Advanced Materials - 2012 - Huang - Graphene Based Electrodes

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REVIEW
Graphene-Based Electrodes
Xiao Huang, Zhiyuan Zeng, Zhanxi Fan, Juqing Liu, and Hua Zhang*
method[1] (or the “scotch tape” method),

Graphene, the thinnest two dimensional carbon material, has become the thermal decomposition of SiC,[9,10] chem-
subject of intensive investigation in various research fields because of its ical vapor deposition (CVD),[11–21] the exfo-
remarkable electronic, mechanical, optical and thermal properties. Graphene- liation and reduction of chemically oxidized
graphite,[22–58] exfoliation of graphite and
based electrodes, fabricated from mechanically cleaved graphene, chemical graphite intercalated compounds,[59–65]
vapor deposition (CVD) grown graphene, or massively produced graphene solvothermal synthesis,[66] organic syn-
derivatives from bulk graphite, have been applied in a broad range of applica- thesis,[67] and so on. Despite of its ability to
tions, such as in light emitting diodes, touch screens, field-effect transistors, yield the high quality single- and few-layer
solar cells, supercapacitors, batteries, and sensors. In this Review, after a graphene sheets, the mechanical cleavage
method is difficult to massively produce
short introduction to the properties and synthetic methods of graphene and
graphene for the practical application. The
its derivatives, we will discuss the importance of graphene-based electrodes, CVD method, on the other hand, has been
their fabrication techniques, and application areas. recognized as one of the most promising
processes to reliably generate high-quality
graphene films, particularly used for elec-
1. Introduction to the Properties and Fabrication tronic and optoelectronic devices. Since Kong et al. reported the
CVD growth of few-layer graphene films on the polycrystalline
Methods of Graphene
Ni substrate in 2009,[18] tremendous efforts have been made
Graphene, a two-dimensional (2D) form of carbon atoms with to produce the uniform graphene films with controllable layer
the hexagonal lattice structure, has been considered as one of the number and minimized defects.[13,19–21] For example, Li et al.
most important materials in the current century. Since the direct successfully demonstrated the growth of large-area, continuous
investigation of mechanically exfoliated graphene by Novoselov graphene films (95% of the film is single-layer) on the flexible
et al. in 2004,[1] tremendous research efforts have been devoted copper foil with the film size up to 30 inches.[13] More recently,
to the study and applications of graphene as well as graphene- the further development in CVD growth of graphene has been
based materials.[2,3] Graphene is a zero-gap semimetal with achieved, including the near room temperature (25–160 °C)
a small overlap between its valence and conduction bands.[1] synthesis of graphene films on the nonconducting substrates,[20]
It shows a strong ambipolar electric field effect with the high the preparation of millimeter-size single crystal graphene grains
charge carrier mobilities of ≈10 000 cm2 V−1 s−1 at room temper- on the re-useable Pt substrate,[19] and the growth of strictly
ature.[1] The suspended graphene, on the other hand, exhibits a single-layer graphene on the Ni-Mo alloy with 100% surface
mobility approaching 200 000 cm2 V−1 s−1 for the carrier den- coverage.[21] All these advances are expected to enable more
sity below 5 × 109 cm−2 at a low temperature.[4] In addition, the possibilities for use of CVD-graphene in various electronic and
white light absorbance of a suspended graphene monolayer is optoelectronic applications.
2.3% (or transmittance of 97.7%) with a negligible reflectance of Because of the relatively high cost and low throughput of
<0.1%.[5] Moreover, graphene exhibits the excellent thermal sta- the CVD process, the large-quantity fabrication of graphene
bility and conductivity (3000 ≈ 5000 W m−1 K−1),[6] high Young’s and its derivatives from the bulk graphite has also been sub-
modulus (≈1 TPa),[7] and large theoretical specific surface area ject to intensive investigation for their potential applications in
(SSA, 2630 m2 g−1).[8] All these outstanding properties have thus touch screens, energy storage devices, electrochemical sensors,
aroused great research interest from the fundamental study to fuel cells and so on, where the extremely high conductivity of
various applications of graphene. graphene film is not required.[68] Chemical species, such as
To synthesize graphene and its derivatives, numerous N-methyl-pyrrolidone (NMP)[60,61] and sodium dodecylbenzene
methods have been employed, such as the mechanical exfoliation sulfonate (SDBS),[69] have been successfully used as intercalates
to assist the exfoliation of the intercalated graphite. Remark-
ably, the reintercalation of thermally exfoliated expandable
Prof. H. Zhang, Dr. X. Huang, Z. Zeng, Z. Fan, graphite (EG) with tetrabutylammonium hydroxide (TBA) and
Dr. J. Liu oleum (fuming sulphuric acid with 20% free SO3) has led to
School of Materials Science and Engineering the preparation of single-layer graphene with a yield of ≈90%
Nanyang Technological University after purification.[70] In addition, the electrochemical method
50 Nanyang Avenue, Singapore 639798, Singapore
E-mail: hzhang@ntu.edu.sg; hzhang166@yahoo.com
has also been used to prepare isolated graphene sheets, such as
the electrochemical exfoliation of graphite in ionic liquids,[71,72]
DOI: 10.1002/adma.201201587 the electrochemical Li-intercalation and subsequent exfoliation
Adv. Mater. 2012, 24, 5979–6004 © 2012 WILEY-VCH Verlag GmbH & Co. KGaA, Weinheim wileyonlinelibrary.com 5979
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of graphite in ethanol or water.[73,74] Importantly, an alterna-

REVIEW
tive strategy, probably one of the mostly explored and applied Hua Zhang studied at
methods, is the reduction of highly oxidized graphene oxide Nanjing University (B.S.,
(GO) sheets from the exfoliated graphite oxide,[55] to yield the M.S.), and completed his
reduced GO (rGO), functionalized graphene sheets (FGSs) Ph.D. at Peking University
or the chemically converted graphene (CCG). The graphite (with Zhongfan Liu) in 1998.
oxide is obtained based on the Hummers method by reacting After postdoctoral work at
graphite with potassium permanganate (KMnO4) and concen- Katholieke Universiteit Leuven
trated sulfuric acid (H2SO4).[30,37–44,75,76] Hence, the GO sheets (with Frans De Schryver) and
are highly oxidized with abundant residual epoxide, carbonyl, Northwestern University (with
hydroxide and carboxylic acid groups anchoring on their sur- Chad Mirkin), and working
face.[77–79] Until now, many reduction methods have been at NanoInk Inc. and the
reported to obtain rGO sheets, such as the chemical reagent Institute of Bioengineering
reduction,[30,31,37–58,80,81] thermal reduction,[82–89] photochem- and Nanotechnology (Singapore), he joined Nanyang
ical reduction,[90–94] sonolysis,[95] photothermal reduction,[96,97] Technological University (2006). His current research inter-
microwave-assisted reduction[98] and electrochemical reduc- ests focus on synthesis of 2D and low-dimensional nano-
tion.[99–102] Recently, a KOH-activated method has also been materials and carbon materials (graphene and CNTs), and
applied to prepare graphene from thermal-exfoliated graphite exploration of their applications in nano- and biosensing,
oxide (TEGO) and microwave-exfoliated graphite oxide (MEGO), clean energy, etc.
which gives rise to a porous graphene network containing
mostly single layers of sp2-bonded carbon, together with an ult- Xiao Huang received her B.E.
rahigh specific surface area up to 3100 m2 g−1.[103] This type of from the School of Materials
porous graphene-based material is ready for fabrication of elec- Science and Engineering
trodes used for high-performance energy storage devices. of Nanyang Technological
Having briefly introduced the properties and synthesis University in Singapore in
methods of graphene, in the following context, we will first 2006 and completed her
emphasize the importance of graphene-based electrodes, intro- Ph.D. under the supervision
duce their fabrication methods, and then provide a detailed dis- of Professor Hua Zhang and
cussion on graphene-based electrodes in various applications. Professor Freddy Boey in
2011 at the same university.
She is currently working
as a postdoctoral fellow in
2. Graphene-Based Electrodes
Prof. Hua Zhang’s group. Her research interests include
the synthesis and applications of graphene-based hybrid
2.1. The Importance of Graphene-Based Electrodes materials.
Up till now, many reports have suggested that graphene-

