Journal of Power Sources 369 (2017) 87e94

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Journal of Power Sources

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

Boron- and nitrogen-doped reduced graphene oxide coated separators

for high-performance Li-S batteries
Pauline Han, Arumugam Manthiram*
Materials Science and Engineering Program & Texas Materials Institute, The University of Texas at Austin, Austin, TX 78712, USA

h i g h l i g h t s g r a p h i c a l a b s t r a c t

Separators coated with hetetroatom-

doped graphene oxide suppress pol-
ysulfide shuttling.

Boron- and nitrogen-doped graphene
oxide offer thin, lightweight coatings.

Hetetroatom-doped graphene oxide
coating enables high sulfur content
and loading.

Hetetroatom-doped graphene oxide
coating imparts long cycle life.

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

Article history: Lithium-sulfur (Li-S) batteries are regarded as a potential next-generation energy storage system but
Received 28 June 2017 they are hampered by low active-material utilization, polysulfide shuttling, and rapid capacity fade. We
Received in revised form present here the use of lightweight boron- and nitrogen-doped reduced graphene oxide (B-rGO, N-rGO)
20 September 2017
coated separators to suppress polysulfide diffusion and enhance active material utilization at high sulfur
Accepted 2 October 2017
Available online 9 October 2017
contents. B-rGO and N-rGO are synthesized through a facile modified Hummer's method involving the
exfoliation of graphite sheets. Upon reduction, the carbon forms valuable interlayers with dynamic
spacings for polysulfide trapping. Freeze-drying is utilized to preserve the structure of the pillow-like
Keywords:
Lithium-sulfur batteries
carbon, which is then slurry-coated onto a separator and placed against a sulfur cathode. The advan-
Reduced graphene oxide tages of boron and nitrogen and their affinity towards polysulfides is compared while noting the lighter
Coated separator carbon coatings with good electrochemical stability. The cells attain a loading of 4.0 mg cm2 with a high
sulfur content of 66.5 ± 0.5 wt % on including the weight of the coatings. After a long cycle life of 400
cycles, N-rGO and B-rGO are still able to maintain a specific capacity of, respectively, 430 mA h g1 and
367 mA h g1.
© 2017 Elsevier B.V. All rights reserved.

1. Introduction energy, there has been great interest invested in developing high
performance rechargeable batteries. Intercalation compounds used
Due to the rapidly increasing demand for portable electronic in such batteries struggle with meeting the requirements of grid-
devices and the positive environmental impact of renewable storage and electric vehicle (EV) markets due to their high cost,
safety issues, and insufficient theoretical energy density
(350e400 W h kg1) [1]. On the heels of the currently developed
* Corresponding author. and widely used lithium-ion technology are lithium-sulfur (Li-S)
E-mail addresses: paulinejhan@utexas.edu (P. Han), manth@austin.utexas.edu batteries, which are popular due to their advantageous theoretical
(A. Manthiram).

https://doi.org/10.1016/j.jpowsour.2017.10.005
0378-7753/© 2017 Elsevier B.V. All rights reserved.
88 P. Han, A. Manthiram / Journal of Power Sources 369 (2017) 87e94

