sustainability

Article
Sustainable Waste Tire Derived Carbon Material as a
Potential Anode for Lithium-Ion Batteries
Joseph S. Gnanaraj 1, *, Richard J. Lee 1 , Alan M. Levine 1 , Jonathan L. Wistrom 2 ,
Skyler L. Wistrom 2 , Yunchao Li 3 , Jianlin Li 4 ID , Kokouvi Akato 5 , Amit K. Naskar 5
and M. Parans Paranthaman 3, *
1 Energy Division, RJ Lee Group, 350 Hochberg Road, Monroeville, PA 15146, USA;
RLee@RJLeeGroup.com (R.J.L.); ALevine@rjleegroup.com (A.M.L.)
2 Practical Sustainability, 1402 N College Drive, Maryville, MO 64468, USA;
jonathanwistrom@yahoo.com (J.L.W.); sky_wistrom@hotmail.com (S.L.W.)
3 Chemical Sciences Division, Oak Ridge National Laboratory, Oak Ridge, TN 37831, USA; yli107@utk.edu
4 Energy & Transportation Science Division, Oak Ridge National Laboratory, Oak Ridge, TN 37831, USA;
lij4@ornl.gov
5 Materials Science & Technology Division, Oak Ridge National Laboratory, Oak Ridge, TN 37831, USA;
kakato@utk.edu (K.A.); naskarak@ornl.gov (A.K.N.)
* Correspondence: JSGnanaraj@gmail.com (J.S.G.); paranthamanm@ornl.gov (M.P.P.);
Tel.: +1-860-405-4914 (J.S.G.); +1-865-574-5045 (M.P.P.)




Received: 17 July 2018; Accepted: 7 August 2018; Published: 10 August 2018


Abstract: The rapidly growing automobile industry increases the accumulation of end-of-life tires
each year throughout the world. Waste tires lead to increased environmental issues and lasting
resource problems. Recycling hazardous wastes to produce value-added products is becoming
essential for the sustainable progress of society. A patented sulfonation process followed by pyrolysis
at 1100 ◦ C in a nitrogen atmosphere was used to produce carbon material from these tires and utilized
as an anode in lithium-ion batteries. The combustion of the volatiles released in waste tire pyrolysis
produces lower fossil CO2 emissions per unit of energy (136.51 gCO2 /kW·h) compared to other
conventional fossil fuels such as coal or fuel–oil, usually used in power generation. The strategy used
in this research may be applied to other rechargeable batteries, supercapacitors, catalysts, and other
electrochemical devices. The Raman vibrational spectra observed on these carbons show a graphitic
carbon with significant disorder structure. Further, structural studies reveal a unique disordered
carbon nanostructure with a higher interlayer distance of 4.5 Å compared to 3.43 Å in the commercial
graphite. The carbon material derived from tires was used as an anode in lithium-ion batteries
exhibited a reversible capacity of 360 mAh/g at C/3. However, the reversible capacity increased
to 432 mAh/g at C/10 when this carbon particle was coated with a thin layer of carbon. A novel
strategy of prelithiation applied for improving the first cycle efficiency to 94% is also presented.

Keywords: battery grade carbon; waste tires; lithium-ion batteries; pouch cells; disordered carbon
microstructure; surface coating

1. Introduction
Rechargeable lithium-ion batteries (LIBs) are being used as the most promising power source for
small-scale applications such as consumer portable electronics, power tools and large-scale applications
such as advanced power load leveling for smart grids to meet the energy demands of modern mobile
technology, electric vehicles (EVs), and hybrid electric vehicles (HEVs) [1]. Graphite is the most widely
used anode material due to its high thermal and chemical stabilities, and the practical reversible
specific capacity reaching closer to the theoretical capacity of 372 mAh/g corresponding to a fully

Sustainability 2018, 10, 2840; doi:10.3390/su10082840 www.mdpi.com/journal/sustainability

Sustainability 2018, 10, 2840 2 of 13

lithiated stoichiometric LiC6 compound [2]. Currently, graphite is being used as an anode in LIBs
that powers electric vehicles such as Tesla Model S [3,4]. However, fast charging LIBs pose safety
concerns due to lithium platting on the surface of the graphite anode leading to the formation of
lithium dendrites, causing inner short-circuiting and capacity fading [5].
Other types of carbonaceous materials such as hard carbons (HCs) and soft carbons (SC) have
been investigated as alternate anode materials to enhance the performance characteristics of LIBs [4].
The unique amorphous structure in SC enables fast charging in LIBs even when the micron-sized
particles are used, but it suffers from very low specific capacity of 250 mAh/g. The disordered
structure in HC is a short-range order which cannot be graphitized even upon high temperature
treatments [6]. Hard carbon is less susceptible to exfoliation due to the random orientation of the
small graphitic grains. The nanovoids present between the grains reduce isotropic volume expansion.
Thus, nanovoids and defects provide additional gravimetric capacity, allowing the capacity to exceed
the theoretical capacity of graphite. HCs have demonstrated the ability to store more lithium than
graphite and do not exfoliate during repeated cycling in LIBs [7]. Together, these properties make
HCs a high capacity high cycle life material. Nevertheless, it suffers from large irreversible capacity
loss, which is generally attributed to the high surface area, exposed edge planes in high fraction that
increase the absolute quantity of solid electrolyte interphase (SEI) formed, reducing the coulombic
efficiency in the first few cycles, and voltage hysteresis [8]. The first cycle irreversible capacity loss in
LIBs has been studied extensively and is attributed to the formation of a passivating SEI during the
first lithiation process, due to the electrolyte reduction at the negatively polarized graphite surface
and the deposition of a number of organic and inorganic compounds, trapping lithium irretrievably in
the inner pores of carbon, through chemical bonding with surface functional groups or by reaction
with adsorbed oxygen/water molecules [9–14]. Various surface pretreatment methods, such as carbon
coating, chemical fluorination, oxidation, doping, etching, and acid treatments, are reported to improve
the electrochemical characteristics of the active carbon material [13]. The surface treatment allows
a more defined control in terms of surface chemistry, composition, and reactivity, eliminate surface
functional groups and reduce the surface area and thereby reducing the irreversible capacity loss due
to SEI formation [15,16].
Graphitic carbon material production requires expensive synthesis conditions and very high
temperature treatments close to 3000 ◦ C, to provide the mobility for carbon atoms to rearrange and
crystallize carbon into a graphite structure [17]. However, carbon produced from waste tires requires
a simple sulfonation process followed by pyrolysis in a nitrogen atmosphere at 1100 ◦ C [18–22].
Sulfonated tire-derived carbons have been tested as anodes in a half-coin cell lithium-ion battery
configuration [18]. This process needs to be scaled up and demonstrated in a pouch full-cell
configuration. The waste tires as a raw material also add a high value to the end-of-life tire rubber
and provide a sustainable solution to the huge amount of waste tires generated worldwide on an
annual basis. The carbon production cost and energy savings can be less than half of the graphite
production cost, due to low temperature pyrolysis and the availability of low-cost raw waste tire
rubber material. The demand to produce new tires to meet the needs of the rapidly growing auto
industry increased to 4.3 percent every year to 2.9 billion tires in 2017 [22]. This paper demonstrates
the successful scale up production of carbon material in kg quantities with 20–40 µm size particles
from waste tires and reported its electrochemical performances as a promising anode in both coin and
pouch LIB cell configurations. The micronized carbon materials coated with a thin layer of carbon
using a chemical vapor deposition (CVD) approach and investigated the effects of carbon coating
towards the improvements in electrochemical performances in LIB cells is also reported. In addition,
a simple prelithiation strategy to improve the first cycle efficiency to 94% is also presented.
 Sustainability 2018, 10, 2840 3 of 13
Sustainability 2018, 10, x FOR PEER REVIEW 3 of 12