based electrodes are promising candidates in a wide range of
applications, such as field-effect transistors (FETs),[38,104–106]
solar cells,[41,107–118] light emitting diodes (LEDs),[119–121] which compromises their performance in solar harvesting and
touch screens,[12,122] electrochemical sensors,[99,121,123–145] bat- certain NIR-based optoelectronic devices.[184] In contrast, the
teries[146–159] and supercapacitors.[103,160–180] CVD-graphene-based thin film, with comparable conductivity
For electronic and optoelectronic devices, like solar cells and and transparency to ITO,[185] has shown many attractive and
LEDs, doped metal oxides, particularly indium tin oxide (ITO), competitive advantages, such as the excellent flexibility and
have been widely used as electrode materials due to their low good thermal and chemical stability, which suggest that the
sheet resistance (e.g., 10–30 Ω sq−1) and high optical transmit- graphene-based electrode is the ideal replacement for ITO in
tance (>90% at 550 nm).[68] Unfortunately, concerns have been future electronic devices.
raised over the limited indium source, stringent deposition In electrochemical applications, carbon-based materials
conditions, and consequently high costs.[181] In addition, ITO such as activated carbon, fullerenes (C60), carbon nanofibers
also suffers from several technical disadvantages. For example, and carbon nanotubes (CNTs) have been widely used as elec-
its brittle nature leads to cracks and fracture at a low strain of trodes,[186–188] because they have many advantageous properties
2–3%.[181,182] It is not stable in basic or acidic environments, like good conductivity, wide potential window, and good elec-
which causes a shortened life time.[181,183] Furthermore, the trocatalytic activity for various redox reactions.[189] Furthermore,
ITO film has a relatively high index of refraction (n ≈ 2.0), crystalline carbon structures, such as C60, CNTs, and diamond,
which can result in unwanted reflections when they are coated possess sp2/sp3 hybridized domains, which allow for chemical
on substrates with relatively lower refraction indices.[181] Other modification and are very important for surface reactions.[189]
potential issues associated with the ITO thin film are the ion In fact, graphene, the building block of these crystalline carbon
diffusion from the ITO to the polymer layer in solar cells, materials,[190] exhibits similar attractive properties. Moreover,
and the poor transparency in the near infrared (NIR) region, since both sides of a graphene sheet are exposed, graphene
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REVIEW
provides a larger theoretical specific surface areas (SSA) for elec- low-yield production and lower reproducibility of the cleavage
trochemical reactions compared to the other types of crystalline technique.
carbon structures. Importantly, the capability of being mass- The CVD method, as mentioned above, has realized the pro-
produced from bulk graphite makes graphene-based materials duction of large-area continuous graphene films with excellent
even more attractive for development of the cost-effective, high- electronic properties. Transferring a prepatterned graphene film
performance electrochemical devices like supercapacitors and from its catalyst surface to an arbitrary substrate has been dem-
batteries. onstrated by Hong and coworkers.[12] As shown in Figure 1a–b,
after the growth of a graphene film on a prepatterned Ni sub-
strate, a polydimethylsiloxane (PDMS) stamp is attached to the
2.2. Fabrication of Graphene-Based Electrodes graphene film, followed by etching the Ni layer and transferring
the graphene film to a target substrate. Alternatively, by direct
To date, graphene-based electrodes can be categorized in four etching the Ni substrate, a floating graphene film is obtained,
groups based on the different graphene materials used, i.e., which can be subsequently brought into contact with any arbi-
the pristine graphene electrode, the CVD-grown graphene trary substrate by the simple scooping (Figure 1c). The obtained
electrode, the chemically modified graphene electrode, and the film showed a transmittance of ≈80% with a sheet resist-
graphene composite electrode. ance as low as 280 Ω sq−1. Afterwards, a roll-to-roll transfer
To fabricate the pristine graphene electrode, the graphene is technique was employed by the same group[185] to prepare a
obtained by the mechanical cleavage method. This has recently graphene film with a large lateral size up to 30 inches. Briefly,
been applied in a tunneling field-effect transistor.[191] How- a large-area graphene film, grown on a flexible Cu foil,[13] was
ever, the application of mechanically cleaved pristine graphene firstly attached to a polymer film by passing them through
has only been used in fundamental studies, because of the two rollers (Figure 1d). The Cu foil was then etched away in
Figure 1. a) Photograph of a transparent and flexible graphene film on a PDMS stamp. b) Photograph of the PDMS stamp making conformal contact
with a silicon dioxide substrate. c) Photograph of a floating graphene film after etching the nickel substrate. Reproduced with permission.[12] Copyright
2009, Nature Publishing Group. d) Schematic illustration of the roll-based production of a graphene film grown on a copper foil. The process includes
the adhesion of a polymer support, copper etching (rinsing) and dry transfer-printing on a target substrate. Wet-chemical doping can be carried out
using a setup similar to that used for etching. Reproduced with permission.[185] Copyright 2010, Nature Publishing Group. e) Schematic illustration of
the bubbling transfer process of graphene from a Pt substrate. The PMMA/graphene/Pt was used as a cathode, and a Pt foil was used as the anode.
The PMMA/graphene was gradually separated from the Pt substrate driven by the H2 bubbles produced at the cathode after applying a constant cur-
rent. f) Photograph of the separated PMMA/graphene (indicated by an arrow) and Pt foil. Reproduced with permission.[19] Copyright 2012, Nature
Publishing Group.
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REVIEW
Figure 2. a) Schematic illustration for patterning graphene strips and cross-strips by the evaporation-induced self-assembly (EISA) method. b) Photo-
graph of graphene patterns on a 4-inch SiO2/Si wafer. Optical images of (c) striped and (d) cross-striped graphene patterns. Reproduced with permis-
sion.[192] Copyright 2012, American Chemical Society.
a 0.1 M ammonium persulphate solution before the polymer to a target substrate.[120] Kim et al. developed a lithography-free
support was released and the graphene film attached to a target method to effectively produce graphene micropatterns by using
substrate. Further acid doping of the obtained graphene film an evaporation-induced self-assembly (EISA) process, which is
led to improved conductivity. It is shown that an acid-treated based on the continuous stick-slip motion of the contact line
monolayer graphene thin film prepared from this procedure at the liquid-substrate interface.[192] In a typical process, after a
has a sheet resistance of ≈125 Ω sq−1 with an optical transmit- CVD-grown graphene film was transferred to a target substrate,
tance of 97.4%, and the four-layer film has resistance down to a cylindrical roll was placed between the graphene film and a
≈30 Ω sq−1 with a transmittance of ≈90%. However, the process motorized plate which was programmed to slide at a defined
of etching the catalyst layer, i.e., a high purity metal film/ speed (Figure 2a). A PMMA solution was then introduced
foil, has been considered destructive and cost-ineffective. To to form a thin meniscus between the roll and the graphene
address this issue, Gao et al. recently grew graphene films on under the capillary force. The faster solvent evaporation near
a Pt foil, and then incorporated the PMMA-coated graphene/Pt the pinned contact line led to the outward flow of the solution,
as a cathode in an electrochemical cell. After that, the PMMA/ resulting in the deposition of PMMA. As the roller moved, the
graphene was separated from the Pt foil upon H2 evolution by contact line underwent repeated stick-slip cycles. Thus, an array
applying a constant current across the cell (Figure 1e–f).[19] This of PMMA lines on graphene was generated, which was subse-
method is nondestructive to both the graphene film and the Pt quently used as an etch mask to make graphene stripe patterns
foil, evidenced by the fact that the Pt foil can be reused as a (Figure 2b–c). By repeating the aforementioned procedure,
catalyst substrate for repeated growth of graphene films. a crossed-strip pattern was fabricated, where the double-layer
In addition to the large-area continuous films, patterned graphene regions and single-layer regions were used as elec-
graphene films are also required for applications like LED trodes and channels in FETs, respectively (Figure 2d).
arrays and FETs. Photolithography has been mostly applied to The fabrication of chemically modified graphene electrodes
either define a catalyst layer before CVD-growth of graphene[12] usually involves solution-phase processes, requires no special
or pattern a continuous graphene film after it was transferred equipment, making them relatively low-cost. Spin coating,[192]
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drop casting[193] Langmuir–Blodgett (LB) method,[194] self- electrodes, such as MnO2/GO,[201] SnO2/rGO,[202] Cu2O/rGO,[56]
REVIEW
assembly,[124] and vacuum filtering[195] are the most commonly ZnO/rGO[41] and Fe3O4/rGO,[203] can be obtained by various
used methods to prepare thin films of GO or rGO from their methods in the presence of GO or rGO. Postsynthetic hybridi-
dispersions. The obtained GO film can be subsequently reduced zation is also applicable to generate graphene-inorganic nanos-
by hydrazine vapor,[192] thermal annealing,[196] electrochemical tructure composites via electrostatic interactions[204] or π–π
reduction[124] and laser irradiation.[195] In some applications like stacking.[205] Some other examples of graphene composite elec-
batteries or supercapacitors, where a large amount of graphene trodes include graphene-fullerene (C60) hybrid,[206] graphene-
materials is required, the dry powder of rGO can be physically CNT hybrid[116,117,150] and graphene-polyaniline (PANi) hybrid
mixed with a binder and then cast on a copper foil or Ni cur- electrodes.[207–215] For instance, graphene-CNT hybrid electrodes
rent collector, respectively. For example, Zhu et al. mixed the have been prepared by in situ growth of CNTs on free standing
activated graphene powder with 5 wt% polytetrafluoroethylene graphene papers via CVD, which were then used in both dye-
(PTFE) in water into a paste using a mortar and pestle, which sensitized solar cells (DSSCs) and flexible lithium-ion batteries
was then rolled into sheets and punched into ≈1-cm-diameter (LIBs).[150]
electrodes for supercapacitor applications.[103] To make pat-
terned rGO electrodes, oxygen plasma etching can be applied
to an rGO film with a shadow mask.[197] Our group developed 2.3. Applications of Graphene-Based Electrodes
an alternative method by simply using a sharp nonmetal object
to directly scratch rGO films. By mounting the nonmetal object
2.3.1. Solar Cells
on a micromanipulator, which controlled the movement of the
object, the regular rectangular-shaped rGO patterns have been ITO has dominated the market of transparent window elec-
produced.[38] The scratching process could also be conducted by trodes for solar cells, owing to its good conductivity, transpar-
an AFM tip, programmably controlled in a NSCRIPTOR DPN ency and a desirable work function (≈4.8 eV).[68] Unfortunately,
system[198] to generate various shaped patterns like ribbons, tri- as mentioned in Section 2.1, the ITO film suffers from several
angles and squares.[199] drawbacks, which drive the continuous development of substi-
The graphene composite electrode has been mostly incor- tution and alternative materials. To date, much effort has been
porated in electrochemical sensing and energy storage devices. made to incorporate graphene-based thin films as transparent
For example, a graphene–metal nanoparticle hybrid electrodes electrodes in organic solar cells[41,107–118] and dye-sensitized
can be prepared by the in situ reduction of the metal precursor solar cells (DSSCs).[112–118,183] Examples of graphene-based elec-
with a chemical reducing agent[200] or via electrochemical trodes for organic solar cells and DSSCs and their best perform-
reduction.[123] On the other hand, graphene–metal oxide hybrid ance are listed in Table 1 and Table 2, respectively.
Table 1. List of graphene-based electrodes used in organic solar cells.
Electrode material Preparation method Transmittance Sheet resist- Configuration PCE [%] FF Ref.
ance [kΩ sq−1]
[118]
Hydrazine reduction & thermal annealing 69% 17.9 rGO/PEDOT:PSS/P3HT:PCBM/ 0.13 0.25
rGO
at 700 °C LiF/Al
Hydrazine vapor reduction & thermal 85–95% 100–500 rGO/CuPc/C60/BCP/Ag 0.4 0.34 [109]
rGO
annealing at 400 °C
Hydrazine reduction & thermal annealing 60–95% ≈100 rGO/PEDOT:PSS/P3HT:PCBM/Al 0.1 [108]
rGO at 200 °C, followed by Cl-doping via SOCl2

