolution and precipitation of the whole particle. This case study of cathode-healing™ applied to a
Accepted 8 January 2020
battery recall demonstrates an industrial model for recycling of lithium-ion, be it consumer electronic or electric
vehicle (EV) batteries. The comprehensive process includes extraction of electrolyte with carbon dioxide, indus-
trial shredding, electrode harvesting, froth flotation, cathode-healing™ and finally, building new cells with
recycled cathode and anode. The final products demonstrated useful capability in the first full cells made from
direct recycled cathodes and anodes from an industrial source. The lessons learned on recycling the prototypical
chemistry are preliminarily applied to EV relevant chemistries.
© 2020 The Authors. Published by Elsevier B.V. This is an open access article under the CC BY-NC-ND license (http://
creativecommons.org/licenses/by-nc-nd/4.0/).

1. Introduction In comparison to the other direct approaches, cathode-healing™ is a

In the early 2000's, a lithium-ion battery recall became an opportu-
nity for development of direct recycling technology [1]. The recycling
framework of the time was not well suited for the challenges and oppor-
tunities specific to lithium-ion, including: (1) electrolyte reactivity,
(2) environmental health and safety (3) high-purity harvesting tech-
niques for whole electrodes and (4) direct recycling through reintro-
duction of lithium to spent cathode materials. These challenges and
opportunities are especially relevant for today's growing EV market.
This report provides a case-study of the first development of direct
recycling technology on lithium cobalt oxide (LCO) and other EV rele-
vant cathodes.
Direct recycling approaches include cathode-to-cathode, mechani-
cal, electrochemical, and cathode-healing™ technologies [2–10]. Each
approach recovers the functional cathode particle without decomposi-
tion into substituent elements as practiced with classical hydrometal-
lurgy [11] and hydrometallurgical electrode synthesis [12].
⁎ Corresponding author.
E-mail addresses: ssloop@onto-technology.com (S. Sloop),
lcrandon@onto-technology.com (L. Crandon), marshall.j.allen@utexas.edu (M. Allen),
kara.koetje@nrlssc.navy.mil (K. Koetje), Lori.Reed@vranalytical.com (L. Reed),
lgaines@anl.gov (L. Gaines), michael.lerner@oregonstate.edu (M. Lerner).
1
Current affiliation: Ocean Science Division, U.S. Naval Research Laboratory, 1005 Balch
Blvd., Stennis Space Center, MS 39529 United States
self-limiting hydrothermal reintroduction of lithium to the spent cath-
ode material, rather than a solid-state stoichiometric addition of lithium
[13]. The approach is nondestructive and resolves structural and chem-
ical deficiencies that develop during life [2,3]. For example, used cath-
odes have lithium inventory deficiencies of 10–15%, along with
structural changes that impede lithium transport. Cathode-healing™ re-
generates the lithium capacity/conductivity structure-property rela-
tionships in spent cathodes and can be applied to the many varieties
and mixtures used in lithium-ion batteries. Others have reproduced
the cathode-healing™ approach on controlled-scenario, laboratory-
built cells composed of LCO and lithium nickel cobalt manganese
oxide (NCM) [14]. Modeling suggests that direct recycling is the most
efficient approach to provide for low-cost, recycled, EV relevant
material [15].
One of the challenges for direct recycling is isolating the electrode.
Organic solvents, such as NMP, can be used to harvest electrodes; how-
ever, purification and toxicity issues are persistent. Alternatively, liber-
ating electrode particles through the thermal decomposition of the
binder produces HF that can damage the cathode and be a hazard to
workers. To improve the cost and safety at the industrial level, this
work develops aqueous methods to both harvest and separate
electrodes.
This paper reports on the comprehensive recycling, including
cathode-healing™ of commercial materials from a battery recall, using

https://doi.org/10.1016/j.susmat.2020.e00152
2214-9937/© 2020 The Authors. Published by Elsevier B.V. This is an open access article under the CC BY-NC-ND license (http://creativecommons.org/licenses/by-nc-nd/4.0/).
2 S. Sloop et al. / Sustainable Materials and Technologies 25 (2020) e00152