2.2.Experimental
Experimental

2.1.
2.1.Material
MaterialSynthesis
Synthesis
Tire
Tirerubber
rubbercrumb
crumbofofsizesize1.51.5was
wassoaked
soakedatat70 ◦ Cfor
70°C for1212hhininaaconcentrated
concentratedsulfuric
sulfuricacidacidbath
bath
which
whichyielded
yieldedsulfonated
sulfonatedrubber
rubber slurry
slurry[18]. The
[18]. slurry
The was
slurry wasthen filtered,
then washed,
filtered, washed, andandpyrolyzed at
pyrolyzed
1100 °C. ◦The
at 1100 furnace
C. The waswas
furnace ramped
ramped upup from
fromroom
room temperature
temperature toto 400°C◦ Catata arate
400 ◦ C/minand
rateofof11 °C/min and
further
furtherincreased
increasedtoto11001100°C◦ Catata rate ofof
a rate 2 ◦C
2 °C /min andand
/min held for for
held 2 h 2and then
h and allowed
then to cool
allowed down
to cool to
down
room temperature
to room temperature under flowing
under flowingnitrogen gas.gas.
nitrogen Similarly, the the
Similarly, sulfonated
sulfonatedslurry waswas
slurry alsoalso
heated to
heated
1400
to 1400 ◦ C. carbon
°C. The The carbonsample was removed
sample and ground
was removed to 20–40
and ground toμm20–40sizeµmparticles and usedand
size particles for used
further
for
studies
further[21]. The[21].
studies carbonThesample
carbonwas alsowas
sample coated
alsowith a thin
coated withlayer
a thinof layer
carbon using Toluene
of carbon as an
using Toluene
aromatic hydrocarbon
as an aromatic feedstock
hydrocarbon in a fluidized
feedstock bed chemical
in a fluidized vapor vapor
bed chemical deposition (CVD)(CVD)
deposition reactorreactor
(see
Figure 1) at 800
(see Figure 1) at°C800 ◦
under flowing
C under nitrogen.
flowing The Toluene
nitrogen. sourcesource
The Toluene was keptwasatkept
70 °C at and
70 C◦ bubbled with
and bubbled
nitrogen gas at gas
with nitrogen a flow
at arate
flowofrate
2 L/min for 30 min.
of 2 L/min for 30The thickness
min. of the carbon
The thickness coating
of the carbon was 10-nm.
coating The
was 10-nm.
commercial graphite
The commercial of ~20ofμm
graphite ~20size
µmparticles was obtained
size particles from MTI
was obtained fromCorp., Richmond,
MTI Corp., CA, USA
Richmond, CA, and
USA
used
and as a standard
used electrode
as a standard material
electrode for comparison.
material for comparison.

Figure 1. Schematic fluidized bed reactor for carbon coating.

Figure 1. Schematic fluidized bed reactor for carbon coating.

2.2. Material Characterization

2.2. Material Characterization
The carbon materials recovered from tires were characterized for their particle size, surface
The carbon materials recovered from tires were characterized for their particle size, surface area,
area, porosity, pore volume, morphology and crystallography. Nitrogen adsorption desorption
porosity, pore volume, morphology and crystallography. Nitrogen adsorption desorption isotherms
isotherms were obtained with a Quantachrome NovaWin1000 Surface Area and Porosity Analyzer
were obtained with a Quantachrome NovaWin1000 Surface Area and Porosity Analyzer at 77.4 K.
at 77.4 K. The specific surface area was determined by the Brunauer-Emmett-Teller (BET) method.
The specific surface area was determined by the Brunauer-Emmett-Teller (BET) method. The pore
The pore size distribution was obtained by the Barret-Joyner-Halenda (BJH) method. Raman spectra
size distribution was obtained by the Barret-Joyner-Halenda (BJH) method. Raman spectra were
were collected with a Horiba LabRam HR using an excitation wavelength of 473 nm, a 600 g/mm
collected with a Horiba LabRam HR using an excitation wavelength of 473 nm, a 600 g/mm grating
grating and high spatial and spectral resolutions (800-mm monochromator). The X-ray powder
and high spatial and spectral resolutions (800-mm monochromator). The X-ray powder diffraction
diffraction (XRD) analysis was performed on a Rigaku Miniflex600 diffractometer with Cu Kα
(XRD) analysis was performed on a Rigaku Miniflex600 diffractometer with Cu Kα radiation. A Zeiss
radiation. A Zeiss Merlin VP scanning electron microscope (SEM), Thornwood, NY, USA operated at
Merlin VP scanning electron microscope (SEM), Thornwood, NY, USA operated at 3 kV was used to
3 kV was used to characterize the surface morphologies of the samples. Interlayer distances of the
characterize the surface morphologies of the samples. Interlayer distances of the carbons were
carbons were determined by a Hitachi HD-2300 A scanning transmission electron microscopy (STEM),
determined by a Hitachi HD-2300 A scanning transmission electron microscopy (STEM), Clarksburg,
Clarksburg, MD, USA with a field emission source operated at 200 kV in bright-field imaging mode at
MD, USA with a field emission source operated at 200 kV in bright-field imaging mode at a 2.1 Å
a 2.1 Å resolution.
resolution.
2.3. Electrochemical Characterization of Half Cells
2.3. Electrochemical Characterization of Half Cells
The electrode was prepared using a doctor blade coating technique by casting a slurry containing
The electrode was prepared using a doctor blade coating technique by casting a slurry
80 wt % tire derived carbon material or graphite, 10 wt % conductive carbon (C-NERGY Super C45,
containing 80 wt % tire derived carbon material or graphite, 10 wt % conductive carbon (C-NERGY
Super C45, Imerys Graphite & Carbon), and 10 wt % polyvinylidene difluoride (PVDF) binder in n-
Sustainability 2018, 10, 2840 4 of 13

