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Fei Zhao, Huhu Cheng, Zhipan Zhang, Lan Jiang, and Liangti Qu*
Environmental energy harvesting devices hold great promise
for the next generation electronics. Nowadays, there are varieties of available energies as the candidates, such as thermal
power, hydropower, nuclear energy, but their applications are
suffering from the environmental pollution and/or large-scale
supporting equipments. In recent years, nano-/microelectronics
has provided new possibility of clean and renewable energy
power sources by developing piezoelectric,[14] triboelectric,[58]
and fluidicelectric[912] generators. However, an urgent challenge is to effectively convert these potential energies into the
directly utilized power without much loss of accompanied electrical, thermal, and mechanical energy during the conversion.
Ideally, the highly effective energy conversion is induced by a
spontaneous process (e.g., diffusion), such that there is no temperature variation, mechanical movement, and by-produced
pollutant (chemical energy loss).
Graphene-based materials with tunable properties provide
considerable opportunities for development of future-generation energy-transform devices.[1012] Among them, graphene
oxide (GO), rich in oxygen-related functional groups such as
hydroxyl and carboxyl groups, is of great interest for the potential applications in electronics, energy-related devices, and
smart systems that strongly depend on the agile regulation of
oxygen content.[1321] In this regard, we have demonstrated the
unique GO-based stimuli-responsive systems due to the sensitivity of GO with the moisture.[16,20] Meanwhile, the ionic and
electronic conductivities of GO vary with the alternation of
relative humidity (RH).[13,15,20] These results suggest the importance of the interaction between the oxygen-rich GO and water
molecules to tune the properties and functions of the final
materials and devices.
In this work, we present a power-generating phenomenon
of single GO film (GOF) with a preformed oxygen-containing
group gradient (also named as gradient GOF, g-GOF). The

F. Zhao, H. Cheng, Dr. Z. Zhang, Prof. L. Qu

Beijing Key Laboratory of Photoelectronic/
Electrophotonic Conversion Materials
Key Laboratory of Cluster Science
Ministry of Education
School of Chemistry
Beijing Institute of Technology
Beijing 100081, PR China
E-mail: lqu@bit.edu.cn
Prof. L. Jiang
Laser Micro-/Nano-Fabrication Laboratory
Ministry of Education
School of Chemistry
Beijing Institute of Technology
Beijing 100081, PR China

DOI: 10.1002/adma.201501867

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g-GOF was prepared by a moisture/electric field co-induced

gradient process of oxygen-containing groups on a vacuum-filtrating GOF, and this strategy developed here was called moistureelectric annealing (MeA). The as-prepared g-GOF is able
to provide moisture-enabled voltage output of 35 mV with a
power density of 4.2 mW m2 by harvesting energy from moisture diffusion with energy conversion efficiency of up to 62%,
which surpassed the fluidicelectric generators and were even
better than those of piezoelectric generators with optimized
structure. More interestingly, an extra-power-free respiratory
monitor has been built by utilizing the moisture flow of human
breath as a clean and renewable power source.
To prepare a g-GOF, we developed the MeA method in
which a constant bias (4 V) was applied between the two sides
of GOF in an enclosed container with an RH of 70% (Figure
S1, Supporting Information). The initial GOF was formed by
filtration of an aqueous suspension of GO nanosheets through
a filter membrane with pore size of 1 m, which was sandwiched between two pieces of gold electrodes connecting with
external circuit as shown in Figure 1a. During this process,
the RH in the enclosed container and current intensity of
GOF were monitored in real time and kept in range of 70%
2% and 0.010.1 mA cm2, respectively. A GOF with a size of
0.5 cm 0.5 cm was utilized in this study although it could be
scaled up by simply using large-area GOFs and electrodes.
The thickness of g-GOFs is 2.8 m which could be readily
tunable by filtrating desirable amount of GO dispersion with
a certain concentration (Figure 1b). Remarkably, the cross-sectional element mapping of g-GOF demonstrated the gradient
distribution of the oxygen component on a typical layered
GOF (Figure 1c,d). The oxygen content gradually increases
from the top side (the negative-electrode-contacting side in
Figure 1a) to the bottom side (the positive-electrode-contacting
side in Figure 1a). On the other hand, X-ray diffraction (XRD)
patterns of g-GOF reveal that the top and the bottom sides
have the distinct peak shift (Figure 1e) nonanalogous to the
initial GOF, which suggests the MeA has indeed induced
the change of interlayer structure. In contrast to GOF with
a calculated interlayer spacing of 0.8 nm for both sides, the
top and bottom sides of MeA-treated GOF has an interlayer
spacing of 0.68 and 0.85 nm, respectively, implying a partially
reduced top GO layers and a slightly oxidized bottom layers
of g-GOF in consistence with the corresponding element mapping (Figure 1d). The composition through the layers of g-GOF
was further determined by X-ray photoelectron spectroscopy
(XPS). As shown in Figure S2 (Supporting Information), the
XPS survey spectra of both the top and bottom surfaces show
predominant graphitic C 1s peak at 284 eV and O 1s peak at
532 eV. The O/C atomic ratio for the bottom side of g-GOF is
0.52, slightly higher than that of GO starting material (0.45)