Fig. 1. Scalable Cathode-healing™ process. Electrolyte from Li-ion batteries is extracted with CO2, then the cells are safely shredded. Battery components such as plastics and metals are
separated, and electrodes undergo hydrothermal treatment. Froth flotation separates cathode and anode, and the cathode material is heated to produced healed cathodes.

the process flow diagram outlined in Fig. 1. Here-in we demonstrate in-
dustrially scalable extraction of electrolyte [16], harvest of the electrode,
cathode-healing™ treatment, and manufacturing lithium-ion cells with
the recycled materials.
numeric controlled saw (OnTo Technology, Battery-buster). The excised
jelly rolls were then shredded in the same manner as described above.
2.3. Cathode-healing™

2. Material and methods 2.3.1. Hydrothermal

The harvested cathode (i.e. 700 g) was sealed in a pressure vessel
2.1. Discharge and electrolyte extraction (Autoclave Engineers, 1 L) with a saturated, high ionic strength, lithium
aqueous solution (approximately 4 M with various corresponding an-
Lithium-ion cells (LG-Chem 2.2 Ah, LCO) from recalled packs [1] ions). After hydrothermal treatment, the electrode material was re-
with an excess of 300 cycles were sorted and discharged to 0.75 V moved from the vessel and rinsed with deionized water.
using a sodium bicarbonate brine solution. The cycle numbers were
identified through the compatible laptop computer internal operating
2.3.2. Separation of carbon and metal oxides
system. Electrolyte was then extracted from batteries using a liquid car-
Harvested material consisted of a mixture of cathode, carbon black,
bon dioxide extraction system (OnTo Technology, Bend, Oregon; 23 L
binder, and graphite. Froth flotation of carbon from LCO was employed
vessel, 48 h, 25 °C, 900 psi). Gas chromatography (GC) was used to eval-
after the hydrothermal treatment during which the binder is removed.
uate extracted electrolyte. The GC analysis was performed with an
A sample of harvested material (10 g) was placed into a vessel
HP5890 series II instrument using a cryogenic cooling system and a
(100 mL) with water and approximately 0.5 g of a surfactant. The mix-
flame ionization detector (FID). Each sample (5 μL) of methylene chlo-
ture was agitated with a homogenizer (Omni International, GLH) for
ride was on-column injected at −15 °C to minimize sample decomposi-
15–20 s to achieve a visible separation of carbon (float) and metal
tion, and the column (DB-5) was heated to 230 °C at 10 °C/min.

