ARTICLE

Hybrid Nanogenerator for Concurrently

Harvesting Biomechanical and
Biochemical Energy
Benjamin J. Hansen,† Ying Liu,† Rusen Yang, and Zhong Lin Wang*
School of Material Science and Engineering, Georgia Institute of Technology, Atlanta, Georgia 30332. †These authors contributed equally.

he ever increasing energy demand

T of modern society is perhaps among

the greatest challenges humankind
is and will continue to face. Research in en-
ABSTRACT Harvesting energy from multiple sources available in our personal and daily environments is
highly desirable, not only for powering personal electronics, but also for future implantable sensor-transmitter
devices for biomedical and healthcare applications. Here we present a hybrid energy scavenging device for
ergy includes but is not limited to the fol-
potential in vivo applications. The hybrid device consists of a piezoelectric poly(vinylidene fluoride) nanofiber
lowing major areas: mega-scale energy con-
nanogenerator for harvesting mechanical energy, such as from breathing or from the beat of a heart, and a flexible
version, renewable and green energy,
efficient energy transmission, energy stor- enzymatic biofuel cell for harvesting the biochemical (glucose/O2) energy in biofluid, which are two types of
age, energy harvesting, and sustainable energy available in vivo. The two energy harvesting approaches can work simultaneously or individually, thereby
power source for micro- or nanosystems. In boosting output and lifetime. Using the hybrid device, we demonstrate a “self-powered” nanosystem by powering
addition to large-scale energy harvesting a ZnO nanowire UV light sensor.
from “renewable” sources, such as wind, hy-
dro, and solar, there is also significant op- KEYWORDS: hybrid cell · piezoelectric · PVDF · electrospinning · nanogenerator ·
portunity to harvest the wasted energy in biofuel cell · energy harvesting
our personal environments, such as from
walking, typing, speaking, and breathing. If
powering implantable nanodevices for bio-
efficiently harvested to its full potential,
sensing using energy scavenging/harvest-
many of the modern energy requirements
ing technology is rather challenging be-
needed for small devices and even personal
cause the only available energy in vivo is
electronics could be fulfilled. This is a new
mechanical, biochemical, and possibly elec-
trend in the worldwide effort in developing
tromagnetic energy, whereas thermal en-
technologies related to energy
ergy cannot be harvested due to lack of an
scavenging.1⫺3
adequate temperature gradient, and solar
Energy harvested from the environment
energy is not available for devices im-
will likely be sufficient for powering nan-
planted inside the body.
odevices used for periodic operation, ow-
A recent breakthrough in harvesting me-
ing to their extremely low power consump- chanical energy by nanowire based nano-
tion and small sizes. For example, an generators (NG) has demonstrated an excel-
implantable device that wirelessly commu- lent route for harvesting the biomechanical
nicates the local glucose concentration for energy created from tiny physical motion,
diabetes management, the local tempera- such as the inhaling/exhaling of lungs or
ture for infection monitoring after surgery, the beat of a heart.4⫺8 In addition, ap-
or a pressure difference to indicate block- proaches have been demonstrated for con-
age of fluid flow in the central nervous sys- verting the biochemical energy of glu-
tem and blood clotting can all be foreseen cose/O2 in biofluid using active enzymes as *Address correspondence to
as potential applications that need implant- [email protected].
catalysts in a compartmentless biofuel cell
able energy sources. Powering such de- (BFC).9⫺11 In this paper, we demonstrate the Received for review April 21, 2010
vices could be accomplished by concur- first integrated operation of a hybrid nano- and accepted May 24, 2010.
rently harvesting energy from multiple generator composed of a nanogenerator
Published online May 27, 2010.
sources within the human body, including and biofuel cell for simultaneously or inde- 10.1021/nn100845b
mechanical and biochemical energy to aug- pendently harvesting mechanical and bio-
ment or even replace batteries. However, chemical energy, with the aim of building © 2010 American Chemical Society