energy density (2600 W h kg1) when paired with a lithium-metal (NMP) overnight. The resulting slurry was tape-casted onto a
anode and the high theoretical specific capacity of 1672 mA h g1 polypropylene separator (Celgard 2500) and dried in a vacuum
for the sulfur cathode [1e3]. Sulfur as an active material possesses oven at 50 C overnight. The coated separators were then punched
great advantages as it is readily available due to its natural abun- out for cell assembly. The B-rGO-coated separator and N-rGO-
dance and has a low environmental impact. However, functionality coated separator had thicknesses of 25e35 mm. B-rGO had a weight
of Li-S batteries is hindered by several factors involved in the redox loading of 0.17 mg while N-rGO had a weight loading of 0.21 mg.
process [4,5]. Both sulfur and its end discharge product (Li2S) are The resulting N-rGO- and B-rGO-coated separators had electrical
insulating materials that decrease electrochemical utilization. The conductivities of, respectively, 900 S m1 and 15 S m1 as measured
intermediate polysulfides formed during cycling are easily dis- with a four-point probe (S-302e4, Lucas Labs Resistivity, USA). The
solved in the widely used ether-based electrolyte and readily coated separator was able to support bending and crinkling, further
diffuse across the separator. Inactive sulfides deposited on the indicating that utilizing PVDF as a heteroatom-rGO binder created a
electrode surface are highly detrimental to the desired practical highly flexible and ductile support for the coated separator.
capacity, resulting in increased resistance within the cell and
shortened cell life [6e8]. Upon the lithiation of sulfur, there is a 2.2. Electrochemical measurements
large volume change (up to 80%) within the cathode, resulting in
loss of electrochemical capability [9e13]. CR2032 coin cells were assembled in a glove box under an argon
There have been large efforts focused towards improving con- (Ar) environment. For the sulfur cathode, a slurry was prepared
ductivity and impeding polysulfide shuttling with carbon nano- with sulfur (Sigma Aldrich), super p carbon (TIMCAL), and PVDF (7:
structures [14e18]. Carbon barriers are of high interest due to their 1.5: 1.5 wt ratio) in NMP. The slurry was then tape-casted onto an
high electrical conductivity and good polysulfide trapping abilities. aluminum foil current collector and dried in a vacuum oven at 50  C
Examples of carbon barriers include free-standing interlayers overnight. The resulting cathode has a high sulfur loading of
[19e21], a sandwiched cathode [22,23], a sponge structure 4.0 mg cm2 and a sulfur content of 70 wt %. Including the mass
[24e26], or as a coated separator [27e29]. Among these, coated loading of the coated layer, the cells assembled with B-rGO, N-rGO,
separator technology is one of the most promising approaches and rGO were controlled to a total sulfur content of 66.5 ± 0.5 wt %.
because the carbon loading can be tailored to be as thin as possible. The cathode was then punched out and placed in a bottom cell cap
The polypropylene separator acts as a pillar to support thinner with organic electrolyte and the prepared coated separator was
carbon structures and lower carbon loadings for high sulfur content placed on top of it. A sheet of lithium metal was placed over the
Li-S batteries [30]. Among the two-dimensional (2D) carbon ma- separator, followed by a nickel foam spacer, and the top cell cap was
terials, self-standing reduced graphene oxide (rGO) substrates has placed to close the cell. The organic electrolyte consisted of 1.85 M
been shown to give good performance and a long cycle life in Li-S lithium trifluoromethanesulfonate salts (LiCF3SO3, Acros Organics)
batteries. Synthesis of rGO through bulk exfoliation of graphite in a solvent mixture of 1,2 dimethoxyethane (DME, Acros Organics)
can be tuned for larger interlayer spacings and increased dispers- and 1,3-dioxolane (DOL, Acros Organics) in a 1:1 volumetric ratio
ability, which manifest in a lightweight cotton-like nanostructure with 0.1 M lithium nitrate salts (LiNO3, Acros Organics). Galvano-
[24,31]. The intricate web of this type of carbon has (i) an sp2 carbon static cycling experiments were carried out with a battery cycler
structure that allows for fast electron and ionic transport and (ii) (Arbin) within a voltage window 1.6e2.8 V at various cycling rates
mechanical flexibility to accommodate the volume changes or from C/20 to C/2 at room temperature.
stress during cycling without significant structural defects [32e35].
In this article, we investigate lightweight boron- and nitrogen- 3. Results and discussion
doped rGOs (referred hereafter as B-rGOs and N-rGOs) coated on
to a Celgard separator and focus on their intrinsic properties for the 3.1. Configuration and morphology of the coated separators
performance of high sulfur content Li-S cells. The reduction of polar
heteroatoms onto the intricate carbon framework can significantly To expand upon Li-S technology, heteroatom-doped rGOs were
improve the sites for polar polysulfide absorption while the light- assembled into the sulfur cathode architecture in the form of a thin
weight, pillow-like carbon creates longer pathways for polysulfide and lightweight coated separator. Graphene oxide was synthesized
retention [36e39]. The heteroatom dopants provide meaningful from graphite flakes in a one pot modified Hummer's method via
binding opportunities with polysulfide species during cycling for high surface area exfoliation. The heteroatom-doped B-rGOs and N-
active material retention and improve the wettability of carbon in rGOs were doped with, respectively, adding 2.5 mmol of boric acid
the organic electrolyte. (H3BO3) or cyanimide (C2H2N4) into the hydrothermal reaction. The
solid structures are retained and shown in Fig. 1. These structures
2. Experimental section are stable, and robust free-standing, which are then sliced into
pieces, lyophilized, and ground into a powder. The material is then
2.1. Sample preparation slurry-casted as a smooth coating onto a polypropylene membrane
(Fig. 1d). The even distribution of the heteroatom-doped rGOs
Graphene oxide was exfoliated from graphite flakes with a improves the physical contact between the coating and the sepa-
modified Hummer's method [40]. The heteroatom-doped B-rGOs rator and the coating and the cathode.
and N-rGOs were synthesized by, respectively, adding 2.5 mmol of Figure S1 demonstrates the excellent durability after folding and
boric acid (H3BO3, Fisher Scientific) or cyanimide (C2H2N4, Sigma- bending of the fabricated separators for B-rGO and N-rGO. Despite
Aldrich) into 60 mL of rGO (concentration of ~2.5 mg mL1) in being folded, twisted, and bent in different directions, the coated
deionized (DI) water. The hydrothermal reaction was carried out at separator is still able to retain its initial composition on the surface.
180  C for 12 h rGO was synthesized through the same hydro- The separator retains a strong coating and shape with minimal
thermal route in DI water without any additives. These structures damage on the surface of the coated carbon, proving its physical
were then washed repeatedly with DI water and ethanol. The capabilities. The good mechanical properties of being folded, bent,
structures were then lyophilized and ground into a powder. The and crumpled emphasize that these carbons are durably coated
carbons were then combined with polyvinyledene fluoride (PVDF, onto a propylene separator, a critical factor for effective coated
Kureha) in a 80: 20 wt ratio and stirred in 1-methyl, 3-pyrrolidone separator technology.
 P. Han, A. Manthiram / Journal of Power Sources 369 (2017) 87e94 89