treatment
[111]
Hydrazine reduction 86% 0.24 rGO-CNT/PEDOT:PSS/ 0.85 0.42
rGO-CNT
P3HT:PCBM/Ca:Al
ITO/GO:SWCNT/P3HT:PCBM/ 4.10 0.628 [116]
ITO-GO/SWCNT
Ca/Al
Hydrazine vapor reduction & thermal 61.2% 0.42 rGO/ZnO/P3HT/PEDOT:PSS/Au 0.31 0.33 [41]
rGO
PMMA assisted LbL transfer combined 90% 0.08 Graphene/MoO3+ PEDOT:PSS/ 2.5 0.45-0.51 [115]
CVD-grown graphene
with acid doping P3HT:PCBM/LiF/Al
[114]
Etching Ni followed by scooping 87% 0.606 Graphene/PEDOT:PSS/ 2.6 0.48
CVD-grown graphene
P3HT:PCBM/TiOx/Al
PMMA-assisted transfer 92% 0.25 Graphene/PEDOT:PSS/CuPc/ 0.85 0.36 [113]
CVD-grown graphene
C60/BCP/Ag
Thermal releasing tape-assisted LbL ITO/ZnO/P3HT:PCBM/GO/ 2.5 0.44 [112]
CVD-grown graphene
transfer graphene (inverted type)
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REVIEW
Table 2. List of graphene-based electrodes in DSSCs.
Electrode material Preparation method Properties PCE (%) FF I0(Sun) Ref.

Dip-coating of GO solution on quartz; thermal annealing at 1100 °C Sheet resistance: 0.26 0.36 1.0 [183]
Quartz-rGO
1.8 kΩ sq−1
FTO-graphene platelets Drop casting of graphene platelet solution on FTO Rct: 50 Ω cm2 5.00 0.52 1.0 [222]
FTO-FGSs[a] Thermal exfoliation of GO to get FGSs; spin coating FGS dispersion on FTO Rct: 0.64 Ω cm2 5.0 0.60 1.0 [223]
[224]
ITO-rGO-PEDOT:PSS PB[b] modified rGO mixed with PEDOT:PSS then spin-coated on ITO 4.5 0.48 1.0
Thermal annealing of GO at 1050 °C, then mixed with acid treated CNT, Rct: 13.56 Ω cm 2 6.11 0.70 1.0 [225]
FTO-rGO-CNT-TiO2
TiO2 paste, coated on FTO
Hydrazine reduction of GO, screen printed on FTO followed by thermal Rct: 1.2 Ω cm2 6.81 0.54 1.0 [216]
FTO-rGO
ITO-rGO Microwave reduction of GO, mixed with NMP[c], coated on ITO 2.19 0.56 1.0 [226]
[227]
FTO-MWCNT-rGO rGO film with MWCNT grown on top, transferred onto FTO 3 0.70 1.0
Microwave reduction of GO, mixed with CNT suspension, electrophoretically Rct: 9.8 Ω cm2 6.17 0.613 1.0 [228]
Graphite-rGO-CNT
deposited on graphite paper electrode
rGO dip-coated on PDDA[d] modified FTO, mixed with H2PtCl6, thermal Rct: 7.7 Ω cm2 6.09 0.73 1.0 [229]
FTO-rGO-Pt
reduced at 350 °C
Electrophoretic deposition of rGO suspension on FTO, thermal annealing Rct: 38 Ω cm2 5.69 0.653 1.0 [230]
FTO-rGO
at 600 °C
FTO-graphene platelets Graphene platelet solution drop-casted on FTO, annealed at 500 °C Rct: 0.7 Ω cm2 9.3 0.70 1.0 [220]
FTO-graphene platelets Graphene platelet solution drop-casted on FTO, annealed at 500 °C Rct: 3.3 Ω cm 2 9.4 0.72 1.0 [221]
FTO-TiN/N-doped Reduction of GO via the decomposition of C3N4 polymer in the presence Rct: 5.67 Ω cm2 5.78 0.64 1.0 [193]
graphene of Ti precursor, then drop-coated on FTO

Vertically aligned CNT grown on graphene paper Sheet resistance: 6.05 0.624 1.0 [150]
Graphene paper-CNT
0.05 kΩ sq−1
[a]Functionalized graphene sheets (FGSs). [b]1-pyrenebutyrate. [c]N-methyl-pyrrolidone. [d]poly(diallyldimethylammonium chloride).
2.3.1.1. Organic Solar Cells: In a typical process to fabricate TiO2/Al. It is worth mentioning that the performance of these
rGO electrode for an organic solar cell, GO solution is firstly devices is governed by the transparency of the rGO electrode if
spin-coated on a quartz substrate followed by reduction in the transmittance is less than 65%, and when the transmittance
hydrazine vapor and subsequent heat treatment. For example, is above 65%, the device performance is mainly determined by
Wu et al. applied the hydrazine reduction and thermal annealing the charge transport efficiency at the rGO electrode.
at 400 °C to prepare a rGO electrode, which showed a sheet Despite of the low cost and ease of fabrication, organic solar
resistance of 100–500 kΩ s q−1 and transmittance of 85–95% at cells based on rGO electrodes generally exhibit a poor PCE of
550 nm.[109] By applying the obtained rGO electrode in an organic less than 0.5%,[108,109,118] mainly caused by the relatively large
solar cell with a configuration of rGO/copper pthalocyanine sheet resistance of rGO thin films compared to ITO or CVD-
(CuPc)/C60/bathocuproine (BCP)/Ag, a power conversion effi- grown graphene. One of the effective approaches to improve
ciency (PCE) of 0.4% and a fill factor (FF) of 0.34 were achieved. the conductivity of rGO thin film is to composite it with carbon
In another example, our group incorporated the rGO electrode nanotubes (CNTs). For example, Tung and coworkers prepared
in an organic/inorganic hybrid solar cell with a structure of a stable dispersion of rGO-CNTs by the one-pot reduction of GO
quartz/rGO/ZnO/poly(3-hexylthiophene) (P3HT)/poly(3,4-eth- and acid-treated CNTs in the pure hydrazine without addition of
ylenedioxythiophene) (PEDOT):poly(styrenesulfonate) (PSS)/ any surfactants, which involves the formation of a hydrazinium
Au, in which the ZnO nanorods as the electron acceptor were compound comprised of the negatively charged CNTs and
first electrochemically deposited on the rGO electrode.[41] It was N2H5+ counterions.[111] The obtained rGO-CNT hybrid material
found that the thermal annealing at 1100 °C not only improves can then be spin-coated on a substrate followed by mild heat
the conductivity of the rGO film but also modulates its work treatment at 150 °C. Because of the surfactant-free fabrication
function from –5.0 to –-4.5 eV, which leads to a better match process, the rGO-CNT hydride thin film exhibited a small sheet
between the Fermi level of the rGO film and the conduction resistance of 240 Ω sq−1 and a transmittance of 86%. A PCE
band of the ZnO layer, and thus improves its efficiency in solar of 0.85% was thus achieved when the hybrid film was incorpo-
harvesting (Device II in Figure 3a). We later demonstrated that rated in an organic solar cell with a configuration of rGO-CNT/
rGO films can also be deposited onto polyethyleneterephthalate PEDOT:PSS/P3HT:PCBM/Ca:Al (Figure 3b).
(PET) substrates to fabricate the flexible organic solar cells,[47] The CVD-grown graphene film, with much better electrical
with a configuration of PET/rGO/PEDOT:PSS/P3HT:PCBM/ conductivity compared to the rGO thin film, is anticipated
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REVIEW
Figure 3. a) Under simulated globe sun illumination, the obtained I–V curves for ZnO/P3HT hybrid solar cells by using I) one-step and II) two step
reduced GO films as electrodes. Inset: schematic illustration of the fabricated solar cell. Reproduced with permission.[41] b) Current density-voltage
(J–V) curves in the dark (red) and under simulated AM1.5G irradiation (100 mW cm-2) using a xenon-lamp-based solar simulator (black). Reproduced
with permission.[111] Copyright 2009, American Chemical Society.
to give higher PCE in solar cells. As an example, Wang et al. individual graphene layers to improve their extrinsic conduc-
transferred CVD-grown few-layer graphene film onto a Si/SiO2 tivity. The LbL, acid-doped, four-layer graphene film exhibited a
substrate with a polydimethylsiloxane (PDMS) stamp, and then low sheet resistance of ≈80 Ω sq−1 with a transmittance of 90%,
functionalized the graphene film with pyrene buanoic acid which is comparable to ITO. The four-layer graphene film was
succidymidyl ester (PBASE) via the π–π interaction.[107] Such further modified with a layer of evaporated MoO3 before being
noncovalent modification not only retains the good conduc- incorporated in an organic solar cell with a configuration of
tivity of the graphene film, but also adjusts its work function graphene/MoO3/PEDOT:PSS/P3HT:PCBM/LiF/Al. The pres-
from –4.2 to –4.7 eV, which results in the increased PCE and ence of hydroxyl groups of MoO3 improves the spreading of
FF with values of 1.71% and 0.513, respectively (with a device the spin-coated PEDOT:PSS overlayer. In addition, the MoO3-
structure of PBASE-graphene/PEDOT:PSS/P3HT:PCBM/LiF/ coated graphene showed an improved work function from
Al). Recently, a layer-by-layer (LbL) method was employed by –4.36 to –5.47 eV, which favors the barrierless hole extraction
Wang et al. to prepare graphene films that are free of organic at the graphene-MoO3/PEDOT:PSS interface (Figure 4b). With
residues between the adjacent graphene layers (Figure 4a).[115] these combined beneficial effects, the obtained device exhib-
During the LbL transfer process, HCl was used to dope the ited an outstanding PCE of 2.5%, which is 83.3% of the PCE
obtained from a control device fabricated on
an ITO electrode (Figure 4c).[115]
The superior flexibility of graphene film
compared to ITO was demonstrated by
Gomez De Arco et al.[110] In their report,
the graphene/PET-based flexible solar cells
maintained the good performance under
bending condition with a bending angle up
to 138°, while the ITO/PET-based solar cell
suffered from cracks when a bending con-
dition of only 60° was applied. Meanwhile,
the graphene/PET-based and ITO/PET-based
solar cells showed comparable performance
with PCE of 1.18 and 1.27%, respectively.
2.3.1.2. Dye-Sensitized Solar Cells (DSSCs):
The first solid-state DSSC based on the
graphene electrode was demonstrated by
Müllen and coworkers.[183] In this work, a
typical rGO thin film was prepared by dip
coating of an aqueous GO dispersion on
a pretreated quartz substrate, followed by
Figure 4. a) Schematic illustration of multilayer graphene films made by (A) the normal wet
thermal reduction at 1100 °C. The as-pre-
transfer and (B) direct coupling LbL assembly. b) Energy level diagram at the anode side of
the photovoltaic cells without (top) and with (bottom) the MoO3 + PEDOT:PSS layer. c) Current pared thin film exhibited a conductivity of
−1
density-voltage (J–V) characteristics of devices with ITO or MoO3-coated graphene as anode. 550 S cm and transmittance of 70% over
Reproduced with permission. [115] the 1000–3000 nm range but dropped to
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50% at 400 nm. The fabricated rGO/TiO2/dye/spiro-OMeTAD/

