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Sponge-Like Piezoelectric Polymer Films for Scalable and
Integratable Nanogenerators and Self-Powered Electronic
Systems

Yanchao Mao, Ping Zhao, Geoffrey McConohy, Hao Yang, Yexiang Tong,
and Xudong Wang*

Nanogenerators (NGs) are an emerging technology that uses mechanical energy harvesting and is a challenge to seam-
piezoelectric nanomaterials to efficiently and effectively har- lessly integrate with many electronic devices. New designs
vesting mechanical energy from ambient sources on the are needed to realize practical and effective NG operations
nanometer scale.[1–3] Because of the superior mechanical and in common daily environments. Furthermore, fabrication
electromechanical properties of nanoscale structures, NGs of NGs typically relies on the integration of a tremendous
have demonstrated promising capability in scavenging energy amount of nanostructure building blocks, which remains a
from mechanical deflections,[4] acoustic waves,[5–7] fluid or critical obstacle for scaling up the NG manufacturing. There-
air flows,[8,9] and even human activities.[10] Currently, the fore, for a practical and integratable NG, the functional piezo-
output of NGs has reached the sub-milliwatt level, which is electric material should be easily fabricated in large scale and
sufficient to power many small electronic devices, including highly integratable with other electronic devices.
light-emitting diodes (LEDs),[4] laser diodes,[11] pH sensors,[12] β-Phase polyvinylidene fluoride (PVDF) is the most broadly
UV sensors,[12] speed/weight sensors,[13] and toxic pollutant studied piezoelectric polymer material.[18–20] Due to its high
sensors.[14] The piezoelectric output of NGs was also used to piezoelectric coefficient, excellent stability, and desirable flexi-
directly drive electrochemical reactions including lithium ion bility, nanostructured PVDF polymer has been used in a variety
intercalation,[15] electrodegradation of dyes,[16] and electro- of NG designs for mechanical energy harvesting.[8,9,15,21–23]
chemical water splitting.[17] This research illustrated the pos- For instance, PVDF nanowires fabricated by electrospinning
sibility of realizing self-powered electronic systems, which showed an enhanced mechanical energy conversion effi-
is a greatly desired concept for developing care-free sensor ciency.[22] By integrating PVDF polymer with an electrochem-
networks, implantable biomedical devices, and next-gener- ical system, a self-charging power cell was fabricated as a sus-
ation personal electronics. To date, most demonstrations of tainable power source.[15] The biocompatible nature of PVDF
NG prototypes rely on bending, deflection, or vibration of allows it to be applied to harvest energy inside biological sys-
the piezoelectric components to harvest mechanical energy. tems[8] and from human respiration.[9] Combined with its high
These processes require considerably large open spaces, and mechanical resistance, dimensional stability, and chemical sta-
thus may not be practical in many circumstances of ambient bility, the flexible PVDF polymer holds good potential for inte-
gratable NGs in self-powered electronic systems.
In order to enhance the piezoelectric performance, PVDF
should possess well controlled nanomorphology, high purity of
Y. C. Mao, Prof. X. D. Wang the β-phase, and excellent flexibility and durability. Moreover, a
Department of Materials Science and Engineering facile method for fabricating large-area nanostructured piezo-
University of Wisconsin-Madison electric PVDF NG is desired. Here, we report a novel sponge-
Madison, WI, 53706, USA
E-mail: [email protected] like mesoporous piezoelectric PVDF thin-film structure for NG
Y. C. Mao, H. Yang, Prof. Y. X. Tong development. The mesoporous PVDF thin films were fabri-
MOE Laboratory of Bioinorganic and Synthetic Chemistry cated using a simple casting-etching process in the wafer scale.
KLGHEI of Environment and Energy Chemistry The mesoporous PVDF NGs can be directly attached to the sur-
School of Chemistry and Chemical Engineering face of an electronic device (e.g., a cell phone) and effectively
Sun Yat-sen University
convert mechanical energy from ambient surface oscillations to
Guangzhou, 510275, China
electricity using the device’s own weight to enhance the ampli-
Prof. P. Zhao
Department of Mechanical and Industrial Engineering tude. Multiple PVDF NGs can be readily integrated and operate
University of Minnesota-Duluth synchronically to raise the output power for the operation of
Duluth, MN, 55812, USA electronic devices. This technique is scalable and integratable,
G. McConohy providing a promising solution for developing practical self-
Department of Engineering Physics powered electronic devices.
University of Wisconsin-Madison
Madison, WI, 53706, USA The mesoporous PVDF thin film was fabricated by casting
a mixture of PVDF solution and ZnO nanoparticles (NPs) onto
DOI: 10.1002/aenm.201301624 a flat surface, followed by HCl acid solution etching to remove