2.2. Harvest of electrodes

After extraction of electrolyte, the whole cells were safely shredded

(SSI Model 600E, 25 HP, Dual rotor shear shredder) at a rate of one ton
per hour. The shredder residue was placed into a blender-vessel with an
aqueous wash solution and delaminated from the current collector
through action of the blender (i.e. 30 s of activation). The electrode ma-
terials were separated from the other components (plastics, metal cas-
ing, copper/aluminum current collectors) by filtration. The electrode
solids settled with an essentially quantitative yield. The collected elec-
trode material is referred to as “harvested”.
Battery casings were removed from a sample subset to compare pu- Fig. 2. Electrolyte extraction system. Liquid CO2 at 25 °C and 900 psi is pumped into a A,
rity of the end product LCO. This was accomplished using a computer and after 48 h electrolyte is collected in B.
 S. Sloop et al. / Sustainable Materials and Technologies 25 (2020) e00152
Fig. 3. Bulk extracted electrolyte and corresponding gas chromatographic trace. The
electrolyte extracted with liquid CO2 produced a clear sample that contains 3:1 alkyl
carbonate: ethylene carbonate and was dry, with only 19 ppm water.
oxide (sink). The float was immediately decanted. The metal oxide set-
tled under gravity (1G) and was dried under vacuum.
2.3.3. Heating LCO
The captured, hydrothermally treated cathode was heated under air
to 800 °C with a ramp rate of 5 °C/min, dwell time of 9 h, and final nat-
ural cooling to room temperature at approximately 5 °C/min.
2.3.4. Recycled graphite preparation
Graphite recovered from the float was rinsed in acid (0.25 M nitric
acid) to dissolve trace metals. Subsequent rinses used deionized water
and acetone. The product was dried at 120o under vacuum and sifted
through a 45-μm mesh sieve. A final heating at 500 °C under flowing ni-
trogen was applied to dry the material.
Fig. 4. Copper and iron contamination. Post shredding, whole cells produced the highest
level of contamination. Disassembly of the cell by removing the metal casing reduced
contamination by a factor of 10. Subsequent cathode-healing™ process reduced the
contamination to baseline levels.
3
2.4. Characterization of LCO after cathode-healing™
2.4.1. Structural characterization
X-Ray diffraction patterns for baseline, harvested, and healed cath-
odes were obtained using a Bruker D2 Phaser. The morphology was ex-
amined by scanning electron microscopy (SEM) using a FEI QUANTA
600F environmental SEM, and results were obtained using an Oxford
X-max 100 TLE windowless SDD X-ray detector and incorporated into
the same SEM described above.
2.4.2. Half cell construction
Half-cells were made in-house at OnTo from harvested and treated
cathode materials to evaluate capacity in real-time while developing
process steps. To do this, approximately 10 g of cathode was homoge-
nized (OMNI) with a 6% solution of PVDF (Kynar) in n-methyl pyrrol-
idine. The slurry was applied to an aluminum current collector and
coated using a Gardco casting knife applicator with the thickness set
to approximately 10 μm. The coating was dried in air and calendered
with a pneumatic hot-press. The uniformity of the coating was verified
through gravimetric analysis of multiple 1cm2 electrode punches and
contained 3.13 mg of active material. These punches were used as elec-
trodes in half-cells. They were placed into a button-cell against lithium
with a Teklon™ micro-porous membrane separator imbibed with elec-
trolyte (1 M LiPF6 EC:EMC, Novolyte). The cell was sealed with a Hoshen
hand crimper and removed from the dry box (Vacuum Atmospheres,
Nexus One) for cycling.
2.4.3. Full cell construction
Full cells were built using recovered material. The full cells were
composed of LCO cathodes coated on an aluminum current collector
against graphite anodes coated on a copper current collector. The elec-
trodes were stacked alternately and separated by porous polyethylene
separators (PE, Celgard). A typical cathode electrode formulation uti-
lized 3.5% polyvinyl difluoride (PVDF, Arkema), 2% carbon black (Timcal
Super-P), 2.5% artificial graphite (SGP, SEC carbon) and 92% active ma-
terial. Typical industrial electrode mixing and coating processes were
employed to build electrodes, but on a smaller, lab scale and detailed
as follows. The powder materials and N-Methyl-2-pyrrolidone (NMP,
BDH) were mixed in a planetary mill. During the mixing process the
slurry properties were tested to compare the healed and new cathodes.
Physical measurements including viscosity (Rhe-3000, Brookfield), and
lower coating thickness limit without scratch by big or agglomerated
particles (Hegman gauge) were very similar between healed and the
new cathodes. After mixing, the slurry was slot-die coated onto a cur-
rent collector foil (aluminum, Sam-A). The NMP was dried out using a
convection oven, and the electrode coating was roll pressed to enhance
the conductivity and interfacial adhesion between the current collector
and the electrode.
A negative electrode was built using artificial graphite (93 wt%)
and carboxymethyl cellulose binder (7 wt%). The anode was made
using the same slurry coating process as the cathode. Prior to coat-
ing, the copper electrode was rinsed with oxalic acid to remove ox-
idation layers and improve the bonding strength between the
electrode and substrate. The slurry was cast onto copper foil, dried,
and calendered with a warm roll press. Electrode tapes were dried
at 120 °C under vacuum for 10 h. Leaves were cut from tapes with
a template (3 cm by 4 cm with tabs), stacked with separator, then
sealed in a pouch cell with an opening for electrolyte injection.
The electrolyte (ethylene carbonate/ethyl-methyl carbonate LiPF6
1.2 M, Soulbrain) was imbibed into the cell with assistance of the
dry box vacuum and the cell was sealed. The fully assembled cells
were first cycled (Maccor or Arbin) between 3.0 and 4.2 V at a
C/20 constant current for both charge and discharge. Any formation
gas was not removed from the cells in these cases. Life cycle testing
was done at 30 °C (Shel Lab oven) with C/10 and C/2 charge/
discharge rates (Arbin), respectively.
4 S. Sloop et al. / Sustainable Materials and Technologies 25 (2020) e00152

Fig. 5. SEM of harvested and healed LCO. Harvested LCO on the left shows metal oxide and carbon particulates. Healed LCO in the middle and right show smooth LCO particles at 4 and
10 μm respectively.

