Energy 95 (2016) 483e493

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Energy
journal homepage: www.elsevier.com/locate/energy

A kish graphitic lithium-insertion anode material obtained from

non-biodegradable plastic waste
T. Sri Devi Kumari a, Adriel J.J. Jebaraj b, T. Antony Raj c, D. Jeyakumar a, T. Prem Kumar d, *
a
Functional Materials Division, CSIR-Central Electrochemical Research Institute, Karaikudi, Tamil Nadu, India
b
Department of Chemistry, Case Western Reserve University, Cleveland, OH, USA
c
Tata Autocomp GY Batteries Ltd., Pune, India
d
Electrochemical Power Systems Division, CSIR-Central Electrochemical Research Institute, Karaikudi, Tamil Nadu, India

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

Article history: Graphitic carbon continues to dominate as the choice anode material in lithium-ion batteries despite its
Received 30 October 2014 theoretical specic capacity of 372 mAhg
1. Tailored forms of graphite with higher practical capacities
Received in revised form should, therefore, be of interest to the industry. This paper reports the production of a kish graphitic
27 November 2015
anode material from polyvinyl chloride by simultaneous carbonization of the polymer and dissolution of
Accepted 29 November 2015
Available online 6 January 2016
the resulting carbon in an iron melt to produce a supersaturated solution of carbon in iron, and sub-
sequent precipitation of the carbon as graphite upon cooling. Our study presents a process for converting
non-biodegradable plastic wastes that litter our surroundings into a technologically useful product. The
Keywords:
Kish graphite
new material exhibits a rst-cycle reversible capacity of 444 mAhg
1 and sustains at least 200 cycles at
Catalytic graphitization C/10 rate before its capacity drops below 372 mAhg
1.
Anode material 2015 Elsevier Ltd. All rights reserved.
Lithium insertion
Lithium-ion battery
Plastic waste

1. Introduction Most plastic materials are non-biodegradable, which has

Ubiquitous and manifesting in a multitude of forms in everyday
products, plastics are among the most wonderful materials inven-
ted in the twentieth century. Products made of plastics rank among
the fastest growing markets in the world due to their low cost and
versatility. However, because the utility period of plastic products is
relatively short, humongous quantities of plastic waste accumulate
rapidly, which is increasingly becoming a serious environmental
problem. In fact, environmentalists have begun to consider plastic
waste as hazardous [1] not only because plastics threaten wildlife
[2] and marine life [3] but also because some plastics are potentially
toxic [4] or absorb pollutants [5]. According to a 2014 report titled
Valuing Plastic from the United Nations Environment Program [6],
nancial damages per year to marine ecosystems due to plastic
waste accounts for 1.3  1010 US dollars. Sustainable development
thus calls for proper strategies to deal with such solid waste [7].
* Corresponding author. Tel.: 91 4565 241414, 91 4565 241141; fax: 91 4565
227999.
E-mail addresses: premlibatt@yahoo.com, prem@cecri.res.in (T.P. Kumar).
resulted in a colossal accumulation of such litter, accentuated by
the throw away culture. For example, around one trillion plastic
bags are discarded each year worldwide, with most of them ending
up in landlls, dumpsites and water bodies. The booming elec-
tronics industry is another major culprit. Disposal in landlls is
increasingly being constrained by legislations. The use of recycled
plastic in concrete has also been studied extensively [8]. However,
these options mean that the energy content in the waste is not
recovered. The inherent energy in the plastic can be recovered by
incineration. However, because incineration leads to the conversion
of most of the carbon in the plastic into carbon dioxide, pyrolysis is
often considered a preferred waste management option [9]. Ther-
mal degradation of plastics yield a variety of products including
high-value products such as hydrogen (by pyrolysis of municipal
solid waste [10] and catalytic steam pyrolysisegasication of
polypropylene [11]), producer gas [12], a wide range of hydrocar-
bons (from municipal solid waste [10], contaminated plastic solid
waste [13] and mixed real-world plastic waste [14]), and liquid fuels
(from plastic waste [15]). In another study of industrial signicance,
plastic waste was remediated into carbon nanotubes [16]. In this
paper, we report a method to convert such industrial and e-waste
into technologically useful products.

