Nano Energy 115 (2023) 108697

Contents lists available at ScienceDirect

Nano Energy
journal homepage: www.elsevier.com/locate/nanoen

4D printed shape memory metamaterials with sensing capability derived

from the origami concept
Wei Zhao a, 1, Nan Li a, 1, Xu Liu a, Liwu Liu a, Chengbin Yue a, Chengjun Zeng a, Yanju Liu a, *,
Jinsong Leng b, *
a
Department of Astronautical Science and Mechanics, Harbin Institute of Technology (HIT), P.O. Box 301, No. 92 West Dazhi Street, Harbin 150001, People’s Republic
of China
b
Center for Composite Materials and Structures, Harbin Institute of Technology (HIT), P.O. Box 3011, No. 2 YiKuang Street, Harbin 150080, People’s Republic of China

A R T I C L E I N F O A B S T R A C T

Keywords: Mechanical metamaterials have unprecedented properties that contribute to the development of science and
4D printing technology. However, once the mechanical metamaterials are fabricated, the single configuration will limit their
Shape memory application, especially in areas requiring rich programmability and efficient shape reconfigurability, etc. To
Mechanical metamaterials
break through this limitation and explore more potential of mechanical metamaterials, this work proposes a
Programmable
novel design strategy for 4D printed metamaterials with programmable stiffness. Deriving from the origami
Energy harvesting
concept, the stiffness of the structure can be adjusted not only by changing the geometric parameters but also by
changing the geometric configuration utilizing the shape memory property. Through numerical simulation,
theoretical analysis and experimental tests, the design strategy is verified in the 4D printed mechanical meta­
materials. With this strategy, the stiffness of the structure can be adjusted, and the mechanical programmability,
shape reconfigurability and adaptability can be significantly improved. Utilizing excellent energy absorption
performance, we design and fabricate a kind of shoe sole. By integrating the sensor function of the Triboelectric
Nanogenerator (TENG) into the sole, gait monitoring is successfully realized. The 4D printed shape memory
metamaterials show extraordinary potential in the field of programmable shock absorption and intelligent
monitoring.

1. Introduction modular units, metamaterials with various mechanical properties can be

obtained, which can be freely selected and adjusted according to the
To achieve supernormal mechanical properties, it is usually to design requirements[23,24]. Origami, as an ancient art, has been deeply
specific artificial microstructural units in three-dimensional space, and involved in the field of science and engineering[5,24,25]. Origami
the resulting structure is generally called metamaterials [1–6]. Me­ structure is rich in forms, and many of them have metamaterial char­
chanical metamaterials can achieve many different supernormal prop­ acteristics, which can transform the folding principle of origami into a
erties, including lightweight and high strength, adjustable stiffness, complex three-dimensional structure design concept to realize various
negative compressibility, negative Poisson’s ratio and bistable [7–10]. functions [26–33].
The unusual properties are limited by their constituent materials but By introducing the origami concept, the construction and design of
mainly depend on their micro-structural units and spatial combinations, unit-cell can break through the limitations of a single form, and obtain
which can be designed according to the performance requirements more mechanical metamaterials with special properties [34–36]. By
[11–14]. The design idea of mechanical metamaterials opens up a new geometric design, the origami-derived stacked metamaterials can obtain
way for the research and development of new structures and shows great self-locking characteristics[28], adjustable stiffness[2], and quasi-zero
potential in sensors [15–17], energy absorption structures[18–20], and stiffness characteristics[28], which can be used in the field of shock
reconfigurable antennas[21,22], etc. energy dissipation. For a fold pattern, in addition to the manufacturing
Through periodic or aperiodic geometric optimization design of materials, the mechanical properties are mainly determined by the