Despite being ground down and assembled onto a polypropylene

membrane, the coating shows both a stacked formation of the
graphene layers and their inherent interconnected structure. The
pores within the framework are demonstrated to exhibit sizes of
~3e5 mm in diameter with the majority of the pores <10 mm in
diameter. Furthermore, if the plane of the separator is set as x and y,
there is a clear indication of stacking in the z direction among the
heteroatom-doped rGOs. The clear affinity towards flat, layered
stacking gives way to (i) space for improved physical polysulfide
trapping ability, (ii) space in order to compensate for physical
volume changes during cell cycling, and (iii) chemical LiPS ab-
sorption ability among the graphene sheets themselves for better
sulfide to heteroatom covalent bonding [41,42]. The improved
method of bulk 2D stacking leads to longer polysulfide diffusion
paths, improved electrically conductive contact with carbon, and
better electrochemical reutilization of the active material. Fig. 2c
and d shows the microstructure analysis surface view of the
heteroatom-doped coated separators after galvanostatic cycling.
The surfaces of the coated separators demonstrate good retention
of their original layered stacking configuration after cycling.
Figure S2a and S2b depict the surface of the sulfur cathode facing
the coated separator after cycling. The cathode structure is main-
Fig. 1. Images of the heteroatom doped-rGO sample: (a) side-view after hydrothermal tained and there is no visible change or damage to the cathode. The
treatment, (b) sliced sample before freeze-drying treatment, (c) sliced sample after microstructural view depicts good structural stability and a low
freeze-drying treatment, and (d) as a coated separator. number of defects after cycling.
Fig. 3a and b depict the cross-sectional SEM images captured of
the B-rGO- and N-rGO-coated separators, demonstrating the (i)
The morphology of the heteroatom-doped rGOs is shown in
interconnected porous morphology of 2D rGO sheets and (ii) their
Fig. 2. The images were taken with scanning electron microscopy
good adherence with the separator. The pristine coated separators
(SEM). The images in Fig. 2a and b shows the surface view of,
used for assembly prior to cycling have a cross-sectional width of
respectively, the pristine B-rGO- and N-rGO-coated separators
25e35 mm, a B-rGO loading of 0.15 g cm2, and a N-rGO loading of
before cycling at different magnifications. There is evidence of 2D
0.19 g cm2. These factors benefit the electrochemical capabilities
graphene-like structure from the synthetic route detailed above.

Fig. 2. Microstructural analysis of the surface of the (a) fresh B-rGO-coated separator, (b) fresh N-rGO-coated separator, (c) cycled B-rGO-coated separator, and (d) cycled N-rGO-
coated separator.
90 P. Han, A. Manthiram / Journal of Power Sources 369 (2017) 87e94