http://dx.doi.org/10.1016/j.energy.2015.11.069
0360-5442/ 2015 Elsevier Ltd. All rights reserved.
484 T. Sri Devi Kumari et al. / Energy 95 (2016) 483e493
With this in mind, we describe here a process by which non-
biodegradable plastics such as polyvinyl chloride is converted
into kish graphite, a product that holds much promise as an anode-
active material in lithium-ion batteries [17e19]. It is obtained by
precipitating the excess carbon from a supersaturated solution of
carbon in steel. These graphitic products have been shown to be
aky carbon forms with nanocarbon structures embedded in them
[20]. The remarkable lithium insertion properties of these materials
are attributed to the presence of nanostructured carbons in the kish
graphite products [17e19]. Conventionally, kish graphite is gener-
ated from coke and coconut charcoal, which are used as carbon
precursors in foundries. Kish graphite-like materials have also been
produced in the laboratory. Krivoruchko et al. [21] observed the
sub-normal melting of iron nanoparticles and the movement of
FeeC particles in a liquid layer during the catalytic conversion of
amorphous carbon into graphite. In a subsequent study on the
interaction of amorphous carbon lms with iron, cobalt and nickel
particles by electron microscopy at temperatures between 600 and
750  C, Krivoruchko et al. [22] found that at these temperatures the
metals interact with the carbon, transit to the liquid state and move
from the carbon lm, leaving behind graphite tracks. In their
studies on the catalytic graphitization of amorphous carbon, ob-
tained by catalytic carbonization of polyvinyl alcohol on iron par-
ticles between 600 and 800  C, these authors found that the
products contained nanocarbon structures: multi-walled graphite
shells wrapping the catalyst particles, cockle-shelled graphite la-
ments and MWCNTs [23]. Chernozatonskii et al. [24] reported the
synthesis of inclusions of fullerenes and nanotubes in alloys of
FeeNieC and FeeNieCoeC at temperatures between 1250 and
1300  C. Reports on the electrochemical lithium insertion proper-
ties of such precipitated graphitic products rst appeared in 2003
[17,18] and again in 2011 [19]. These investigators employed the
customary coke or coconut charcoal as carbon precursors. This
study presents results of studies on the electrochemical lithium
insertion behavior of kish graphite obtained with PVC, a non-
biodegradable solid plastic waste, as a carbon precursor.
2. Experimental
The preparative procedure for the generation of kish graphite is
given in Fig. 1. PVC and cast iron used in this study were obtained
from local sources. Cast iron was melted in a cupola crucible and
maintained at 1700  C. A calculated amount of PVC in the form of
small beads was dropped on to the melt. Carbon dioxide released in
the initial carbonization step resulted in a non-oxidizing column of
gas over the melt, preventing further burning of the polymer. The
carbonaceous pyrolytic products then readily dissolved in the
molten steel, resulting in a saturated solution of carbon. The cupola
crucible was kept shaking to allow uniform dissolution of the car-
bon in the melt. The melt was poured on to a sand bed and allowed
to cool, whereupon the excess dissolved carbon precipitated out as
kish graphite between the grain boundaries in the grey steel
product. The moulds were then machined into ingots of convenient
sizes. The graphite in the ingots was recovered by leaching the
metal with 4 M HCl and silica with 20% HF, washing with Millipore
water, and drying.
The grain structure of the grey steel was examined by a metal-
lurgical microscope (MTI MM500T) tted with a digital camera. The
samples for metallographic examination were prepared by unidi-
rectional polishing of the ingots with sandpapers of successively
increasing neness. The polished, mirror-nish surfaces were
nally rinsed with water and acetone to remove soil traces. The
surface morphology of the graphite obtained by acid leaching was
examined by scanning electron microscopes (Hitachi S-3000H and
Jeol JSM 35-CF), a Carl Zeiss eld-emission scanning electron
microscope (Supra 55 VP) and an FEI transmission electron mi-
croscope (Tecnai 20 G2). A PerkineElmer CHN-2000 elemental
analyzer was used for determining the elemental composition of
the products. However, the iron content was determined by an
inductively coupled plasma mass spectrometer (Thermo Electron X
Series 2). The X-ray diffractograms of the products were recorded
on a Bruker D8 Advance X-ray diffractometer tted with a nickel-
ltered monochromated Cu-Ka radiation source (l 1.5418 )
between scattering angles of 10 and 80 in steps of 0.05 . Laser
Raman spectroscopic measurements were performed in the
1000e2000 cm
1 region with a laser radiation wavelength of
632.8 nm (Renishaw InVia; HeeNe laser). The Raman results were
tted with Renishaw software.
The lithium insertion-deinsertion properties of the graphite ma-
terials were studied in standard 2032-type coin cells (Hohsen). The
graphite powder was made into a slurry with 8% PVdF binder (Aldrich)
and 2% conducting carbon black additive (Timcal) in NMP (Merck).
Test electrodes were made by slurry-coating on an oxide-free copper
sheet (Hohsen), dried overnight, pressed and cut into discs. Lithium
metal (Cyprus Foote Mineral) was used as the reference/counter
electrode and a 1 M solution of LiPF6 in a 1:1 (v/v) mixture of ethylene
carbonate (EC) and diethyl carbonate (DEC) (Ferro) was used as the
electrolyte. A Celgard 2320 membrane was used as the separator.
Galvanostatic charging and discharging of the cells were done at C/10
rate between 2.000 and 0.005 V, unless otherwise stated, by using a
