Accepted Manuscript

High-performance piezoelectric nanogenerator based on microstructured P(VDF-

TrFE)/BNNTs composite for energy harvesting and radiation protection in space

Shibo Ye, Can Cheng, Xiaoming Chen, Xiaoliang Chen, Jinyou Shao, Jie Zhang,
Hanwen Hu, Hongmiao Tian, Xiangming Li, Li Ma, Wenbao Jia
PII: S2211-2855(19)30300-3
DOI: https://doi.org/10.1016/j.nanoen.2019.03.096
Reference: NANOEN 3615

To appear in: Nano Energy

Received Date: 15 February 2019

Revised Date: 20 March 2019
Accepted Date: 31 March 2019

Please cite this article as: S. Ye, C. Cheng, X. Chen, X. Chen, J. Shao, J. Zhang, H. Hu, H. Tian, X. Li,
L. Ma, W. Jia, High-performance piezoelectric nanogenerator based on microstructured P(VDF-TrFE)/
BNNTs composite for energy harvesting and radiation protection in space, Nano Energy (2019), doi:
https://doi.org/10.1016/j.nanoen.2019.03.096.

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 ACCEPTED MANUSCRIPT

Title
High-Performance Piezoelectric Nanogenerator Based on Microstructured P(VDF-TrFE)/BNNTs
composite for Energy Harvesting and Radiation Protection in Space

The table of contents entry

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A piezoelectric nanogenerator (PENG) based on P(VDF-TrFE)/boron nitride nanotubes
nanocomposite micropillar arrays suitable for harsh environment applications is prepared by a

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reliable and scalable nanoimprint lithography. The PENG demonstrates outstanding piezoelectric
performance and superior radiation resistance, which is promising for high-efficiency

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biomechanical energy harvesting (e.g. astronaut body motion) and effective protection of humans
from neutron radiation under extreme space environments.

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ToC figure
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High-Performance Piezoelectric Nanogenerator Based on Microstructured

P(VDF-TrFE)/BNNTs composite for Energy Harvesting and Radiation
Protection in Space
Shibo Ye,1 Can Cheng,2 Xiaoming Chen,1* Xiaoliang Chen,1 Jinyou Shao,1* Jie Zhang,3 Hanwen

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Hu,4 Hongmiao Tian,1 Xiangming Li,1 Li Ma,5 Wenbao Jia2, 6*
1
Micro- and Nanotechnology Research Center, State Key Laboratory for Manufacturing Systems

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Engineering, Xi’an Jiaotong University, Xi’an, Shaanxi 710049, China
2
Department of nuclear Science and Engineering, College of Materials Science and Engineering,

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Nanjing University of Aeronautics and Astronautics, Nanjing, Jiangsu 210016 China
3
Electronic Materials Research Lab, Key Lab of the Ministry of Education, Xi’an Jiaotong
Univeristy, Xi’an, Shaanxi 710049, China

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4
Department of Mechanical Engineering and Materials Science, Duke University, Durham, North
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Carolina 27708, USA
5
Department of Applied Chemistry, School of Science, MOE Key Laboratory for Nonequilibrium
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Synthesis and Modulation of Condensed Matter ,Xi’an Jiaotong University, Xi’an, Shaanxi
710049, China
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Collaborative Innovation Center of Radiation Medicine of Jiangsu Higher Education Institutions,
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Suzhou, Jiangsu 215000, China

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*To whom correspondence should be addressed. xiaomingchen@xjtu.edu.cn (X. Chen),

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jyshao@xjtu.edu.cn (J. Shao) and jiawb@nuaa.edu.cn (W. Jia)

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Keywords: piezoelectric nanogenerator, piezoelectric nanocomposite, neutron radiation shielding,

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boron nitride nanotube (BNNT), nanoimprint lithography

Abstract

Stable and durable piezoelectric nanogenerators (PENGs) with good flexibility, high performance

and superior radiation resistance under harsh environments are promising for space exploration.

Here, a novel PENG based on P(VDF-TrFE)/boron nitride nanotubes (BNNTs) nanocomposite

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micropillar arrays with enhanced performance and excellent neutron radiation shielding is

prepared by a reliable nanoimprint lithography. The PENG comprised of a microstructured

P(VDF-TrFE)/0.3 wt% BNNTs nanocomposite demonstrates an outstanding output voltage of 22

V and a sensitivity of 55 V/MPa under the pressure of 0.4 MPa, which are 11-fold higher than

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those of pristine P(VDF-TrFE) film. This dramatic enhancement in performance is ascribed to

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synergistic contributions from strong piezoelectric BNNTs and a strain confinement effect of the

nanocomposite microstructure. In practice, the PENG is capable of scavenging various

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mechanical and biomechanical energy for lighting up commercial LEDs, an LCD screen and a

digital watch. More importantly, the as-obtained PENG exhibited 9% neutron radiation shielding

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with neutron cross section increase reaching 260% when compared to the film without BNNTs.
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Moreover, the high output is retained after 2 h of neutron radiation exposure. Overall, the as-

prepared microstructured nanocomposites look promising for high-efficiency piezoelectric

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nanogenerators for the self-powered and wearable electronic devices, in particularly, under the
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extreme space environments.

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1. Introduction
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As space exploration missions last longer and occur farther from earth, lightweight, highly

efficient power generation systems with extended durability and superior stability are crucial for
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successful missions. Conventional power sources like fuel cells and bulky batteries dramatically
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increase the mass of the spacecraft, reducing mission capability and rendering space access less

affordable. Therefore, the exploitation of lightweight and high-performance energy generation

devices for harvesting clean and renewable power from space is essential. To this end, harvesting

energy from ambient space environments like mechanical, thermal and chemical is an attractive

alternative to conventional rechargeable batteries to extend the limit of power production in space
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and to provide power to various smart electronics.[1,2]

In the last few decades, piezoelectric materials have attracted increasing attention due to their

outstanding capabilities in converting mechanical energy into electrical energy to power smart

electronic devices. A variety of studies have been reported to fabricate piezoelectric

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nanogenerators (PENGs) based on piezoelectric materials.[3–9] Various piezoelectric inorganic

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materials, such as lead zirconate titanate (PZT)[10,11] and barium titanate (BaTiO3) [12,13] have

great piezoelectric coefficients and superior energy conversion efficiencies but still suffer from

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poor toughness, heavy weight, low durability, and high toxicity. Compared to inorganic materials,

piezoelectric polymers, such as polyvinylidene fluoride (PVDF) and their copolymers like

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polyvinylidene fluoride-trifluoroethylene (P(VDF-TrFE))[14] are advantageous in terms of
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lightweight, flexibility, conformability, and simple processing. However, PENGs based on PVDF

have lower electric outputs than those of PENGs made of inorganic materials. To overcome these
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issues, several approaches have been attempted, including incorporation of nanofillers with high
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inherent piezoelectricity within a PVDF matrix to form flexible nanocomposites with improved
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piezoelectric performances without compromising the flexibility.[2,15–19] On the other hand,

formation of micro/nanostructures in piezoelectric materials can enhance PENGs performances