Imerys Graphite & Carbon), and 10 wt % polyvinylidene difluoride (PVDF) binder in n-methyl-2-
pyrrolidone (NMP) solvent onto a copper foil. The typical loading amount of active material was
2–2.5 mg/cm2 . The electrochemical performance and cycling tests were carried out in a CR2032 coin
cell configuration. The coin cells were fabricated in an argon-filled glove box, using tire derived carbon
with and without carbon coating or graphite electrode as the working electrode (10-mm diameter),
metallic lithium foil as the counter electrode (13-mm diameter), Celgard 2325 as the separator and
the solution of 1.0 M LiPF6 in ethylene carbonate (EC)–dimethyl carbonate (DMC)–diethyl carbonate
(DEC) (1:1:1 by volume) as the electrolyte. The coin cells were charge and discharge cycled using
an Arbin BT2000 potentiostat/galvanostat multichannel system at room temperature under various
constant current rates between C/5 (0.20 mA/cm2 ) and C/50 (0.02 mA/cm2 ) with the voltage cut off
at 5 mV and 3.0 V.

2.4. Electrochemical Testing of Full Cells

The electrodes for pouch cells were made using a slot-die coater (Frontier Industrial Technology,
Towanda, PA, USA) at Oak Ridge National Laboratory’s (ORNL) Battery Manufacturing Facility (BMF)
by following the coating procedures reported in detail elsewhere [23]. The cathode slurry contains
90% the active LiNi0.5 Mn0.3 Co0.2 O2 (NMC532, Toda America, Battle Creek, MI, USA), 5% carbon black
(Vulcan XR72C, Billerica, MA, USA), and 5% PVDF (PowerFlex, Kynar, Arkema Inc., Prussia, PA, USA)
in NMP solvent. The anode slurry consists of 88% tire derived carbon material, 4% conductive carbon
C45 and 8% PVDF binder (9300, Kureha America, New York, NY) in NMP solvent. The slurries were
mixed separately in a high speed Ross planetary mixer (Charles Ross & Son Company, Hauppauge,
NY, USA). The cathode and anode slurries were coated onto aluminum foil and copper foil respectively
on a single side using the slot-die coater and transferred to a vacuum oven for drying at 120 ◦ C
overnight. A Celgard 2325 separator was used with an electrolyte composed of 1.2 M LiPF6 in EC:
DEC (3:7 wt ratio). The electrochemical performance characteristics and cycling tests were carried out
in a pouch cell configuration. Pouch cells of dimensions: 84.4-mm long × 56.0-mm wide were
fabricated in the dry room facility at BMF maintained at <0.5% (−53 ◦ C dew point) humidity.
The cycling performance tests were conducted at various charging and discharging current rates
between C/5 and C/50 and the voltage between 2.0, 2.5 and 4.2 V using a potentiostat (VSP, BioLogic,
Seyssinet-Pariset, France).

3. Results and Discussion

3.1. Material Characterization

Raman spectroscopy is being used as a nondestructive standard characterization tool to study
crystalline, nanocrystalline, and amorphous carbons [24]. The position and width of the G and D bands
and the intensity ratio of ID /IG are widely used for characterizing the degree of graphitization and
the quantity of defects present in the graphitic materials [24–26]. The Raman spectra of commercial
graphite exhibit a huge sharp G-band frequency centering at 1585 cm−1 and a small weak D-band at
1368 cm−1 (Figure 2a). The G peak is due to the bond stretching modes of all pairs of sp2 atoms in both
rings and chains. The D peak is due to the breathing modes of sp2 atoms in the rings. The intensity ratio
of ID /IG is calculated to be 0.123, with a small amount of disorder structure present in the commercial
graphite compared to the perfect graphite where D band intensity is almost zero and therefore the
ratio ID /IG = 0. The measured full-width-at-half-maximum (FWHM) of G band is 19.2 cm−1 compared
to the perfect graphite which has 14 cm−1 on a basal plane and 18 cm−1 in the prismatic edges [26].
The Raman spectrum of tire derived carbon sample pyrolyzed at 1100 ◦ C and 1400 ◦ C shown in
Figure 1b,c illustrate well-resolved two broad G and D bands. The carbon pyrolyzed at 1100 ◦ C exhibits
a broad G band centering at 1599 cm−1 and D band at 1363 cm−1 (Figure 2b) while pyrolyzed at 1400 ◦ C
exhibits also a broad G band centering at 1604 cm−1 and D band at 1363 cm−1 (Figure 2c); however the
peaks in the sample pyrolyzed at 1400 ◦ C are relatively narrower than those that in 1100 ◦ C. The average
Sustainability 2018, 10, 2840 5 of 13

Sustainability 2018, 10, x FOR PEER REVIEW 5 of 12

ID /IG ratio obtained are 0.86 and 0.99 and FWHM(G) are 127 cm−1 and 89 cm−1 respectively for carbon
pyrolyzed
[24,27]. Theatratio
both oftemperatures indicatingtoa the
ID/IG is proportional disorder
numbercrystalline structure
of aromatic rings.[24,27]. The ratiorelationship
The increased of ID /IG is
proportional to the
in the ID/IG ratio number
and G band of aromatic
position rings.
for theThe increased carbons
tire-derived relationship in the
shows IDmore
that /IG ratio
sp2 and G band
amorphous
position for the tire-derived carbons shows that more sp 2 amorphous carbon turns into nanocrystalline
carbon turns into nanocrystalline graphite at higher temperatures. The D band has a high sensitivity
graphite at higher
to disorder temperatures.
in the carbon materialThe D bandattributed
is usually has a hightosensitivity to disorder
the graphitization in the and
process carbon
thematerial
formation is
usually attributed
of crystal to theThis
growth [28]. graphitization
intensity ofprocess and the
the D band formation
increase of crystal
through growth [28].
heat treatment Thisbeintensity
could related
of the D band increase through heat treatment could be related to the nano-crystallite
to the nano-crystallite graphite growth in the tire carbon caused by the defects and amorphous graphite growth
in the tire carbon caused by the defects and amorphous carbon.
carbon.