2.5. Survey of new cathodes soaked in aqueous conditions
Other cathode chemistries were considered here to compare and
contrast harvest methods for more broad applicability. Basic, neutral,
and acidic aqueous harvesting techniques were surveyed and evaluated
for various new cathodes materials, including lithium cobalt oxide (LCO,
MTI), lithium nickel manganese cobalt oxide (NMC532, Spear Power),
lithium manganese oxide (LMO, MTI), and lithium iron phosphate
(LFP, MTI). Cathode samples were stored in an atmosphere controlled
dry box and transferred to the laboratory prior to treatment. 2 g samples
of cathode were placed into 20 mL vials and 15 mL of aqueous solution
was added. The solutions included 0.25 M NH4OH, deionized water, and
0.25 M HCl. The cathode/solution samples were kept in ovens at 25 °C or
50 °C. After two days, the solution was decanted from the cathode for
metal content analyses. The wet cathode solids were dried in a vacuum
oven at 120 °C overnight, with dry argon back-fill, and transferred to the
dry box to be prepared for electrochemical evaluation. Cathode charac-
terization included XRD and SEM to compare material before and after
treatment.
formed during life and recycling (i.e. shredding) of batteries [20].
Extraction of the electrolyte, before shredding/pulverization of the
battery, reduces potential generation of toxic materials through the
controlled removal of reactants.
The extraction apparatus, shown in Fig. 2, removed approximately
50% of the electrolyte from whole cells. CO2 pressure breaks the seal
on the cylindrical cell and imbibes fluid to the internal reaches of the as-
sembly or jellyroll. The static system dissolves and displaces electrolyte
from the pores of the separator and electrodes. After approximately
48 h, clear electrolyte (Fig. 3 inset photo) liberally flowed from the ex-
tractor to the collector. GC analysis (Fig. 3) shows two major solvent
components (3:1 alkyl carbonate: ethylene carbonate), with only
19 ppm water. Approximately 1/3 of the salt was removed in the pro-
cess due to preferential organo‑carbonate extraction with carbon
dioxide.
The removal of electrolyte can be improved to 89% through kinetics
(i.e. supercritical carbon dioxide N33 °C and 1200 psi), CO2 flow, addi-
tive solvents such as acetonitrile or propylene carbonate, and removal
of the battery casing [21].

2.5.1. Inductively coupled plasma (ICP) analysis

Samples were dissolved ultra-high purity nitric acid (BDH ARISTAR
ULTRA®; lot 1214110) and ultra-high purity hydrochloric acid (BDH
ARISTAR ULTRA®; lot 4213110).
The samples were analyzed for a subset of the elements Li, Al, Cr, Mn,
Fe, Co, Ni or Cu by inductively coupled plasma-mass spectrometry (ICP-
MS; Agilent 7700×). A custom internal standard (SPEX CertiPrep; lot
27–110CR) prepared at 1 μg/mL In, Lu, Sc, Tb, and Y was mixed in-line
with samples to correct for possible instrument drift or matrix differ-
ences. The ICP-MS instrument was calibrated using one blank and four
elemental standards prepared from NIST-traceable custom reference
standards (SPEX CertiPrep; lots 6–79WL and 26–169CR) in 2% nitric
acid/0.5% hydrochloric acid diluent.

3. Results and discussion

3.1. Discharge and electrolyte extraction

Discharge was done with sodium bicarbonate bath, but to avoid so-
dium contamination, water management, and corrosion, a solid-state
resistor can be used instead [17]. Solid-state resistors can discharge bat-
teries to a lower voltage, which transfers and conserves lithium in the
cathode.
Toxic electrolyte reaction products such as fluorophosphates, Fig. 6. Frothing carbon from the lithium metal oxide. Froth flotation performed after
fluoroethanol, hydrogen fluoride, and fluoroethylene [18,19] can be hydrothermal treatment to separate carbon from metal oxides.
 S. Sloop et al. / Sustainable Materials and Technologies 25 (2020) e00152 5

Fig. 7. Particle Size Distribution. The harvested material shows two particle size distributions with 600-μm agglomerates, and 18-μm particles (blue trace). Hydrothermal treatment frees
the particles from binder agglomerations, and froth flotation separates the metal oxide (red trace). Heating removes the residual carbon (green trace).