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and energy conversion efficiency due to a geometrical strain confinement effect, strain tolerance

capability, and better alignment of dipoles.[20–22] However, several challenges still remain that
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prevent the use of PVDF-based nanogenerators in space exploration. These harsh conditions of a
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space environment require electronics that are stable and lightweight with intrinsic radiation

shielding. Radiation is a serious pollution issue in space, causing catastrophic malfunctions of

some devices and instruments and threatening human health. As a result, piezoelectric materials

used in space should possess high resistance to radiation (e.g. neutrons, electrons).[23]

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The aforementioned issues could be resolved by developing flexible composite films with

added nanofillers and enhanced piezoelectric properties, which could absorb or shield radiation to

prevent detrimental effects simultaneously. A one-dimensional nanomaterial composed of

hexagonal B-N bond network, boron nitride nanotubes (BNNTs), possessing excellent

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mechanical properties and high thermal and chemical stabilities[24–26], are promising

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reinforcing filler materials for light, strong, and durable nanocomposites for space

applications.[27–29] On the other hand, neutron radiation shielding capability of BNNTs owing

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to presence of isotope B with high neutron absorption is experimentally revealed.[27] In

addition, several theoretical and experimental studies have been performed to investigate the

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piezoelectricity of BNNTs.[27,30–32] The unique neutron shielding, strong piezoelectric
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characteristics with their extraordinary chemical and thermal stability enable BNNTs and

BNNTs-based piezoelectric materials to be promising multifunctional material candidates for

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nanogenerators in space exploration.

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In this work, a piezoelectric energy generator comprised of a P(VDF-TrFE) and BNNTs

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composite with flexible, light weight, high efficiency and tolerant to neutron radiation was

prepared and tested. To further improve the performance of flexible PENGs, nanoimprint
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lithography was employed to facilitate the fabrication of longitudinal micropillars on the

nanocomposite film. It was found that the PENG based on the microstructured P(VDF-
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TrFE)/BNNTs nanocomposite film exhibited enhanced performances due to a synergistic effect

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of BNNTs and vertically well-aligned micropillar arrays. The PENG prepared with 0.3 wt%

BNNTs generated an output voltage of 22 V and a power density of 11.3 µW·cm-2 under

maximum stress reaching 0.4 MPa, which is an enhancement by a factor of 11 compared to the

pristine P(VDF-TrFE) film. Meanwhile, it was found that the PENG exhibited 9% neutron

radiation shielding with cross section increase reaching 260% compared to the film prepared
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without BNNTs. Until now, studies dealing with BNNTs-based piezoelectric nanogenerators

remained largely unexplored, and no work has so far been reported on development of

nanogenerators with superior output performances and excellent neutron radiation shielding

capabilities using microstructured BNNTs incorporated P(VDF-TrFE) nanocomposites. The

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extraordinary properties of power generation using BNNTs-based piezoelectric materials in terms

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of great efficiency, compact size, flexibility and neutron radiation shielding would increase the

capability of space missions with extended lifetime and scope and might protect astronauts from

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the hazards of neutron radiation in space simultaneously.

2. Results and discussion

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Figure 1(a-e) illustrate the main fabrication processes of piezoelectric nanocomposite
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micropillar arrays-based nanogenerator. Briefly, 1 g P(VDF-TrFE) powder and 0 ~ 0.5 wt%

BNNTs were dispersed in 10 ml N, N-Dimethylacetamide solvent (DMAc) under stirring (73 h)

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and subsequent sonicating (1 h) to obtain a homogeneous piezoelectric nanocomposite

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suspension (Figure 1(a)). Subsequently, the uniform suspension was dropped on a clean Si
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substrate to form a flat, thin film. The solvent was then completely evaporated in a vacuum oven

at 60 °C for 12 h (Figure 1(b)). After drying, the nanocomposite thin film was peeled off from the
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substrate, followed by deposition of 120 nm Cr/Au layer on backside of the film as bottom

electrode. In Figure 1(c), the prepared film was hot pressed by a predefined porous PDMS mold
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at 180 oC for 1 h (above PVDF melting temperature) to generate micropillar structures inside the
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PDMS mold. After peeling the PDMS mold, the nanocomposite micropillar array was obtained

(Figure 1(d)). To prevent breakdown of the microstructured nanocomposite film during high

voltage electric poling process, an insulating layer consisting of PDMS was deposited on top of

the micropillar array layer by spin-coating at a speed of 1500 rpm for 60 s. The obtained PDMS

layer not only served as protective layer by partially filling of the space between micropillars in
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the axial direction but also increased the mechanical durability of the composite film.

Subsequently, a highly conductive Ag nanowire was coated on the uneven top surface of

nanocomposite film to fill the remaining space between micropillars and served as the top

electrode. Finally, a 10 MV·m−1 electric field parallel to normal direction of the film was applied

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to align the dipole moments of P(VDF-TrFE) along the direction of external electric field and to

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enhance the piezoelectric properties (Figure 1(e)). The flexible PENG with sandwich-like

structure was finally obtained (Figure 1(f)), in which a piezoelectric nanocomposite micropillar

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array was encapsulated and sandwiched between a Cr/Au and a Ag nanowires layer which served

as bottom and top electrodes respectively. Figure 1(g) shows the photograph of bending PENG

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with 1 cm2 area, demonstrating good flexibility and confirming suitability in wearable electronics.
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Figure 1(h) demonstrates a schematic diagram of the PENG for harvesting biomechanical energy

in space environment. Due to the intrinsic flexibility and good radiation shielding capability, the
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PENGs can be attached to astronaut’s body for generating power from different human activation
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in space (e.g. walking on Mars or Moon), such as finger bending, elbow bending, knee bending
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and foot stepping to power up portable and wearable electronic device. When human body moves,

the PENG is deformed and the P(VDF-TrFE)/BNNTs active piezoelectric composite generates
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positively and negatively charged electrons.

The BNNTs employed in this study were produced by the High-Temperature Pressure method,
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and originally provided in the form of dry cotton-like fibrils.[24] The scanning electron
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microscopy (SEM) image in Figure 2(a) shows several protruding as-synthesized BNNTs prior to

dispersion. Figure 2(b) displays four highly crystalline multi-walled BNNTs with diameters

ranging from 4.3 to 9.3 nm and with very clean surfaces, which is consistent with previous

studies showing BNNTs contain mostly 1-10 tube walls.[24,25,33] The highly crystalline, long

and small nanotubes can be expected to be ideal piezoelectric nanomaterials.[30] The inset
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provides the Raman spectra of BNNTs, displaying one peak at 1369 cm-1 ascribed to E2g

vibration mode.[34] For the purpose of facilitating the fabrication of BNNTs nanocomposites,

DMAc was applied to enhance the dispersion of BNNTs, which exhibits the most stable and

uniform dispersion.[35] Images of BNNTs dispersion in DMAc and P(VDF-TrFE)/DMAc are

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shown in Figure S1. After stirring and sonication, vials containing BNNTs and P(VDF-

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TrFE)/BNNTs appear as turbid white solutions, which are indicative of dispersed BNNTs.

