OPEN Unusual High Oxygen Reduction

SUBJECT AREAS:
Performance in All-Carbon
ELECTROCATALYSIS
BATTERIES
Electrocatalysts
Wei Wei1,4*, Ying Tao1,4*, Wei Lv2*, Fang-Yuan Su2, Lei Ke2, Jia Li2, Da-Wei Wang3, Baohua Li2,
Received Feiyu Kang2 & Quan-Hong Yang1,2,4
4 July 2014
Accepted 1
Key Laboratory for Green Chemical Technology of Ministry of Education, School of Chemical Engineering and Technology, Tianjin
15 August 2014 University, Tianjin, 300072, China, 2Engineering Laboratory for Functionalized Carbon Materials, Graduate School at Shenzhen,
Tsinghua University, Shenzhen, 518055, China, 3School of Chemical Engineering, The University of New South Wales, Sydney,
Published NSW 2033, Australia, 4The Synergistic Innovation Center of Chemistry and Chemical Engineering of Tianjin, Tianjin, 300072,
5 September 2014 China.

Correspondence and Carbon-based electrocatalysts are more durable and cost-effective than noble materials for the oxygen
reduction reaction (ORR), which is an important process in energy conversion technologies. Heteroatoms
requests for materials
are considered responsible for the excellent ORR performance in many carbon-based electrocatalysts. But
should be addressed to whether an all-carbon electrocatalyst can effectively reduce oxygen is unknown. We subtly engineered the
Q.-H.Y. (qhyangcn@ interfaces between planar graphene sheets and curved carbon nanotubes (G-CNT) and gained a remarkable
tju.edu.cn) or D.-W.W. activity/selectivity for ORR (larger current, and n 5 3.86, ,93% hydroxide 1 ,7% peroxide). This
(da-wei.wang@unsw. performance is close to that of Pt; and the durability is much better than Pt. We further demonstrate the
application of this G-CNT hybrid as an all-carbon cathode catalyst for lithium oxygen batteries.We
edu.au)
speculate that the high ORR activity of this G-CNT hybrid stems from the localized charge separation at the
interface of the graphene and carbon nanotube, which results from the tunneling electron transfer due to the
Fermi level mismatch on the planar and curved sp2 surfaces. Our result represents a conceptual
* These authors
breakthrough and pioneers the new avenues towards practical all-carbon electrocatalysis.
contributed equally to
this work.

H
igh-energy metal-air batteries are of paramount importance for the resolution of fossil fuel depletion and
CO2 emission. These batteries are key parts for future renewable energy framework because of their
extraordinary energy density, which is at least ten times larger than that of lithium-ion batteries1.
Oxygen reduction reaction (ORR) on the air-breathing cathodes of metal-air batteries plays a determinant role
in maximizing the overall device performance. Theoretically, the complete reduction of oxygen in aqueous
electrolytes produces OH2 (alkaline) or H2O (acidic), giving rise to an electron transfer number (n) of 42,3.
The state-of-the-art electrocatalyst for ORR is Pt. ORR catalyzed by Pt-based catalysts has demonstrated high
onset potential and fast kinetics and is a four-electron transfer process. But Pt-based catalysts are often expensive
and less resistant to dissolution, coalescence or poisoning4. Among many kinds of non-noble ORR catalysts3–8,
heterogeneous carbon materials have shown increasing importance. Enormous studies elucidated the improved
ORR activity in different kinds of doped carbon materials, such as carbon nanotubes (CNTs), graphene sheets,
and nanoporous carbons9. These metal-free catalysts prevent the leaching or poisoning of metal atoms and hence
render superb stability. The common dopants are nitrogen10–14, boron15, sulfur16, or sulfur/nitrogen co-dopant17.
These dopants are usually covalently bonded with carbon atoms. Theoretical simulation speculated the mech-
anism of doping is to generate charge separation in the charge-neutral sp2 carbon lattice, which facilitates oxygen
adsorption14.
Unlike the covalent doping (charge injection), we propose a non-covalent doping strategy to enhance the ORR
activity of all-carbon electrocatalysts. The idea is to make use of the different electronic structures of carbon
allotropes18,19. The adsorption of dioxygen molecules and the transfer of electrons are the rate determining steps
for ORR catalyzed by carbon materials3. The p electrons in a sp2 carbon lattice distribute homogeneously; whereas
doping-induced uneven charge distribution is the key to high ORR activity. Non-covalent doping of sp2 carbon
can be induced by the work function difference between metal and graphene20,21. For example, Au can attract
electrons from graphene due to its larger work function, and hence apply a p-type doping to graphene22. The
electron transfer from graphene to CNTs was also attributed to the larger work function of CNTs23,24.