multi-channel battery tester (Arbin BT2000).
Thermal stability studies were carried out using a Mettler
Toledo temperature-modulated differential scanning calorimeter
(DSC1) between 25 and 400  C at a temperature ramp of 5  C min
1
under argon. The samples for the safety studies were obtained by
opening the coin cells at different states-of-charge with a Hohsen
coin cell disassembling unit. The active material for the thermal
stability studies as well as for the ex situ XRD and Raman studies
was maintained at pre-determined potentials in the Arbin battery
cycling unit for 48 h before disassembly. The active material scra-
ped from the copper discs was freed of excess electrolyte by
pressing with Kimwipes tissue paper, and transferred into
aluminum cups and sealed inside a glove box (MBraun G-120B).
However, for ex situ XRD and Raman measurements, the scraped
material was rinsed in an excess of diethyl carbonate (Merck) and
dried inside the glove box. Washing of the material was especially
important for Raman spectral studies as any remnant LiPF6 in the
test sample can lead to uorescence effects that could obscure the
Raman signal [25]. For ex situ X-ray diffraction studies, the scraped-
out products were spread on a glass plate holder (Bruker Scientic),
onto which a double-sided PE tape border was xed. The product
was then covered with a Mylar sheet, which spread snugly on the
PE tape, allowing no contact between the active material and the
surroundings. A similar procedure was followed for ex situ Raman
studies except that a thin microscopic glass plate was used in the
place of the Mylar lm.
3. Results and discussion
3.1. Morphology of kish graphite
The catalytic graphitization of carbons in carbon-rich iron melts
was rst noted by Austerman et al. [26]. The subject has since been
well documented [27e31]. The graphitization process is believed to
be due to either the G effect [31], a process by which carbon dis-
solves in the iron and precipitates out as graphite between the
grains of the resulting grey cast steel, or to the formation and
decomposition of carbide intermediates [29,31]. According to
Oberlin and Rouchy [29] melting a non-graphitic carbon with iron
results in the formation of a composite of graphite and a
 T. Sri Devi Kumari et al. / Energy 95 (2016) 483e493
Fig. 1. Procedure for the generation of kish graphite.
graphitizable phase. It is believed that an unstable phase of iron
carbide is formed, which subsequently decomposes to yield iron
globules surrounded by a shell of graphitizable carbon [29]. The
size and shape in which the graphite is present in the matrix is
largely a function of parameters such as solidication temperature,
cooling rate, inoculant and nucleation state of the melt.
The grain structure of the grey steel obtained in this study is
shown in the metallurgical microscopic image given in Fig. 2.
Fig. 2. Metallurgical image showing vermicular graphite at the grain boundaries.
Magnication: 500X.
485
The precipitated carbon can be seen to be present as a
vermicular carbon form. The structural and morphological
characteristics of graphitic materials obtained by the catalytic
graphitization process depend, among other things, on the na-
ture of the precursors and thermal history [32]. SEM images of
the graphitic products presented in Fig. 3 show akiness, which
is a characteristic of graphites precipitated from carbon-rich iron
melts [33,34]. If carbon atoms are assumed to be present as
discrete atoms in a matrix of liquid iron [35], molecular as-
semblies of carbon may be expected to form by strong bonding
in the a direction as described by the chicken-wire model [36].
The resulting hexagonal monolayers can extensively bond in the
c direction to form akes. The formation of fullerene or tubular
structures by rolling or wrapping planar graphene layers is un-
clear, but it appears that they could have been generated by
molecular addition in the c direction. It must be noted that for
reasons of stereological matching, the specic oriented-folding of
the hexagonal sheets to form the hexagons and pentagons that
make up the fullerene and nanotubular structures would involve
the elimination of a few carbon atoms. Additionally, the growth
potential of these molecules is small [37], which explains the
limited formation of fullerene- and nanotube-like structures. The
SEM images also show nodular and lamentous nanocarbon
structures embedded in the graphite. Other types of nano-
structures including hollow shells and serpentine-like carbons
could be seen from the TEM images presented in Fig. 4. Electron
microscopic images showing other nanoscopic carbon forms are
486 T. Sri Devi Kumari et al. / Energy 95 (2016) 483e493
Fig. 3. (a) and (b) SEM images of the kish graphite showing its characteristic aki-
ness; and (c) an FE-SEM image showing nanocarbon structures embedded in the
graphite.
presented in Fig. S1 (see Supporting information). An HR-TEM
image of the kish graphite is shown in Fig. 5. The inter-layer
spacing, as deduced from the image by using ImageJ software,
is 3.38 .
3.2. Elemental analysis
The H/C ratio of the graphitic product is 0.074. Carbons with
high H/C ratios are known to show high irreversible capacities and
large voltage hysteresis [38e41]. The amount of residual iron in the
graphite, as determined by ICP-MS, was in ppb levels.
3.3. X-ray diffraction
The X-ray diffraction patterns of the graphite materials are
shown in Fig. 6. All the diffraction patterns show sharp peaks with a
high degree of crystallinity even though the preparation tempera-
ture was as low as 1700  C. The sharp XRD peaks indicate that