2.3.2. Light Emitting Diodes
Au device showed a PCE of 0.26%, lower than that (0.84%) of
the corresponding FTO-based device. Therefore, the improve- Inorganic semiconductors, such as GaAs and GaN, are popular
ment on the sheet resistance and optical transmittance of rGO materials in light emitting diodes (LEDs) owing to their high
thin film is the key challenge in maximizing the efficiency of a carrier mobility and radiative recombination rates, along with
DSSC based on rGO-electrode. the long-term stability.[231,232] Unfortunately, the difficulty in
As for the liquid-electrolyte DSSC, in order to replace the separating the high-quality semiconductor film from its epi-
most widely used Pt-FTO counter electrode, graphene-based taxial support and transferring it to a foreign substrate poses
materials have been used to modify the commercial electrode of the major obstacle for the use of inorganic semiconductors
ITO, FTO, or graphite. For example, after the hydrazine-reduced in flexible LEDs. Graphene films are flexible and possess the
GO sheets were dispersed in a terpineol solution containing hexagonal lattice structure to provide a possible substrate for
5 wt% of ethylcellulose, Zhang et al. screen-printed this disper- the van der Waals epitaxial growth of inorganic semiconduc-
sion onto an FTO slide followed by annealing it at 400 °C to give tors. Chung et al. took these advantages of graphene and devel-
the 3D network of rGO films.[216] An improved charge transfer oped a method to prepare epitaxial GaAs thin film on pristine
at the electrode-electrolyte interface was thus achieved with the graphene layers, with the assistance of vertically aligned zinc
enlarged effective reaction area in the 3D network, indicated oxide nanowalls as an intermediate layer.[233] The resulting
by the small charge transfer resistance at the counter electrode GaAs-based LED device with graphene as the electrode can
(Rct = 1.2 Ω cm2) and a high PCE of 6.81%, which is comparable be readily transferred to any foreign substrate, such as glass,
to that obtained by the Pt-FTO-based counter electrode. plastic and metal (Figure 5a,b). The same group extended this
The performance of DSSCs based on the mostly employed idea and used a large-area CVD-grown graphene film to direct
redox mediator, i.e., I3−/I−, has been limited by the low redox the epitaxial growth of high-quality coaxial GaN/ZnO nanorod
potential of ca. 0.35 V vs SHE.[217] Therefore, other redox sys- heterostructures,[119] which displayed the strong blue emission
tems, such as polypyridine complexes of Co(III)/(II) coupled even under the room light illumination.
with donor-bridge-acceptor sensitizers, have been explored and Besides the single LED fabricated on a continuous graphene
showed promising results.[218] Michael Grätzel, the inventor of film, patterned graphene electrodes can be used to produce LED
DSSC, and his coworkers recently reported the currently highest arrays with the added flexibility and mechanical robustness. For
power conversion efficiency of 12.3% based on the Co(bpy)33+/ example, Kim et al. fabricated a stretchable, micrometer-scale
Co(bpy)32+ redox electrolyte with a redox potential of 0.56 V vs array of inorganic LEDs with a structure of p-GaAs/p-AlGaAs/
SHE.[219] The same group extended the Co(III)/(II) systems to p-InAlP/quantum well (AlGaInP/InGaP/AlGaInP)/n-InAlP/n-
DSSCs based on graphene electrodes.[220,221] For instance, a AlGaAs/n-GaAs, in which the graphene patterns act as both
solution of commercial graphene nanoplatelets (GNPs) con- the transparent electrodes and stretchable interconnects via a
taining several layers of graphene with an average thickness simple lamination process.[120] The obtained graphene-based
of ≈5 nm was dip-coated onto an FTO electrode. The hybrid LED array can accommodate strains of over 100% in a com-
GNP-FTO electrode, compared to the Pt-FTO electrode, showed pletely reversible fashion.
the better electrocatalytic activity for the Co(bpy)33+/Co(bpy)32+ In comparison with the inorganic LEDs, organic LEDs
redox couple, which partly arises from the presence of defects (OLEDs) which are normally fabricated on ITO-coated PET sub-
and oxygen-containing surface groups of GNPs.[221] Moreover, strates have been developed with better flexibility and at lower
the GNP-FTO electrode exhibited the excellent cycling stability cost. However, the alternative flexible substrates, such as con-
without observable change of Rct (3.3 Ω cm2) after 10 cycles of ducting polymer and CNT films, exhibit the relatively high film
the fast voltammetry scanning and impedance measurement, resistivity (typically 100–1000 Ω sq−1), which is not comparable to
whereas the Pt-FTO electrode showed an increase of Rct from that of the ITO-based electrodes (typically 10–100 Ω sq−1).[234,235]
5.5 to 19.3 Ω cm2 after 10 cycles of the similar test. Remarkably, Graphene film with a small sheet resistance and good transmit-
under the 1.0 simulated global sunlight, the device based on tance[185] has been suggested as a promising candidate to replace
the GNP-FTO electrode showed considerably high PCE and FF ITO, but its relatively low work function (4.4 eV) may cause dif-
of 9.4% and 0.72, respectively, outperforming those obtained ficulty for its widespread applications. Recently, Han and col-
from the standard Pt-FTO electrode. leagues applied two procedures to reduce the sheet resistance
It is worth noting that despite the possible replacement of of CVD-grown graphene film and modulate its work function,
the commonly used Pt electrode with a graphene thin film in respectively.[121] In their study, the sheet resistance of a 4-layer
DSSC, an FTO or ITO supporting electrode is still required in graphene film was improved to ≈30 Ω sq−1 by p-doping treat-
most of the reported devices (Table 2). An all-carbon electrode ment with HNO3 or AuCl3. The doped-graphene film was then
was demonstrated by Li and coworkers,[150] by growing verti- modified with a specially designed organic layer, also referred
cally aligned CNTs (VACNT) on a free-standing graphene paper to as the gradient hole injection layer (GraHIL), comprising of
(GP), referred to as the VACNT/GP electrode. The combina- PEDOT:PSS and a tetrafluoroethylene-perfluoro-3,6-dioxa-4-me-
tion of the GP and the VACNTs not only reduces the charge thyl-7-octenesulfonic acid copolymer (Figure 5c,d). A work func-
transfer resistance at the electrode-electrolyte interface, but also tion gradient was thus created which raised the work function
facilitates the enhanced I3− ion transportation via the porous at the GraHil-graphene surface to 5.95 eV, enabling the holes
CNT film. Such a highly flexible all-carbon electrode showed a to be injected efficiently into the overlying hole transport layer
high PCE of 6.05% without the need of FTO or ITO supporting (i.e., 1,1′-bis[(di-4-tolylamino)phenyl]secyclohexane, TAPC). The
electrode. thus-produced devices exhibited exceptionally high luminous
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REVIEW
Figure 5. a) Schematic illustration of the fabrication and transfer processes for thin-film LEDs grown on graphene-layer substrates. b) Optical images
of light emission from the as-fabricated LED on the original substrate and transferred LEDs on the foreign metal, glass, and plastic substrates. Repro-
duced with permission.[233] Copyright 2010, American Association for the Advancement of Science. c) Schematic illustration of a phosphorescent OLED
device, in which the graphene anode was modified with a gradient hole injection layer (GraHIL). TPBI: 1,3,5–tri(phenyl-2-benzimidazolyl)–benzene;
CBP: 4,4’-N,N’-dicarbazolylbiphenyl; TCTA: 4,4’,4’’–tris(carbazol-9-yl)–triphenylamine. d) Comparison of the luminous efficiency of phosphorescent
OLEDs based on the graphene and ITO electrodes. Reproduced with permission.[121] Copyright 2012, Nature Publishing Group.
efficiencies (37.2 lm W−1 in fluorescent OLEDs, 102.7 lm W−1 in thin film of Cu or Ag to serve as hybrid electrodes for pentacene-
phosphorescent OLEDs), which outperform, for the first time, FETs.[239] The decreased work function of the electrodes and the
those obtained in devices based on ITO anodes (24.1 lm W−1 in reduced contact resistance between the electrodes and semicon-
fluorescent OLEDs, 85.6 lm W−1 in phosphorescent OLEDs). ductor have led to a high carrier mobility of 0.53 cm2 V−1 s−1,
which is about ten times higher than that with the pure Cu or
2.3.3. Field-Effect Transistors Ag contact electrodes.
Recently, a CNT-based FET, that is free from metal contacts,
Metals such as gold and platinum are commonly used as has been developed by our group,[38] where the single SWCNT
source/drain (S/D) electrodes in nanoelectronics, such as semi- was directly grown between the rGO electrodes generated by
conductor nanowire-based FETs,[236] CNT-based FETs,[237] as the “scratching” method (Figure 6). Our approach presents sev-
well as organic FETs.[238] For example, in organic transistors, eral advantages in the fabrication of CNT-FET devices. First, the
Au electrodes have the favorable working function that matches “scratching” method, as mentioned in previous section (Section
well with the energy levels of p-channel organic semiconduc- 2.2), is able to prepare the regular rGO electrodes with uniform
tors, so that the holes are injected and transported through the thickness and controllable gaps between adjacent electrodes.
organic material.[238] However, a large contact resistance usu- Second, the direct growth of SWCNT across the rGO electrodes
ally exists between the organic semiconductor and the metal allows for the formation of a good electrical contact between
S/D electrodes, especially in transistors with a bottom-contact the rGO and SWCNT. Third, this method is free from the
geometry. Zhu and coworkers deposited graphene on patterned conventional fabrication processes, such as lithography-based
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REVIEW
Figure 6. (1–4) Schematic illustration of the experimental procedures for the generation of a CNT-based electronic device with patterned rGO as
electrodes. (1) Preparation of rGO film on SiO2. (2) Creation of electrode patterns in rGO film. (3) Deposition of catalyst in selected positions on the
substrate. (4) Controlled growth of CNTs to bridge rGO electrodes by CVD. a) SEM image of patterned rGO electrodes generated by our “scratching”
method. b) 3D AFM image of the edge of a typical rGO electrode. The measured thickness of the rGO film is 10.7 nm. c) SEM (left) and AFM (right)