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Theoretically speaking, non-covalent p-doping of graphene can be disk electrode (RDE) and rotating ring disk electrode (RRDE)
achieved by taking CNTs as electron acceptors25. The charge sepa- measurements. A commercial Pt/C catalyst was tested as a
ration would naturally occur at the interfaces of CNT and graphene25. reference (20 wt. % Pt, HiSPEC 3000 from Johnson Matthey Fuel
In this communication, we successfully engineered the interface Cells, Figure S4). In a N2-saturated electrolyte, redox features are
between CNTs and graphene sheets, and developed a CNT-doped negligible for both G-CNT100/20 and Pt/C (Figure 3a). While in
graphene hybrid (G-CNT) for the use as an all-carbon ORR catalyst, an O2-saturated electrolyte, the G-CNT 100/20 exhibits a
free from metal or non-carbon dopants. Such an all-carbon catalyst pronounced cathodic ORR peak at 20.22 V versus an Ag/AgCl
developed a 3D hierarchical porous open network consisting of reference electrode which is the same as shown by doped
entangled graphene sheets and CNTs. Although sole carbon allo- graphene16,17,30–32, although it is lower than that of Pt/C. It is worth
tropes have limited ORR selectivity (2,n,3)8,26, we demonstrate noting that its peak current densityis about twice that for Pt/C,
the enhanced ORR selectivity (n53.86) and reaction current in our suggesting the high ORR activity of G-CNT 100/20. From the
G-CNT hybrids where the interface structure is delicate. We show for results shown in Figure 3b, it also shows a much higher ORR
the first time that all-carbon materials are electrocatalytically active activity than a pure graphene monolith (Figure S5) and a physical
and stable, and most importantly, more cost effective. We speculate blend of graphene and CNTs (Figure S6), revealing the uniqueness of
that the high ORR activity of this G-CNT hybrids stems from the the carefully engineered G-CNT hybrid. These results emphasize
charge separation at the interface of the graphene and carbon nano- that a physical blend of graphene and CNTs could not develop an
tube, which results from the electron tunneling due to the Fermi level equivalent activity to that of the G-CNT 100/20 sample, and that the
mismatch at the planar and curved sp2 surfaces.Taking into account sample processing approach could sensibly alter the catalytic nature
of the facilitated oxygen diffusion paths, and the excellent ORR of the hybrids.
activity, we evaluated the 3D hybrid in a Lithium-O2 cell which RDE measurements were used to reveal the ORR kinetics of G-
showed high performance. CNT100/20 and Pt/C. The linear-sweep voltammetry (LSV) curves
of G-CNT100/20 at different rotation speeds are shown in Figure 3c.
Results The onset potential and the half-wave potential of G-CNT100/20 are
Fabrication and structure characterization of all-carbon catalysts. lower than those of Pt/C, but the limiting diffusion current is higher
For the preparation of a typical G-CNT monolith, a homogeneously than that of Pt/C in the range of 20.5 , 20.8 V (Figure S7).
mixed aqueous suspension of graphene oxide (GO) and CNTs with According to the LSV curves at various rotation rates, the