Figure 2. Raman spectra with peak deconvolution of (a) commercial graphite, and carbon produced
Figure 2. Raman spectra with peak deconvolution of (a) commercial graphite, and carbon produced
from used tire with the pyrolysis temperatures of (b) 1100 °C, and (c) 1400 °C.
from used tire with the pyrolysis temperatures of (b) 1100 ◦ C, and (c) 1400 ◦ C.

Deconvolution of the first order Raman spectrum of tire derived carbon pyrolyzed at 1100 °C
◦C
was Deconvolution
fitted with 6 curves of theattributed
first ordertoRaman spectrum
the vibration modesof tireofderived
hexagonal carbon pyrolyzed
carbon at 1100
ring active at G-
was
bandfitted
(1599with cm−16)curves
representsattributed
an ideal to the vibration
graphitic modes ofwhile
structures, hexagonal
D1 (1363 carbon
cm−1ring
), D2active
(1676atcm G-band
−1), D3

(1599 cm − 1 ) represents an ideal graphitic structures, while D1 (1363 cm −1 ), D2 (1676 cm−1 ), D3

(1547 cm ), D4 (1177 cm ) and D5 (1464 cm ) bands relate to the defects in the disordered carbon
−1 −1 −1

(1547 cm−(Figure
structure
1 ), D4 (1177 cm−1 ) and D5 (1464 cm−1 ) bands relate to the defects in the disordered carbon
2b). Similarly, the tire derived carbon pyrolyzed at 1400 °C was also fitted with 6
structure (Figure(1603 2b). cm Similarly, the tire ◦ C was also fitted
curves: G-band −1), D1 (1363 cmderived
−1), D2 (1688carboncm−1 pyrolyzed
), D3 (1547 atcm
1400
−1), D4 (1217 cm−1), and with
D5
6(1440
curves: G-band (1603 cm − 1 ), D1 (1363 cm − 1 ), D2 (1688 cm − 1 ), D3 (1547 cm −1 ), D4 (1217 cm−1 ),
cm ) (Figure 2c). The D1 band appears the most intense is normally assigned to the A1g
−1

and D5 (1440
symmetry in thecm−graphitic
1 ) (Figure 2c). The D1 band appears the most intense is normally assigned to the
lattice vibration mode. The origin of the D1 band in disordered carbon is
Adue symmetry in the graphitic
1g to the vibration mode of large latticenumber
vibration ofmode.
small The origincrystallites
graphitic of the D1 band in theinpolycrystalline
disordered carbon tire
is due to the vibration mode of large number of small graphitic
derived carbon atoms, at the edge of the graphene layers [29,30]. Another feature observed crystallites in the polycrystalline
in the
tire derived
spectra carbon
is related toatoms,
the lineatbroadening
the edge ofof thethegraphene
G and D1 layers
bands, [29,30]. Another
indicating thatfeature observed in
the distribution of
the spectra is related to the line broadening of the G and D1 bands,
phonons activated by disorder corresponds to crystallites of different sizes. The intensity of the D1 indicating that the distribution
of phonons
curve increased activated
by 36% byanddisorder
G band corresponds
by 29% and tothe
crystallites
FWHM is ofreduced
differentfor sizes.
D1 andTheGintensity
bands by of45%
the
D1 curve
for the increased
sample by 36%
pyrolyzed and °C
at 1400 G band
comparedby 29% and °C
to 1100 theillustrating
FWHM is higher reduced for D1 and pyrolysis
temperatures G bands
by 45% for the sample pyrolyzed at 1400 ◦ compared to 1100 ◦ C illustrating higher temperatures
graphitizes the nanocrystals in a short rangeCorder and making it as disordered graphitic. Other defect
pyrolysis
bands D3 graphitizes
and D4 bands the in nanocrystals
carbon pyrolyzed in a short range°Corder
at 1100 and making
are assigned to theit as disordered
amorphous graphitic.
carbon and
Other defect bands D3 and D4 bands in carbon pyrolyzed at 1100 ◦ C are assigned to the amorphous
hydrocarbons connected to the basic structural units of graphitic carbon respectively [31,32]. The
carbon
intensity andofhydrocarbons
D3 and D4 connected curves aretodecreased
the basic structural
by 10% unitsand 25% of graphitic carbonwhen
respectively respectively [31,32].
the pyrolysis
The intensity increased
temperature of D3 andfrom D4 curves
1100 °C aretodecreased
1400 °C. by The10%D5 and
band25% respectively
is detected at 1464when cmthe pyrolysis
−1 for carbon
temperature increased from 1100 ◦ C−1to 1400 ◦ C. The D5 band is detected at 1464 cm−1 for carbon
pyrolyzed at 1100 °C and 1440 cm for carbon pyrolyzed at 1400 °C assigned to hydrocarbons
pyrolyzed ◦ C and 1440 cm−1 for carbon pyrolyzed at 1400 ◦ C assigned to hydrocarbons trapped
trapped inatthe 1100
carbon pores [33].
in theFigure
carbon3a pores [33]. a low magnification scanning electron microscopy (SEM) image of tire
illustrates
derivedFigurecarbon 3a illustrates
particles ofa various
low magnification
micron sizesscanningand shapes electron microscopy
with macro- (SEM) image
and meso-pores of tire
visible on
derived
the sample carbon particlesFigure
surface. of various 3b micron
illustratessizesthe
andhigh-resolution
shapes with macro- and meso-pores
scanning transmission visible on the
electron
sample
microscopy surface. Figure 3b
(HR-STEM) illustrates
image the high-resolution
of uncoated carbon pyrolyzed scanning
at 1100 transmission
°C, of bothelectron
graphitemicroscopy
layers and
(HR-STEM) image of uncoated carbon pyrolyzed at 1100 ◦ C, of both graphite layers and amorphous
amorphous carbon phase pattern. Figure 3c illustrates a cross-sectional layered structure of carbon
carbon
with thephase contrast pattern.
profileFigure
of ~4.53cÅillustrates
interlayer aspacing.
cross-sectional
Figure 3d layered
illustratesstructure of carbon
the selected areawith the
electron
contrast profile of ~4.5 Å interlayer spacing. Figure 3d illustrates
diffraction (SAED) patterns of uncoated carbon showing the coexistence of short range ordered the selected area electron diffraction
(SAED)
graphitepatterns
phase of and uncoated
amorphous carbonregions.
showingThe the coexistence of shortthe
fringes represent range ordered
stacks graphite phase
of graphene layersand of
amorphous
polyaromatic regions. The fringes
structures [34]. Theserepresent the stacks
fringes are very of graphene
short andlayers of polyaromatic
completely structures
disoriented. Figure[34].3e
illustrates a HR-STEM image of carbon coated tire derived carbon, showing a uniform carbon coating
of ~10 nm thickness on the surface of the carbon. The carbon coating enables the reduction of the
surface area from 110 to 20 m2/g.
Sustainability 2018, 10, 2840 6 of 13