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Figure 1. Processing and structure of mesoporous PVDF thin films. a) Schematic procedure for fabricating mesoporous piezoelectric PVDF thin films.
b) SEM image of a mesoporous PVDF thin film fabricated from a ZnO-PVDF mixture with 50% ZnO mass fraction. The inset is a higher-magnification
SEM image showing that the pore size matches ZnO NP size. c) A photograph of an as-fabricated wafer-scale mesoporous PVDF thin film (18.5 cm
in diameter). The inset shows a small piece of the mesoporous PVDF thin film well adhered to the finger surface.

ZnO (Figure 1a). HCl solution was selected because PVDF is a could interact with the PVDF CF2 or CH2 groups that have
hydrophobic polymer with excellent chemical stability against negative and positive charge densities, respectively, and thus
corrosive solvents including acids.[24,25] Introducing ZnO NPs initiated the β-phase nucleation. This mechanism is consistent
to PVDF has two purposes: 1) to create porosity in the PVDF with the surface charge-induced crystallization phenomenon
film to modulate its mechanical property; and 2) to seed the that has been discovered in many PVDF composites with
formation of the piezoelectric β-phase. Additionally, ZnO has fillers such as BaTiO3,[34] clays,[35–37] hydrated ionic salts,[38]
several unique advantages compared to other inorganic (e.g., polymethylmethacrylate (PMMA),[39] TiO2,[40] ferrite,[40] Pd,[41]
SiO2) or organic (e.g., polystyrene) NP templates for the fabrica- Au,[42] and carbon nanotubes.[43,44]
tion of porous nanomaterials, including low-cost, non-toxicity, Using this method, a large-area mesoporous PVDF thin film
good scalability, and facile removal by acidic solution.[26–30] (18.5 cm in diameter) was fabricated (Figure 1c), demonstrating
Scanning electron microscopy (SEM) images (Figure 1b) show the capability of producing high quality piezoelectric polymer
the sponge-like mesoporous structure of the PVDF thin film thin films in large scales. The film thickness can be facilely
after removing ZnO NPs. The pore sizes are consistent with adjusted by the amount of casting mixture. The as-fabricated
those of the ZnO NPs (35–45 nm in average, inset of Figure 1b thin film was translucent, soft, and very flexible. It can be seam-
and Supporting Information Figure S1). The pores are inter- lessly attached to rough and curvy surfaces, such as human
connected allowing ZnO NPs to be completely removed via skin (inset of Figure 1c).
chemical etching. This was evidenced by the energy disper- The mesoporous PVDF film provides an excellent platform
sive X-ray spectroscopy (EDS) spectrum where only C and F for developing integratable NGs, which only need two layers
elements were detected (Figure S2, Supporting Information). of metal electrodes (Cu foil in our case) to be attached to both
Fourier transform infrared (FTIR) spectrum was used to con- sides of the film. The simple design ensures high volume
firm the crystal phase of the mesoporous PVDF thin film. The power density of the NGs. The flexible thin film configuration
characteristic peaks of the β-phase at 509, 840 and 1280 cm−1 allows the NG to be directly attached to electronic devices and
can be clearly observed in the FTIR spectrum (Figure S3, Sup- uses the device’s own weight as the proof mass to amplify the
porting Information).[31,32] The formation of β-phase PVDF can oscillation of the PVDF film. In our experiment, a piece of alu-
be attributed to the interactions between the PVDF dipoles and minum block was used in place of an electronic device to test
surface charges on ZnO surfaces. In wurtzite ZnO crystals, the the energy harvesting ability (see setup details in the Experi-
(0001) surfaces are terminated with Zn cations and always posi- mental Section). As schematically shown in Figure 2a, a PVDF
( )
tively charged, while the 0001 surfaces are O-terminated and NG (2 cm × 1 cm × 28 µm) with an aluminum block (65 g)
exhibit negative charges.[33] The intrinsic ZnO polar surfaces was placed on a flat surface. An oscillator was located 6 cm