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ARTICLE

Figure 1. (a) Schematic of the electrospinning process to obtain aligned PVDF NFs. (b) Optical image of aligned PVDF NFs
on Kapton film and high resolution SEM of NF surface morphology shown in the inset (400 nm). (c) FTIR transmission spec-
trum of PVDF NFs. (d) Schematic of the high field in-plane poling of PVDF NFs.

self-powered nanodevices/nanosystems for in vivo bio- encasing the device in PDMS and performing high-
medical and other applications where the two types of field (⬃0.2 MV/cm) in-plane poling (Figure 1d) for ⬃15
energy are available, such as living plants. We have also min (see Experimental Methods for details).
used the hybrid nanogenerator to drive a single The working principle of the PVDF NG is based on
nanowire-based UV nanosensor to demonstrate the the insulating property of the PVDF NF and the cre-
possibility of a “self-powered” nanosystem. ation of an inner piezoelectric field during applied ten-
sile strain.5,12 As the device is deformed under alternat-
RESULTS AND DISCUSSION ing compressive and tensile force (Figure 2c,d), the NF
Harvesting Mechanical Energy by Nanogenerator. The NG acts like a “capacitor” and “charge pump”, which drives
based on a single ZnO nanowire that is laterally bonded a flow of electrons back and forth through the external
onto a polymer substrate was first demonstrated by circuit. This charging and discharging process results in
our group.5 Based on a similar mechanism and design, an a.c. power source.
a NG using a single piezoelectric poly(vinylidene fluo- The strain rate dependence on the open-loop volt-
ride) (PVDF) nanofiber (NF) was reported recently.12 In age and short-circuit current produced by a PVDF NG
our hybrid design we use PVDF nanofibers as the work- undergoing cyclic mechanical loading is presented in
ing component for the mechanical energy harvester. Figure 2a,b. The induced strain was fixed at ⬃0.05% and
Cheng et al. used near-field electrospinning to synthe- applied over 0.06, 0.04, and 0.03 s. By increasing the
size the single PVDF NFs, where the high electric field strain rate over this range, the open loop voltage in-
used to draw the NF was suggested to naturally align creased from 15 to 20 mV and the short circuit current
the dipoles along the NF long axis. Alternatively, we increased from 0.2 to 0.3 nA, which is consistent with pi-
used conventional electrospinning (see Experimental ezoelectric theory.15 The output voltage is dictated by
Methods for details) with the two electrode technique13 individual nanowire, while the output current is the
to synthesize and pattern an array of aligned NFs, fol- sum of those from all of the active nanowires. The out-
lowed by a post, in-plane poling process (Figure 1a⫺d). put of the PVDF NG could be improved by replacing
A scanning electron microscopy (SEM) image (Figure PDMS with a material having a higher breakdown volt-
1b, inset) reveals the textured morphology on the NF age, so that higher poling fields could be applied to ob-
surface, presumably resulting from the formation of tain a greater remnant polarization.16,17 In addition, hun-
small crystallites. Fourier transform infrared spectros- dreds of NFs could potentially be integrated together
copy (FTIR) was used to characterize the crystal phases and connected in series and/or parallel to further im-
present in the PVDF NFs. The FTIR transmission spec- prove the power output.7
trum of the as-spun PVDF nanofibers is presented in Harvesting Biochemical Energy by Biofuel Cell. An enzy-
Figure 3c. A mixture of the polar ␤ phase and the non- matic BFC was used to convert the chemical energy of
polar ␣ and ␥ phases was indexed.14 The random di- glucose and oxygen in biofluid into electricity. The BFC
pole orientation of the polar ␤ phase was oriented by configuration used in this study is illustrated in Figure
3648 VOL. 4 ▪ NO. 7 ▪ HANSEN ET AL. www.acsnano.org
 ARTICLE
Figure 2. Open-loop voltage (a) and short-circuit current of a PVDF NG as a function of strain rate with a maximum strain of
⬃0.05%. (c) The PVDF NF lies on a Kapton substrate, with both ends bonded with silver paste and the entire device encap-
sulated with PDMS. (d) Mechanical bending of the substrate creates tensile strain and a corresponding piezoelectric field
along the fiber that drives the electrons through an external load back and forth following the cycled mechanical action.