the mass ratios of 100/20 was hydrothermally treated in a Teflon- Koutecky-Levich plot at a potential of 20.35 V is shown in the inset
lined autoclave at 150uC for 20 h to form a hybrid hydrogel (Figure of Figure 3c. The electron transfer number is 3.86 from the slopes of
S1), which was then freeze-dried and annealed at 300uC for 2 h and Koutecky-Levich plots for G-CNT 100/20, very close to that of a
800uC for 3 h in Ar. A series of G-CNT hybrids were obtained commercial Pt/C catalyst (n53.94), and the variances of G-CNT
following the protocol in Figure 1. These samples are denoted 100/20 and Pt/C are 8.6 3 1024 and 6.2 3 1024, respectively. The
G-CNT X/Y, where X5100 (GO content) and Y520, 10, 5, 3.3, dependence of electron transfer number (n) on the CNT fraction is
and 2 (CNT content). The details for the preparation are provided shown in Figure 3d. With the larger percentage of CNTs, the higher n
in the method section. number is obtained. This strongly indicates that CNTs function like a
The microstructure and morphology of the as-prepared G- ‘‘dopant’’ to activate the catalytic nature of the pure graphene and the
CNT100/20 were investigated by scanning electron microscopy hybrids; or vice versa that graphene can ‘‘dope’’ CNTs to trigger the
(SEM) and transmission electron microscopy (TEM). The SEM activity and adjust the selectivity. The as-obtained G-CNT hybrid
images (Figure 2a and Figure S2) show that the graphene sheets exhibits a close to 4e selectivity for ORR; whereas both the pristine
and CNTs are entangled forming a continuous all-carbon 3D net- CNTs and graphene with metal impurities present a 2e ORR pathway
work (Figure S3). TEM images (Figure 2b and Figure 2c) show that (Table S1), which is reasonable as metal-nitrogen complexes are
the CNTs are tightly attached to the few-layer graphene sheets. The believed as the active sites for 4e ORR5. It is also noted that small
nitrogen adsorption isotherm of a G-CNT100/20 (Figure 2d) is char- amount of residual metals does not enhance the ORR activity of the
acterized by combined features, suggesting the hierarchical pore G-CNT hybrid. Therefore we could conclude that the trace amount
structure. The hybrid shows a specific surface area of ,480 m2 metals determined in our undoped graphene or carbon nanotubes do
g21, calculated by the Brunauer-Emmett-Teller (BET) method. The not show the same ‘‘visible’’ electrocatalytic behavior as those
high surface area and the hierarchical pore structure allow fast mass observed in the metal-nitrogen complexes, or in the high amount
transfer and provide many accessible catalytic sites for ORR27,28. conditions.
To further verify the ORR catalytic performance of G-CNT 100/
The ORR kinetics performance of the G-CNT. Alkaline solution is 20, RRDE measurement was conducted to monitor the amount of
the mostly used electrolyte for metal-air batteries1,2,29. Therefore, the H2O2 generated at the disk electrode during the ORR process. The
ORR performance of our G-CNT hybrids were tested in a 0.1 M disk and ring currents were measured and are shown in Figure 3e.
KOH electrolyte. We combined cyclic voltammetry (CV), rotating The measured H2O2 yield is below 12% over the potential range of