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Figure 2. Characterization of PVDF thin film NGs. a) Schematic setup for characterizing PVDF thin film NGs for harvesting mechanical energy from
surface oscillations. The mesoporous PVDF thin film-weight system can be simplified as a free vibration system with damping, as shown in the inset.
b) The voltage output of a PVDF thin film NG (fabricated from a 50% ZnO mass fraction mixture) generated during one cycle of surface oscillation.
The blue and red curves were collected under forward and reverse connections, respectively. c,d) The voltage (c) and current (d) output of the PVDF
NG under continuous surface oscillation. Insets show the output curve features during one cycle of surface oscillation.

away from the NG system and generated surface oscillations output current was not indicated).[9] As shown in the insets
with a controlled frequency. The oscillations were transported of Figure 2c,d, within one surface oscillation cycle, the output
across surface and created a slight up-and-down motion of the signal peaked and quickly dropped to the base level, indicating
aluminum block. Thus, the PVDF NG located in-between was large damping of the PVDF film like a sponge layer. The NG
pressed accordingly and produced piezoelectric output. Here, was able to work over a long period of time under a constant
the PVDF-weight system can be simplified as a free vibration oscillation without noticeable degradation in the output signal
system with damping (inset of Figure 2a). The open-circuit (Figure S4, Supporting Information).
voltage (VOC) of the NG under the forward and reverse connec- Porosity is an important feature that controls the mechanical
tions was measured during the oscillation. The upper panel of energy harvesting ability of the mesoporous PVDF films. To
Figure 2b shows the VOC signal generated during one surface investigate the porosity effect, PVDF thin films with different
oscillation cycle (the driving oscillator was operated at 40 Hz). porosities were prepared from mixtures with a series of ZnO
In the case of reverse connection, the VOC demonstrated iden- mass (or volume) fractions (Figure S5, Supporting Informa-
tical amplitude with reversed polarization (the lower panel of tion). The VOC of these mesoporous PVDF thin films with iden-
Figure 2b), which confirmed the genuineness of the piezoelec- tical thicknesses (28 µm) was measured at a frequency of 40 Hz,
tric output signals. Figure 2c,d show the VOC and short-circuit and their peak values were plotted as a function of porosity
current (ISC) of the NG, respectively, when the supporting sur- (Figure 3a). The peak VOC increased from 3.5 V to 11.0 V as
face was oscillating at 40 Hz. The average peak values of the VOC the porosity increased from 6.5% to 32.6% (ZnO mass frac-
and ISC were found to be about 11.0 V and 9.8 µA, respectively. tion increased from 10% to 50%), and then decreased to 8.3 V
This output performance was higher than the recently reported as the porosity further increased to 45.5% (ZnO mass fraction
values for other PVDF based NGs, such as single PVDF increased to 70%). The optimal porosity for achieving the max-
nanofiber (30 mV/3 nA, 6.5 µm diameter/600 µm length),[22] imum VOC output was identified to be ≈11.0 V. The porosity-
PVDF nanofibers (20 mV/0.3 nA, sample thickness and area output relationship was found directly related to the amount of
were not indicated),[8] PVDF film (0.4 V, 1.5 µm thickness, β-phase PVDF. Meanwhile, the total amount of PVDF per unit
output current was not indicated),[45] PVDF mats (≈1 V, 100 µm volume decreased as the ZnO ratio increased. As evidenced by
thickness/1 cm2 area, output current was not indicated),[46] FTIR spectra (Figure S6, Supporting Information), the amount
porous PVDF film (1.3 V/0.3 µA, 5 µm thickness/1 cm2 area),[23] of α-phase in as-prepared PVDF films monotonically decreased
PVDF nanofiber membranes (≈2.2 V/≈4.5 µA, 140 µm thick- as the ZnO ratio increased. The amount of β-phase increased
ness/2 cm2 area),[47] PVDF microbelts(≈6 V, 26 µm thickness, as the ZnO mass ratio increased from 10% to 50%, and then