3c. The electrodes were patterned onto Kapton film trodes, it has been shown that CNTs help promote the
and coated with multiwall carbon nanotubes electron transfer between the enzymes and the
(MWCNTs), followed by immobilization of glucose oxi- electrodes.18⫺20 The operating principle of the BFC is il-
dase (GOx) and laccase to form the anode and cathode, lustrated in Figure 3d. When the device is in contact
respectively (see Experimental Methods for details). In with a biofluid that contains glucose (such as blood),
addition to immobilizing the enzymes onto the elec- the corresponding chemical processes occurring at the

Figure 3. Open-loop voltage (a) and short-circuit current (b) of the BFC as a function of glucose concentration in PBS solution.
(c) Schematic illustration of the fabricated BFC device. (d) Simplified schematic of the BFC operating mechanism.

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ARTICLE

Figure 4. (a) Open-loop voltage of the independent and combined operation of the BFC and PVDF NG. (b) Circuit diagram
used for integration of the hybrid BFC-NG device. Note, with considering the inner resistance of the NG, the time required
to charge the capacitor is much longer than the period at which the strain was applied to the NG, so that the output V is a
sum of those from BFC and NG. (c) Schematic of hybrid device integration. (d) Conceptual design of a BFC-NG hybrid device.

two electrodes is:9 glucose is electro-oxidized to glu- zymes to a redox hydrogel, the output of the BFC can
conolactone at the anode, be further optimized in the future.21⫺23 In addition, mul-
GOx
glucose 98 gluconolactone + 2H+ + H2O, and dis- tiple BFCs could be integrated together to boost power
output.
solved O2 is electro-reduced to water at the cathode, Hybrid Biochemical and Biomechanical Nanogenerator. One
laccase
1 / 2O2 + 2H+ + 2e- 98 H2O. of the major hurdles of a glucose/O2 BFC is the perfor-
mance degradation over time due to the decay of the
The open-loop voltage and short-circuit current pro-
living enzymes.11,20 Therefore, a hybrid BFC-NG, which
duced by the BFC operating in phosphate buffer solu-
concurrently harvests mechanical and biochemical en-
tion (PBS, pH 7.0) with glucose concentrations of 0.5, 5, ergy, is highly attractive for its increased power output
and 50 mM is presented in Figure 3a,b. Both the current and lifetime. The BFC has the benefit of high power
and the voltage were found to increase with increas- density, whereas the PVDF NG has the benefit of poten-
ing glucose concentration. Human blood has a glucose tially operating over much longer times because the
concentration that fluctuates between ⬃4 and 6 mM lifetime is only limited by the mechanical fatigue of the
and has a pH of 7.35⫺7.45.9 At 5 mM, the open loop device and can eventually be engineered to last.
voltage was found to be 50 mV and a short-circuit cur- The independent and integrated operation of the
rent of 11 nA. The power density of the BFC depends on PVDF NG, the BFC, and the hybrid BFC-NG is presented
load matching and was found to have a maximum at in Figure 4a⫺c. To integrate the AC voltage of the PVDF
⬃10 M⍀ with a corresponding power density of ⬃2.2 NG with the DC voltage of the BFC, a simple RC high
nW/cm2 and a current density of ⬃58 nA/cm2 (see Sup- pass filter (Figure 4b) was used, which effectively blocks
porting Information). the DC voltage of the BFC in one direction while pass-
The highest theoretical voltage that may be ob- ing the AC voltage of the NG. By integrating the two de-