wavelength of 488 nm and were fit with a Lorentzian function. We

compared the signals of B-rGO and N-rGO in order to compare the
differences in the disruption and disorder of the rGO plane. In the
Raman spectra of rGOs, typically the G-band stems from planar sp2
carbon vibrations while the D-band arises out of structural defects.
The Raman spectrum shows a D band around 1350 cm1 and the G
band is exhibited at 1582 cm1 in both the heteroatom-doped
samples [43e45]. The wide 2D-band around 2800 cm1 is attrib-
uted to the carbon structure in rGO. The graphite flakes used as the
starting material have a strong G-band attributed to E2g symmetry.
In our heteroatom-doped rGOs, we are able to see E2g peak
broadening due to the increase in double bonds and an increased
peak area of the D-band due to the introduction of defects. The high
D band to G band intensity ratios or defect ratios (ID/IG) for B-rGO
and N-rGO powders are indicative of disruptions in the planar rGO
lattice. As a comparison, the Raman spectrum of rGO was collected
and observed to have an ID/IG ratio of 0.95 (Figure S3). N-rGO
demonstrates an ID/IG ¼ 1.08 while B-rGO demonstrates a higher
intensity ratio at ID/IG ¼ 1.13, indicating a slightly increased amount
of sp3 domains and defects. The increase in defects have been
shown to contribute to better initial capacity and cycle stability and
physically mediate lithium polysulfides (LiPSs). However, increased
defects are unable to support stable long-term cyclability due to the
loss of electrochemical contact as observed in previous reports
[46e48].
Powder X-ray diffraction (XRD) was utilized to further charac-
terize the synthesized carbon samples. The XRD pattern of com-
mercial graphite flakes in Fig. 4b shows the typical sharp d002 peak
at 2q ¼ 26.7, which gives an interlayer spacing of 0.33 nm. In the
XRD pattern of the heteroatom-doped rGOs, this peak is broadened.
In B-rGO, this peak is shifted to 2q ¼ 24.2 and has an interlayer
spacing of 0.37 nm. The peak is also broadened in the nitrogen-
Fig. 3. Microstructural analysis of the cross-sectional views of (a) B-rGO-coated
separator and (b) N-rGO-coated separator. EDX mapping of the cross-sectional images
doped sample and is shifted to 2q ¼ 24.3 with an interlayer
of the (c) B-rGO-coated separator and (d) N-rGO-coated separator after cycling. spacing of 0.37 nm. These peaks can be attributed to the hydro-
thermal reduction of oxygen groups throughout the rGO network.
They are broadened due to the disorder along the stacking axis as
immensely and can be attributed to the retention of the fluffy 3D the oxygen groups are removed [49,50]. The poor crystallinity in
structure largely due to the freeze-drying process applied before the stacking direction gives indication of single layer sheets as
coating. The spaces created with lyophilization are maintained expected for the heteroatom-doped rGO. As a comparison, we also
through the grinding and slurry-coating process and creates observed the peak shift of the pristine, un-doped rGO, which
enough pathways that allow for lithium mobility while effectively demonstrates an interlayer spacing of 0.35 nm and has a broad peak
trapping polysulfides. Furthermore, the interconnected material shifted to 2q ¼ 25.4 . This, as mentioned before, occurs as the
can facilitate a low loading coating, benefitting the sulfur loading interlayer spacing decreases when oxygen groups are reduced. The
and sulfur content of the cathode. This is further supported by the shift of the d002 peak is further right-shifted for N-rGO-coated
cross-sectional view of the coated separator (Fig. 3c and d) after separator than the B-rGO-coated separator, indicating that the N-
cycling. This uniqueness of the coated separator architecture offers rGO has a smaller interlayer spacing than the B-rGOs, enabling
good contribution to high physical polysulfide trapping ability and longer cyclability due to polysulfide entrapment and active-
improved performance. The generous spacing of the coated mate- material retention. Interestingly, there is a small sharp peak for
rial supported by cross-sectional analysis (Fig. 3a and b) allows for N-rGO observed at 2q ¼ 14.3 with d001 ¼ 0.62 nm, corresponding
accommodating any size or volume constraints necessary during to a slight improvement in crystallinity and large interlayer stack-
charge and discharge. The material is able to create a turbulent ing distance of rGO sheets (d001). An interlayer distance in this or-
pathway for diffusing polysulfides and hence offer physical ab- der of magnitude is beneficial for mitigating polysulfide dissolution
sorption abilities inside the architectural matrix. The elemental while accommodating significant volume changes. This allows the
mapping (EDX) analysis for the cross-sectional views imaged after heteroatom-doped graphene interlayer to assemble into a stacked
cycling is shown alongside their images in Fig. 3c and d. The EDX formation of optimal structure for electronic/ionic transport with
mapping confirms the heteroatom-doped rGO-coated separators as minimal consequences to the structural integrity of the cathode.
good polysulfide absorbers, retarding bulk diffusion to the anode. X-ray photoelectron spectroscopy (XPS) was used to identify the
The cross-sectional EDX mapping after cycling shows good reten- successful doping of boron and nitrogen into the respective B-rGO
tion of active material on the cathode facing side of the coated and N-rGO materials. The XPS measurement data is shown in
separator. Fig. 5a, comparing the surface composition peaks between B-rGO
In Fig. 4a, we utilized Raman spectroscopy to compare the and N-rGO powders with the starting graphite material. Fig. 5c and
structure based on the composition of defects within the carbon e compare the C 1s peaks of, respectively, the B-rGO and N-rGO
samples, as the homogeneity and crystallinity of the heteroatom- powders. Both samples exhibit strong peaks at a binding energy of
doped rGOs are highly sensitive to the synthetic procedure. The 284.6 eV, which is indicative of their carbon-carbon sp2 bonds. The
Raman spectra for the samples were collected at an excitation bonds between the heteroatoms or oxygen and carbon are shown
 P. Han, A. Manthiram / Journal of Power Sources 369 (2017) 87e94 91

Fig. 4. (a) Raman spectra of the B-rGO and N-rGO powders, fit with a Lorentzian function. (b) XRD patterns of the starting graphite flakes, rGO, B-rGO, and N-rGO powders after
lyophilization.

Fig. 5. XPS survey plot with the surface compositions of (a) B-rGO, N-rGO, and graphite. XPS spectra of the surface composition of (b) B 1s and (c) C 1s in the B-rGO-coated separator
and the surface composition of (d) N 1s and (e) C 1s in the N-rGO-coated separator.