catalytic graphitization occurred at temperatures well below the
otherwise high temperatures at which graphitization is normally
expected to occur. The extraordinarily strong peak at a 2q value of
26 , seen in Fig. 6 (a), corresponds to the (002) reection of
graphite. The interlayer spacing (d002) was 3.350 . It must be noted
that this value is slightly lower than the standard value of 3.355
[42]. In fact, the d002 value is the average of a multitude of layer
spacings including those in the non-lamellar, but graphitic nodular
and lamentous structures. The strong (002) reection dwarfs the
other peaks, which are shown in Fig. 6 (b) and (c). Fig. 6 (b) shows
weak reections at 17.7 and 20.7, which correspond, respectively,
to the (220) and (311) reections of fullerene-like structures (JCPDS
00-044-0558). Other weak reections, shown expanded in Fig. 6
(c), correspond to (100) (42.6 ), (101) (44.7 ), (004) (54.8 ), (103)
(60.0 ) and (110) (77.6 ) of graphite (JCPDS 00-12-0212).
3.4. Electrochemical studies
In Fig. 7, the voltage proles in the 1st, 2nd, 3rd, 5th, 10th, 100th,
200th, 300th, 400th and 500th cycles are presented. The voltage
hump around 0.74 V vs. Li/Li during the rst insertion process is
attributed to the formation of a solid electrolyte interphase (SEI) on
the carbon. A differential capacity curve plotted with the rst-cycle
data (Fig. 8) shows a reduction peak at about 0.74 V vs. Li/Li in the
rst cycle. As can be seen from the gure, there are four well-
dened peak potentials during lithium insertion (charging of
graphite), at 0.15, 0.10, 0.07 and 0.03 V vs. Li/Li. During the dein-
sertion process, the peaks appeared at 0.11, 0.15, 0.18 and 0.22 V vs.
Li/Li. What is signicant is that all the electrochemical activity or
contribution to capacity occurred below 0.22 V, and this involves
the graphitic phase as well as the nanostructured carbon materials
[17e19]. The cathodic peaks correspond to the following: (a) the
dilute phase to the 4th stage up to around 0.20 V; (b) 4th to the 3rd
stage, followed by the 3rd to the 2nd stage between 0.20 and
0.09 V; and nally (c) 2nd to the 1st stage at more negative po-
tentials. The characteristic golden color of the fully lithiated LiC6
phase is shown in Fig. S2 (see Supporting information).
Both the charge and discharge proles are at, being charac-
teristic of graphitic materials. The rst-cycle insertion and dein-
sertion capacities of the graphite at C/10 rate between 2.000 and
0.005 V were 536 and 444 mAhg
1, respectively. Thus, the rst-
cycle irreversible capacity was 91 mAhg
1, which accounts for a
loss of 17% in capacity. However, the coulombic efciency improved
to >97% in the subsequent cycles (Fig. 9). The average fade in ca-
pacity over 500 cycles was 0.438 mAhg
1 cycle
1. The rst-cycle
consumption of lithium is related to the formation of an SEI layer
and the occupation of nearly all the available sites in the graphite
matrix by the intercalant lithium. The lithium lost in the formation
of the SEI as well as what could not be retrieved during the dein-
sertion process accounts for the rst-cycle irreversible capacity. SEI
formation is primarily due to reaction of lithium with surface
groups, which can inuence the electrochemical chargeedischarge
 T. Sri Devi Kumari et al. / Energy 95 (2016) 483e493
Fig. 4. TEM images showing serpentine-like and hollow shell carbon structures.
characteristics [43]. The presence of oxygen-bearing surface groups
on carbonaceous materials is well established.
It may be noted that deinsertion capacity of the graphite in the
rst cycle was 444 mAhg
1, which is much higher than the
372 mAhg
1 that is theoretically possible with perfectly graphitic
Fig. 5. An HR-TEM image of the PVC-derived kish graphite.
487
structures. In fact, the material was able to sustain 206 cycles before
its deinsertion capacity dropped below 372 mAhg
1. The unusually
high reversible capacity of the graphite needs a close examination.
The hydrogen content of the carbons is a factor contributing to
capacities well above the theoretical value. However, the graphite
under scrutiny has an H/C ratio of only 0.074, which is too low to
account for the excess lithium capacity. The kish graphitic product
obtained from PVC has nanocarbon particles with undened mor-
phologies (cf. SEM and TEM images). Such carbon structures can
account for additional lithium accommodation sites. In their
studies with kish graphites obtained by conventional methods, Lee
et al. [17,18,20] observed a variety of embedded nanocarbon
structures. Carbon structures reported by these authors included
laments, fullerene-like, hairy and cage-like structures. Nanoscopic
forms of carbon such as carbon nanotubes can take up more than
1000 mAh/g of lithium [44]. We attribute the excess capacity to
the presence of nanoscopic carbon structures that can provide
additional lithium storage sites. Table 1 compares the behavior of
kish graphites obtained by various methods as a lithium insertion
anode. It is clear that our study presents a double advantage of
higher capacities and a waste-to-wealth method for clearing our
surroundings of plastic litter. As will be seen below, the thermal
stability of the product is superior to that of a commercial sample,
which is an additional desirable feature for battery application. In
order that the kish graphite production process is not undermined
by arguments of handling gaseous products and iron chlorides,
mechanisms can be put in place to address the concerns. Of
particular interest is the fact that the instantaneous carbonization
and carbon dissolution occur under greatly reduced oxygen
488 T. Sri Devi Kumari et al. / Energy 95 (2016) 483e493