Meanwhile, the dispersion state of BNNTs in the nanocomposite film was characterized using

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high-resolution transmission electron microscopy (HRTEM). The TEM image captures several

individual nanotubes protruding from the P(VDF-TrFE)/BNNTs nanocomposite film, as shown in

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Figure 2(c). This indicates that BNNTs are well dispersed in the nanocomposite film. Figure 2(d-
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e) presents the SEM images of a fabricated P(VDF-TrFE)/BNNTs nanocomposite micropillar

array with and without the PDMS insulating layer. The corresponding laser scanning confocal
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microscopy three-dimensional topographies and two-dimensional cross-sectional profiles are

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depicted in Figure S2. It is apparent that the micropillar array prepared without PDMS layer
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appeared vertically well-defined, with identically shaped pillars of 80 µm in diameter and 120 µm

in height. After PDMS coating, the space between pillars became partially filled, yielding a
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PDMS layer height is nearly 10 µm less than that of the micropillars (Figure S2(d)). The

difference in height ensured that the Ag nanowires filling on top could serve as electrode and
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guaranteed direct contact between the electrode and micropillar (Figure 2(f)).
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The piezoelectric performance of a P(VDF-TrFE) based nanogenerator mostly depends on

electroactive phase content. Fourier transform infrared (FTIR) absorption spectroscopy is

commonly used to identify and quantify the phase content of P(VDF-TrFE).[15,17] Figure 3(a)

shows the FTIR absorption spectra of P(VDF-TrFE) and P(VDF-TrFE)/0.3 wt% BNNTs

nanocomposite films prepared with and without electric poling respectively, from which we can
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see P(VDF-TrFE) and its nanocomposite are mainly composed of α and β phases. As shown in

the Figure 3(a), the characteristic peaks at 840, 1279 and 1400 cm-1 bands[36,37] are ascribed to

the electroactive β phase of P(VDF-TrFE). The negligible vibration band at 766 cm-1 is attributed

to the non-polar α phase. Comparison of four profiles reveals almost identical spectra in P(VDF-

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TrFE) and P(VDF-TrFE)/BNNTs nanocomposite films. Hence, the results indicate that the

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addition of BNNTs and external electric poling have insignificant effect on internal structure of

P(VDF-TrFE) polymer within the measurement limit of FTIR. Assuming FTIR absorption

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following the Lambert-Beer law, the relative fraction of the β phase can be calculated by using

the following equation:[38]

F (β ) =
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(1)
( K β / Kα ) Aα + Aβ

where F(β) represents β phase content, Aα and Aβ are the absorbances at respective wavenumbers
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of 766 and 840 cm−1, and Kα and Kβ are the absorption coefficients at corresponding
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wavenumbers of 6.1 × 104 and 7.7 × 104 cm2·mol−1. The FTIR results reveal the maximum
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content of 80% β phase content is achieved at 0.3 wt% BNNTs loading in the composite prepared

with 10 MV·m−1 electric poling. By comparison, the lowest β phase fraction of 78% is recorded
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for pure P(VDF-TrFE) film prepared without any treatment. It should be noted that F(β) is

estimated to be 79% for both unpoled P(VDF-TrFE)/BNNTs and poled P(VDF-TrFE) polymer
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films. The fraction of β phases in four specimens do not show apparent differences, suggesting
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that BNNTs and electric poling process do not induce any apparent influence on the content of β

phase in P(VDF-TrFE). These results are not surprising due to the TrFE monomer unit favoring

the all-trans conformation and inducing high-content ferroelectric β phases in P(VDF-TrFE).[39]

In addition, XRD was also empolyed to confirm the crystalline phases of pure P(VDF-TrFE) and

its nanocomposite film. In Figure 3(b), a characteristic peak is observed at 19.91° in both spectra,

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resulting from the overlapped (110) and (200) reflection of β crystalline plane.[15]. Meanwhile, a

new peak around 26.8° is found to appear in the P(VDF-TrFE)/BNNTs nanocomposite film,

which is assigned to single and dominant h-BN (002) phase.[40] These data demonstrate

coexistence of β phase and BNNTs in the nanocomposite film. The intensities and shapes of the

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crystalline peak at 19.91° looked comparable, indicating that addition of BNNTs has little impact

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on crystallographic orientation of polymer chain structures in P(VDF-TrFE). These results agree

with those of FTIR, suggesting possible enhancement in nanocomposite piezoelectric properties

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due to changes in crystalline structure are negligible.

To better assess the role of BNNTs in P(VDF-TrFE) polymer, preliminary piezoelectric

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performances of flat P(VDF-TrFE)/BNNTs nanocomposite film were evaluated under
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periodically vertical mechanical stress using an electromechanical vibrator. In Figure 4(a), the

output voltage of P(VDF-TrFE)/0.3 wt% BNNTs based PENG was recorded as 2.6 V under
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cyclic pressing and releasing processes with the maximum vertical stress of about 0.2 MPa at 2
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Hz frequency and 0.166 s pulse width. To confirm generation of the output voltages from PENGs
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through piezoelectric phenomenon instead of triboelectric contribution, polarity switching tests

were carried out and the results are gathered in Figure 4(a-b). It is clearly seen that the amplitude
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of the output voltage is estimated to 4.9 V, with positive value of 2.6 V when the PENG is

connected in the forward connection (Figure 4(a)). After reversing the connection, the peak to
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peak voltage remains constant with negative value of -2.6 V (Figure 4(b)). In addition, the
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sequence of curve rising and falling looks totally reversed between the two kinds of connections.

The obvious reversible signals confirmed entirely piezoelectric signals issued from the

nanogenerator. Meanwhile, the performance of the PENG based on un-poled nanocomposite was

tested by the same procedure as the poled PENGs. No obvious values for the open circuit voltage

and short circuit current under periodic mechanical impact were observed, as shown in Figure S3,
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which further renounced the existence of triboelectric and electrostatic effects contribution to

output signals in the PENGs structure. The influence of BNNTs concentration on output

performances of PENGs was investigated by preparing several nanogenerators based on

nanocomposite films with various mass fractions of BNNTs. Figure 4(c-d) show the output

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voltage of PENGs based on different BNNTs concentrations ranging from 0 to 0.5 wt%. The

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output voltages initially rise from 1.0 to 2.6 V as the amount of BNNTs increases from 0 to 0.3

wt%. Afterward, the output voltages gradually decrease from 2.6 to 1.7 V as concentration

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further increase from 0.3 to 0.5 wt%. The piezoelectric voltage generated from PENG prepared

with the nanocomposite containing 0.3 wt% BNNTs is nearly 2.6-fold higher than that of the neat

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P(VDF-TrFE)-based nanogenerator. The reasons for this could be linked to several factors. First,
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Incorporation of BNNTs, acting as reinforcements, can enhance the elastic modulus of

composite.[41,42] The stiff P(VDF-TrFE)/BNNTs nanocomposite can effectively reinforce the

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stress applied to BNNTs, leading to increased local deformations within the nanocomposite film
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via strong interfacial interaction when it is subjected to the load[28], resulting in larger
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piezoelectric potential. Second, BNNTs might act as the center of field concentration to enhance

the alignment of P(VDF-TrFE) dipole with aid of external electric field. Third, BNNTs possess
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higher piezoelectric coefficients than PVDF and their copolymer,[32] hence an increase in