3.2. Harvest of electrodes contaminate to a degree as observed with whole-battery shredding;

Industrial shredding is widely used in lithium battery recycling [22],
in addition to problems with reactivity, it introduces contamination and
material losses. Shredding encapsulates electrodes, foil, plastics, and
casings into a small unit that cannot be easily liberated. Encapsulation
occurred at about 10% in this study. Blending or granulating splits the
encapsulated parts at an additional cost. This activity results in a high
degree of iron and copper contamination as shown in Fig. 4.
The iron is sourced from the packaging can, and copper from the
anode current collector. Disassembly of batteries is one way to improve
the purity of recovered components in recycling [23]. Removal of the
metal can prior to shredding reduced iron contamination by a factor of
ten (Fig. 4). Copper, while still present in the shredder residue, did not
presumably, low copper contamination is due to minimized processing
for encapsulation.
3.3. Cathode-healing™ spent LCO
3.3.1. Hydrothermal
The harvested electrode material is a mixture of LCO, graphite,
carbon-black, and polymers that bind these particles into agglomerates.
The entire mixture goes through hydrothermal treatment to (1) reintro-
duce lithium into the spent cathode material; (2) remove the binder to
facilitate separation; (3) remove impurities such as copper and iron;
and (4) safely eliminate traces of electrolyte.

Fig. 8. XRD of graphite float, and cleaned graphite. Frothed graphite contains some LCO and LiOH, which is removed with subsequent acid-washing.
6 S. Sloop et al. / Sustainable Materials and Technologies 25 (2020) e00152
Hydrothermal methods have been used to synthesize LCO from
CoOOH and LiOH (i.e. concentrated solution, 160 °C, five days) [24,25].
Kim previously used a hydrothermal method to recycle LCO; however,
that mechanism completely dissolves and reprecipitates LCO [26]. A
modified method has been shown to recycle NCM from full cells [9].
The cathode-healing™ approach here is a shorter, direct method that
maintains the particle morphology from harvest through the final prod-
uct, as shown by the Fig. 5 SEM of the healed LCO with layered, crystal-
line character.
This provides a viable industrial process with relatively low energy
input as compared to original syntheses. There are lower kinetic re-
quirements to maintain an already-formed bulk crystalline lattice than
to dissolve, reprecipitate, and form a new one. Trace metal contamina-
tion (from shredding and battery use) is removed during the hydrother-
mal step of cathode-healing™. Fig. 4 ICP analysis of healed LCO shows
62.5 ppm Fe, and 123.6 ppm Cu, which is similar to typical baseline
LCO. The hydrothermal process removes surface-bound metal and
metal oxide particles yielding healed LCO with 99.98% purity, which is
the same as the baseline material.
3.3.2. Separation of carbon and metal oxides
The hydrothermal step removes the binder without thermal decom-
position [27] that releases HF and fluorinates the cathodes. With parti-
cles free from agglomeration, froth flotation (with water and a
surfactant) easily separates metal oxides and carbon, as shown in
Fig. 6 [28,29]. Previous studies typically applied froth flotation or
dense fluid separation immediately following harvest steps where ag-
glomerates must be an issue [30–33].
Fig. 7 shows the hydrodynamic radius for agglomerates from har-
vested and free particles from hydrothermal treatment. Cathode-
Fig. 9. XRD of LCO materials. The peak intensity ratio I(003) / I(104) of each sample is shown in the inset. The higher peak ratio indicates well-ordered material. The healed LCO has the highest
ratio indicating a high degree of layered character in the material.
healing™ avoids contamination, and environmental health and safety
issues of dense fluids and/or thermal decomposition.
3.3.3. Graphite
After being washed and dried, the graphite recovered from froth flo-
tation can reused. As measured in half-cells against lithium, electro-
chemical performance of hydrothermally treated graphite samples
improved, with a specific capacity of 340 mAh/g relative to the har-
vested graphite, which had 300 mAh/g. Hydrothermal processing
removes electrochemically inactive materials, such as binder, metals/
metal oxides, and washes away the SEI to improve the capacity. The
XRD in Fig. 8 shows the progress of cleaning harvested graphite. How-
ever, trace cobalt and copper can remain N500 ppm. Commercial prep-
aration of natural graphite uses thermal and chemical methods to
remove contaminants to undetectable levels [34]. Similar steps can be
applied to recycled graphite, perhaps in OEM preparation, to reuse the
material and address critical availability [35].
3.4. Characterization of LCO after cathode-healing™
3.4.1. Structural characterization
Used LCO develops cubic-spinel characteristics as a degradation
mechanism [36,37]. XRD diffraction patterns of cubic and hexagonal
LCO are similar; however, peak intensities may differ due to c/a lattice
parameter differences consistent with spinel-like locations for cobalt
and lithium in the lattice [38]. The XRD peak intensity analysis along
with electrochemical characterization (to follow in the next section)
show that cathode-healing™ reinstates lithium inventory and hexago-
nal character to used or otherwise degraded LCO.
LCO I(003)/I(104)
Harvested 1.96
Healed 5.99
 S. Sloop et al. / Sustainable Materials and Technologies 25 (2020) e00152 7