in the shoulder region, indicating the presence of C-O, C-N, C-B nitrogens have a lower binding energy with LiPSs, but can improve
single bonds and C¼O double bonds. Examining the B-rGO powder, the Liþ ion binding affinity in LiPSs.
there is evidence of the B 1s peak at a binding energy of 192.6 eV Porosity analysis indicates similar porous characteristics for B-
with an atomic wt percent of 2.4% in the sample (Fig. 5b). The B 1s rGOs and N-rGOs, as shown in Figure S4 and Table S1. The values of
peak for B-rGO shows three regions for B 1s, which are BC3, BC2O, specific surface area, total pore volume, and average pore size are,
and BCO2 and correspond to the bonding of B 1s as a heteroatom to respectively, 15e19 m2 g1 (Brunauer-Emmett-Teller, 7-point BET
the carbon network within rGO. There are no more B2O3 residuals method), 0.31e0.45 cm3 g1, and 15e20 nm (calculated based on
remaining on the solid material after the hydrothermal treatment. the pores with diameter smaller than 220 nm). The nitrogen
The N-rGO sample demonstrates evidence of the N 1s peak at a adsorption-desorption isotherms in Figure S4a show the IUPAC
binding energy of 399.9 eV, doping (3.6%) throughout the sample type II isotherms that represent a macroporous adsorbent behavior.
(Fig. 5d). The three peaks can be convoluted and attributed to the At P/P0 ¼ 0.4, an adsorption hysteresis at P/P0 ¼ 0.4 could possibly
pyridinic, pyrrolic, and quaternary nitrogens and correspond to the be attributed to the stack of rGO nanosheets giving rise to a slit-
heteroatom doping of carbons with nitrogen at either the edges or shape porous architecture. The limited micropores and meso-
the defect sites in the basal plane of the rGO network, with the pores are confirmed by the t-plot method of micropore analysis,
pyrrolic-type nitrogens being the most stable nitrogen species for showing almost no micropores and volume in the pore size dis-
the absorption and mediation of LiPSs [51e53]. Pyridinic-type ni- tribution data (Fig. S4b). This demonstrates that the heteroatom
trogens also have a high binding energy for LiPSs, improving the dopants along with the intricate rGO network and stacking are the
absorption and retention of active material. Quaternary-type primary reasons for active material retention and redox
92 P. Han, A. Manthiram / Journal of Power Sources 369 (2017) 87e94

accessibility, as LiPSs are known to interact unfavorably with lower range. The RCT for B-rGO cells is 60.87 U and for N-rGO cells is
surface area carbons. 86.2 U. The cell assembled with the rGO-coated separator is used as
a comparison and it exhibits an RCT of 105.8 U, indicative of higher
cell impedance without polarized heteroatom dopants. The lower
3.2. Electrochemical characterization of assembled cathodes
RCT values for the B- and N-rGO cells indicate that heteroatom
doping of either electron withdrawing groups or electron donating
Electrochemical tests were performed in a 2032 coin cell with
groups offer good conductivity and electron transport in rGO
Li-S batteries, heteroatom-doped-rGO-coated Celgard separator,
within the cathode. There is a drop in RCT when comparing the
and a lithium anode. The control cells were assembled with a bare
heteroatom-doped rGO-coated separator cells with the bare sepa-
separator. To gather further insights into the reaction kinetics, the
rator control cell (RCT ¼ 295 U), indicative of the large RCT of a bare
charge-transfer impedance (RCT) was examined with electro-
separator. This indicates electrochemical contact has improved
chemical impedance spectroscopy (EIS) data in Fig. 6a. The figure
within the cathode region with the addition of the heteroatom-
demonstrates a comparison of the Nyquist plots of the cells fabri-
doped coating onto the bare separator. These favorable RCT values
cated with the B-rGO-coated separators (B-rGO cells) and the N-
can also be attributed to the coating process used, which offers
rGO-coated separators (N-rGO cells) as well as a bare separator
improvements in fast transport properties due to the low loading of
control cell for reference. All three demonstrate a semicircle under
carbon and high active material content.
medium frequency and a tail with a slope in the lower frequency

Fig. 6. Electrochemical data of the assembled electrodes: (a) Nyquist plots of control, B-rGO, N-rGO, and rGO cells before cycling. (b) Electrochemical performances of the B-rGO
cells at C/2, C5, and C/10 cycling rates. (c) Extended cycling performance data of the B-rGO cell at C/10 cycling rate. (d) Electrochemical performances of the N-rGO cells at C5, C/10,
and C/20 cycling rates. (e) Extended cycling performance data of the N-rGO cell at C/5 cycling rate.
 P. Han, A. Manthiram / Journal of Power Sources 369 (2017) 87e94 93