Fig. 7. Voltage proles during insertionedeinsertion of lithium in the kish graphite at

different cycle numbers (C/10 rate).

concentrations. The reduced emissions would greatly minimize the

need for exhaust treatment machinery such as gas scrubbers [45].
The ability of the graphitic product to sustain high-rate charge
and discharge was also examined. As may be seen from Fig. 10, the
material delivered average capacities of 420, 318, 265, 199, 111 and
65 mAhg
1 when cycled at C/10, C/5, C/2, C, 2C and 5C rates,
respectively. What is remarkable is that after such a high-rate
regimen, the material could sustain an average capacity of
324 mAhg
1 at C/10 rate between cycle numbers 101 and 150. The
ability of the material to sustain high-rate cycling and to regain to
nearly its original capacity is of practical interest as applications
demand varying drains.

3.5. X-ray diffraction studies at different states-of-charge

In order to elucidate changes that take place during the lith-

iation and delithiation processes, ex situ X-ray diffraction and ex situ
Raman spectral patterns were recorded with materials lithiated/
delithiated to different potentials. Because the structural features

Fig. 6. Powder X-ray diffraction pattern of the kish graphite between 2q values of (a)
10 and 80, showing the high intensity of the (002) reection; (b) 17 and 21 ; and (c) 40
and 80 .

Fig. 8. Differential capacity plot for the rst insertion-deinsertion cycle.