These fringes are very short and completely disoriented. Figure 3e illustrates a HR-STEM image of
carbon coated tire derived carbon, showing a uniform carbon coating of ~10 nm thickness on the
surface of the2018,
carbon. ThePEER
carbon coating enables the reduction of the surface area from 110 to 20 m122 /g.
Sustainability 10, x FOR REVIEW 6 of

Sustainability 2018, 10, x FOR PEER REVIEW 6 of 12

Figure 3. Tire derived carbon (a) scanning electron microscope (SEM) image, (b) high-resolution
Figure 3. Tire derived carbon (a) scanning electron microscope (SEM) image, (b) high-resolution
scanning transmission electron microscopy (HR-STEM) images showing both planar and cross-
scanning
Figure transmission
3. layered electron
Tire derived carbonmicroscopy (HR-STEM) microscope
images showing both planar
(b)and cross-sectional
sectional structures, (c)(a)
thescanning
contrast electron (SEM)
profile of ~4.5 Å spacings, image,
(d) Selectedhigh-resolution
Area Electron
layered structures,
scanning (c) the contrast
electron profile
microscopyof ~4.5 Å spacings,
(HR-STEM) (d)
images Selected
showing Area
both Electron
Diffraction pattern (SAED), and (e) HR-STEM image of carbon coated tire derived carbon.and cross-
transmission planar Diffraction
pattern (SAED), and (e) HR-STEM image of carbon coated tire derived carbon.
sectional layered structures, (c) the contrast profile of ~4.5 Å spacings, (d) Selected Area Electron
Diffraction pattern (SAED),
X-ray photoemission and (e) HR-STEM
spectroscopy image ofofcarbon
(XPS) spectra coated tire derived
the tire-derived carbonscarbon.
are shown in Figure
X-ray
4. The C1sphotoemission
spectra in Figure spectroscopy
4a for both(XPS)
carbon spectra
samplesof the tire-derived
of carbon coatedcarbons are shown
and uncoated showina Figure
sharp 4.
Thepeck X-ray
C1satspectraphotoemission
284.8 eV, which is4adue
in Figure spectroscopy
fortoboth (XPS)
the carbon spectra
sp configuration.
2 of
samples ofThe the tire-derived
fittingcoated
carbon carbons
resultsand are shown
for uncoated
C1s spectra in Figure
showa that
show sharp
4.
theThe C1s spectra isinnarrow
Figure 4a
peck atCarbon
284.8 peak
eV, which to for
the both
is due consistent carbon samples
sp2 configuration.
with C-C bondThe of carbon
and coated
there are
fitting and uncoated
no C–O
results or C=O
for C1s show aon
show sharp
groups
spectra thethe
that
peck at 284.8
surface. Figure eV,
4 bwhich
shows isthe
due
S2pto scans
the spof2 configuration. The fitting results for C1s spectra show that
the samples. The peak at C–O
aboutor164 eV is relatedontothe
thesurface.
thiol
Carbon peak is narrow consistent with C-C bond and there are no C=O groups
the Carbon
group. peakdoublet
is narrow consistent with C-C bond and theretoare
theno C–O or C=Oofgroups on the
Figure 4 bAshows
small the S2p scans spike at
of around 165.2
the samples. eV
Thecould
peakbe at due
about 164 trace
eV isamount
related to sulfate
the thiol group
group.
surface.
present. Figure 4
It wasspikeb shows
shown the S2p scans of the samples. The peak at about 164 eV is related to the thiol
A small doublet at that
around the 165.2
sulfateeVgroups
couldare completely
be due removed
to the trace fromofthe
amount sample
sulfate groupwhen the
present.
group.
pyrolysisA small doublet
temperature spike at
is increased around
further 165.2 eV could
to 1600 °C [22]. be due
The XPS to the trace
elemental amount
analysis of sulfate
for the group
It was shown that the sulfate groups are completely removed from the sample when thesamples
pyrolysis
present.
is shown Itinwas
Tableshown
1. The that the sulfate
carbon coating groups
◦ increasesarethe
completely
carbon removed from
percentage by thewhile
4.7% sample thewhen
O2s the
and
temperature
pyrolysis is increased
temperature further
is increasedto 1600
furtherC [22].
to 1600The°C XPS
[22]. elemental
The XPS analysis
elemental for the
analysis samples
for the is shown
samples
S2p are reduced by 16.78% and 0.84%, respectively.
in is
Table
shown1. The carbon
in Table 1. Thecoating
carbon increases the carbon
coating increases thepercentage by 4.7%by
carbon percentage while
4.7%the O2s
while theand
O2sS2pandare
reduced
S2p areby 16.78%by
reduced and 0.84%,
16.78% andrespectively.
0.84%, respectively.