tained from a GOx/laccase-based BFC is dictated by vices, the peak voltage was nearly doubled from ⬃50
thermodynamics and is ⬃1 V.9 To obtain this voltage, to ⬃95 mV. Furthermore, the PDMS packaging of the
various factors need to be optimized, but the most im- PVDF NG allows for operation inside biofluid and in vivo
portant one is the enzyme surface interactions. By environments. In addition, using a flexible Kapton film
cross-linking or “wiring” the immobilized redox en- substrate for the BFC permits the devices to be
3650 VOL. 4 ▪ NO. 7 ▪ HANSEN ET AL. www.acsnano.org
 ARTICLE
integrated back-to-back as conceptually illustrated in
Figure 4d. It is important to point out that our goal here
is not to maximize the output of BFC; instead, we keep
the output of the BFC to be in a reasonable range so
that the hybridization of the BFC and NG can be clearly
illustrated.
The power output of the hybrid nanogenerator is
the sum of the BFC and NG. The voltage output of the
BFC is VBFC, and the output voltage of the ac NG is ⫾VNG.
Considering the infinitely large resistance of the PVDF
nanofiber, the output voltage of the NG component is
⫾VNG, even with the presence of a load. The inner resis-
tance of the BFC is rather low because it is dictated by
electron transfer between the active center of the en-
zymes and the CNT electrodes. In such a case, the volt-
age applied to an external load R is VBFC ⫾ VNG, which
gives an output power of (VBFC ⫾ VNG)2/R. The average
peak output power for each cycle of the mechanical ac-
tion is [(VBFC ⫹ VNG)2/R ⫹ (VBFC ⫺ VNG)2/R]/2 ⫽ (VBFC)2/R
⫹ (VNG)2/R. In addition, methods can eventually be de-
veloped for rectification of the a.c. NG output to obtain
a d.c. signal and integration with the d.c. output of the
BFC to give an overall enhanced d.c. output.
Figure 5. Integration of the hybrid BFC-NG device with a UV
Powering Nanosensor by Hybrid Cell. The hybrid BFC-NG nanosensor to demonstrate a “self-powered” nanosystem. (a) Volt-
was also used to drive the operation of a ZnO nanowire- age drop across the ZnO NW UV light sensor when the UV light is
based UV light sensor (Figure 5b). When there was no off and on. For illustration purposes, only stabilized signals are dis-
played. (b) Schematic illustration of the self-powered hybrid nano-
UV light, the resistance of the ZnO nanowire was ⬃7 system.
M⍀ (see Supporting Information), and the correspond-
ing peak voltage drop on the nanosensor was ⬃5 mV,
have demonstrated the first hybrid cell for simulta-
as shown in Figure 5a. Upon irradiation with UV light,
neously harvesting solar and mechanical energy.24 Here,
the nanowire resistance dropped to ⬃800 k⍀ and the
peak voltage drop across the nanowire device was re- we have demonstrated a hybrid device that can be
duced to ⬃2.5 mV. This demonstrates the potential of a used to simultaneously scavenge both biochemical
fully “self-powered” nanosystem for in vivo applications. and mechanical energy for in vivo applications. The hy-
brid device takes advantage of its two constituent parts,
CONCLUSION leading to a higher output and potentially longer oper-
Developing energy scavenging technology that har- ating lifetimes. In addition, the hybrid device was used
vests multiple-type energy sources from our personal to power a UV nanosensor, demonstrating the out-
environments is highly desired for sustainable energy standing potential for a completely self-powered nano-
production and unique applications. Previously, we system for in vivo biomedical applications.