 T. Sri Devi Kumari et al. / Energy 95 (2016) 483e493
Fig. 9. Cycling behavior of the kish graphite (C/10 rate; 2.000e0.005 V).
obtainable with these techniques represent those of the bulk ma-
terial while the electrode potential is determined by the concen-
tration of lithium at the surface, the compositional homogeneity of
the test samples was sought to be ensured by allowing the samples
to equilibrate under potentiostatic conditions at pre-determined
potentials for 48 h before the coin cells containing them were
dis-assembled. Upon lithium intercalation, graphite undergoes
several structural transitions, usually called staging. At very low
lithium intercalation levels, the dilute stage-1 composition is
formed. Further intercalation leads to successive stages such as
stage-4, stage-3, liquid-type stage-2, stage-2 and stage-1. The onset
of these stage transitions are characterized by well-dened com-
positions (x in LixC6) that determine the potential of the phase.
Ex situ XRD patterns recorded at different potentials are pre-
sented in Fig. 11. Park et al. [46] reported a shift of the (002) peak
from 26.4 to 23.7 with lithiation and a shift in the opposite di-
rection upon delithiation of graphite. The absence of such a large
shift in our case must be due to differences in the structural features
of conventional graphites and the kish graphite. Several authors
have also reported inter-layer distances of 3.35 and 3.70 for
graphite and LiC6, respectively [47]. In our case, the spacings were
3.350 and 3.675 for the unlithiated kish graphite and the fully
lithiated composition, respectively.
Peaks characteristic of the different staged compounds can be
seen to gradually appear as lithium insertion proceeds and then
disappear as lithium is deinserted (Fig. 11). In fact, three staged
compounds co-exist in the variously lithiated states: the stage-1
LiC6 (strong peak at 24.5 ), stage-2 LiC12 (weak peak at 25.6 ) and
the stage-3 LiC18 (weak and wide peak at 26 ) (Fig. 12). The co-
existence of these compounds suggests that the differences in the
values of their chemical potentials are rather not high enough to
drive fast diffusion of lithium among these compositions at room
temperature over the equilibration period. In fact, Reynier et al. [48]
Table 1
Electrochemical lithium insertion behavior of different kish graphites.
Precipitating melt 1st Cycle capacities (mAhg
1)
Insertion
Amorphous carbon in boron-inoculated cast iron 358
Coke in 300 ppm boron- inoculated pig iron 462
Coke in 100 ppm bismuth-inoculated cast iron 480
PVC in cast iron 536
489
have noted macroscopic inhomogeneities in composition along
electrode thickness in their XRD studies on the electrochemical
intercalation of graphite. The clear shift of the (001) peak of LiC6 to
higher 2q values as the level of lithiation increases can be noted in
Fig. 12. Similar to the strong peaks of the lithiated phases, the less
intense peaks, the (004) peak of LiC12 and (002) peak of LiC6, pro-
gressively increase in intensity with lithiation, only to fade upon
delithiation (Fig. 13). The slight shift of the (002) peak of the LiC12
phase is related to a transition from stage-2 liquid phase to stage-2
solid phase [47]. There is also an emergence of a new peak at 23 at
high lithium concentrations (Fig. 12), whose identity is unclear.
3.6. Raman spectroscopy
Raman spectra of graphite at different states-of-charge are
shown in Fig. 14. Two bands can be seen in all the spectra: the D
band (A1g vibrational mode) at around 1330 cm
1 and the G-band
(E2g vibrational mode) at around 1585 cm
1. The G-band is an
inherent Raman band for the ideal graphite structure [49]. The D-
band is forbidden for the two-dimensional lattice of graphite ac-
cording to selection rules. However, for graphite crystallites of nite
sizes, the A1g mode will become Raman active. This band is assigned
to the break in symmetry at the edges of graphite particles and
linked to imperfections such as defects, discontinuity in crystallites
and stacking disorder in the crystal structure [49].
It can be noted from Fig. 14 that the intensities of the D and G
bands decrease upon lithiation. In fact, the D band nearly disap-
pears with increasing lithiation. It is believed that lithium insertion
leads to a loss in coherence for the ring-breathing modes associated
with the D band [50]. Dresselhaus and Dresselhaus [51] showed
that prior to stage-2, the Raman spectra of graphite intercalation
compounds exhibited a characteristic splitting of the singlet E2g
peak. In our case, a broadening of the G band can be seen, which
upon close examination may be considered as a merging of two G
doublet bands. Our results are in agreement with the results of
Migge et al. [52], who in their in situ Raman studies showed the
appearance of two closely lying G bands at 1578 and 1608 cm
1 at
low and medium levels of lithiation, which are intercalation com-
pounds with stage numbers n  3 [53,54]. The low- and high-
wavenumber bands are associated, respectively, with the interior
and boundary layers in the graphite [55,56]. Upon further lithiation,
the split G bands collapse into a single band. Inaba et al. [57] in their