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Direct Power Generation from a Graphene Oxide Film

under Moisture

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Figure 1. Preparation processes and characterizations of g-GOF. a) MeA process of GOF with applied voltage under humid environment. The e and
O represented electrons and oxygen-containing ions, respectively. b) Cross-section scanning electron microscopic (SEM) image and c,d) the corresponding carbon and oxygen mapping from X-ray energy dispersive spectroscopy. e) XRD patterns of different sides of as-prepared GOF and g-GOF.
f) XPS spectra of different surfaces of g-GOF. The surfaces contacting with the top and bottom electrodes in (a) are noted as Top and Bottom,
respectively.

but much higher than that of the top surface (0.22), demonstrating the distribution variation of oxygen-containing groups
from top to bottom as shown in Figure 1a. Moreover, the high
resolution C 1s spectra (Figure 1f) confirmed the presence of
C O bands (286.6 eV) and C O bands (288.5 eV) on both
sides of the g-GOF.[14] In contrast with the corresponding
spectra of initial GOF sample (Figure S3, Supporting Information), the top side had the weakened C O and C O peaks,
indicating that the oxygen-containing groups on the top layers
of g-GOF were partially removed. In the meanwhile, the signals from bottom side presented the stronger C O and C O
peaks, implying the increasing O/C atomic ratio of bottom side
probably associated with the further oxidation. These results
also explained the inconsistent interlayer spacing change of
two sides of g-GOF observed by XRD.

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Along with the basic principle of electric generators, the

middle layer (i.e., the g-GOF used in this study) served as both
dielectric layer and functional layer in a GO-based moisture
electric energy transformation (MEET) device7 as shown in
Figure 2a. When the device was exposed to moisture (e.g., RH =
30%) and inserted in a test circuit, the voltage and current output
were observed. Subsequently, when the environmental RH went
back to the initial state, the signals of reverse current with negative voltage were collected. Accordingly, the device reverts to the
original state and a whole MEET cycle was finished.
Based on the operation procedure mention above, the
g-GOF-based MEET device could provide voltage and current
output of 20 mV and 5 A cm2 within 3 s under a RH
of 30% as demonstrated in Figure 2b,c. Notably, unlike other
kinds of electric generators, the output voltage and current

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Figure 2. Operation of MEET process. a) Schematic illustration of a MEET cycle. The V and A represented the induced voltage and current along the
direction of arrows, respectively. b) Voltage and c) current output cycles of a prototype MEET device of g-GOF in response to the intermittent and periodic RH variation (RH = 30%). Experimental data of single d) voltage and e) current output cycle from (b) and (c) matched with RH. f) Thickness
change ratio, i.e., thickness change (d) divided by original thickness (d), and g) resistance alteration ratio, i.e., resistance alteration (R) divided by
original resistance value (R) of g-GOF matched with RH. For clarity in interpretation, ON and OFF in (d)(g) represent the injection and ejection of
moisture in experimental environment, respectively.