Figure 1 | Scheme of fabrication process for the G-CNT material and its ORR catalysis.

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Figure 2 | Structure and morphology of G-CNT 100/20. (a) SEM image; (b) low magnification and (c) high magnification TEM images; (d) Nitrogen
adsorption/desorption isotherm and pore size distribution (inset), demonstrating the hierarchical pore structure.

20.3 , 21.2 V, giving an electron transfer number of ,3.8 consist- stability of the G-CNT 100/20, indicating the superior stability
ent with Koutecky-Levich analysis (Figure 3f). We tested the ORR compared with the Pt/C reference shown in Figure 4b. We also
performance of the all-carbon catalyst on a nickel foam in both conducted the RDE measurement in an electrolyte containing
aqueous (Figure 3g) and organic (Figure 3h) electrolytes. The linear 0.5 M methanol to characterize the resistance G-CNT 100/20 and
relationships existed between the peak current and v1/2 indicate that Pt/C to methanol poisoning (Figure 4c and d). The ORR activity of
this stationary ORR reaction is a diffusion-controlled process (Figure Pt/C is dramatically reduced. In contrast, the G-CNT 100/20 exhibits
S8 and S9). This all-carbon catalyst showed a satisfactory activity in a excellent resistance to methanol poisoning with little activity loss.
Lithium-O2 cell (Figure S10). It is noted that there are many macro-
pores which can provide numerous gas diffusion channels, and they
Discussion
could continuously supply oxygen to the interior of the electrode
We demonstrated that the sample processing approach is key to the
when the G-CNT hybrid is used as a gas diffusion cathode in
Lithium-O2 batteries (Figure S10). The ORR performance of our high oxygen reduction activity (Figure 3b). The uniform distribution
all-carbon G-CNT catalysts, covalently doped graphenes and gra- during the ultrasonication process and high pressure in the hydro-
phene-supported metals or metal oxides are compared in thermal process following by high-temperature annealing may help
Figure 3i8,17,30,33–38. This comparison highlights the position of the to develop the delicate contact and interaction between the CNTs
G-CNT hybrids as a new kind of promising oxygen reduction cata- and graphene sheets. This could result in non-covalent ‘‘doping’’
lysts (Table S1 and S2). between the two carbon allotropes that renders a high ORR perform-
ance. We combined atomic force microscopy (AFM), Kelvin probe
The cyclic stability and durability of G-CNT. Another main force microscope (KPFM), Raman spectroscopy and simulation to
challenge of an ORR catalyst for its application is the cyclic identify the interaction between graphene sheets and CNTs in the G-
stability and durability. We assessed the cyclic stability of G-CNT CNT hybrid. A typical AFM image of a dispersed sample and the
100/20 using the accelerated durability test protocol (Department of corresponding height profile are shown in Figure 5a and 5c, which
Energy, USA) by cycling the catalysts on a RDE at 50 mV s21 for 8000 show a CNT overlapping with a graphene sheet. Figure 5b shows the
cycles in an O2-saturated 0.1 M KOH solution7. After each of the 1st, surface potential image of the marked area in Figure 5a, from which a
1000th, 3000th, 5000th and 8000th cycles, LSV measurement was higher surface potential along the direction of CNT is revealed. This
performed at 1600 rpm. Figure 4a shows the excellent cyclic result demonstrates that the modified local charge density distri-

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Figure 3 | Performance of G-CNT 100/20 as an all-carbon catalyst. (a, b) CV curves of G-CNT 100/20, a commercial Pt/C catalyst and some reference
samples including a graphene monolith and a simple mixture of graphene and CNT in N2-saturated (dashed line) and O2-saturated (solid line)
electrolytes (Note that the loading density of catalyst materials is the same in these tests); (c) LSV curves of G-CNT 100/20 in O2-saturated electrolytes at
different rotation rates (in rpm), The inset shows the corresponding Koutecky-Levich plot of G-CNT 100/20 and Pt/C derived from the RDE curves at
20.35 V; (d) Electron transfer number of CNT, graphene monolith and G-CNTs; (e) RRDE voltammogram of G-CNT 100/20 in an O2-saturated
electrolyte; (f) Percentage of H2O2 and the electron transfer number of G-CNT 100/20 at various potentials, based on the corresponding RRDE data in e;
The CV curves of catalyst loaded electrode of G-CNT 100/20 in O2-saturated 0.1 M KOH solution (g) and 1M LiCF3SO3 in TEGDME (h); (i) comparison
of ORR performance for some typical all-carbon materials, doped graphenes and graphene-supported metals or metal oxides.