Figure 4. X-ray photoelectron spectroscopy (XPS) data of tire derived carbon, uncoated (top), and
carbon coated (bottom) of scans of (a,d) C1s, (b,e) O2s, and (c,f) S2p.
Figure 4. X-ray photoelectron spectroscopy (XPS) data of tire derived carbon, uncoated (top), and
Figure 4. X-ray photoelectron spectroscopy (XPS) data of tire derived carbon, uncoated (top),
carbon
Table 1.coated (bottom)
XPS surface of scans of (in
concentration (a,d) C1s, (b,e)
atomic O2s, andof(c,f)
percentages) S2p.and uncoated tire derived carbon
coated
and carbon coated (bottom) of scans of (a,d) C1s, (b,e) O2s, and (c,f) S2p.
samples.
Table 1. XPS surface concentration (in atomic percentages) of coated and uncoated tire derived carbon
XPS Atomic % Peak BE FWHM eV Area (P) CPS eV SF
Material
samples.characterization studies clearly demonstrate that the carbon material synthesized from
Scans Coated Uncoated Coated Uncoated Coated Uncoated Coated Uncoated Coated Uncoated
waste XPS
tires has97.82
C1s a unique disordered
93.3
Atomic %
nanoporous
284.79Peak 284.79
BE
structure
1.10FWHM eVwith a 87,813.38
1.15 large interlayer
69,670.55
Area (P) CPS eV
distance
1 than1 that of
SF
graphite.
O2s
Scans This novel
1.23 carbon
5.2 material
533.02 synthesis
532.9 technology
1.77
Coated Uncoated Coated Uncoated Coated Uncoated from
2.67 tires demonstrates
2701.93
Coated Uncoated Coated sustainable
9541.84 more
2.93 2.93
Uncoated
S2p
C1s 0.96
97.82 1.5
93.3 164.19
284.79 164.19
284.79 1.03
1.10 0.91
1.15 1546.58
87,813.38 2012.37
69,670.55 1.67
1 1.67
1
and efficient use of resources.
O2s 1.23 5.2 533.02 532.9 1.77 2.67 2701.93 9541.84 2.93 2.93
S2p
Material0.96 1.5
characterization164.19 164.19
studies clearly1.03 0.91
demonstrate that the1546.58 2012.37
carbon material 1.67 1.67
synthesized from
waste tires has a unique disordered nanoporous structure with a large interlayer distance than that
Material characterization studies clearly demonstrate that the carbon material synthesized from
waste tires has a unique disordered nanoporous structure with a large interlayer distance than that
Sustainability 2018, 10, 2840 7 of 13

Table 1. XPS surface concentration (in atomic percentages) of coated and uncoated tire derived
carbon samples.

XPS Atomic % Peak BE FWHM eV Area (P) CPS eV SF

Scans Coated Uncoated Coated Uncoated Coated Uncoated Coated Uncoated Coated Uncoated
C1s 97.82 93.3 284.79 284.79 1.10 1.15 87,813.38 69,670.55 1 1
Sustainability 2018, 10, x FOR PEER REVIEW 7 of 12
O2s 1.23 5.2 533.02 532.9 1.77 2.67 2701.93 9541.84 2.93 2.93
S2p 0.96 1.5 164.19 164.19 1.03 0.91 1546.58 2012.37 1.67 1.67
of graphite. This novel carbon material synthesis technology from tires demonstrates more
sustainable and efficient use of resources.
3.2. Electrochemical Measurements of Half Cells
3.2.Uncoated
Electrochemical
carbonMeasurements
materials of of38Half
µmCells
and 20 µm particle sizes and carbon coated carbon materials
of 20 µm particle size were utilized in
Uncoated carbon materials of 38 μm and half coin
20cells having sizes
μm particle lithium
andmetal
carbonascoated
the counter
carbonelectrode
materials in
standard
of 20 μm electrolyte solutions
particle size were cycled
were utilized in half at various
coin currentlithium
cells having rates are presented
metal in Figure
as the counter 5. Theincell
electrode
with
standard electrolyte solutions were cycled at various current rates are presented in Figure 5. Theatcell
larger particle size (38 µm) exhibited an initial first cycle coulombic efficiency of 51% C/3
charge/discharge
with larger particle current rate.μm)
size (38 Theexhibited
first cycleancoulombic
initial first efficiency was increased
cycle coulombic efficiencytoof60%
51%when
at C/3the
starting particle sizecurrent
charge/discharge was reduced to 20
rate. The µm
first andcoulombic
cycle to 66% forefficiency
carbon coated tire derived
was increased carbon
to 60% whensamples.
the
starting
Further particle
cycling size was the
exhibited reduced to 20 μm
coulombic and to 66%
efficiency for to
close carbon
100%coated
for alltire
thederived
samples. carbon
Thesamples.
reversible
Furtherofcycling
capacity uncoatedexhibited
carbon thematerial
coulombic is efficiency
247 mAh/g closeat to 100%
C/5 for all the samples.
charge/discharge The reversible
current rate and it
capacitytoof364
increased uncoated
mAh/gcarbon material
for smaller sizeis particles
247 mAh/g (20 atµm)C/5andcharge/discharge currenttorate
it increased further 437 and
mAh/git
increased
with carbontocoated
364 mAh/g
sample.for smaller
Loweringsize particles
the charge (20 discharge
μm) and it cycling
increased further
rate to 437and
to C/7.5 mAh/gC/50withalso
carbon coated
increased sample. capacity
the reversible Loweringtothe 300charge
mAh/g discharge
and 430 cycling
mAh/g raterespectively
to C/7.5 andcorresponding
C/50 also increased
to 65%
the reversible capacity to 300 mAh/g and 430 mAh/g respectively
and 92% respectively to the first cycle capacity. These results are interesting because corresponding to 65%theandlithium
92%
respectively
utilization to thecurrent
at C/50 first cycle capacity.
rate cyclingThese
is 92%results
which aremeans
interesting because
the actual the lithiumcapacity
irreversible utilization at is
loss
C/50 current rate cycling is 92% which means the actual irreversible capacity loss is only 8%. This
only 8%. This indicates that the apparent first cycle irreversible capacity loss was not due to the SEI
indicates that the apparent first cycle irreversible capacity loss was not due to the SEI formation rather
formation rather it is related to the polarization caused by the poor conductivity of the carbon material.
it is related to the polarization caused by the poor conductivity of the carbon material. When the
When the carbon was coated with a thin layer of carbon the capacity increased to 432 mAh/g at C/10
carbon was coated with a thin layer of carbon the capacity increased to 432 mAh/g at C/10 current
current rate. The increased capacity for the carbon coated sample can be related to the increased
rate. The increased capacity for the carbon coated sample can be related to the increased conductivity
conductivity due to high carbon concentration of 98% and lower oxygen percentage of 1.23% as found
due to high carbon concentration of 98% and lower oxygen percentage of 1.23% as found from XPS
from XPS (Table
studies studies1).(Table 1).