pulses of g-GOF-based MEET device show an asymmetric

behavior that the peak value on the positive pulses is always
significantly higher than that on the negative pulses. The
unique output behavior of the single cycle was investigated corresponding to the RH. As shown in Figure 2d, the induced

Adv. Mater. 2015, 27, 43514357

positive voltage rapidly rose up once the RH increased, and

returned to zero prior to the reduction of RH. Meanwhile,
during the RH decrease, the voltage evolved negatively and
remained for several seconds after the environmental moisture
was removed completely. The identical phenomenon arose in

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the case of current output as shown in Figure 2e. Therefore,

the MEET process should be directly related to the interaction
between water molecules and g-GOF. According to our previous investigations, water molecules could insert the interlayer space of GO quickly, but the desorption process would
take more time.[16,20] The adsorption and desorption behavior of
water molecules was reflected by the moisture induced change
of thickness and resistance.[13,15] As shown in Figure 2f,g, the
thickness and resistance change of g-GOF closely correlate with
RH variation. Once moisture is on, the increase of thickness
and the decrease of resistance of g-GOF are observed. On the
contrary, a slight hysteresis appears during RH reduction due
to a relatively slow water release from g-GOF (Figure 2f,g).
Along with the analysis mentioned above, the blue dashed
line in Figure 2dg labeled as ON represented the injection

of moisture and the moment that RH, voltage, current density, thickness change ratio (d/d), and resistance alteration
ratio (R/R) begin to increase, indicating the moisture adsorption induced positive electric output. At the time of moisture
ejection marked by OFF (red dashed line), the RH, d/d and
R/R started to decrease and the negative output appeared,
suggesting the moisture desorption induced negative electric
output. Several seconds later after RH return to zero, the electric output stopped when the d/d and R/R gently reduced
to zero, implying the desorption induced electronic output
was dominated by the release of residual water molecules in
g-GOF. Moreover, when the injection of moisture was maintained after the presence of positive plus, the negative signals
appeared once the moisture ejection process began (Figure S4,
Supporting Information), which was further substantiated that

Figure 3. Harvesting the body energy hidden in the respiratory moisture-tide and self-powered monitoring of body condition. a) MEET device that is
responsive to human breathing increased and decreased RH with exhale and inhale, respectively. b) The g-GOF was sandwiched in two gold electrodes
with vents to construct the MEET device. c) Voltage and d) current output generated by respiratory moisture-tide with a RH of 21%. e) Self-powered
monitoring of respiratory frequency relating to heart rate after different intensity of exercise.

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These results experimentally revealed that the close relevance

of heart rate with respiratory frequency with a coefficiency of
4.1 for different body condition (Figure S15, Supporting Information). This simple demonstration has indeed presented the
great potential of g-GOF device in self-powered body condition
monitor toward clinical diagnosis.
Based on the analysis above, a proposed mechanism of
MEET process was illustrated by a schematic in Figure 4. The
g-GOF adsorbs water molecules upon exposure to moisture
due to the strong hydrophilicity of oxygen-containing groups
(e.g., OH, COOH). With the accumulation of water molecules in the O-rich part of g-GOF, a regional solvation effect
will weaken the O H+ bond in oxygen-containing groups,
thus releasing free H+.[13,15] The g-GOF possessed a gradient
distribution of oxygen-containing groups (Figure 4a), which
accordingly led to the concentration gradient of H+ (Figure 4b).
The induced potential and free electron movement of external
circuit were thereupon generated once the diffusion of H+
occurred due to the drive of concentration gradient (Figure 4c).
Meanwhile, the induced electric field tends to force the H+ drift
back to high concentration side. Therefore, when the diffusion and drift effect reached a dynamic balance, the induced
potential was stabilized, and hence free electron movement
of external circuit was terminated. In contrast, the desorption of moisture accelerated the recombination of negatively
charged groups (e.g., COO) and H+, weakening the diffusion
driving effect of concentration gradient. As a result, H+ drifted
back and hence induced negative potential with a consequent
reverse electron movement (Figure 4d). After the release of
residual water molecules, the g-GOF returned to the initiate
state.