BNNTs will effectively provide more piezoelectric polarization and lead to generation of higher
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voltage outputs. Forth, excessive amount of BNNTs would lead to aggregations of BNNTs owing
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to poor solubility.[35] This would increase size and relative permittivity and decrease field

concentration effect, confining movements of P(VDF-TrFE) dipole[43] and eventually

weakening the electromechanical coupling effect and polarizability of piezoelectric

nanocomposite film. To evaluate the piezoelectric properties of nanocomposite films, the

polarization vs. electric field hysteresis loops for P(VDF-TrFE)/ BNNTs composite films from 0
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to 0.5 wt% of BNNTs concentration were recorded and the data are shown in Figure 4(e). The

remnant and maximum polarization values look substantially different. The values increase with

increasing the concentration of BNNTs up to 0.3 wt% and decrease with a larger nanofiller

concentration in the range of 0.3 to 0.5 wt%. Compared to the pure P(VDF-TrFE) film,

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introduction of 0.3 wt% BNNTs into the P(VDF-TrFE) polymer matrix increase remnant

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polarization from 5.7 to 7 µC/cm2 and maximum polarization from 8.6 to 11.2 µC/cm2, which

clearly reveals that BNNTs dramatically improve the ferroelectric properties. This data agrees

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with the performances of the PENGs based on different BNNTs concentrations shown in Figure

4(c-d). Furthermore, piezoresponse force microscopy (PFM) was also used to confirm the

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promotion of piezoelectric properties in the presence of BNNTs as composite materials. Figure
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4(f) shows the PFM results of amplitude for the P(VDF-TrFE) film and nanocomposite film

prepared with BNNTs concentration of 0.3 wt%. The piezoresponse amplitude loops issued from
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applied voltages appear as butterfly-shaped hysteresis curves, corresponding to strain-electric

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field (S-E) behavior of piezoelectric materials, which is related to local piezoelectric

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coefficient.[44] It is worth noting that the amplitudes are not directly comparable to the ones

measured by piezoelectric strain measurement, but they are indicative of enhanced properties due
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to the presence of BNNTs. The amplitude obtained with the nanocomposite is almost twice as

high as that of pristine P(VDF-TrFE) film, indicating that BNNTs could rapidly enhance
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piezoelectric properties. Therefore, 0.3 wt% BNNTs is the optimal concentration for the highest
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piezoresponse P(VDF-TrFE)/BNNTs nanocomposite films and thus was used in subsequent

experiments to investigate the performances of P(VDF-TrFE)/BNNTs nanocomposite-based

PENGs.

As a PENG aims to harvest irregular mechanical energy and may experience thermal

fluctuation in space environment, it is essential to study the effects of frequency and temperature
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on the piezoelectric outputs of the microstructured nanocomposite-based PENG with 0.3 wt%

BNNTs. The output signal generated from the PENG was fully characterized under cycling

frequencies ranging from 1 Hz to 50 Hz. As shown in Figure S4(a), the output voltage slightly

increases with increasing of frequency from 1 to 10 Hz. The results can be explained by the fact

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that impedance decreases with the increase of strain rate.[2] In addition, it is noted that the output

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responses slowly decreases in the frequency range of 10 - 50 Hz, which can possibly be ascribed

to the high strain rate and relatively slow recovery of piezoelectric charge polarization at high

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frequencies.[45] On the other hand, the dependence of PENG’s output on various temperatures

ranging from 0 to 80 °C were investigated. The responses of PENG at different temperatures are

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shown in Figure S4(b). The results show the output voltage slightly decreases with an increase of
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temperature and the PENG performs with a relatively high output at elevated temperatures. The

voltage response of PENG was not studied above 90 °C because the Curie temperature of PVDF
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is in the region of 100 °C. These aforementioned experiments show the feasibility of PENG for
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harvesting energy from human motions at low frequency and ambient harsh environments.
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The comprehensive performance analysis of the PENG based on a poled microstructured

nanocomposite film was carried out, and open circuit voltage and short circuit current were
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measured under cyclic compression forces up to 40 N and a frequency of 2 Hz with an effective

size of 1 cm2. As shown in Figure 5 (a-b), the maximum voltage and current outputs reach 22 V
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with peak to peak voltage of 40 V and current of 640 nA. The inset figures show the enlarged
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views of voltage and current output signals, exhibiting one positive and negative voltage peak

corresponding to vibrator compressing and releasing process during one cycle. Figure 5(c)

depicts the dependence of piezoelectric voltage on applied compressing forces of four different

piezoelectric generators based on bulk P(VDF-TrFE) film, bulk P(VDF-TrFE)/BNNTs

nanocomposite film, P(VDF-TrFE) micropillar array and P(VDF-TrFE)/BNNTs nanocomposite

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micropillar array, respectively. The piezoelectric potential generated by all four PENGs increases

linearly with the applied force increasing, which is due to higher compressive forces resulting in

larger deformations on piezoelectric materials, eventually leading to an enhanced electric

potential in PENGs. The P(VDF-TrFE)/BNNTs micropillar array-based PENG demonstrates the

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greatest voltage output under the same working conditions when compared to the other three

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PENGs. At a compressing load of 20 N corresponding to mechanical stress of about 0.2 MPa

(Figure 5(d)), the maximum voltage output from pristine P(VDF-TrFE) film, bulk P(VDF-

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TrFE)/BNNTs nanocomposite film, P(VDF-TrFE) micropillar array and P(VDF-TrFE)/BNNTs

nanocomposite micropillar array were recorded as 1 V, 2.6 V, 4.2 V and 11 V, respectively.

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These results demonstrate that a PENG based on the P(VDF-TrFE) micropillar array greatly
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enhance the piezoelectric performance by a factor of 4.2 compared to pristine flat P(VDF-TrFE)

film. By comparison, the introduction of BNNTs within the microstructured P(VDF-TrFE) film
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adds nearly another 2.6-fold enhancement, totaling to a 11-fold enhancement. The high
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performances of PENGs based on P(VDF-TrFE)/BNNTs nanocomposite micropillar array are

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primarily ascribed to the synergistic effect due to flexible micropillar structure and high

piezoelectric BNNTs nanofiller. The mechanical stress induced piezoelectric potential output can
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be expressed by[17]

d33
V= E ⋅ε ⋅ L
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(2)
εr
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where d33 and εr represent the piezoelectric coefficient and relative permittivity, E is Young's

modulus, ε is strain along the vertical direction, and L is thickness of the film.