bution around the contact area. It is already known that CNTs can of the hole doping from CNTs to graphene sheets25, and more fun-
create a positively charged area on graphene sheets22. Therefore the damental simulation studies are ongoing. As increasing the amount
positive potential should be of the top graphene sheet; this means the of CNTs, the density of active sites increases, and hence the ORR
nanotube is beneath. Raman spectroscopy provides a sensitive probe activity becomes better, as demonstrated in Figure 3d.
for electronic structures of carbon materials including doped ones, We propose our understanding of the mechanism. KPFM results
and the doping-induced shift of the Raman-active tangential G-band demonstrate the charge separation at the interface of the graphene
results from the electronic structure changes (changes of Fermi and carbon nanotube (Figure 5). Due to the smaller work function of
level)39. The Raman spectra of G-CNT (Figures 5e and S11) show a graphene than that of carbon nanotubes, the Fermi level of graphene
stepwise downshift of the G-band as CNT fraction increases, which is is higher. According to the quantum tunneling theory, it is easier for
usually caused by hole doping in graphene39,40. This agrees with the the electrons in the graphene to tunnel through the vacuum barrier
KPFM results. and jump into carbon nanotubes. The interfacial electron tunneling
The oxygen adsorption of G-CNTs was conducted to determine induced by the mismatch of the Fermi level on the planar and curved
the enhanced oxygen adsorption capacity due to the non-covalent sp2 surfaces eventually enables the charge separation at the interface
‘‘doping’’ (Figure 5f). Figure 5g demonstrates that the larger fraction (Figure 6). It is also shown that only particularly engineered interface
of CNTs induces the higher adsorption amount, which is consistent can support such delicate electron tunnelling. The combined hydro-
with the improved ORR activity (Figure 3d). Furthermore, the affin- thermal and high-temperature annealing treatment is responsible for
ity of the all-carbon catalyst surface to oxygen was also studied by the formation of such subtle interface between the two nanocarbon
using differential scanning calorimetry (DSC) analysis, as shown in allotropes with different electronic characteristics19,25. The activated
Figure 5h. The exothermal peak for G-CNT 100/20 is lower than the interface between graphene and CNT provides an ideal active place
pure graphene monolith (without CNTs) and G-CNT 100/5 by 81uC for enabling high ORR performance14,41–43. Very Recently, Cheon
and 17uC, respectively. This suggests the much easier chemisorption et al. have also used work function to understand the activity and
of oxygen on G-CNT 100/20 (oxidation of carbon atoms), which is in reaction kinetics of ORR for heteroatom-doped carbons44, and in
strong agreement with its higher adsorption capaicty for oxygen. their case, a similar concept is proposed to what we used above to
These results confirm that the enhanced charge separation at the explain the unusual ORR activity of the all-carbon material, G-CNT
G-CNT interfaces is reponsible for the improved ORR activity. hybrid.
Our simulation illustrated the disturbed charge distribution in the In summary, we have combined hydrothermal and high-tem-
G-CNT hybrid (see Supplementary Information). We noticed the perature annealing methods to engineer the interface between
positive charge (0.232) on a graphene sheet in the hybrid compared graphene and carbon nanotubes. The all-carbon product is highly
to the zero charge on a graphene sheet without a CNT. This is evident active for oxygen reduction reaction; and the high activity/select-

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Figure 4 | RDE polarization curves of (a) G-CNT 100/20 and (b) Pt/C after the 1st, 1000th, 3000th, 5000th and 8000th in an O2-saturated 0.1 M
KOH solution; RDE polarization curves of (c) G-CNT 100/20 and (d) Pt/C in an O2-saturated 0.1 M KOH solution with or without 0.5 M methanol.
G-CNT 100/20 exhibits a dramatically improved tolerance to methanol poisoning compared with Pt/C.

ivity is triggered by the electron tunnelling and charge separation cyclic stability and durability. More notably, the 3D open network
because of the distinct work functions between graphene and of the all-carbon product is advantageous for gas diffusion and has
CNTs. Overall, the unique G-CNT hybrid shows comparable cata- shown promising potential as Lithium-O2 battery cathode
lytic performance to a commercial Pt/C catalyst and much higher catalysts.

Figure 5 | Evidence for the charge separation at the interface of the graphene and carbon nanotube. (a) AFM image and (c) corresponding height profile
of G-CNT; (b) Surface potential image and (d) corresponding potential distribution of G-CNT; (e) Raman spectra of G-CNTs and some reference
samples including CNT and graphene monolith; (f) Oxygen adsorption/desorption isotherm of G-CNT 100/20; (g) The oxygen adsorption amount at the
relative pressure of 0.95 for G-CNTs; (h) DSC curves of G-CNT100/20, G-CNT100/5 and graphene monolith.

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Acknowledgments NoDerivs 4.0 International License. The images or other third party material in
We appreciate the help from the National Supercomputing Center in Shenzhen and the this article are included in the article’s Creative Commons license, unless indicated
support from National Basic Research Program of China (2014CB932403), National otherwise in the credit line; if the material is not included under the Creative
Science Foundation of China (Nos. 51232005, 51372167 and 51302146), NSF of Tianjin, Commons license, users will need to obtain permission from the license holder
China (No. 12JCZDJC27400) and Shenzhen Basic Research Project (Nos. in order to reproduce the material. To view a copy of this license, visit http://
JC201104210152A and JCYJ20130402145002430). D.-W.W. appreciates the support from creativecommons.org/licenses/by-nc-nd/4.0/
Australian Research Council Discovery Project Scheme (DP110100550).We also thank the
financial support from Guangdong Province Innovation R&D Team Plan (No.
2009010025).

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