Figure 5. Cycling performance of lithium ion coin cells having lithium metal foil as the counter
Figure 5. Cycling
electrode performance
and uncoated of lithium
tire derived carbon ion
of 38coin cells20having
μm and lithium
μm size particlemetal foilcarbon
size and as thecoated
counter
electrode and uncoated
tire derived tire
carbon of 20 μmderived carboncycled
size particles of 38 µm and 20current
at various µm size particle size and carbon coated
rates.
tire derived carbon of 20 µm size particles cycled at various current rates.
Figure 6 compares charge capacities of uncoated and carbon coated tire derived carbon electrode
material of 20 μm particle size pyrolyzed at 1100 °C and commercial graphite (20 μm) working
electrodes in half coin cells. The uncoated carbon electrode exhibited 364 mAh/g capacity which is
3% higher capacity than that of the commercial graphite (353 mAh/g) while carbon coated exhibited
20% higher capacity of 437 mAh/g. The carbon coating also improved the first cycle columbic
efficiency by 10%. The irreversible capacity and the surface area of the active material are directly
proportional (higher capacity for low surface area of 20 m2/g with carbon coated samples compared
Sustainability 2018, 10, 2840 8 of 13
Sustainability 2018, 10, x FOR PEER REVIEW 8 of 12

Figure 6 compares
The carbon coatingcharge capacities
also reduced theofinterfacial
uncoated and carbonbetween
resistance coated tire
thederived carbon
particles electrode
and improved
material of 20 µm particle size pyrolyzed at 1100 ◦ C and commercial graphite (20 µm) working
the surface conductivity and thus enhanced the reversible capacity [11]. Furthermore, the carbon
electrodes
coating has in reduced
half coin the
cells.voltage
The uncoated carbon
hysteresis electrode
in carbon exhibited
coated 364 (Figure
samples mAh/g 6b) capacity whichto
compared is the
3%
higher capacity than that of the commercial graphite (353 mAh/g) while carbon coated
uncoated carbon sample. The difference in the charge discharge voltage behavior of graphite (Figure exhibited 20%
higher
6c) vs. capacity
the carbonsof 437
wasmAh/g.
found toThe carbonwell
correlate coating
withalso
theirimproved the first cycle
unique structure columbic
[8]. The lithiumefficiency
insertion
by 10%. The irreversible capacity and the surface area of the active material
mechanism at higher voltage starting from ~1.2 V is more of an adsorption behavior while an are directly proportional
(higher capacity
intercalation for low
process surface
occurs at lower of 20 m2 /g
area voltages with
[8,9]. Thecarbon
carbons coated
vs. Lisamples
countercompared
electrodesto in the lower
coin-type
capacity for exceptionally
high surface area 2
cells reveal goodofcycleability,
110 m /g with withuncoated carbon capacity
only moderate samples).fading.

Figure 6. Comparison of cycling performances of uncoated and carbon coated tire derived carbon
Figure 6. Comparison of cycling performances of uncoated and carbon coated tire derived carbon
with commercial graphite as working electrodes vs. lithium metal counter electrode: (a) capacity plot,
with commercial graphite as working electrodes vs. lithium metal counter electrode: (a) capacity plot,
and (b,c) voltage profiles.
and (b,c) voltage profiles.

3.3. Electrochemical Measurements of Pouch Full Cells

The carbon coating also reduced the interfacial resistance between the particles and improved the
The
surface use of tire derived
conductivity and thus carbon as a promising
enhanced anode
the reversible material
capacity [11].inFurthermore,
a lithium-ionthe battery
carbonpouch full
coating
cell reduced
has configuration
the voltagehaving NMC532
hysteresis as cathode
in carbon in standard
coated samples (Figure electrolyte
6b) compared solutions
to the has been
uncoated
carbon sample. The difference in the charge discharge voltage behavior of graphite (Figure 6c) vs.C/50
demonstrated in Figure 7. The formation cycling tests were first performed at C/5, C/20, and the
charge and
carbons wasdischarge current rates.
found to correlate Aftertheir
well with the unique
formation cycling,
structure [8].the
Thecells were insertion
lithium cycled atmechanism
C/5 charge
discharge
at rate loststarting
higher voltage 0.12% capacity per V
from ~1.2 cycles when
is more of the
an voltage cut off
adsorption was limited
behavior whiletoan2.0intercalation
V while the
rest of the cycles lost only 0.08% capacity per cycle at 2.5 V limit. After 160 cycles
process occurs at lower voltages [8,9]. The carbons vs. Li counter electrodes in coin-type cells at C/5, the cellsreveal
were
further cycledgood
exceptionally at lower currentwith
cycleability, rate only
of C/50 showedcapacity
moderate an increase
fading. of 12% in reversible capacity. The
cycling tests demonstrate carbon as a promising anode material in full cell configuration. Further
3.3. Electrochemical
electrochemical Measurements ofwere
characterizations Pouch Full Cells
carried out to design better cell chemistry.
The use of tire derived carbon as a promising anode material in a lithium-ion battery pouch full
cell configuration having NMC532 as cathode in standard electrolyte solutions has been demonstrated
in Figure 7. The formation cycling tests were first performed at C/5, C/20, and C/50 charge and
discharge current rates. After the formation cycling, the cells were cycled at C/5 charge discharge
rate lost 0.12% capacity per cycles when the voltage cut off was limited to 2.0 V while the rest of the
cycles lost only 0.08% capacity per cycle at 2.5 V limit. After 160 cycles at C/5, the cells were further
cycled at lower current rate of C/50 showed an increase of 12% in reversible capacity. The cycling tests
demonstrate carbon as a promising anode material in full cell configuration. Further electrochemical
characterizations were carried out to design better cell chemistry.

Figure 7. Cycling performance of the carbon anode material pyrolyzed at 1100 °C vs. NMC532
cathode at various current rates.
 charge and discharge current rates. After the formation cycling, the cells were cycled at C/5 charge
discharge rate lost 0.12% capacity per cycles when the voltage cut off was limited to 2.0 V while the
rest of the cycles lost only 0.08% capacity per cycle at 2.5 V limit. After 160 cycles at C/5, the cells were
further cycled at lower current rate of C/50 showed an increase of 12% in reversible capacity. The
cycling tests
Sustainability demonstrate
2018, 10, 2840 carbon as a promising anode material in full cell configuration. Further 9 of 13
electrochemical characterizations were carried out to design better cell chemistry.