Table 1
Full cell specification and performance.

Anode-Recycled graphite

Conductive Aid SuperP

Binder Carboxymethyl Cellulose
Adhesion Aid Styrene Butyl Rubber
Solvent Deionized water
Loading 121 g/m2
Comments Smooth coating. 1–2 particles per foot of coating

Cathode-Healed LCO

Conductive SuperP
Aid 1
Conductive Conductive graphite
Aid 2
Binder PVDF
Solvent Anhydrous NMP
Loading 230 g/m2
Comments LCO agglomerates, 10–20 particles per foot. No SuperP or
conductive graphite inclusions

Cell Data

First charge cathode capacity 142.4 mAh/g

Cathode cyclic capacity 121.6 mAh/g
Capacity change −0.54%/Cycle
Discharge rate C/2
# Cycles 16

electrochemical analyses show that healed LCO has a full complement

Fig. 10. (a) Voltage vs. Specific Capacity and (b) dQ/dV for harvested and healed LCO. LCO
harvested from faded cells has low capacity. The capacity of the healed LCO is 144 mAh/g.
The theoretical capacity for LCO is 140 mAh/g.
The XRD of harvested material in this work showed a relatively low
peak intensity ratio (Fig. 9) of I(003)/I(104) indicating a degree of cation
mixing between cobalt and lithium, and generally a decomposition of
the layered character of LCO. After hydrothermal treatment and heating,
the peak intensity ratio increased, which indicates a return to lithium
stationed between the galleries of well-ordered metal oxide layers.
3.4.2. Half cells
The XRD analyses show evidence for transition from a cubic to hex-
agonal character in recycled LCO as a result of cathode-healing™. The
of lithium, with ability to be transported to and from the lattice in a
cell. These measurements show recovered capacity, power, and rate ca-
pability from harvested to healed LCO.
Fig. 10a shows the half-cell charge-discharge specific capacity of the
harvested and healed cathodes. After harvest, the specific capacity was
was low, and after cathode-healing™, it rebounded to 139 mAh/g. The
specific capacity is essentially the same as baseline LCO using the
same charge/discharge cut-off potentials. The Fig. 10b dQ/dV compari-
son shows improvement of the power capability from harvested to
healed material. The improvement in capacity is due to reintroduction
of lithium, and the improvement in power is due to reinstating lithium
mobility in the hexagonally layered cathode structure.
The Fig. 11 rate capability shows that healed LCO maintained a rela-
tively high specific capacity with increasing current density, which pro-
vided confidence to use healed LCO for building full cells against
graphite.

Fig. 12. Specific Capacity vs. Cycle number for recycled LCO build into a full cell with
Fig. 11. Rate capability for healed LCO against Li metal. The healed LCO maintains specific natural graphite anode. The cell maintains capacity and specific capacity like new
capacity as the current density increases, which provided confidence to build full cells materials. The capacity change is approximately −0.2%/cycle, new material in similar
against graphite. These are equivalent to C/12, C/8 and C/5. experiments can show a capacity change of −0.4%/cycle.
8 S. Sloop et al. / Sustainable Materials and Technologies 25 (2020) e00152

Fig. 13. Lithium extracted from cathodes as a function of decreasing pH after soaking for 48 h.