images of a fabricated all-carbon device, i.e., an individual SWCNT-rGO device. Reproduced with permission.[38]
patterning of electrodes, and postsynthetic transfer of SWCNTs, Recently, stretchable electronics has received considerable
which might cause contamination during the lift-off process attention, due to the increasing demand from the human-
and compromise the intrinsic properties of CNTs after acid- interface applications, such as the conformal biosensors and
treatment and vigorous sonication. We subsequently combined rollable displays.[105] The excellent flexibility and mechanical
the “scratching” method and microfluidic patterning technique robustness of graphene thin film make it a suitable candidate
to make rGO electrodes and channels, respectively.[31] The for use in the fabrication of stretchable electronics. For example,
resulting solution-gated all-rGO thin film transistor (TFT) was a highly stretchable graphene-based transistor has been pre-
then used as a protein sensor, which showed good sensitivity pared by Lee et al.[106] In their work, the CVD-grown graphene
and selectivity. For example, fibronectin with a concentration of films were lithographically patterned and transferred to various
as low as 0.5 nM was successfully detected. substrates, including PET, PDMS, as well as a balloon surface,
In another report, all-carbon based transistor arrays were and then functioned as the semiconducting channel as well
fabricated by Hong et al.,[104] consisting of the semiconducting as the S/D electrodes, coupled with the printed ion-gel as gate
channel made from the aligned SWCNTs and S/D electrodes dielectric. The obtained devices exhibited good optical transmit-
made from graphene films. Both the SWCNTs and graphene tance and stretchability, maintaining stable performance at a
layers were produced by CVD, and integrated into FETs by a strain level of up to 5%.
series of lithography-based patterning and transfer printing To date, most reports that involve large-area continuous
processes. The resulting devices showed the ultrathin lay-outs CVD-grown graphene films rely on lithography-based tech-
(SWCNTs combined with 0.6–2.0 nm graphene film) with good niques for either patterning a catalyst film before CVD, or
optical transparency throughout the visible range (75% trans- etching graphene after growth. A simple, scalable, and non-
mittance at 550 nm). In addition, the graphene-graphene S/D lithographic process was recently developed by Kim and cow-
electrode pair was compared with the Pd-Pd pair, giving rise to orkers[192] by using the evaporation-induced self-assembly
≈10% higher current levels, suggesting that graphene is a better (EISA) method (see the detailed technique in Section 2.2 and
contact material for SWCNT-based FETs. Figure 2). In their work, large-area cross-striped patterns of
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REVIEW
Figure 7. a) Schematic illustration of ion-gel gated graphene FET on PET film. Right: the molecular structure of ion gel consisting of ionic liquid and
polymer matrix. b) current-voltage transfer characteristics of the graphene FETs at different Vd values. c) Output characteristics of the graphene FETs.
Reproduced with permission.[192] Copyright 2012, American Chemical Society.
graphene were prepared (Figure 2), so that the regions of 2.3.4. Electrochemical Sensors
single-layer graphene can be used as FET channels, and the As mentioned in Section 2.1, graphene and its derivatives have
regions of double layers, where two single-layer graphene shown great potential to replace or supplement other carbon-
strips cross each other, can be used as S/D electrodes. Thus- based materials like CNTs, C60 and graphite in electrochemical
prepared graphene patterns on Si/SiO2 or PET substrate were sensing.[240–243] Various kinds of electrodes based on functional-
combined with an ion-gel gate dielectric (Figure 7a) and a ized graphene or graphene composites have been fabricated to
PEDOT:PSS gate electrode to fabricate all organic FETs. A typ- detect a wide range of chemical and biochemical species, such
ical FET device can operate at low voltages of ±2 V with a hole as H2O2,[145,244–247] ascorbic acid,[241,248,249] glucose,[99,125–145] dop
and electron mobility of 214 and 106 cm2 V−1 s−1, respectively amine,[124,140,240,241,249–256] DNA,[196,257–261] and antigen.[262,263]
(Figure 7b–c), which are comparable with those of commer- Recently, the electrochemical reduction of GO was independ-
cial devices. ently developed by our group[99] and other groups.[100–102] This
The negative side of the superior conductivity of graphene, method is green, simple and fast, compared to the chemical
resulting from its semimetal nature, is that without bandgap reduction by using toxic hydrazine. Importantly, after the elec-
engineering/opening, graphene-channel FETs have very low trochemical reduction of GO which is assembled on an APTES-
On/Off ratios, typically < 30.[1] Recently, Britnell and colleagues modified glassy carbon electrode (GCE), the GCE-APTES-
have demonstrated a tunneling-field-effect-transistor, which rGO hybrid electrode can be directly used for electrochemical
consists of two monolayers of graphene as electrodes separated sensing. For example, after we modified the GCE-APTES-rGO
by a layer of atomically thin h-BN or MoS2 (Figure 8).[191] Upon electrode with glucose oxidase (GOx) through covalent bonding
application of a gate voltage between one of the graphene elec- via a polymer generated by electrografting N-succinimidyl acr-
trodes and a gate electrode (i.e., an isolated silicon substrate), ylate (NSA),[99] the obtained hybrid electrode with bioactive
carrier concentrations in both graphene layers were changed GOx was successfully used to detect glucose. In another of our
(Figure 8c). A bias voltage applied between the two graphene studies, a GCE-APTES-rGO electrode was used to detect DNA
electrodes induced a tunneling current across the h-BN or by electrochemical impedance spectroscopy (EIS),[260] which
MoS2 layer (Figure 8d), leading to the room temperature On/ is regarded as a label-free and effective approach to detect the
Off ratio of 50 and up to ≈10 000, respectively. This work is the oligonucleotide-DNA interaction, antigen-antibody formation
first demonstration of graphene-based transistor that achieves and biotin-avidin complex. In this work, based on the strong
such a high On/Off ratio at room temperature without bandgap interaction between DNA molecules and the rGO surface, we
engineering of pristine graphene. demonstrated the EIS-based detection of methicillin-resistant
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REVIEW
Figure 8. a) Schematic structure of the graphene tunneling-field-effect transistor. b) The corresponding band structure without gate voltage. c) The
same band structure for a finite gate voltage, Vg, and zero bias, Vb. d) Both Vg and Vb are finite. The cones illustrate graphene’s Dirac-like spectrum.
e) Resistivities of the source and drain graphene layers as a function of Vg. f–h) Carrier concentrations in the two layers induced by gate voltage, which
were calculated from the measured Hall resistivities, ρxy, by using the standard expression, n = B/eρxy, where B is the magnetic field and e is the electron
charge. Close to the neutrality point, the spikes appear (shown by dotted curves) because the above expression is not valid in the inhomogeneous
regime of electron-hole puddles. The shown device has a 4-layer h-BN barrier. Reproduced with permission.[191] Copyright 2012, American Association
for the Advancement of Science.
Staphylococcus aureus (MRSA) DNA, which showed a low detec- addition, when the E-rGO and C-rGO electrodes were used to
tion limit down to 100 fM. detect dopamine (DA) in the presence of uric acid (UA) and
The question remains as to the difference between the elec- ascorbic acid (AA), their electrochemical sensing results were
trochemically reduced and chemically reduced GO, in terms of quite different. By using the E-rGO electrode, the independent
the electrochemical sensing capability. Recently, we carried out electrochemical oxidation of each analyte was observed, evi-
a comparison study on electrochemically-reduced GO (E-rGO) denced by the well-defined oxidation peaks for AA, DA, and
and hydrazine-reduced GO (C-rGO) sheets and found that the UA. In contrast, the C-rGO electrode gave the poor separa-
electrochemical method is more effective to reduce GO films tion among the analytes. This difference can be explained by
compared to the hydrazine vapor reduction method.[124] In the larger amount of oxygen-containing species present on the
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to the macroelectrode.[269,270] In addition to an individual nano-
REVIEW
C-rGO surface than that on the E-rGO, which caused the server
nonselective adsorption/desorption of analyte molecules on the scale electrode, nanoelectrode arrays (NEAs)[271] and nano-
C-rGO.[124] In addition, a comparison study carried out by Gio- electrode ensembles (NEEs)[272–274] have also been fabricated
vanni et al. used GO, E-rGO and thermally reduced GO (T-rGO) by means of membrane-templated electrodeposition,[272,273]
in the impedimetric sensing of DNA.[196] Their results indicated chemical etching[274] or ion beam milling.[271] Despite their
that the GO electrode can lead to a better discrimination among high sensitivity, the multi-step procedure and high cost in fab-
the three different ssDNA targets than does the E-rGO or the rication of NEEs have restricted their widespread application in
T-rGO electrode. They attributed this phenomenon to the larger biosensing. To overcome these limitations, our group recently
density of defects and oxygen-containing groups on GO than developed a facile procedure to prepare GCE-GO-Au NP NEEs,
that on E-rGO or T-rGO. Apparently, whether the oxygen-con- where APTES-modified GCE was used to absorb the GO mon-
taining groups on graphene have a positive or negative effect olayer, onto which Au NPs were electrochemically deposited
on the sensing performance of the graphene-based electrode is to act as individual nanoelectrodes in the GCE-GO-AuNP NEE
dependent on the type of analytes and the detection methods (Figure 9).[123] With the thus-prepared NEE, highly sensitive
employed. Therefore, an in-depth understanding of the sensing DNA detection at 100 fM has been realized.
mechanism is of profound importance in order to choose the
suitable sensing system. 2.3.5. Lithium-Ion Batteries