Figure S5 demonstrates the cyclic voltammetry (CV) profiles of material S or end discharge product Li2S. The reutilization of the
the heteroatom-doped coated separators. The CV plots display two active material can be attributed to the variable interstitial spacing
cathodic peaks, which correlate to (i) the reduction process of sulfur within the rGO network. Furthermore, at a C/10 rate, the B-rGO cell
to lithium polysulfides and (ii) the reduction of lithium polysulfides was able to attain a long cycle life of 400 cycles while retaining a
to lithium sulfide. Upon charging an anodic peak (2.4e2.5 V) ap- specific capacity of 367 mA h g1 (Fig. 6c). From the electrochemical
pears in agreement with the oxidation process back to sulfur data, the heteroatom dopants exhibit both physical and chemical
(Figure S5). In Figure S5a the CV graphs for B-rGO displays relatively properties that are beneficial to attaining desirable performance
sharp reduction peaks, which are indicative of good reversibility with Li-S batteries. They are able to create a good interspacing
and good cycle stability. For the N-rGO cell (Figure S5b), the two among the rGO stacks for efficient polysulfide mediation. The
reduction peaks are broadened for N-rGO, while the oxidation spacing does not compromise the charge-transfer process as the
peaks are overlapped. There is movement of the anodic peaks to a dopants are also able to offer good transport pathways for electrons
higher voltage, indicating high polarization and larger initial to get to the active material.
resistance when compared to the B-rGO plots. Figure S5c shows the In a comparative study, the charge/discharge profiles of the rGO,
CV profile for the rGO control cell with both broad reduction peaks N-rGO and B-rGO cells were examined at C/5 and C/10 rates (Fig. 7).
and oxidation peaks. The rGO cells exhibit the largest peak sepa- There is evidence of the two-step reduction process in the
ration and lowest current densities, indicative of high polarization discharge voltage plateaus. At both C/5 and C/10 rates, the doped-
and lowest conductivity among the three carbons. Furthermore, rGO cells demonstrate higher peak capacities, indicative of the
there is a poor overlap of the CV curves of the rGO cell as compared better polysulfide mediation and electron transfer also observed
to the B-rGO and N-rGO cells, indicative of poor electrochemical previously in the CV profile. Both the heteroatom-doped rGO cells
stability and reversibility in the first few cycles. exhibit higher initial discharge capacities than the rGO cell, indi-
Electrochemical cycling tests were performed in order to cating an even distribution of the active material in the cathode and
distinguish between the heteroatom dopants and to determine the high sulfur utilization. The rGO cell attains a peak discharge ca-
actual contribution of heteroatom doped rGO-coated separators as pacity of 1043 mA h g1 and a RQ ¼ 83% after 50 cycles (Figure S6).
a beneficial architecture in Li-S batteries. At a rate of C/5 In comparison, at a C/5 rate, B-rGO has a RQ ¼ 86% and N-rGO has a
(1C ¼ 1672 mA g1), the B-rGO cells were able to accommodate a S RQ ¼ 91% after 50 cycles (Figure S6b). The improved affinity of the
loading of 4.0 mg cm2 and attain a peak discharge capacity of polar heteroatom-doped rGO to LiPSs is evidenced by the higher
902 mA h g1, while maintaining a reversible capacity of capacity retention rate as compared to the rGO.
435 mA h g1 over 200 cycles (Fig. 6b). Meanwhile, the N-rGO cells Figure S7 shows the charge/discharge profiles of the
were able to accommodate a S loading of 4.0 mg cm2 with a high heteroatom-doped rGO-coated separators at various cycling rates
peak discharge capacity of 856 mA h g1 and a high reversible (1 C ¼ 1672 mA h g1). In the initial cycles, the B-rGO cells
capacity of 495 mA h g1 after 200 cycles (Fig. 6d). In regards to demonstrate longer discharge plateaus and higher discharge ca-
long-term cycling, the N-rGO cell is able to maintain a reversible pacities than the N-rGO cells, demonstrating better electrochemical
capacity of 430 mA h g1 after 400 cycles at C/5 rate (Fig. 6e). This kinetics. After 200 cycles, the N-rGO cells exhibit more stable
factor can be attributed to the more evenly distributed doping of voltage plateaus and a smaller capacity fade as compared to the B-
nitrogen and the resulting improvement in electron transport rGO cells, indicative of good active material reutilization as seen in
properties because of its electron donating properties. The the electrochemical cycling performance.
capacity-retention rate (RQ) is calculated using the reversible ca-
pacity after 200 or 400 cycles and the peak capacity in the initial 4. Conclusion
cycles. At C/5 rate, the B-rGO cell has a RQ ¼ 48% after 200 cycles. At
the same C-rate, the N-rGO cell has RQ ¼ 58% after 200 cycles and a The exfoliation of GO and subsequent doping with either boron
very high RQ ¼ 50% after 400 cycles. The enhanced capacity or nitrogen heteroatoms to give B-rGO and N-rGO created a polar
retention demonstrated by N-rGO can be attributed to the lower carbon lattice favorable for binding LiPSs and acting as a polysulfide
amount of defects in the N-rGO sample than the B-rGO sample as mediator. We combined this carbon material with a lightweight-
demonstrated by the Raman spectroscopy analysis. The better coated separator technology to generate a stable environment for
crystallinity and stacking of N-rGO observed in the XRD analysis sulfur cathode redox activities in high S content Li-S batteries. This
can effectively absorb polysulfides and further supports the work is able to provide a comparison between B-rGO and N-rGO
observed electrochemical performance. The good electrochemical toward cell-performance improvements at a loading of
kinetics and sulfur reutilization from the improved stacking 4.0 mg cm2. The long life of cells with N-rGO-coated separator
structure yields better cycle stability and lower capacity loss for N- with a high sulfur content of 67% is achieved as it reaches 400 cycles
rGO than for B-rGO after 200 cycles. The higher capacity fade at a C/5 cycling rate with a specific capacity of 430 mA h g1. The
witnessed in the B-rGO cell over long cycles can be attributed to the homogeneous distribution of nitrogen atoms in the carbon frame-
higher amount of defects observed in the Raman analysis. The work minimizes severe polysulfide shuttling, benefitting the reac-
defects lead to a loss of electrochemical contact during cycling, tivation of sulfur within the cathode over long cycles. The
resulting in a faster capacity fade. electrochemical data confirm that the nitrogen doping results in
At a cycling rate of C/10, the B-rGO cell was able to attain a peak favorable polar absorption interactions with polysulfide species
discharge capacity of 825 mA h g1, while maintaining a reversible while improving electron transport properties. The B-rGO-coated
capacity of 552 mA h g1 after 200 cycles (Fig. 6b). In comparison, separator cell with a high sulfur content of 66% is able to attain 400
the N-rGO cell was able to attain a peak discharge capacity of cycles at a C/10 cycling rate maintaining a specific capacity of
965 mA h g1, while maintaining a discharge capacity of 367 mA h g1. The improved cyclability is attributed to the favor-
579 mA h g1 after 200 cycles (Fig. 6d). The dynamic RQ at C/10 able binding affinity of boron in the rGO framework towards LiPS
cycling rate for the B-rGO cell is RQ ¼ 67% and for the N-rGO cell is species. Larger amount of defects in the B-rGO structure, however,
RQ ¼ 60%. The dynamic RQ improved for both types of coated result in loss a of electrochemical contact with the active material
separator cells at this rate. This excellent capacity retention with and a higher capacity fade rate than N-rGO over longer cycles. In
cycling is attributed to the good charge-transfer connectivity this comparison, B and N are able to improve the cyclability and
among the rGO, the heteroatom dopants, and the insulating active discharge capacity of Li-S batteries with high sulfur content by
94 P. Han, A. Manthiram / Journal of Power Sources 369 (2017) 87e94