3.4.3. Full cells
The full cell composed of new graphite and healed LCO demon-
strated good capacity retention. The Fig. 10 specific capacity vs. cycle
number shows that healed LCO retained 80% of capacity after 160 cycles.
Table 1 summarizes the specifications and performance of full cells
composed of both recycled graphite and healed LCO. Notably, the first
cycles show high capacity for both electrodes; however, subsequent cy-
cles have greater capacity loss (than for healed LCO with new graphite).
The accelerated loss has contributing factors, including impurities in

Fig. 14. Overlay XRD comparison of NMC soaked in base, deionized, and acidic solutions. The peak intensity decreases markedly for the acid soaked NMC.
 S. Sloop et al. / Sustainable Materials and Technologies 25 (2020) e00152
Fig. 15. Percent capacity of LCO harvested in base, neutral, or acidic conditions before and
after cathode-healing™.
recycled graphite and differences in the manufacturing behavior with
production grade material. These may be addressed with (1) purity im-
provements using existing industrial processes [32] so the material can
meet a specification and (2) adjusting manufacturing approaches to im-
prove mixing of recycled materials into well-established baseline for-
mulations (Fig. 12).
3.5. Survey for aqueous harvest of cathodes
Using the case-study for LCO as a starting point, the impacts of pro-
cessing were applied to other industrial lithium-ion chemistries. The
use of water in harvesting electrode materials avoids the hazards and
costs of organic solvents such as NMP. For direct recycling approaches
a major challenge with water is the potential for irreversible damage
to the cathode material. However, this can be mitigated with pH and
temperature of the harvest solution. In some cases, cathode-healing™
can reverse damage from the harvesting process. This concluding sec-
tion summarizes the impact of harvest pH on various commercial elec-
trode types.
Fig. 13 shows that increasing lithium dissolution occurred with acid-
ity and temperature of the harvest solution. For example, acid exposure
dissolved 30% of available lithium from LCO and NMC after 48 h.
Along with dissolution of lithium, the cathode crystalline order de-
graded. Fig. 14 shows XRD patterns of NMC after soaking in acid, neutral
and basic solution. After soaking in a basic solution, the NMC main-
tained its original structure, but the (003) reflection intensity (and all
of the crystalline layers) decreased with acidity. NMC soaked in base
could be repaired with cathode-healing™. The most flexible material
was LCO, which could be repaired after any rinsing process (Fig. 15).
4. Conclusions
This case study demonstrates the first, industrially scalable direct
recycling of cathodes, anodes, and electrolyte from cells sourced from
a battery recall. Process steps were developed to minimize environmen-
tal/safety hazards and process costs. These include
(1) extraction of electrolyte to mitigate toxicity
(2) cell disassembly to decrease contamination of iron and copper
(3) aqueous harvesting of electrodes to avoid organic solvents, and high
pH to avoid irreversible decomposition of the cathodes such as NCM
(4) one pot, hydrothermal processing that quickly and safely decom-
poses binder, allows for facile separation of anode and cathode with-
out dense fluids, reinstates lithium inventory in the cathode, and
removes trace metals.
The final products demonstrated useful capability in the first full
cells made from direct recycled materials.
9
Acknowledgements
The authors thank the National Science Foundation for support
of recycling LCO and electrolytes under award No. IIP-0750552 and
disassembly under award No. IIP-0946117; the Oregon Nanoscience
and Microtechnologies Institute supported the recycling of lithium
cobalt oxide with a GAP award J1652A-A A2; Defense Logistics
Agency for support of LCO material evaluation under Contract No.
SP4701-15-C-0097; Argonne National Laboratory for support of har-
vest technique evaluation under Contract No. 5F-30582; Oregon De-
partment of Energy Small Energy Loan Program (SELP) #L00655,
and Business Energy Tax Credit generator (BETC) #13122 which sup-
ported capital equipment used for the project. Thanks to Professor
Seung-Tae Hong for helpful technical and business discussions; and
special thanks to Dr. Richard D. and Barbara J. Sloop, Douglas S.
and Margaret A. Smith, and Dr. Sumner “Shep” Wolsky for support
of this effort.
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