Importantly, graphene–metal nanoparticle (NP) composites
have been used as hybrid electrodes for electrochemical sens The lithium-ion battery (LIB) is one of the most widely used
ing,[123,143,145a,244,245,262,264] in order to combine the good con- energy storage systems, which is featured with a large energy
ductivity and large SSA of graphene and the excellent catalytic density with a theoretical value of up to ≈400 W h kg−1,[275,276]
activity of anchored metal NPs. For example, graphene-Au NP arising from its low atomic weight (M = 6.94 g mol−1) and its
composite mixed with chitosan has been used to modify Au high absolute potential (–3.04 V) against the standard hydrogen
electrodes for sensing H2O2 and O2. After a further modifica- cell.
tion with glucose oxidase (GOx), the graphene/Au NPs/GOx/ 2.3.5.1. Carbon-Based Electrodes: Graphite has been commer-
chitosan electrode has demonstrated good sensing ability cialized and widely used as electrodes for LIBs, which exhibit
towards glucose with a linear range from 2 to 10 mM at a high columbic efficiency and a theoretic specific capacity of
–0.2 V.[126] In addition to Au NPs, Pt NPs[244] and Cu NPs[140] 372 mAh g−1 by forming LiC6 upon the Li-intercalation.[277]
have also been composited with graphene to realize the high Exfoliated and isolated graphene layers are thus anticipated to
performance electrochemical sensing. For example, Guo and give even higher specific capacities, because the adsorption of Li
colleagues showed that graphene-Pt NP hybrid nanomaterials ions can take place on both sides of a graphene nanosheet.[186]
exhibited more favorable electron transfer kinetics and much Indeed, Yoo et al. demonstrated that electrodes made from
enhanced electrochemical reactivity than graphene itself.[244] the restacked rGO sheets (containing 6–15 graphene layers)
The same group has also produced the ternary type of graphene with the enlarged surface area compared to graphite showed
based composites, i.e., the graphene-mesoporous silica-gold NP a specific capacity of ≈540 mAh g−1.[206] A much improved
hybrids (GSGHs). They used this type of hybrid materials for capacity of up to ≈800 mAh g−1 was achieved by mixing the
the detection of aptamer-adenosine triphosphate (ATP)[265] and rGO sheets with CNTs or C60, which further expanded the spac-
DNA,[259] leading to the high detection sensitivity of 0.023 nM ings between the graphene layers and creates additional voids
and 10 fM, respectively. The mesoporous silica in the GSGHs among them.[206] Similarly, Fan and coworkers developed a
not only showed the good biocompatibitiy, but also increased facile procedure to prepare carbon fibers on rGO via CVD in a
the electrode surface area for signal amplification. fluidized bed reactor.[278] Nanochannels of graphene layers were
In comparison to the most commonly used macroelec- thus observed to assemble perpendicular to the fiber axis, which
trodes, the microelectrode array (MEA) has shown advantages were believed to benefit the lithium ion diffusion from different
such as higher sensitivity arising from the improved signal-to- directions in the carbon fiber-graphene network. Therefore, an
noise ratio, enhanced mass transportation, and large current enhanced specific capacity of 667 mAh g−1 was achieved with
response.[266] Li et al. have developed a new technique to fab- good reversibility.
ricate rGO-based MEA by using soft lithography.[266] In brief, Increasing the energy density of a supercapacitor or the
after a GO film was generated on an ITO substrate with the power density of a battery still remains the key scientific and
LbL method, a polydimethylsiloxane (PDMS) mold patterned technical challenge in fabrication of high-performance energy
with an array of microwells filled with hydrazine solution was storage devices. Some possible approaches have been pro-
brought into contact with the GO film, resulting in the selec- posed to achieve the high power density in LIBs, such as the
tive reduction of GO regions that were in close contact with the increase of the electrode material’s conductivity to enable the
hydrazine. The rGO MEA was further modified with prussian faster transfer of charge carriers, and the creation of porous
blue (PB) for the detection of H2O2, which showed a detection structures to shorten the diffusion lengths for Li ions.[186]
limit down to 10−8 M, about 10 times lower than that obtained Jang et al. recently developed a novel battery device consisting
by using ITO-PB or ITO-rGO-PB macroelectrodes. As the size of of two graphene-based electrodes, in which the Li-exchange
nanoscale-electrode further decreased, better sensing perform- took place via the ion adsorption and redox reactions on the
ance expected due to the enhanced mass transport, reduced IR graphene surface rather than via Li-intercalation.[279] Different
drop,[267,268] increased Faradic-to-capacitive current ratio at the kinds of carbon materials were studied in their work, such as
electrode surface, and excellent signal amplification compared the thermally exfoliated graphite, graphene from the chemically
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REVIEW
Figure 9. a) Schematic illustration of fabrication of the NEEs and their application in DNA detection. b) DPV curves of the NEEs at different concen-
trations of the target DNA. c) Plot of current vs. concentration of the target DNA (䊏). The control experiment was carried out with m-DNA (䊉). Inset:
linear relationship between current and concentration of the target DNA from 10−9 to 10−12 M. The error bars show the standard deviation in the current
measured from three parallel experiments. Reproduced with permission.[123] Copyright 2012, Royal Society of Chemistry.
reduced graphene oxide (i.e., rGO), graphene from the oxidized instability of the electrode. In order to overcome this problem
artificial mesophase graphite, graphene from the oxidized and to achieve high power density of graphene-based electrodes
carbon fiber, carbon black, oxidized carbon black, and activated for LIBs, Wu et al. used nitrogen- or boron-doped graphene
carbon. The rGO-based cell, containing mostly rGO monol- mixed with carbon black nanoparticles as anode materials.[281]
ayers with surface functional groups, is capable of delivering an The resulting electrodes exhibited high-rate capability and
energy density of 160 Wh kg−1 at a discharge density of 1 A g−1, excellent long-term cyclability, and can be rapidly charged and
which is about 30 times higher than that of conventional sym- discharged within one hour to several tens of seconds. Signifi-
metric supercapacitors, and a power density of ≈100 kW kg−1 at cantly, at a high charging rate of 25 A g−1 (about 30 s to full
200 A g−1, which is about 10 and 100 times higher than that of charge), the large specific capacity of ≈199 and 235 mAh g−1
conventional supercapacitors and LIBs, respectively. were obtained for the N- and B-doped graphene, respectively.
One of the problems that rGO-based electrodes may face is The corresponding power and energy densities are ≈29.1 kW g−1
the capacity fluctuation induced by the surface side reactions, and ≈226 Wh g−1 for the N-doped graphene electrode, and
e.g., the formation of the solid electrolyte interface (SEI).[280,281] ≈34.9 kW g−1 and ≈320 Wh g−1 for the B-doped graphene
At a high starting current density, the surface side reactions electrode, respectively. The benefit of the doping process is
involving the oxygen-containing groups on rGO are very multi-fold. First of all, doping can improve the conductivity
active and sometimes violent, leading to the electrochemical and thermal stability of pristine graphene.[281] Doping-induced
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topographic defects are also favorable to the Li storage.[282,283]
REVIEW
encapsulated nanostructures. Yang et al. constructed an anode
Moreover, doping with nitrogen or boron can increase the electrode based on graphene-encapsulated Co3O4 nanoparticles
hydrophobicity of the graphene sheet, thus improving the wet- via the electrostatic interaction,[204] so that the graphene sheets
tability of the organic electrolyte and benefiting the ion diffu- can separate individual nanoparticles, and meanwhile maintain
sion at electrolyte-electrode interface.[284] In another report, a conducting network to effectively connect all the particles. The
Kumar and coworkers developed an alternative approach to alle- as-prepared electrode exhibited a high specific capacity of over
viate the problem related to the formation of SEI by using NH3- 1000 mAh g−1 for more than 130 cycles. Graphene-enwrapped
reduced graphite oxide in the presence of metallic lithium. The nanoparticles have also been demonstrated in the graphene-
Li-intercalated reduced graphite oxide (referred to as Li-rGO) sulfur battery system by Dai and coworkers,[325] in which the
was directly used as the electrode for LIB, which showed better slightly reduced graphene oxide (rGO) nanosheets decorated
performance compared to both graphite and rGO-based elec- with carbon black NPs were wrapping around poly(ethylene
trodes.[148] In contrast to the huge irreversible capacity lose glycol) (PEG)-modified sulfur nanoparticles. The graphene shell
in the rGO-based electrode due to the formation of SEI, the renders the sulfur nanoparticles good conductivity and traps the
Li-rGO electrode, which possesses the electrochemically active polysulfides during charging-discharging cycles. At the same
defects, can undergo a reversible Li-intercalation/de-intercala- time, the PEG layer also assists to trap the polysulfides and
tion process without the formation of SEI, leading to improved accommodates volume change of sulfur nanoparticles during
capacity and better cycling property.[148,282,285,286] cycling. As a result, the rGO-sulfur composite electrode showed
2.3.5.2 Graphene Composite-Based Electrodes: To date, high and stable specific capacities up to ≈600 mAh g−1 for more
graphene–metal oxide composite electrodes have been inten- than 100 cycles.
sively studied, because of the low cost, abundance and easy Besides the conversion type LIBs, the alloying type LIBs have
preparation of metal oxide nanostructures. Examples of metal also been exploited in graphene-based composite electrodes. The
oxides that have been synthesized on or physically mixed alloy type of electrode materials,[326] e.g., Sn and Si, are known
with the graphene-based materials are MoO2,[149] V2O5,[287] for their large capacity for lithium uptake and high operating