Fig. 7. Charge-discharge profiles of rGO, B-rGO, and N-rGO cells at (a) C/5 and (b) C/10 rates.

creating polar sites to anchor LiPSs onto the carbon structure. This 4530e4538.
[21] Y.-S. Su, A. Manthiram, Nat. Commun. 3 (2012) 1166.
technology combines the (i) lightweight, well-stacked features of a
[22] Z. Yuan, H.-J. Peng, J.-Q. Huang, X.-Y. Liu, D.-W. Wang, X.-B. Cheng, Q. Zhang,
carbon coated separator with the (ii) high electronic and ionic Adv. Funct. Mater 24 (2014) 6105e6112.
transport properties of rGO and the (iii) good chemisorption ability [23] L. Qie, A. Manthiram, Adv. Mater 27 (2015) 1694e1700.
of LiPSs by boron or nitrogen dopants to improve the practical [24] Z. Zhang, Z. Li, F. Hao, X. Wang, Q. Li, Y. Qi, R. Fan, L. Yin, Adv. Funct. Mater 24
(2014) 2500e2509.
viability of high S content Li-S batteries. [25] Y. Xie, Z. Meng, T. Cai, W.-Q. Han, ACS Appl. Mat. Interfaces 7 (2015)
25202e25210.
Acknowledgements [26] S. Lu, Y. Chen, X. Wu, Z. Wang, Y. Li, Sci. Rep. 4 (2014) 4629.
[27] C.-H. Chang, S.-H. Chung, A. Manthiram, J. Mat. Chem. A 3 (2015)
18829e18834.
This work was supported primarily by the National Science [28] S.-H. Chung, A. Manthiram, J. Phys. Chem. Lett. 5 (2014) 1978e1983.
Foundation under Cooperative Agreement No. EEC-1160494 and [29] X. Li, Y. Cao, W. Qi, L.V. Saraf, J. Xiao, Z. Nie, J. Mietek, J.-G. Zhang,
B. Schwenzer, J. Liu, J. Mat. Chem. 21 (2011) 16603e16610.
Welch Foundation grant F-1254. The authors would also like to [30] S. Evers, L.F. Nazar, Acc. Chem. Res. 46 (2013) 1135e1143.
acknowledge Dr. Guangmin Zhou for his assistance with the syn- [31] S. Evers, L.F. Nazar, Chem. Commun. 48 (2012) 1233e1235.
thesis of carbon materials. [32] D. Sun, Y. Hwa, Y. Shen, Y. Huang, E.J. Cairns, Nano Energy 26 (2016) 524e532.
[33] A. Ganesan, A. Varzi, S. Passerini, M.M. Shaijumon, Electrochim. Acta 214
(2016) 129e138.
Appendix A. Supplementary data [34] J.-L. Shi, C. Tang, H.-J. Peng, L. Zhu, X.-B. Cheng, J.-Q. Huang, W. Zhu, Q. Zhang,
Small 11 (2015) 5177, 5177.
[35] K. Xi, P.R. Kidambi, R. Chen, C. Gao, X. Peng, C. Ducati, S. Hofmann, R.V. Kumar,
Supplementary data related to this article can be found at
Nanoscale 6 (2014) 5746e5753.
https://doi.org/10.1016/j.jpowsour.2017.10.005. [36] Q. Pang, D. Kundu, M. Cuisinier, L.F. Nazar, Nat. Commun. 5 (2014) 4759.
[37] T.-Z. Hou, H.-J. Peng, J.-Q. Huang, Q. Zhang, B. Li, 2D Mater 2 (2015) 14011.
References [38] G. Zhou, E. Paek, G.S. Hwang, A. Manthiram, Nat. Commun. 6 (2015) 7760.
[39] G. Zhou, L.-C. Yin, D.-W. Wang, L. Li, S. Pei, I.R. Gentle, F. Li, H.-M. Cheng, ACS
Nano 7 (2013) 5367e5375.
[1] Y.-X. Yin, S. Xin, Y.-G. Guo, L.-J. Wan, Angew. Chem. Int. Ed. 52 (2013) [40] J. Zhao, S. Pei, W. Ren, L. Gao, H.-M. Cheng, ACS Nano 4 (2010) 5245e5252.
13186e13200. [41] Z. Wang, Y. Dong, H. Li, Z. Zhao, H. Bin Wu, C. Hao, S. Liu, J. Qiu, X. W, Nat.