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cycle, from the mesoporous PVDF thin films prepared using

the 50% and 10% ZnO mass fraction mixtures, respectively. The
10%-ZnO sample generated a series of oscillating signals and
relatively slowly decayed from ≈3 V to ≈1 V within ≈20 ms. The
50%-ZnO sample produced significantly higher output (≈11 V),
which quickly decayed to the base line within ≈10 ms. To fur-
ther understand the porosity-related performance, the mechan-
ical properties, specifically the spring constant (K) and damping
coefficient (C), were calculated based on the oscillation patterns
(Figure S8, Supporting Information) for PVDF thin films with
different porosity (Figure S5, Supporting Information). Both
experimental and calculation results agreed that PVDF thin
films with higher porosity (>40% ZnO) were soft and lossy like
a sponge, while lower porosity PVDF thin films were still more
like a rigid plastic film. Therefore, under the same amount of
external impact, the sponge-like high-porosity PVDF thin films
would yield considerably larger displacement, and thus pro-
duced much higher electrical output. Comparing the calculated
data (Table S1, Supporting Information), the spring constant
decreased by 60–70% when the ZnO ratio increased to >40%;
meanwhile, the overall damping coefficient only increased by
≈10%. Therefore, although more mechanical energy was dissi-
pated mechanically in the higher porosity PVDF films, a good
portion of it was converted into electrical energy due to the
larger film displacement (higher Ctotal including higher elec-
trical damping component).
Since the mesoporous PVDF NGs were operated under
forced oscillation conditions with large output (their resonance
frequencies were in the kHz range), the higher damping ratio
can ensure all the input mechanical energy were dissipated
prior to the following impact. With part of the dissipated
mechanical energy being converted into electricity, the output
can remain a constant high value across a relatively wide fre-
quency range. For a 50%-ZnO PVDF NG, VOC were measured
within a frequency range from 20 to 60 Hz, which are common
oscillation frequencies in ambient environments. It was found
that the piezoelectric output was nearly independent to the agi-
Figure 3. Porosity-related voltage output. a) The peak voltage measured
tation frequency (Figure S9, Supporting Information) and the
from PVDF thin film NGs as a function of porosity (or ZnO volume/mass maximum VOC remained between 9.2–11.5 V (square dots in
fraction). All the voltage data were collected from 40 Hz surface oscilla- Figure 3b, the slight increase after 30 Hz was due to necessary
tion. The upper and lower insets show the detailed voltage output features input power increase of the oscillator).
generated during one cycle of surface oscillation from mesoporous PVDF In general, combination of high β-phase ratio and sponge-
thin films fabricated using 50% and 10% ZnO mass fraction mixtures, like mechanical property made the mesoporous PVDF thin
respectively. More rapid signal decay can be observed from the 50%
films a promising candidate for harvesting mechanical energy
ZnO sample. b) Comparison of the peak voltages between a mesoporous
PVDF thin film (50% ZnO mass fraction) and a solid β-phase PVDF thin from surface oscillations. This advantage is clearly illustrated by
film obtained under surface oscillation frequencies from 20 to 60 Hz. comparing the performances of mesoporous PVDF thin films
The voltage outputs show a relatively stable value within the testing fre- with solid β-phase PVDF thin films that were prepared[48] and
quency range (increase at 30 Hz is due to the increase of oscillator driving tested within the same frequency range and under the same
power). The output of mesoporous PVDF thin film was more than two oscillation power. The same size solid PVDF film produced
times higher than that of the solid PVDF thin film.
peak VOC from 3.7 V to 5.3 V (diamond dots in Figure 3b),
which was over two times smaller than that produced by the
decreased when the ZnO mass fraction further increased. The mesoporous PVDF films.
mesoporous PVDF film made from the mixture of 50% ZnO To demonstrate the application potential as a direct current
(by mass) possessed the maximum β-phase quantity, corre- (DC) power source, a mesoporous PVDF NG was connected to a
sponding to the highest piezoelectric potential. capacitor (22 µF) through a full-wave bridge circuit, as shown by
In addition, PVDF films with different porosities yielded dif- the equivalent circuit in the inset of Figure 4a. The alternating
ferent oscillation patterns, which also contributed to the elec- current (AC) piezoelectric output was fully rectified through the
trical output variation. The upper and lower insets of Figure 3a bridge circuit (Figure S10, Supporting Information). Figure 4a
show the voltage output signal generated in one oscillation illustrates the charging process of the capacitor under different