SnO2,[103,202,288–300] Mn3O4,[301] MnO2,[159,302] Co3O4,[204,303–305] voltage. For example, the theoretic specific capacity of Si-based
TiO2,[306–310] Fe2O3,[289,311,312] Fe3O4[203,313–321] CuO,[155,322] and and Sn-based electrode is 3579 mAh g−1 and 992 mAh g−1,
Cu2O.[323] Detailed synthetic/fabrication methods for the respectively.[327,328] However, such high capacity is usually accom-
graphene–metal oxide composites are described in our previous panied with the large volume expansion, e.g., up to ≈300%
review article.[2] volume change for the Si electrode during alloying/dealloying
Most metal oxide nanostructures belong to the conversion- cycles.[329] Accordingly, Ji et al. prepared LIB electrodes based
type electrodes in LIBs, functioning through redox reactions on the multilayered graphene-supported Sn nanopillars.[328] The
between the ionic and metallic states of the metal to facilitate presence of graphene is able to buffer the huge volume change
the Li-insertion/extraction and provide high capacities.[324] of the Sn pillar structures and maintain an electric conduc-
However, the practical application of this type of LIBs is limited tive network upon continuous charge/discharge cycles. Such
by several drawbacks, including the poor conductivity, cycling- a unique 1D/2D hybrid electrode showed a high reversible
induced structure degradation, irreversible volume expansion capacity and excellent cycling performance at a current density
and lose of contact points, as well as the interparticle aggrega- of as high as 5 A g−1. In another example, Zou et al. prepared a
tion. Graphene-based nanosheets, when used as the matrix to novel anode material based on the hierarchical graphene-Sn@
support these metal oxide structures, are able to alleviate these CNT nanostructures,[330] in which Sn was covered by a CNT shell
problems. First, graphene-based materials can form a conduc- and anchored on the graphene sheet (Figure 10). The obtained
tive network to connect all the metal oxide particles,[203,299,301,309] device showed a reversible capacity of 1160–982 mAh g−1 in 100
which ensures a rapid transfer of charge carriers. For example, cycles at 100 mA g−1 and excellent rate capability (828 mAh g−1
an anode made from graphene/Mn3O4 by Wang et al. is able to at 1 A g−1 and 594 mAh g−1 at 5 A g−1). In this work, the pres-
deliver a high specific capacity of ≈900 mAh g−1, which is about ence of the CNT shell not only provided a buffer layer to accom-
two times higher than that obtained from the pure Mn3O4 elec- modate the large volume expansion of Sn, but also prevented
trode and approaching the theoretical capacitance of Mn3O4 the restacking of graphene sheets and enhanced the electrical
(936 mAh g−1).[301] Second, the graphene-based nanosheets pro- conductivity between graphene layers. Besides Sn, Si nanostruc-
vide a large surface area for an even distribution of the anchored tures have also been hybridized with graphene-based templates
metal oxide nanostructures, so that the interparticle aggrega- to yield enhanced electrochemical properties.[327,331]
tion can be partly reduced.[305,323] Moreover, the graphene layers In addition, another type of commonly used electrode
inserted in between the metal oxide nanostructures provide materials is the insertion type,[332,333] with examples including
flexible and elastic supports to accommodate volume expan- graphite and layered metal chalcogenides (e.g., TiS2 and MoS2).
sion of the metal oxides during the charging/discharging cycles Chang and Chen synthesized few-layer MoS2 sheets in the
without the interparticle agglomeration.[203] For example, Wang presence of GO sheets, followed by heat treatment to obtain
et al. prepared a highly ordered hybrid structure comprising the 3D network of MoS2–rGO.[148] This hybrid electrode with a
alternating layers of graphene and SnO2, which exhibited a Mo:C molar ratio of 1:2 exhibited the high specific capacity of
specific capacity of ≈760 mAh g−1 comparable to the theoretical ≈1100 mAh g−1 at a current of 100 mA g−1, along with a good
value for SnO2.[202] cycling stability and high-rate capability.[148]
The aforementioned beneficial effects of graphene layers in Driven by the increasing demand of portable and flexible
the composite electrodes are also demonstrated in graphene electronics, the concept of the flexible battery has also been
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REVIEW
Figure 10. a) Schematic illustration of the growth process of GNS–Sn@CNT. b) Cycling performances of GNS, SnS2, GNS–SnS2, and GNS–Sn@CNT
at 0.1C (1C = 1000 mAg−1). c) Cycling performances of GNS–Sn@CNT at different current rates. Reproduced with permission.[330] Copyright 2011,
American Chemical Society.
invoked recently. To meet this purpose, free-standing, flexible specific surface area (SSA) and good electrical conductivity are
graphene paper has been composited with other electrochem- the two critical requirements for the high performance EDLCs.
ical active materials, such as vertically aligned CNTs[150] and In this regard, graphene-based materials derived from the GO
V2O5.[334] For example, a flexible battery has been constructed, nanosheets, which can be prepared on a ton scale, are prom-
in which the cathode was made by deposition of a layer of ising candidates for EDLCs. Ruoff and coworkers demonstrated
high-quality ceramic film (e.g., V2O5) on a graphene paper via the first rGO-based EDLC, which showed a specific capacitance
pulsed-laser deposition (PLD), and the anode was made of an of 135 F g−1 and 99 F g−1 in the aqueous and organic electro-
electrochemical-lithiated graphene paper.[334] This device can lyte, respectively.[8] After that, a great amount of work has been
deliver both a higher energy and power density, and a better life devoted to optimize the performance of supercapacitors made
cycling performance than those with nonflexible conventional of graphene-derivatives, leading to improved specific capaci-
electrodes, which partly results from the good contact between tance values of ≈200, 120, and 75 F g−1 in aqueous, organic,
the rugged graphene sheets[335–337] and the active ceramic layer. and ionic liquid electrolyte, respectively.[50,340,341] However, the
graphene-derived materials usually show a smaller SSA than
2.3.6. Supercapacitors the theoretical value of graphene monolayer, i.e., 2630 m2g−1.
Recently, the Ruoff group developed a simple but effective
A supercapacitor, or ultracapacitor, is a kind of electrochemical method to prepare the KOH-activated, microwave exfoliated
device that stores and releases energy at high rate (in seconds) graphite oxide (MEGO) or thermal exfoliated graphite oxide
with high power density (10 kW kg−1) and long cycling life.[338] (TEGO) (Figure 11a–c). The obtained materials, which contain
However, the energy density of supercapacitor (e.g., 4–5 Wh mostly single layers of sp2-bonded carbon, are highly porous
kg−1 for those based on the porous activated carbon) is gener- (0.5–6 nm sized pores) and exhibit an ultrahigh SSA value up to
ally lower than that of batteries (e.g., 26–34 Wh kg−1 for lead 3100 m2 g−1, as well as a low oxygen and hydrogen content and
acid batteries).[339] Improving the energy density of supercapac- a high electrical conductivity (≈500 S m−1).[103] The KOH acti-
itors while maintaining their high power density and long cycle vation process was performed by heating a mixture of filtered
life has been the key issue in developing future energy storage MEGO/KOH or TEGO/KOH in a tube furnace at 800 °C for
systems. 1 h under flowing argon. At a current density of 5.7 A g−1, the
Carbon-based materials, such as activated carbon (AC), activated-MEGO electrode showed an exceptionally high energy
CNTs, carbon fibers, and graphene, are electrical double layer density of ≈70 Wh kg−1 and power density of ≈250 kW kg−1.
capacitors (EDLCs), which function through the accumulation Recently, laser irradiation has been applied as an effec-
of charges at the electrode/electrolyte interface. Therefore, large tive reduction method to prepare rGO electrodes.[175,195]
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REVIEW
Figure 11. a) Schematic showing the microwave exfoliation/reduction of GO and the following chemical activation of MEGO with KOH that creates
pores while retaining high electrical conductivity. b) CV curves at different scan rates. Rectangular shapes indicate the capacitive behavior. c) Galvano-
static charge/discharge curves of a MEGO–based supercapacitor under different constant currents. Reproduced with permission.[103]. Copyright 2011,
American Association for the Advancement of Science. d) Schematic illustration of the laser irradiation on the GO film in a computerized LightScribe
DVD drive. As shown in the scheme, the GO film changes from golden brown color to black as it is reduced to laser-scribed graphene (LSG). The
low-power infrared laser changes the stacked GO sheets immediately into a well-exfoliated few-layered LSG film, as shown in the cross-sectional SEM
images below. e) Energy and power densities of LSG-ECs compared with the commercially available AC-EC, aluminum electrolytic capacitors, and a
lithium thin-film battery. The LSG-ECs exhibit electrochemical energy storage with both ultrahigh power and energy densities. Reproduced with permis-
sion.[195] Copyright 2012, American Association for the Advancement of Science.
El-Kady et al. developed a simple strategy to produce graphene- the laser-scribed graphene (LSG) sheets, which showed high
based supercapacitors by laser-irradiation of a GO film coated electrical conductivity (1738 S m−1), large SSA of 1520 m2 g−1,
on a flexible substrate mounted in a commercial CD/DVD and good mechanical flexibility. Moreover, the LSG films can
drive (Figure 11d).[195] After laser irradiation (also called the be directly used as electrodes, functioning as both the active
laser-scribing process), the initially stacked GO sheets in material and current collector in a capacitor, that is, a device
the film were reduced and simultaneously exfoliated to give can be simply made by separating two LSG electrodes with
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REVIEW
Figure 12. a) SEM image of vertically oriented graphene nanosheets. b) Impedance phase angle vs frequency for the graphene nanosheet capacitor.
Measurements from a commercial DLC having an activated carbon electrode and an aluminum electrolytic capacitor are shown for comparison.
Reproduced with permission.[346] Copyright 2010, American Association for the Advancement of Science. c) Schematic illustration of the stacked