[2] A. Manthiram, Y. Fu, S.-H. Chung, C. Zu, Y.-S. Su, Chem. Rev. 114 (2014) Commun. 5 (2014) 5002.
11751e11787. [42] S. Yuan, J.L. Bao, L. Wang, Y. Xia, D.G. Truhlar, Y. Wang, 1501733en/a, Adv.
[3] P.G. Bruce, S.A. Freunberger, L.J. Hardwick, J.-M. Tarascon, Nat. Mater 11 Energy Mater 6 (2016).
(2012) 19e29. [43] A.A.K. King, B.R. Davies, N. Noorbehesht, P. Newman, T.L. Church, A.T. Harris,
[4] S. Zhang, K. Ueno, K. Dokko, M. Watanabe, Adv. Energy Mater 5 (2015), J.M. Razal, A.I. Minett, Sci. Rep. 6 (2016) 19491.
1500117en/a. [44] P. Wang, Z.-G. Liu, X. Chen, F.-L. Meng, J.-H. Liu, X.-J. Huang, J. Mat. Chem. A 1
[5] X. Ji, S. Evers, R. Black, L.F. Nazar, Nat. Commun. 2 (2011) 325. (2013) 9189e9195.
[6] A. Manthiram, Y. Fu, Y.-S. Su, Acc. Chem. Res. 46 (2013) 1125e1134. [45] F. Tuinstra, J.L. Koenig, Raman spectrum of graphite, J. Chem. Phys. 53 (1970)
[7] R. Xu, J. Lu, K. Amine, Adv. Energy Mater 5 (2015), 1500408en/a. 1126e1130.
[8] Y.V. Mikhaylik, J.R. Akridge, J. Electrochem. Soc. 151 (2004) A1969eA1976. [46] K. McGuire, N. Gothard, P.L. Gai, M.S. Dresselhaus, G. Sumanasekera, A.M. Rao,
[9] S.-E. Cheon, K.-S. Ko, J.-H. Cho, S.-W. Kim, E.-Y. Chin, H.-T. Kim, J. Electrochem. Carbon 43 (2005) 219e227.
Soc. 150 (2003) A796eA799. [47] J. Maultzsch, S. Reich, C. Thomsen, S. Webster, R. Czerw, D.L. Carroll,
[10] D. Aurbach, J. Power Sources 89 (2000) 206e218. S.M.C. Vieira, P.R. Birkett, C.A. Rego, Appl. Phys. Lett. 81 (2002) 2647e2649.
[11] M.-K. Song, Y. Zhang, E.J. Cairns, Nano Lett. 13 (2013) 5891e5899. [48] A.C. Ferrari, Solid State Commun. 143 (2007) 47e57.
[12] S.-K. Lee, Y.J. Lee, Y.-K. Sun, J. Power Sources 323 (2016) 174e188. [49] L. Chen, H. Zhou, S. Wei, Z. Chen, Z. Huang, Z. Huang, C. Zhang, Y. Kuang, RSC
[13] C. Zu, A. Manthiram, J. Phys. Chem. Lett. 5 (2014) 2522e2527. Adv. 5 (2015) 8175e8181.
[14] S. Xin, Y.-G. Guo, L.-J. Wan, Acc. Chem. Res. 45 (2012) 1759e1769. [50] E. Rodríguez, I. Came an, R. García, A.B. García, Electrochim. Acta 56 (2011)
[15] J. Guo, Y. Xu, C. Wang, Nano Lett. 11 (2011) 4288e4294. 5090e5094.
[16] G. Zheng, Y. Yang, J.J. Cha, S.S. Hong, Y. Cui, Nano Lett. 11 (2011) 4462e4467. [51] L. Li, G. Zhou, L. Yin, N. Koratkar, F. Li, H.-M. Cheng, Carbon 108 (2016)
[17] N. Jayaprakash, J. Shen, S.S. Moganty, A. Corona, L.A. Archer, Angew. Chem. Int. 120e126.
Ed. 50 (2011) 5904e5908. [52] G. Zhou, S. Pei, L. Li, D.-W. Wang, S. Wang, K. Huang, L.-C. Yin, F. Li, H.-
[18] H.-J. Peng, J.-Q. Huang, M.-Q. Zhao, Q. Zhang, X.-B. Cheng, X.-Y. Liu, W.-Z. Qian, M. Cheng, Adv. Mater 26 (2014) 625e631.
F. Wei, Adv. Funct. Mater 24 (2014) 2772e2781. [53] X. Yuan, L. Wu, X. He, K. Zeinu, L. Huang, X. Zhu, H. Hou, B. Liu, J. Hu, J. Yang,
[19] Y.-S. Su, A. Manthiram, Chem. Commun. 48 (2012) 8817e8819. Chem. Eng. J. 320 (2017) 178e188.
[20] R. Singhal, S.-H. Chung, A. Manthiram, V. Kalra, J. Mat. Chem. A 3 (2015)