In Equation (2), the output voltage is proportional to d33, Young’s modulus and mechanical

strain (deformation) and inversely proportional to permittivity. The addition of nanofiller

BNNTs can improve the piezoelectric coefficients of composites. Our measurements estimate d33

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of P(VDF-TrFE)/BNNTs nanocomposite film as 14 pC/N, which is 4 times larger than that of

pristine P(VDF-TrFE) film (~ 3.5 pC/N). However, it is noteworthy to mention that the obtained

d33 value is lower than that of neat PVDF fibers (~ 22 pC/N)[22], which may be ascribed to the

moderate electric poling voltage. In addition, it is noted that BNNTs might be aligned along its

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axial direction due to shear force induced by filling of the molten polymer flow into PDMS mold

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cavities during the micropillar formation process[46], which is schematically demonstrated in

Figure S5(a). The degree of alignment of BNNTs was estimated using SEM. As shown in Figure

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S5(b, c). The streamlines of composite shear flow in the cross section of nanocomposite

micropillar are obviously captured in SEM view, and some nanotubes might be roughly aligned

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with flow direction. For comparison, a pristine P(VDF-TrFE) micropillar was also fabricated. As
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shown in Figure S5(d), no remarkable streamlines are observed in the cross-sectional view of

micropillar. The alignment of BNNTs might enhance the piezoelectric output either because of
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zigzag BNNTs exhibiting strong longitudinal piezoelectric response in uniaxial strain extension
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or compression.[31] Besides, the existence of micropillar array structures in nanocomposite

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fabricated by the nanoimprint technique would lower the elastic modulus of PENGs. However,

these micropatterns could generate larger mechanical strain/deformation than in flat bulk film
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under the same compressive load, hence increasing the piezoelectric potential. To verify this

point, the displacement and piezoelectric potentials generated inside a nanogenerator were
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calculated by finite element methods of COMSOL simulation. The simulation model for a flat
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bulk film consist of P(VDF-TrFE) layer with a thickness of 60 µm while the model for a

micropillar array-based nanogenerator is composed of micropillars with a diameter of 80 µm and

height of 120 µm. Figure 5 (e-f) shows the displacement of bulk films and nanocomposite

micropillar array under the same stress of about 0.2 MPa. Due to geometrical strain confinement

effect along the axial direction of nanocomposite micropillar, the maximum displacement of the
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microstructured nanocomposite was recorded around 80 nm, which is nearly 4.4-fold larger than

that of the flat bulk film. According to Equation (2), larger displacement/strain would lead to

higher piezoelectric voltages, which can be confirmed by simulations shown in Figure 5(g-h).

The piezoelectric potential shows an average value of 6 V for the flat bulk film while reaching up

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to 35 V for the nanocomposite micropillar array. The simulations demonstrate that the electric

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potential of microstructure have an obvious enhancement due to higher strain producing larger

piezoelectric signals, which are consistent with the experimental observations.

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The nanocomposite micropillar array-based PENG exhibits excellent output performance. At

this point, it is essential to explore how PENGs could actualize in suitable real-world applications.

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In practice, the utilization of electric power depends on the external load. Figure 6(a) illustrates
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dependence of output voltages of microstructured nanocomposite film-based PENG on various

resistances from 1 MΩ to 20 MΩ under a cyclic compressing force of 40 N (pressure 0.4 MPa). It

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is clearly observed that the output voltage gradually increases with the increase of load
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resistances. Meanwhile, the power density of the device can be calculated by the formula: P =
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U2/(RA), where U, R and A represent the output voltage, external load resistance and effective

area, respectively. The maximum value of power density reaches 11.3 mW·cm-2 at a load
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resistance of 6 MΩ (Figure 6(b)). The output performances of the employed PENG are compared

with other hybrid composite-based PENGs and the results are listed in Table 1. It is worthy noted
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that the performances of nanogenerator are strongly influenced by several factors, including the
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piezoelectric coefficients of polymer matrix materials and nanofillers, filler concentration,

external applied stress, and intensity of electric field used for poling. The parameter employed for

evaluating the piezoelectric performance is known as sensitivity: S= U/σ, where U and σ are the

output voltage and applied mechanical stress, respectively. The PENG based on microstructured

P(VDF-TrFE)/ BNNTs composite shows sensitivity up to 55 V/MPa under a compressive load of

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 ACCEPTED MANUSCRIPT

40 N and frequency of 2 Hz, which is superior to recently reported values of other piezoelectric

nanogenerators made of different composites and microstructures, including BaTiO3/PVDF (35

V/MPa)[47], GO/PVDF (13.4 V/MPa)[48], and Pt/PVDF nanofiber (13.8 V/MPa) [22]. However,

Kim et al reported a triboelectric nanogenerator (TNG) made of BaTiO3/PVDF with extremely

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high sensitivity (17385 V/MPa).[49] Clearly, the performance of our PENG is much lower than

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that of the TNG, the reason of which is the different mechanism between PENG and TNG.

Additionally, the physical properties of fillers, like the permittivity, may provide the different

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contributions to the performances of the nanocomposites. Therefore, the proposed PENG is

suitable for harvesting energy from minor human movements and even promising for various

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sensing applications with outstanding sensitivity.
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The stability and durability tests were performed under a 2 Hz cyclic pressing and releasing

force with a force of 40 N for a period of two weeks. In Figure S6, the output voltage around 22
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V appear to have no obvious fluctuations upon compression and release for 7200 cycles in 1 h,
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indicating the PENG has the capability of long-term working. The inset enlarged views clearly
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demonstrate the positive and negative peaks corresponding to compression and release processes

of applied force. In addition, the reproducibility of the PENG was again examined for another
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7200 cycles in the second week under the same conditions. The results show stable output

voltage without any apparent degradation when compared to previous measurements. These
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outstanding performances can be contributed to the design and fabrication of microstructured

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nanocomposite-based PENG. The excellent stability and durability of PENGs without apparent

drop in output voltage confirmed their capabilities as stable and robust energy harvesters.

For practical applications of PENG, the electricity generated from PENG has been stored by a

capacitor for lighting up light-emitting diodes (LEDs). Figure 7(a) displays the schematic circuit

diagram for rectifying, charging capacitors and lighting electronic devices, aiming to convert the
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alternating voltage outputs to direct outputs. In Figure 7(b), rectified voltage outputs reaching 16

V were obtained in energy storage devices, such as capacitors and batteries. Figure 7(c) shows

the voltage-charging time relationship of a 4.7 µF capacitor. Under repeated compressive impacts

of 400 s at 2 Hz frequency, the voltage could be charged to about 2.5 V. The inset shows that the

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red (R), yellow(Y) and green (G) LEDs aligned in series have been successfully lighted up by

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power generated from three 4.7 µF capacitors in series, which were charged by the piezoelectric

nanogenerator. After charging by the PENG, the voltage of the three capacitors reached around 6

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V, which is higher than the turn-on voltage of RYG LED arrays (about 5.7 V) with rated current

of 20 mA. Besides, to demonstrate the PENG as ideal device for harvesting biomechanical

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energy in daily life, the nanogenerator has been used to scavenge different types of body
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movements, such as foot stepping, palm bending, finger taping, and elbow bending as ideal

biomechanical energy sources in space for self-powered devices. Figure 7(d-g) shows the
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piezoelectric voltage generated by the PENG due to different biomechanical motions. As can be
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seen, foot stepping by heel generated output voltages (~100 V) much larger than other conditions
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(palm bending (4.2V), elbow bending (4.5 V) and finger taping (15 V)), which may be ascribed

to significant deformations in PENG induced by human weight. These results prove that the
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power can be generated through different human movements. To visually display a distinct self-

powered system, the foot stepping movement has been analyzed. It is shown in Figure 7(h, i),
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under the continuous foot stepping on the PENG, an LCD screen can be directly lighted up
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without external circuits from the power generated by PENG. Besides, the capacitor can be

quickly charged to drive a digital watch, which shows the self-powered system can be achieved

through foot striking. Hence, PENG devices can be demonstrated as flexible energy harvesters

for scavenging biomechanical energy with great potential in powering portable and smart

electronic devices.
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In addition to all of the above piezoelectric properties, space exploration requires PENGs with

large piezoelectric characteristics and excellent radiation shielding capabilities. Here, the neutron

shielding capability of a BNNTs-based composite has been investigated using neutron activation

analysis and test equipment is presented in Figure 8(a). A cylindrical barrel made of polymethyl