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adsorption and desorption of moisture enabled electric output

of g-GOF rather than the metal electrode contact and the concentration gradient of GO as demonstrated and discussed in
detail in Figures S5S13 (Supporting Information).
The breath of human and other terrestrial animals is one
of the most steady and constant resources of moisture tide.
Generally, the exhale and inhale of adults through nasal cavity
can cause an RH variation. We therefore built a g-GOF based
power generator (Figure 3a,b) to sensitively harvest the energy
of breath. As shown in Figure 3c,d, the calm breathing from a
healthy man (RH = 21%) could provide the voltage and current output of 18 mV and 5.7 A cm2, respectively. This
power generator can indeed serve as a respiratory energy collector to convert body-provided energy to electric power, indicating a promising potential of g-GOF in energy relative
applications.
Beyond the power generation, g-GOF could also work as
the extra-power-free device to monitor the body condition. For
instance, by counting the number of voltage output pulses,
we can monitor the respiratory frequency in relevance to the
heartbeat of a healthy man after exercise with different intensity (Figure 3e). Before jogging, the mans calm breathing was
13 times per minute and caused a RH of 21% (Figure S14,
Supporting Information), corresponding to a heart rate of
58 times per minute. After jogging for 5 min, the breathing
was accelerated to 18 times per minute with incidental RH of
29%, and the heart rate was elevated to 79 times per minute.
Moreover, when the jogging time was extended to 60 min, the
signals representing rapid breathing (28 times per minute) were
observed according to a fast heartbeat of 118 times per minute,
accompanied with the breath induced RH of up to 48%.

Figure 4. MEET process of g-GOF. a) Schematic illustration of the gradient distribution of oxygen-containing groups (e.g., carboxyl and hydroxy) in
g-GOF. b) Free hydrogen ions (H+) were ionized by adsorbed water from oxygen-containing groups and a density gradient of H+ was established.
c) When the free H+ diffused from high density side to low density side, the potential was induced and the electrons moved from bottom electrode to
top electrode along external circuit. d) With the desorption of moisture, the recombination of H+ with negatively charged O-functional groups reduced
the induced potential, resulting in reverse electrons flow in external circuit.

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Figure 5. Importance of oxygen-containing group gradient in g-GOF based MEET. a) Photographs of UV reduced GO (UV-rGO) dispersion (0.5 mg mL1)
with different UV-irradiation time, which were noted as A, B, and C. The different UV irradiation caused variant O/C ratios of 0.46, 0.27, and 0.2 for A, B, and
C, respectively. The UV-rGO dispersions (10 mL) of A, B, and C were filtrated in sequence to prepare GOF with oxygen-containing group steps. b) Voltage
and c) current output of UV-rGO based GOF with oxygen-containing group steps. d) Photographs of GO dispersions (0.5 mg mL1) prepared by hummers
oxidation (HO-GO) for different time which were noted as D, E, and F. The different degree of oxidation also caused variant O/C ratios of 0.46, 0.35, and 0.21
for D, E, and F. The HO-GO dispersions (10 mL) of D, E, and F were filtrated successively to prepare GOF with oxygen-containing group steps. e) Voltage
and f) current output of HO-GO based GOF with oxygen-containing group steps. The electric outputs in (b), (c), (e), and (f) were tested with RH = 30%.