EXPERIMENTAL METHODS gap in the middle by using a mask. The electrospun fibers were
Electrospinning of PVDF Nanofibers. PVDF powder (MW 534000) carefully transferred across the Au electrodes and electrically
was purchased from Sigma-Aldrich and used as received. A to- bonded using silver paint (Ted Pella). A 0.5 mm layer of PDMS
tal of 1.5 g PVDF was dissolved in a mixture of 3 mL of DMF (VWR) was deposited over the device for dielectric protection and bio-
and 7 mL of acetone (VWR) and heated at 60 °C for 30 min so compatibility. The final device was immersed into paraffin oil and
that the solution was homogeneous. The transparent viscous so- 20 kV was applied between the two electrodes for 15 min. After
lution was transferred into a Hamilton 1 mL syringe for electro- poling, the electrodes were shorted for over 12 h.
spinning. A Chemyx Fusion 200 syringe pump and Betran DC Biofuel Cell Fabrication. Glucose oxidase (GOx, from Aspergillus
High Voltage power supply were used, a voltage of 12 kV was ap- niger, type X-S) and laccase powder (from Trametes versicolor)
plied to the syringe needle, and a feed rate of 50 ␮L/min was were purchased from Sigma-Aldrich, multiwall carbon nano-
used. The electrospun fibers were collected onto two grounded tubes from Hanhwa Nanotech (diameter 3⫺9 nm, purity ⬎95%),
copper pieces with a 2 cm gap, placed 15 cm away from the and phosphate buffer solution (PBS, pH 7.0) from Fluka. All
needle, and the fibers were electrostatically aligned across the chemicals were used as received. Carbon nanotubes were dis-
electrode gap. solved in ethanol and sonicated for 1 h to form 2 g/L dispersion.
Fabrication and In-Plane Poling of Nanogenerator. A 1 cm ⫻ 2 cm A 4 g/L solution of GOx in phosphate buffer solution and a 4
⫻ 30 ␮m Kapton@Dupont thin film was used as the supporting g/L solution of laccase in phosphate buffer solution was pre-
substrate. To form two electrodes a 50 nm thick layer of Au was pared. The Kapton film with Au electrodes was prepared as de-
deposited onto the Kapton substrate, leaving a 1 mm uncoated scribed and then bleached and rinsed with deionized water

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ARTICLE before use. A total of 2 ␮L of CNT dispersion was deposited
onto both electrodes and rinsed with deionized water after dry-
12. Chang, C.; Tran, V. H.; Wang, J.; Fuh, Y.; Lin, L. Direct-Write
Piezoelectric Polymeric Nanogenerator with High Energy
ing. GOx solution (2 ␮L) was then deposited onto one of the Conversion Efficiency. Nano Lett. 2010, 10, 726⫺731.
CNT/Au electrodes to form the anode and 2 ␮L of laccase solu- 13. Li, D.; Wang, Y.; Xia, Y. Electrospinning of Polymeric and
tion was deposited onto the other to form the cathode. The de- Ceramic Nanofibers as Uniaxially Aligned Arrays. Nano Lett.
vice was then stored under 4 °C for at least 4 h before use. Prior 2003, 3, 1167–1171.
to use, the electrodes were rinsed in pure PBS. 14. Zheng, J.; He, A.; Li, J.; Han, C. C. Polymorphism Control of
Electrical Measurement. A voltage preamplifier (Stanford Re- Poly(vinylidene fluoride) through Electrospinning.
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Acknowledgment. Research was supported by DARPA (Army/ Aminopropyltriethoxysilane Towards the Fabrication of
AMCOM/REDSTONE AR, W31P4Q-08-1-0009), BES DOE (DE-FG02- Electrochemical Biosensors with Promoted Electron
07ER46394), KAUST Global Research Partnership, NSF Transfer. Electroanalysis 2004, 16, 132–139.
(DMS0706436, CMMI 0403671), MANA WPI program from NIMS, 20. Cai, C.; Chen, J. Direct Electron Transfer of Glucose Oxidase
Japan, and the Georgia Institute of Technology. B.J.H. was sup- Promoted by Carbon Nanotubes. Anal. Biochem. 2004,
ported by a National Science Foundation Graduate Research Fel- 332, 75⫺83.
lowship. We thank Prof. Jing Zhu and Dr. Caofeng Pan for tech- 21. Lumley-Woodyear, T.; Rocca, P.; Lindsay, J.; Dror, Y.;
nical discussions. Thanks to Yagang Yao and Ziyin Lin for FTIR Freeman, A.; Heller, A. Polyacrylamide-Based Redox
work and Hao Fang for Au deposition. Polymer for Connecting Redox Centers of Enzymes to
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as a function of load resistance, hybrid BFC-NG with different Electroreduction of O2 to Water at ⫹0.7 V (NHE) at pH 5.
strain rates, PVDF NG current and voltage polarity reversal tests, J. Am. Chem. Soc. 2001, 123, 5802–5803.
and ZnO nanowire UV sensor I⫺V curves. This material is avail- 23. Mano, N.; Mao, F.; Heller, A. A Miniature Biofuel Cell
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