Figure 7. Cycling performance of the carbon anode material pyrolyzed at 1100 °C vs. NMC532
Figure 7. Cycling performance of the carbon anode material pyrolyzed at 1100 ◦ C vs. NMC532 cathode
cathode at various current rates.
at various current rates.

3.4. Prelithiation of Carbon Anodes

Prelithiation is an important strategy that attracts more and more interest to compensate for
lithium loss in the formation cycle in lithium-ion batteries. Experimentally, it is more challenging to
pre-lithiate anode materials than to pre-lithiate cathode materials since it requires a more reactive
lithium source and the process is hard to control. There are some reports using stabilized lithium
metal power (SLMP), however, this type of material is expensive and hard to disperse in NMP
solution during the slurry preparation [35–37]. It will require a special complex procedure to apply
pre-lithiated anodes.
The goal of using pre-lithiation treatment is to achieve first cycle efficiency of over 90% for the
electrode materials. Here, the pre-lithiation is conducted by direct contacting of lithium metal with
the electrolyte wetted with casted electrode, as shown in Figure 8a [38]. Different contact periods
were studied to optimize the process conditions. Since the electrode was shorted after contact with
Li, the assembled cell has almost 0 V OCV and at this time, first cycle efficiency would be that of the
real second cycle since the first discharge is skipped. It is noticeable that all pre-lithiated cells have a
very high efficiency (over 94%) from the beginning, compared to 60% efficiency of the cell without
pre-lithiation. There are no major differences in the electrochemical performances during the first
22 cycles for different pre-lithiated electrodes shown in Figure 8. However, the long-term cycling test
is needed to fully evaluate the influence of electrode properties.
In the meantime, new methods could be developed to pre-lithiate electrode materials, and they
might be conducted in the future. Half cells with electrodes could be assembled and discharged to
certain voltage, followed by disassembling of the cell and washing of the electrodes, then full cells
can be made with pre-lithiated electrodes. This method can precisely control the amount of lithium
pre-intercalated into the electrodes. Another approach is to use Li3 N as a lithium source additive
when preparing the slurry and make a pouch cell [39]. Li3 N will decompose at 0.44 V during the
formation cycle and the N2 gas generated could be released before the final sealing of the pouch
cell. Successful implementation of this technology would result in a significant reduction in carbon
emissions and possibly result in a lower-cost higher performance lithium-ion battery [40–45].
Li, the assembled cell has almost 0 V OCV and at this time, first cycle efficiency would be that of the
real second cycle since the first discharge is skipped. It is noticeable that all pre-lithiated cells have a
very high efficiency (over 94%) from the beginning, compared to 60% efficiency of the cell without
pre-lithiation. There are no major differences in the electrochemical performances during the first 22
cycles for different
Sustainability 2018, 10,pre-lithiated
2840 electrodes shown in Figure 8. However, the long-term cycling test
10 of 13 is
needed to fully evaluate the influence of electrode properties.

Figure
Figure (a)(a)Schematic
8. 8. Schematicof
of direct
direct contact
contactpre-lithiation
pre-lithiationprocess, electrochemical
process, test data
electrochemical test with
data(b) 20 min,
with (b) 20
(c) 19 h, (d) 23 h contact.
min, (c) 19 h, (d) 23 h contact.

4. In
Conclusions
the meantime, new methods could be developed to pre-lithiate electrode materials, and they
might be conductedbattery
In summary, in thegrade
future. Half cellscarbon
tire-derived with material
electrodes wascould be assembled
successfully preparedand discharged
in high purity in to
certain
large voltage,
quantitiesfollowed by disassembling
and demonstrated of the
as a potential anodecell material
and washing of The
for LIBs. the electrodes,
combustion then fulltire
of waste cells
canrubber
be made with lower
produces pre-lithiated
fossil CO electrodes.
2 emissions This
per method
unit of can
energy precisely
(136.51 gCOcontrol
2 /kW the
· h) amount
compared of
to lithium
other
pre-intercalated into fuels
conventional fossil the electrodes.
such as coalAnother approach
or fuel–oil, usually is to use
used Li3N generation
in power as a lithium source
[40]. additive
The surface
coating
when of the carbon
preparing the slurryimproved
and make the reversible
a pouch cell lithium
[39]. capacity
Li3N willbydecompose
20% and yielded
at 0.44437 mAh/g,
V during the
which is 20% higher than that of the commercial graphite. A novel prelithiation approach
formation cycle and the N2 gas generated could be released before the final sealing of the pouch cell. also yielded
the first cycle
Successful efficiency of 94%.
implementation Thistechnology
of this novel green would
process result
can promote environmental
in a significant sustainability
reduction to
in carbon
add value to the waste tires and benefit the battery industry to solve future
emissions and possibly result in a lower-cost higher performance lithium-ion battery [40–45]. energy crises.

Author Contributions: J.S.G. planned the experiments and wrote the paper, R.J.L., and A.M.L. identified the
research questions, J.L.W., and S.L.W. carried out scale up carbon material synthesis, Y.L., J.L., and K.A. carried
out the experimental work, A.K.N. and M.P.P. came up with the concept and analyzed the data.
Acknowledgments: The research (Y.L., M.P.P.) was supported by the U.S. Department of Energy (DOE), Office of
Science, Office of Basic Energy Sciences, Materials Sciences and Engineering Division. Part of research at RJ Lee
Group was funded by internal funding.
Conflicts of Interest: The authors declare no competing financial interest.
Notice: UT-Battelle: LLC under Contract No. DE-AC05-00OR22725 with the DOE authored this manuscript.
The United States Government retains and the publisher, by accepting the article for publication, acknowledges
that the United States Government retains a non-exclusive, paid-up, irrevocable, world-wide license to publish or
reproduce the published form of this manuscript, or allow others to do so, for United States Government purposes.
The DOE will provide public access to these results of federally sponsored research in accordance with its Public
Access Plan (http://energy.gov/downloads/doe-public-access-plan).
Sustainability 2018, 10, 2840 11 of 13

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