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multiplication of NGs’ AC output without rectifying them
first. In order to demonstrate this merit, two PVDF NGs were
fabricated and attached to the same aluminum block. When
operated under 40 Hz, the peak VOC and ISC output of NG I
and NG II was 11.1 V, 9.7 µA (Figure 5a) and 11.0 V, 9.8 µA
(Figure 5b), respectively. By connecting these two NGs in serial,
the peak VOC output increased to 20.2 V, which was approxi-
mately the sum of the peak VOC of each NGs. Meanwhile, the
peak ISC output was barely affected (9.3 µA) and only 4.1% drop
was observed in comparison to the lower peak ISC (9.7 µA) of
the two individual NGs (Figure 5c). For parallel connection
as shown in Figure 5d, the peak ISC was largely increased to
17.5 µA, which was only 10.3% less than the sum of the peak
ISC of both NGs. Meanwhile the peak VOC remained at nearly
the same individual level (10.5 V). The loss of output could be
attributed to the leakage of electric charge through the connec-
tion circuit.[10] This result revealed that PVDF NG integration
followed the general rules of battery connection, although their
outputs were in AC form.
The excellent integratability allows direct application of
the PVDF NGs onto the surface of an electronic device and
operation by the device’s own weight. As a demonstration,
four PVDF NGs (1 × 2 cm2 each) were attached to the back of
a smart phone, as shown in Figure 5e. These NGs were con-
nected in parallel. The phone was then placed on a flat wood
surface where an oscillator was placed ≈10 cm away (the same
setup for testing PVDF NGs, Figure 5f). When the oscillator
was turned on, the phone followed the surface oscillation and
NGs underneath were activated by the phone’s weight to con-
vert the surface oscillating mechanical energy to electricity (see
Video S1, Supporting Information). The output power was
rectified by a bridge circuit and stored in capacitors. 3.7 V was
reached on a 47 µF capacitor by this phone-NG setup, and the
corresponding charging curve is shown in Figure S11 (Sup-
porting Information). Connecting two capacitors in series after
Figure 4. Characterization of frequency-related energy output. a) Volt-
ages measured across a 22 µF capacitor when it was charged by a
they were charged in parallel could yield high enough electrical
mesoporous PVDF thin film NG (from 50% ZnO mass fraction mixture) energy to activate the turning on of the phone by itself (i.e., the
under different surface oscillation frequencies. Inset is the equivalent cir- phone battery was active; Video S2, Supporting Information).
cuit. b) The output power density calculated from the capacitor charging This demonstrated the promising application potential of the
curves as a function of the surface oscillation frequency. mesoporous PVDF thin films as a supportive energy source
for powering personal electronics using ambient mechanical
energy sources.
agitation frequencies. Higher frequency yielded higher satura- In conclusion, we successfully demonstrated a novel inte-
tion voltage of the capacitor, which is a result of equilibrium gratable NG design based on sponge-like mesoporous piezo-
established between the NG’s charging rate and the capacitor’s electric PVDF thin films. This type of NG can generate con-
leakage rate. The voltage held by the capacitor reached 2.4 V siderable electrical energy by harvesting mechanical energy
in 70 s under an oscillation frequency of 60 Hz. Based on the from surface oscillations. Compared to previous develop-
charging curves, the output power of the mesoporous PVDF ments of NGs, the mesoporous PVDF thin film NG possesses
NG was calculated via the equation: P = CU2/2t, where C is the several unique merits that are critical for harvesting ambient
capacitance of the capacitor, U is the saturation voltage, and t is mechanical energy and developing practical self-powered elec-
the time for the voltage to reach the saturation point. This was tronic systems. First, the method is very simple and effective
the practical power output on the specific capacitor. It mono- for large-scale fabricating mesoporous piezoelectric PVDF thin
tonically increased as a function of oscillation frequency from films. This fabrication method also circumvents the require-
0.02 mW cm–3 to 0.16 mW cm–3 at 60 Hz (Figure 4b). ment of large mechanical strain or high electric field for the
Another unique merit of the mesoporous PVDF NG is its formation of β-phase PVDF. This is a highly desired feature
excellent integratability. Because it does not require additional for manufacturing practical and industrial-level NGs. Second,
component to fulfill the energy harvesting function, multiple the NG uses the electronic device’s own weight to modulate
NGs can be simply integrated into one system and operate its displacement and amplify its electrical output. This unique
with identical phase and frequency. This feature allows direct operation principle realizes a very simple system design. It