geometry, in which graphitic carbon-based materials are randomly oriented with respect to the current collectors. In this case, the electrochemical
surface area is incompletely utilized, because some of the regions are inaccessible to the electrolyte ions. d) Schematic illustration of the operating
principle in case of the in-plane supercapacitor. The new architecture presents the added benefit of increased ability of the electrolyte to percolate
into the layers of graphene to allow for full utilization of the electrochemical surface area. Reproduced with permission.[347] Copyright 2011, American
Chemical Society.
an ionic porous separator. These LSG electrochemical capaci- resistance capacitance (RC) time constant of less than 0.2 ms
tors (LSG-ECs) exhibited competitive electrochemical energy (Figure 12b). Moreover, the film made of these vertically aligned
storage capability with both ultrahigh power and energy density graphene nanosheets with exposed edge planes exhibited greatly
(Figure 12e). increased charge storage as compared to the control device
It has been shown that graphite oxide can be used as a relying on flat graphene sheets. Similar to this work, Yoo et al.[347]
solid-electrolyte, and becomes ionic conductive and electrical developed “in-plane” ultrathin supercapacitors comprised of
insulating when a substantial amount of water is trapped CVD-grown graphene or multilayer rGO sheets. As shown in
in it, which makes it an ideal electrolyte and electrode sepa- Figure 12c,d, in contrast to the stacked configuration, the “in-
rator.[342–345] Taking advantage of this, Gao and coworkers pre- plane” design enables the enhanced interaction between the elec-
pared all-graphene-based supercapacitors[175] by using the laser trolyte and carbon layers, maximizing the interface area by fully
reduction method to write rGO-GO-rGO patterns with different utilizing the surface of graphene layers. The “in-plane” capacitor
configurations, in which the rGO regions serve as electrodes made of as-grown single- to double-layer graphene sheets exhib-
and hydrated-GO regions act as the electrolyte/separator mem- ited high specific capacity up to 80 μF cm−2, and that made of
brane. This approach is facile and scalable, and the resulting rGO sheets showed even higher capacity of 394 μF cm−2.
micropatterned-supercapacitors exhibited good energy storage Moreover, the hybrid electrodes produced from graphene
capacities and cycling stability, which are comparable with the and the other types of carbon materials, such as CNTs,[349–351]
existing thin-film supercapacitors.[175] have also been developed by physical mixing rGO sheets and
In addition to the specific surface area (SSA) and electrical CNTs,[349] or CVD-growth of CNTs on graphene sheets.[350] In
conductivity, the structure and morphology of carbon-based these reports, one of the key contributions of CNTs is that they
electrodes also play a crucial role in controlling their perform- provide highly conductive pathways between graphene layers,
ance.[348] Miller and coworkers deposited vertically oriented since the spacing between the stacked graphene layers can cause
graphene nanosheets on a heated Ni substrate (Figure 12a) an increase of the series resistance along the stacked direction.
using radio frequency plasma-enhanced chemical vapor deposi- The incorporation of CNTs can also enlarge the SSA of the
tion (PECVD).[346] The thus-made electrode showed an SSA of hybrid electrode, and enhance the cycling stability by preventing
≈1100 m2 g−1, and efficient filtering of 120 Hz current with a the restacking of graphene sheets.[350] In addition to CNTs,
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REVIEW
Figure 13. a) SEM image of 3D graphene networks grown on Ni foam after CVD. b) Specific capacitance of NiO/graphene electrode as a function of
scan rate. Reproduced with permission.[180]
Lei et al. demonstrated the preparation of 3D carbon archi- electrolyte interaction. Moreover, the direct CVD growth of
tectures comprising of mesoporous carbon spheres inserted graphene on the current collector of Ni foam leads to a good
between graphene sheets.[352] The fabrication process involves electrical contact between the active materials and the current
the self-assembly of positively charged mesoporous silica collector. The thus-obtained NiO/graphene hybrid electrode
spheres (MSS) and negatively charged GO sheets, followed by showed a high specific capacitance of ≈816 F g−1 at a scan rate
the simultaneous reduction of GO and CVD-growth of porous of 5 mV s−1 and a stable cycling performance without detectable
carbon on the MSS templates. The silica templates are subse- capacitance loss after 2000 cycles.
quently removed, leaving the mesoporous carbon spheres inter- As mentioned in the previous section, supercapacitors can
calated between rGO sheets with a high SSA of 1496 m2 g−1. provide higher power density but lower energy density com-
The obtained electrodes based on this 3D carbon architecture, as pared to batteries. This problem can be addressed by two
compared to those made from hydrazine-reduced rGO sheets, effective approaches, that is, by either increasing the device
showed a lower O/C ratio, lower series resistance, higher power capacitance via the incorporation of novel electrode materials,
capability, and excellent cyclability with 94% retention of capaci- or increasing the cell voltage (V ) by means of, for example,
tance after 1000 cycles of charge-discharge. using organic or ionic liquids as electrolytes which have a wider
The pseudo-capacitor is another type of widely used super- potential window (typically larger than 2 V) than that of aqueous
capacitor, which relies on a rapid redox reaction in the elec- electrolyte solution.[179,187] However, the organic electrolyte has
trode.[353] Metal oxides (e.g., RuO2, NiO and MnO2) and con- poor electrical conductivity and poses potential environmental
ducting polymers (e.g., Polyaniline, PANi and Polypryrrole, problems, while the ionic liquid is relatively expensive. As an
PPy) are typical substances used for such electrodes, which can alternative approach, the asymmetric supercapacitor, formed by
provide the higher specific capacitance (1 to 5 F m−2) compared incorporating different electrode materials that work in a dif-
to the porous carbon electrodes (0.1 to 0.2 F m−2).[354] However, ferent potential window in the same electrolyte, can broaden
these materials are usually less conductive and more expensive the cell voltage and thus increase the energy density.[179,365,366]
than the carbon-based materials. Therefore, the combination of In this regard, graphene-based asymmetric capacitor systems
EDLCs and pseudo-capacitors presents a better alternative to fab- with different configurations have been developed.[176,179,367]
ricate capacitors with good performance at a relatively low cost. For example, Cheng and coworkers built an asymmetric
To date, graphene-based nanosheets have been compos- capacitor by combining a negative electrode made of graphene
ited with various metal oxides, such as ZnO,[355,356] CeO2,[166] and a positive electrode made of MnO2 nanowire/graphene
SnO2,[357] Co3O4,[162,358] MnO2,[164,170,171,173,176,177,201,359–362] composite,[367] in which a high operating voltage of ≈2.0 V is
[ 363] [ 364]
MnO3, RuO2, and Fe3O4,[316] to prepare supercapac- acquired accompanied with a high energy density up to 30.4
itor electrodes. In most configurations, the metal oxides con- Wh kg−1. Afterwards, asymmetric capacitors with different con-
tribute to the large capacitance via the redox reaction between figurations of rGO-RuO2rGO-PANi,[179] rGO-MnO2activated
the oxidation states of the metal, while graphene or its deriva- carbon nanofiber[176] and rGO-Ni(OH)2porous graphene[368]
tive provides the added capacitance via the double-layer charge have also been fabricated, showing enhanced energy density
absorption, and also provides a conductive network to connect and cycling stability.
the anchored metal oxide nanostructures.[359] Recently, our
group reported a large-scale fabrication of three-dimensional
(3D) graphene network by direct CVD-growth of graphene 3. Conclusions and Outlook
films on a Ni foam charge collector and then electrochemical
deposition of NiO nanostructures on the 3D graphene network The recent advances in the synthesis of graphene and graphene-
(Figure 13).[180] The hybrid 3D porous structure of the NiO/ based materials have created more opportunities for their
graphene electrode showed a large SSA for the electrode/ wider applications. The CVD synthesis of uniform, continuous
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REVIEW
graphene film on flexible copper foils combined with the roll- CREATE programme: Nanomaterials for Energy and Water Management,
to-roll process has enabled the scalable production of graphene and NTU under the Start-Up Grant (M4080865.070.706022) in
electrodes for various electronic and optoelectronic devices. Par- Singapore.
ticularly, the p-doped graphene film has shown the sheet resist- Received: April 21, 2012
ance of ≈30 Ω sq−1 with a transparency of ≈90% at 550 nm,[185] Revised: June 26, 2012
which is comparable with, and in some cases outperforms, the Published online: August 24, 2012
ITO thin film. The advantageous electronic and optical prop-
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Advanced Materials - 2012 - Huang - Graphene Based Electrodes

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15214095, 2012, 45, Downloaded from https://onlinelibrary.wiley.com/doi/10.1002/adma.201201587 by CNR Bologna, Wiley Online Library on [07/11/2022].

method[1] (or the “scotch tape” method),

of graphite in ethanol or water.[73,74] Importantly, an alterna-

Up till now, many reports have suggested that graphene-

Table 1. List of graphene-based electrodes used in organic solar cells.

rGO at 200 °C, followed by Cl-doping via SOCl2

Table 2. List of graphene-based electrodes in DSSCs.

Electrode material Preparation method Properties PCE (%) FF I0(Sun) Ref.

graphene of Ti precursor, then drop-coated on FTO

[a]Functionalized graphene sheets (FGSs). [b]1-pyrenebutyrate. [c]N-methyl-pyrrolidone. [d]poly(diallyldimethylammonium chloride).

50% at 400 nm. The fabricated rGO/TiO2/dye/spiro-OMeTAD/

to the macroelectrode.[269,270] In addition to an individual nano-

topographic defects are also favorable to the Li storage.[282,283]

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