To further demonstrate the mechanism that the gradient of

oxygen-containing groups induced the MEET under moisture,
we established a GOF consisting of three layers of GO with
different oxygen content (Figure 5a). GO with an O/C ratio of
0.46 was controllably reduced as exposed to the UV irradiation for certain periods.[14] The UV-reduced GO with O/C ratio
of 0.46, 0.27, and 0.2 were filtrated successively to form a GOF
with gradient steps of O-related groups. The obtained GOF
based MEET device presented a power-generating behavior
similar to that of g-GOF-based one (Figure 5b,c). Additionally,
GOFs with the steps of oxygen-containing groups can also be
established by filtration of GO dispersions with different oxidation degree (Figure 5d), where the O/C ratios were intended to
0.46, 0.35, and 0.21. The output of voltage (0.2 mV) and current
(10 nA cm2) were comparable with UV-rGO-based MEET device
(Figure 5e,f). These results demonstrate the mechanism that the
gradient of oxygen-containing groups within the GOF indeed
induced the MEET effect under moisture. Because of the limited
gradient interfaces of oxygen-containing group within the GOF,
the low output voltage and current for the GOF is understandable. Since the MEET was based on a diffusion-drift balance, the
value of induced potential (Ui) could be expressed by:[22]
Ui =

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qD dc
dx

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(1)

where q, D, , dc/dx are electric quantity of elementary charge,

diffusion coefficient of H+, ionic conductivity of water, and
concentration gradient of H+ along an x-axis perpendicular to
surface of GOF (see thermodynamic analysis of MEET in the
Supporting Information for details). It means that Ui directly
depends on the concentration gradient of H+, and hence the
gradient of oxygen-containing groups. This conclusion is consistent with the experimental data from GOF with oxygen-containing group steps, in which the gradient of oxygen-containing
groups was located at the interfaces of GO steps.
Considering that there is no additional energy involved in
one MEET cycle, the chemical potential drop of water diffusion
process (equals to minus Gibbs free energy, GM, also see calculation of MEET efficiency in the Supporting Information for
details) is the sole energy source for the MEET, we can evaluate
the MEET efficiency based on the ratio of GM to output power
(WM). It is found that the MEET efficiency of g-GOF generator is
up to 62%, which is 3 times higher than that of piezoelectric
zinc oxide (ZnO),[1] 61 times higher than that of fluidicelectric chemical vapor deposition graphene (CVD-G)[12] and hundreds of times higher than the fluidicelectric carbon nanotube
(CNT).[9] Meanwhile, without the systematic optimization of the
devices performance in this preliminary study, the power density
is up to 4.2 mW m2 at the output voltage of 30 mV, which is 50
times higher than that of piezoelectric gallium nitride (GaN),[23]

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Supporting Information
Supporting Information is available from the Wiley Online Library or
from the author.

Acknowledgements
This work was supported by NSFC (Nos. 21325415, 21174019), National
Basic Research Program of China (2011CB013000), and Beijing Natural
Science Foundation (2152028).
Received: April 19, 2015
Revised: May 12, 2015
Published online: June 18, 2015

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21 times higher than that of fluidicelectric CNT[24] and

18 times higher than that of fluidicelectric CVD-G (also see
Table S1, Supporting Information).[12] We believe the power density could be further improved by optimizing the assembly of
GO, the regulation of oxygen groups and scaling up of film size.
In summary, GOF with gradient oxygen-containing groups
has been fabricated by an MeA method. This strategy provides a
simple but effective approach for the construction of the g-GOF,
through which the MEET devices have been achieved to have
a high sensitivity to moisture variation (RH of less than 5%),
and possess a high energy-conversion efficiency of 62% and a
power density of 4.2 mW m2 under the tidal moisture. Even
the respiratory moisture of human can be converted into electric power, and more impressively, the g-GOF device can ingeniously track the body conditions in a real time manner without
any external power supply promising for energy-generating and
sensing applications. Although the g-GOF MEET device only
produces intermittent power in the preliminary study, it could
be combined with energy-storage unit for sustained use.

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