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methacrylate with 60 cm in height, 60 cm in diameter and having a 1 cm wall thickness is filled

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252
with 5 wt% boric acid and used to contain and shield 2.8 µg Cf source. The distance of the

neutron source from the center of the barrel was 12 cm. A polyethylene block with thickness of 4

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cm was placed in front of the 252Cf neutron source to moderate neutrons. The neutron source was

collimated by using a borated polyethylene block with dimensions of 10×10×2 cm3. The

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collimator was then squared with an area of 1×1 cm2, and indium foils (1.5×2×0.3 cm3) covered
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by the materials were used to obtain neutron fluxes. The irradiation time was set to 120 min to

capture two half-lives (T1/2= 54 min) with an additional 1 min cooling time. The foils were
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measured with a High-purity Germanium (HPGe) detector, performed in lead chamber. The foils
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were located at the surface of detector for 20 min. Here, the count rate of delayed gamma-ray
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with energy of 0.417 MeV was utilized to evaluate the shielding performances (Figure 8(b)), and

delayed gamma-ray spectrum of indium is shown in Figure S7.

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The results indicate that the counts are related to the BNNTs mass and have nothing to do with

the microstructures of specimens. In this experiment, pure P(VDF-TrFE) film is considered with
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no shielding effect and poor absorbance of neutrons, and the neutron shielding rate of BNNTs
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based composite film according to counts change was recorded as 9% (Figure 8(c)). The

significant enhancement of neutron shielding is due to the addition of 0.3 wt% BNNTs. The

theoretical linear macroscopic thermal neutron cross sections Σ (cm-1) of compound consisting of

i elements can be calculated by:[54]

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ρ Nav
Σ = ∑i fiσ ai (3)
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where ρ (g·cm-3) is density, Nav is Avogadro’s number, M (g·mol-1) is the Molar mass, fi is

number of i element, and σai (cm2) is the microscopic absorption thermal neutron cross section of

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i element. The microscopic absorption cross sections σa of interesting elements of P(VDF-TrFE)

and BNNTs are listed in Table S1.[55] It is noted that both boron and nitrogen in the BNNTs are

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received in their natural isotopic ratios. The neutron cross section of pristine P(VDF-TrFE)

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calculated according to Equation (3) is estimated to 0.008 cm-1. For comparison, the P(VDF-

TrFE)/0.3 wt% BNNTs composite has a neutron cross section of 0.029 cm-1, resulting mostly

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from neutron capture by boron and to a smaller extent, nitrogen. Hence, the macroscopic
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absorption cross-section is approximately enhanced by 260% in the presence of 0.3 wt% BNNTs

when compared to pristine P(VDF-TrFE). In this work, the masses of BNNTs and boron atoms
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within flat bulk film and mictrostructured composite films are identical, and thermal neutrons are
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mainly absorbed by boron atoms, which result in the macroscopic absorption cross sections and

the performance of neutron absorption of these two materials were nearly same. To investigate
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the influence of neutron radiation on piezoelectric performance of P(VDF-TrFE)/BNNTs

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composite film-based PENG, output voltages before and after 2 h thermal neutron radiation were

performed and the results are gathered in Figure 8(d). The voltages of about 11 V generated
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under 20 N applied force remain nearly unchanged, indicating the PENG has a good neutron
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shielding properties without degrading piezoelectric performances. Hence, this flexible, thin,

easily processable composite film based PENGs with very low BNNTs content can pave the way

for achieving extraordinary neutron shielding.

3. Conclusion

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In summary, we have demonstrated a high-performance nanogenerator based on P(VDF-

TrFE)/boron nitride nanotubes (BNNTs) nanocomposite micropillar arrays for space exploration.

The addition of BNNTs and micropatterning of P(VDF-TrFE)/BNNTs composite film greatly

enhance the output voltage of PENG. The maximum output voltage, power density and

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sensitivity of microstructured P(VDF-TrFE)/BNNTs composite based piezoelectric device reach

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up to 22 V, 11.3 µW·cm-2 and 55 V/MPa with an optimized ratio of 0.3 wt%, which are 11-fold

higher than those of pristine P(VDF-TrFE) film. The dramatically enhanced performances of

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PENG are ascribed to the synergistic contribution of strong piezoelectric BNNTs and the strain

confinement effect of the composite micropillar array structure. In addition, the obtained PENG

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based on BNNTs (0.3 wt%) is shown to be a reliable power generator by harvesting energy from
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mechanical and biomechanical movements to light up commercial LEDs, an LCD screen and a

digital watch. Furthermore, PENG was found to exhibit 9% neutron radiation shielding capability
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with effectiveness increase by about 260% when compared to neat P(VDF-TrFE) film. The high
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performances and radiation shielding properties of PENG make it promising candidate for
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scavenging energy under the harsh space environment.

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4. Experimental Section

4.1 Materials
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P(VDF-TrFE) powder with a molar ratio of 70:30 was obtained from Kunshan Hisense
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Electronics Co., Ltd (China). The BNNTs employed in this study, which were purchased from

BNNT LLC, were synthesized using High-Temperature Pressure (HTP) methods and were

originally in dry and cotton-like fibrils. N, N-Dimethylacetamide (DMAc, analytical grade) was

purchased from Tansoole. All chemicals were used as received without further purification.

4.2 Fabrication of P(VDF-TrFE)/BNNTs composite film

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First, 1 g P(VDF-TrFE) powder was dispersed in 10 ml DMAc under constant stirring for 1 h

in a water bath at 60 oC to obtain uniform solution. Afterward, 0 ~ 5 mg BNNTs (0 ~ 0.5 wt%,

with respect to P(VDF-TrFE)) were added to the mixture and stirred at room temperature for 72 h

and subsequent 1 h of sonicating the stirred sample to yield homogeneous solution. The as-

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prepared solution was then dropped onto a clean Si substrate and dried at 60 oC for 12 h to

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evaporate residual solvent and obtain uniform and flat piezoelectric nanocomposite film. Finally,

the film was peeled off from the substrate and cut into proper size of 1x1 cm2.

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4.3 Fabrication of PENGs

To fabricate the nanogenerator, thin Cr/Au film was evaporated onto backside of the prepared

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composite film as bottom electrode. A predefined PDMS mold with microporous structure was
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then pressed against the film under 0.1 MPa pressure followed by annealing at 180 oC above

melting temperature of P(VDF-TrFE) for 1 h to yield high crystallinity. After de-molding, a

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P(VDF-TrFE)/BNNTs composite micropillar array was generated, and PDMS was spin-coated at
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1500 rpm for 60 s to form an insulating layer. Finally, the Ag nanowires suspension was dropped
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on top of micropillar as top electrode to form sandwich-like PENGs.