studies with highly oriented pyrolytic graphite, showed a similar
splitting of the G band at potentials close to 200 mV, which cor-
responds to lithiated graphite [25,58]. This band disappears at
potentials close to 5 mV, which has been noted in earlier studies
[51,58]. Several authors have reported a near disappearance of the G
band at 5 mV (stage-1 lithium graphite intercalation compound)
[25,51,58], which is attributed to a reduction in the optical skin
depth by the highly conductive LiC6 [57]. However, in our study we
notice that the G band persists even at 5 mV.
It must be noted that unlike in earlier reports, where the authors
used lamellar graphite forms, we have used in our study a form of
graphite that has several nanocarbon forms embedded in it. Noting
100th Cycle deinsertion Ref.
capacity (mAhg
1)
Deinsertion Irreversible
308 14% e [17]
365 21% 356 [18]
405 16% 381 [19]
444 17% 411 This work
490 T. Sri Devi Kumari et al. / Energy 95 (2016) 483e493
Fig. 10. Reversible capacities at different C rates.
that the capacity far exceeds the theoretical limit of 372 mAhg
1,
the composition of the fully lithiated kish graphite goes beyond the
stage-1 compound (LiC6). We, therefore, suggest that the differ-
ences in the Raman spectra must be attributed to the fact that the
stacking of the graphite layers in the fully lithiated kish graphite
does not correspond to the normal AeAeAeA form. There is also an
increase in the FWHM of the D and G bands with increase in lith-
iation. The value of the ID/IG ratio decreases and then increases as
more and more of lithium is inserted. Thus, lithiation seems to lead
to generation of structural defects and an attendant decrease in the
crystallinity of the material. However, as the potential reaches that
of the stage-1 graphite intercalation compound, there is a notable
decrease in the ID/IG ratio. The trend reects the structural transi-
tion from the ordered graphitic structure to the ordered stage-1
compound through intermediate compositions that are complex
mixtures of different stage-n compounds (n > 1).
3.7. Thermal stability
Thermal runaway in full cells has been correlated with thermal
events of individual constituents in the cell as well as of initial
reaction products thus generated [59]. According to Maleki et al.
[59], full-cell thermal runaway is initiated by a breakdown of the
Fig. 11. XRD patterns recorded at different states-of-charge during lithium insertion
and deinsertion.
Fig. 12. Ex situ XRD patterns showing the evolution of staged lithium graphite inter-
calation compounds upon lithiation and delithiation.
SEI lm on the anode; this is followed by thermal decomposition/
reaction of electrolyte with the negative electrode; thereafter,
thermal decomposition of the cathode and its constituents take
over. Therefore, an understanding of the thermal behavior of the
anode material in contact with the electrolyte and binder is bene-
cial in screening new materials with improved safety and stability.
Three sets of thermal events can be seen to occur between 25
and 400  C (Fig. 15):
(a) an exothermic region between 80 and 120  C, which can be
attributed to a transformation of the SEI on the graphite [55].
Obviously, the SEI layer is stable up to 80  C. However, at
temperatures above 80  C, the constituents of the SEI
(lithium alkyl carbonates, lithium alkoxides) react with the
lithiated graphite and the electrolyte [60]. The 80e120  C
exotherm is accompanied by the formation of several
Fig. 13. Ex situ XRD patterns showing changes in selected diffraction peaks.
 T. Sri Devi Kumari et al. / Energy 95 (2016) 483e493
Fig. 14. Ex situ Raman spectra recorded at different potentials.
gaseous products (C2H4, CO2, O2, PF5, PF3O) and solid prod-
ucts (Li2CO3, LiF, Li2O) in addition to intermediates (HF, H2O)
that further react with the lithiated graphite [61e65].
(b) a second exothermic region between 120 and 180  C, which
becomes more and more predominant as the level of lith-
iation is increased, and should, therefore, be related to re-
actions between the lithiated graphite and the electrolyte
solution [51]. The destruction of the SEI by thermal events up
to 80  C leaves a layer on the graphite that is predominantly
composed of LiF and Li2O [55]. However, this layer is not
protective enough and upon further heating allows reduction
of solvent molecules by the lithiated graphite. The solute,
LiPF6, also decomposes in this temperature region to LiF and
PF5. The PF5 formed generates LiF and Li2O by further
Fig. 15. DSC scans recorded with kish graphite samples from disassembled cells.
Temperature ramp: 5  C min
1; atmosphere: argon.
491
reaction with the alkoxides and alkyl carbonates present in
the passive layer as well as in the intercalated graphite
[66,67].
(c) a third exothermic region beyond 250  C is due to further
reactions of the lithiated graphite with solution species and
their decomposition products as well as due to thermal
disintegration of the PVdF binder [68]. According to Du
Pasquier et al. [69], rapid reactions occur between PVdF
and LixC6 above 300  C. The reactions lead to dehydro-
uorination of PVdF [70] and formation of LiF and H2. The