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Figure 5. Operation demonstration of mesoporous PVDF thin film NGs. a,b) Voltage and current outputs of two individual NGs, I and II, respectively.
c,d) Voltage and current outputs measured from NGs I and II when they were connected in series (c) and in parallel (d), respectively. Corresponding
connection conditions are shown in the top insets. e) A photograph of four mesoporous PVDF thin film NGs (1 × 2 cm2 each) attached on the back
side of a smart phone. They were connected in parallel. f) Operation of the integrated phone-NG system driven by surface oscillation, and the electrical
output was recorded by the oscilloscope.

also provides an ideal solution for directly integrating multiple by the Bruker Tensor 27 spectrometer. To make a PVDF NG, the
NGs into one system to boost the output without rectifying or mesoporous PVDF thin film was cut into 1 × 2 cm2 pieces. Both sides
synchronizing individual signals. Third, the controllable nano- of the PVDF thin film were taped with Cu foils as electrodes. The PVDF
film was then poled at room temperature in an oil bath. An electric field
porosity enables adjustable mechanical property of the PVDF of 60 V µm–1 was applied between the top and bottom Cu electrodes
films. At high porosity, the PVDF film acts as a flexible and soft for 2 h. The PVDF samples were stable throughout the entire poling
sponge. Although the high-porosity films would dissipate more process. No short circuit or noticeable voltage fluctuation was detected.
mechanical energy, a good portion of it could be converted into The poled PVDF NG was taped on the bottom surface of a piece of
electrical energy due to the large film displacement resulting aluminum block (65 g), which was used in place of an electronic device.
in large electric output under small surface oscillations. Last, The aluminum block was placed on a flat wood surface. The surface
oscillation was generated by an oscillator located ≈6 cm away from
the forced oscillation allows the PVDF NG to be operated away
the aluminum block. The oscillator impacted the wood surface with a
from its resonant frequency with large outputs. This unique controlled frequency. The electrical output signal from the PVDF NG was
feature opens another route toward broad-band mechanical recorded by an Agilent DSO1012A oscilloscope.
energy harvesting. Integrating the PVDF NGs with a smart
phone demonstrated the unique merits discussed above. It pro-
vides a promising solution for developing practical self-powered
personal electronic devices.
Supporting Information
Supporting Information is available from the Wiley Online Library or
from the author.
Experimental Section
Fabrication of Mesoporous PVDF Thin Films: PVDF powder (Sigma
Aldrich) was dissolved in N,N-dimethylformamide (DMF) solvent Acknowledgements
(10 wt%) at 65 °C and then mixed with ZnO NPs (35–45 nm, US
The authors thank M. B. Starr and C. J. Tao for providing their phones
Research Nanomaterials, Inc.). The mass ratio between ZnO NPs to
for our experiments. X.W. thanks the support of DARPA under grant
PVDF was adjusted to create different porosity. The mixture was treated
No. N66001-11-1-4139, Air Force under award FA9550-13-1-0168, and
in ultrasonic bath for 30 min and yielded a uniformly-mixed PVDF/ZnO
National Science Foundation CMMI-1148919. Y.M. thanks the China
NP suspension. The suspension was cast into a film shape in a petri
Scholarship Council for financial support. Y.T. thanks the support of
dish and dried in atmosphere at 75 °C. The films were then immersed
NSFC (21273290) and the Research Fund for the Doctoral Program of
in a 37 wt% HCl solution for 3 h to completely remove the ZnO NP
Higher Education of China (No.20120171110043).
template. After acid etching, the films were washed by deionized (DI)
water and mesoporous PVDF thin films were obtained.
PVDF NG Design and Testing: The morphology and structure of the Received: October 24, 2013
PVDF thin films were characterized using a LEO 1530 scanning electron Revised: November 24, 2013
microscope. FTIR characterizations of the PVDF films were performed Published online:

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