4.4 Characterization
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The performances of PENGs were evaluated by an experimental set up consisting of

electromechanical vibrator, function generator, and oscilloscope. The open circuit voltage was
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recorded by a Tektronix DPO 3034 oscilloscope with a 100 MΩ probe, and the short-circuit
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current was measured by using a low-noise current preamplifier (Model No. SR570, Stanford

Research Systems, Inc.). An amplifier/controller (TREK 610E H.V.) was used to ensure electric

poling process. The morphological analyses were performed by scanning electron microscopy

(SEM, HITACHI SU8010) operated with an acceleration voltage of 5 KV. The high-resolution

transmission electron microscopy (HRTEM) images of BNNTs were obtained by JEM 2100F
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TEM (JEOL Ltd) at accelerating voltage of 120 - 200 kV. The Raman spectrum was obtained by

Renishaw InVia Confocal Raman microscope at 532 nm wavelength excitation laser and nominal

power of 50 mW. The crystallographic properties of P(VDF-TrFE) and BNNTs were analyzed by

X-ray diffraction (D8 ADVANCE A25) with Cu Kα-radiation (λ = 1.5418 Å) and 2θ range of 15

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to 35°. Fourier transform infrared absorption spectroscopy (Bruker VERTEX 70) was employed

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to investigate polymorph composition of piezoelectric nanocomposite materials with 2 cm-1

spectral resolution and wavenumber ranging from 600 to 1500 cm-1. A laser scanning confocal

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microscope (LSCM, Olympus OLS4000) was used to obtain the cross section and three-

dimensional topographies of nanocomposite structures. The polarization hysteresis loops (P-E

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loops) were measured by ferroelectric test system (Premier 2-10v) at applied triangular pulses
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from -200 to 200 MV/m. The Piezoresponse force microscopy (PFM) measurements were carried

out by atomic force microscopy (Cypher AFM). The amplitude hysteresis loops were collected
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by sweeping at DC bias from -25 V to 25 V. The performances of neutron shielding of the

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materials were evaluated by a setup located at the Institute of Nuclear Analysis Techniques,
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Nanjing University of Aeronautics and Astronautics[56]. The neutron shielding measurements

were carried out by neutron activation analysis. 252Cf was used as source of neutrons for exposing
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BNNTs contained nanocomposite film. The BNNTs shielded the thermal neutron according to

the reaction:
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0n + 5B
1 10
→ 115 B → 37 Li + 24 He + γ
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The BNNTs based nanocomposite was placed between the neutrons source and indium foil. The

indium was then activated according to the reaction:

0n +
1 115
In → 116 In + γ

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The delayed gamma-ray counts emitted by indium were measured for calculating the shielding

effectiveness of P(VDF-TrFE)/BNNTs nanocomposite film. The count of indium foil activity

was measured by High-purity Germanium HPGe detector (ORTEC: GMX30P4-70).

Multichannel analyzer (ORTEC: DSPEC-50) and related MASTERO software were used to

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collect and analyze the spectra. The number of delayed gamma-ray counts C in the detector

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resulting from In foil activity is given by:[57]

C = φ kσ NT (1 − e−λT0 )e−λT1 (1 − e−λT2 ) (4)

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whereφ (cm-2·s-1) is the neutron flux at location of the foil, k is a proportionality constant

(detection efficiency, emission probability of identifying gamma-ray, etc.), σ (cm2) is the cross-
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U (s-1) is decay time constant, and T0, T1

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section, NT is total number of In atoms in the target,

and T2 (s) are respectively irradiation time, cooling time and measuring time.
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Acknowledgements
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This work was funded by the national natural science foundation of China (NSFC) (Grant
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Numbers: 51705411, U1737106, 51303148) through the State Key Laboratory for Manufacturing

Systems Engineering at Xi’an Jiaotong University.

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Figure 1: (a-e) Experimental processes used for fabrication of piezoelectric nanogenerator based
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on P(VDF-TrFE)/BNNTs nanocomposite micropillar array. (f) A schematic diagram represents

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the structure of piezoelectric nanogenerator. (g) Photograph of flexible nanogenerator. (h) A

schematic diagram of the PENG’s application for space energy harvesting.

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Figure 2: (a) SEM image of as-synthesized raw BNNTs material. (b) Representative HRTEM

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image of multi-walled BNNTs (The inset is Raman spectrum pattern of the BNNTs). (c) HRTEM
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image of P(VDF-TrFE) /BNNTs nanocomposite film with several well-dispersed protruding
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nanotubes. (d) SEM image of nanocomposite micropillar array. (e) SEM image of micropillar

array after coating PDMS. The inset shows the enlarged view of micropillars surrounded by
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PDMS. (f) SEM image of the top electrode comprising Ag nanowires. The inset shows the
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magnified view of Ag nanowires.

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Figure 3: (a) FTIR spectra of: (i) unpoled P(VDF-TrFE) film, (ii) unpoled P(VDF-TrFE)/BNNTs

nanocomposite film, (iii) poled P(VDF-TrFE) film, and (iv) poled P(VDF-TrFE)/BNNTs

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nanocomposite film. (b) XRD spectra of P(VDF-TrFE) and P(VDF-TrFE)/BNNTs
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nanocomposite film.
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Figure 4: (a, b) Output voltage of nanocomposite film based nanogenerator containing 0.3 wt%
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BNNTs in the forward and reverse connection. (c, d) Output voltage of P(VDF-TrFE)/BNNTs
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nanocomposite film based nanogenerator with different BNNTs concentrations. (e) The

polarization hysteresis loops (P-E loops) of P(VDF-TrFE)/ BNNTs composite films with BNNTs

concentration from 0 to 0.5 wt%. (f) The PFM amplitude hysteresis loops of pristine P(VDF-

TrFE) film and P(VDF-TrFE)/ 0.3 wt % BNNTs nanocomposite film.

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Figure 5: (a, b) Output voltage and current of microstructured nanocomposite micropillar array

based PENGs under continuous compressive load of 40 N. (c) The dependence of output voltage

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on applied forces for different piezoelectric nanogenerator based on bulk P(VDF-TrFE) film,

bulk P(VDF-TrFE)/BNNTs nanocomposite film, P(VDF-TrFE) micropillar array, and P(VDF-

TrFE)/BNNTs nanocomposite micropillar array. (d) Comparison of output voltages of four

nanogenerators under 20 N applied force. Simulated displacement (e, f) and piezoelectric

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potential (g, h) distribution of flat film and micropillar array.

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Figure 6: The dependence of output voltages (a) and power densities (b) generated from

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microstructured nanocomposite film-based PENGs on various external resistances.

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Figure 7: (a) A schematic circuit diagram of rectifying, charging capacitors, and lighting
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electronic devices. (b) Rectified voltage under continuous compression. (c) Voltage-charging

time relationship of a 4.7 µF capacitor using the PENG under continuous compression force at
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frequency of 2 Hz. The Inset shows three LED bulbs lighted up by power source generated from
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PENG. (d-g) Output voltage generated from flexible PENGs subjected to different working

conditions: (d) palm bending, (e) elbow bending, (f) finger tapping, and (g) foot stepping. The

inset shows respective photographs. (h) An LCD screen directly lighted by PENG under foot

stepping without external circuits. (i) A digital watch driven by a capacitor charging from PENG

through human foot stepping.