broad exotherms seen in the DSC patterns and spread over
a large temperature range of nearly 80  C indicate the slow
kinetics of the thermal events. The slow reaction rates may
be related to slow diffusion of lithium from the interior of
the graphite lattice for exothermic reactions with the
electrolyte.
In the case of the DSC curves of the graphite lithiated to 150 and
80 mV vs. Li/Li, an endotherm appears in the 180e210  C range
followed by an exothermic hump around 220  C. The endotherm
has been attributed to the decomposition of DEC while the exo-
therm to the decomposition of EC [62,63,71]. The absence of this
feature in the DSC curves of the graphite lithiated to 50 and 5 mV vs.
Li/Li suggests that in these cases there was no remnant electrolyte
and that the electrolyte had already been consumed completely in
reaction with the highly lithiated graphites.
The solute, LiPF6, is known to react with solvents. With EC, it is
known to generate trans-esterication products between 190 and
230  C [72,73]. Between 225 and 280  C, a polymerization reaction
sets in, producing polyethylene oxide and CO2 [72,73]. LiPF6 also
reacts with DEC by two endothermic processes at 183 and 253  C
and by an exothermic process at 202  C [74], with products such as
CH3CH2F, FCH2CH2Y (YOH, F), CO2, etc. [75].
Several authors have reported two exotherms sandwiching an
endotherm at temperatures above 200  C [55,62,63,71]. The
intervening endotherm is attributed to exfoliation of graphite. The
exfoliation exposes more of the graphite, allowing a further
decomposition of the electrolyte, which accounts for the second
exotherm [55]. We suggest that the absence of a similar doublet
exotherm sandwiching an endotherm in the case of kish graphite is
due to its peculiar morphology and the presence of nanoscopic
carbon structures. The aky part of the kish graphitic product in
this study can easily be graphenized by simple ultrasonication (as
noted by us in an on-going study), rendering the exfoliation
redundant, and eliminating in the event the second exothermic
peak. Furthermore, the other peculiar morphological features of the
kish graphite such as bers and nodules do not yield to exfoliation
as easily as layered graphite.
The thermal behaviour of the kish graphite was compared with
that of a commercial sample. Fig. S3 (see Supporting information)
compares the DSC curves of the kish and commercial graphite
samples lithiated to 5 mV vs. Li/Li. The onset temperatures and the
exothermic heat generated for the two major thermal events (event
I: 120e180  C; event II: beyond 250  C) were compared for the fully
charged (5 mV vs. Li/Li) kish and the commercial graphites
(Fig. S3). For the rst thermal event, they were 122.5  C (70.4 J/g)
and 127.7  C (62.0 J/g), respectively, for the kish and commercial
samples. The corresponding values for the second thermal event
were 273.8  C (26.1 J/g) and 283.2  C (27.5 J/g). Thus, from the point
of view of thermal safety, the commercial sample should be ex-
pected to be safer than the kish graphitic product. However, it must
be borne in mind that the capacity of the fully charged kish graphite
is 444 mAhg
1 compared to only 360 mAhg
1 for the commercial
product, which should translate into a safety advantage for the
former.
492 T. Sri Devi Kumari et al. / Energy 95 (2016) 483e493
4. Conclusions
The following aspects of the study must be highlighted:
[1] In this study, PVC, an environmentally hazardous non-
biodegradable polymer, has been converted into a high-
capacity, long-cycling kish graphitic anode material for
lithium-ion batteries. Patents have already been led for this
process [76].
[2] Electron microscopic images reveal the presence of nano-
structured carbon forms embedded in the product.
[3] The product sustains a rst-cycle reversible capacity of
444 mAhg
1 and lasts 206 cycles before its capacity drops
below 372 mAhg
1. The capacities are much higher than
those obtained with kish graphites generated by use of other
precursors and inoculants.
[4] Thermal safety studies suggest that the kish graphitic prod-
uct is superior to a commercial sample considering the
higher reversible capacity of the former.
[5] Although only an off-the-shelf sample of PVC was used, the
study is a demonstration of the possibility of clearing human
habitats around the world of the accumulating PVC and other
non-biodegradable plastic wastes and converting them into a
technologically useful kish graphitic product.
Acknowledgements
Financial assistance for this work was obtained from the Council
of Scientic and Industrial Research (CSIR), Government of India
through IAP-04, an Inter Agency Project under the XI Five Year Plan.
TSDK thanks CSIR for a senior research fellowship. The authors
gratefully acknowledge the help received from Messrs P. Kamaraj, J.
Kennedy and A. Rathish Kumar in electron microscopic imaging.
We also place on record our sincere thanks to Mr. S. Kuppuswamy
of PSG Foundries, Coimbatore for help in making grey steels.
Appendix A. Supporting information
Supporting information related to this article can be found at
http://dx.doi.org/10.1016/j.energy.2015.11.069.
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