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Figure 8: (a) Schematic diagram presenting the experimental setup used for detection of neutron
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absorption. (b) Counts of 0.417 MeV γ energy spectrum of three activated Indium foils with

shield of bulk P(VDF-TrFE) film, flat bulk P(VDF-TrFE) film containing 0.3 wt% BNNTs, and
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P(VDF-TrFE) nanocomposite micropillar array containing 0.3 wt% BNNTs after 2 h neutron

radiation. (c) Macroscopic thermal neutron cross sections and neutron shielding rates of pristine
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film and nanocomposite film. (d) Comparison of output voltages generated by P(VDF-TrFE)/ 0.3
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wt% BNNTs nanocomposite micropillar array-based PENG before and after neutron radiation.

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Table 1. Performance comparison of different nanocomposites-based PENGs

Composite Filler’s Applied Electric field Output voltage Power Sensitivity Refs
materials concentration stress for poling and current Density
BaTiO3/PVDF 70 wt% 1 MPa 2 KV for 8 h 35 V/600 nA None 35 V/MPa [47]

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GO /PVDF Unknown 0.32 MPa 30 MV/m at 105 °C 4.3 V/1.88 µA 7.52 µW·cm-2 13.4 V/MPa [48]
Gr-BT/PVDF 0.15 wt% Gr, Bending None 11 V 0.656 µW·cm-2 None [15]

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15 wt% BT
BaTiO3/PVDF 20 wt% 0.5 MPa 20 MV/m 13.2 V/330 nA 12.7 µW·cm-2 26.4 V/MPa [50]

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Ce3+-doped 7.7 wt% Finger tapping None 11 V/6 nA 0.58 µW·cm-2 None [51]
Gr/PVDF
BaTi2O5/PVDF 5 vol% Vibration 20 MV/m at 80°C 35 V 27.4 µW·cm-3 None [52]

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Pt/PVDF 12.5 wt% 2.17 MPa 150 KV/m 30 V 22 µW·cm−2 13.8 V/MPa [22]
2.4 µW·cm-3

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PZT/PDMS 50 wt% Bending 15 kV at 150°C 8 V/175 nA None [53]
BNNTs/PVDF 0.3 wt% 0.4 MPa 10 MV/m at 90 °C 22 V/640 nA 11.3 µW·cm-2 55 V/MPa This work

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Shibo Ye received his bachelor degree from Xi’an Jiaotong University in 2017. Now he is a
master candidate in Xi’an Jiaotong University. His research interests include nanocomposite
material, piezoelectric devices based on micro and nano-fabrication and their applications in self-

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powered sensor and energy harvesting.

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Can Cheng is currently a Ph.D. student from College of Materials Science and Engineering,
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Nanjing University of Aeronautics and Astronautics. He received his Master degree from Nanjing
University of Aeronautics and Astronautics (2016). His research interests include prompt
gamma-ray activation imaging and Monte Carlo simulation.
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Xiaoming Chen received the Ph.D. degree from State University of New York at Binghamton,
Binghamton, USA, in 2014. He is currently a Professor at the State Key Laboratory for
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Manufacturing Systems Engineering, Xi’an Jiaotong University. His research interests at

microscale 3D printing technique and structural multifunctional nanocomposites for energy and
electronics applications.
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Xiaoliang Chen was born in Jiangxi Province, China, in 1989. He received the Ph.D. degree
from Xi’an Jiaotong University, Xi’an, China, in 2018. He is currently an assistant professor at
the State Key Laboratory for Manufacturing Systems Engineering, Xi’an Jiaotong University. His
research work is focused on renewable energy harvesting and piezoelectric flexible sensors.

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Jinyou Shao received the Ph.D. degree from Xi’an Jiaotong University, Xi’an, China, in 2009.
He is currently a Professor at the State Key Laboratory for Manufacturing Systems Engineering,
Xi’an Jiaotong University. His research interests include micro/nanomanufacturing techniques,

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flexible electronics and systems, nanosensors and devices. Prof. Shao received the First Prize
Technology Invention Award of the Ministry of Education of China in 2015. He is awarded
Changjiang Scholars –Young Category, NSFC Fund for Excellent Young Scholars, New Century

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Excellent Talents by MoE of China, Shaanxi Young Talents in Science and Technology, ACS
Membership Award, etc.

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Jie Zhang received her Ph.D. degree from Technische Universitaet Dresden (TUD), German in
2012. Now she is an assistant professor at Electronic Materials Research Lab, Key Lab of the
Ministry of Education in Xi’an Jiaotong Univeristy (XJTU). Her scientific interests focus on
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design and application of the multifunctional nanocomposites.

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Hanwen Hu received his B.S. degree of mechanical engineering in Xi’an Jiaotong University
(Xi’an) in 2018. He is currently a master student of mechanical engineering in Duke University.
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His current research focuses on optimal controller design and stability analysis methods based on
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the evaluation of linear matrix inequalities (LMIs)。

Hongmiao Tian received the Ph.D. degree from Xi’an Jiaotong University, Xi’an, China, in
2014. He is currently an associate Professor at the State Key Laboratory for Manufacturing
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Systems Engineering, Xi’an Jiaotong University. He has authored/coauthored more than 40

research papers in international journal and conference proceedings and authorized 22 national
invention patents. His research interests at the flexible sensors and actuators.

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Xiangming Li received the Ph.D. degree from Xi’an Jiaotong University, Xi’an, China, in 2014.
Since 2014, he has been a Postdoctoral Researcher in instrument science and technology at Xi’an
Jiaotong University. He has published more than 40 peer-reviewed research papers. His research

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interests include energy storage materials and devices, flexible electronics and systems,
micro/nano manufacturing technologies, and nanosensors and devices. He received the silver
prize of HIWIN Doctoral Dissertation Award.

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Li Ma received her B.S.degree from Northwest Normal University in 2017. Now she is a
doctoral candidate in Xi’an Jiaotong University. Her research focuses on materials science and
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engineering, dielectric energy storage materials, shape-memory polymer and self-healing

materials.
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Wenbao Jia is now a Professor at Nanjing University of Aeronautics and Astronautics. He

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received his B.S. degree in Northwest Normal University (1989). He received his Master degree
(1992) and Ph.D. degree (1999) in Lanzhou University. His research interests are prompt gamma-
ray neutron activation analysis, radiation protection and Monte Carlo simulation.

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The highlights of the paper are as following:

(1) The high piezoelectric nanomaterial BNNTs were adopted into the highly crystallized
P(VDF-TrFE) polymer to improve the piezoelectricity of the nanocomposite materials, which
increased by 260% with only 0.3 wt% BNNTs loading.

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(2) The piezoelectric enhanced nanocomposite film was imprinted into vertically well aligned
nanocomposite micropillar array to further improve the piezoelectricity (11-fold enhancement)
and sensitivity (55 V/MPa). The performance is superior to reported values of other piezoelectric

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nanogenerators made of different composites and microstructures.

(3) The microarchitectured nanocomposite film-based PENG demonstrated excellent neutron

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shielding effectiveness with the help of BNNTs.

(4) The PENG demonstrated outstanding piezoelectric performance and superior radiation

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resistance, implying it is promising for high-efficiency biomechanical energy harvesting and
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effective protection of humans from neutron radiation under extreme space environments.
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