* Corresponding authors.
E-mail addresses: [email protected] (Y. Liu), [email protected] (J. Leng).
1
These authors contributed equally

https://doi.org/10.1016/j.nanoen.2023.108697
Received 25 April 2023; Received in revised form 5 June 2023; Accepted 11 July 2023
Available online 13 July 2023
2211-2855/© 2023 Elsevier Ltd. All rights reserved.
W. Zhao et al. Nano Energy 115 (2023) 108697

geometric parameters, so the consistency of repeated elements results in TENG, it can be used as a sensing device or connected with other sensors
the single mechanical properties. However, there are certain circum­ to monitor gait. For example, Kim et al. [43] designed a kind of Covalent
stances in which structures with gradual stiffness and programmable Organic Frameworks-based TENG and integrated them into the
performance are more appropriate. For example, regarding the car body hand-strengthening device for exercise monitoring, showing excellent
design, the variable stiffness structure will gradually improve the results. Furthermore, Kim et al. [37] fabricated a multi-axis pressure
structural bearing capacity, to protect vehicle occupants from re-injury sensor with temperature compensation using additive manufacturing
due to extrusion. technology, which was integrated into shoes for human motion moni­
With the development of the Internet of Things technology, elec­ toring and force sensing, opening up a wide range of applications.
tromechanical systems have presented a broad application prospect in In this work, we design a series of origami-derived mechanical
the fields of human health, infrastructure and military environmental metamaterials with different topological parameters, which exhibit
monitoring. It has the development trend of integration, intelligent excellent mechanical properties. Further, by combining structures with
function and wireless mobility [37,38], so the energy supply is partic­ different topological parameters, structures with gradient stiffness are
ularly prominent. Using conventional batteries to power an entire obtained. We fabricate the mechanical metamaterials by 4D printing
network is expensive to maintain, difficult to recycle and polluting to the technology and shape memory polymer [44–47]. The 4D printed
environment. One possible alternative method is to capture the energy origami metamaterials can change their configuration and stiffness by
in the environment. Triboelectric Nanogenerator (TENG) [39–42] was utilizing the shape memory effect (SME), which is different from most
invented by Wang Zhonglin’s team in 2012. It is a nano energy tech­ origami-derived metamaterials. It breaks through the limitation that the
nology based on the coupling effect of mechanical interface tribo­ mechanical properties and geometrical configuration of metamaterials
electrification and electrostatic induction. When two materials with can not be changed once they are fabricated. On the basis of studying the
different abilities to gain and lose electrons come into contact, their energy absorption characteristics of the origami mechanical meta­
surfaces will generate equal amounts of positive and negative charges materials, we select one of the representative structures to explore its
due to friction. When the two materials are separated under the action of application in the sole. Furthermore, the metamaterial structure-based
load, the positive and negative electrostatic charges are separated in triboelectric nanogenerator (MS-TENG) [39–42] is fabricated to
space, and the induced potential difference is generated on the upper monitor gait and realize self-power and self-sensing.
and lower surface electrodes. When there is a short circuit between the
two electrodes or a load in an external circuit, the induced potential
difference will drive the flow of electrons between the two electrodes,
resulting in a current. Based on the self-powered performance of the

Fig. 1. Parameter definition and structural design of Miura-ori metamaterials (a) Geometric parameter definition of Miura-ori metamaterial (b) Assembly of Miura-
ori metamaterials (c) Parametric design of in-plane gradient metamaterials (d) Parametric design of out-of-plane gradient metamaterials.

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W. Zhao et al. Nano Energy 115 (2023) 108697

2. Results and Discussion by Miura elements, so their geometric characteristics remain consistent
throughout. As the angle η changes, the Angle θ, m, n and dvaries
2.1. Structure design of Miura-ori metamaterials monotonically. When η = 0, the Miura-ori unit is in a fully folded state,
and when η = π, the Miura-ori unit is in a fully unfolded state. The
How to achieve performance programmability through appropriate geometric relation of the unit cell satisfies:
geometric topology design and create artificial material structures with

M = m1 + m2 + m2
√̅̅̅̅̅̅̅̅̅̅̅̅̅̅̅̅̅̅̅̅̅̅̅̅̅̅̅̅̅̅̅̅̅̅̅̅̅̅̅̅̅̅̅̅̅̅̅̅̅
( )2̅ √̅̅̅̅̅̅̅̅̅̅̅̅̅̅̅̅̅̅̅̅̅̅̅̅̅̅̅̅̅̅̅̅̅̅̅̅̅̅̅̅̅̅̅̅̅̅̅̅̅̅
( )2̅ ( )
1 − ℓcos(θ/2)cos− 1 αi + j s2 − ℓcos(θ/2)cos− 1 αi β
= a1 sin α1 √̅̅̅̅̅̅̅̅̅̅̅̅̅̅̅̅̅̅̅̅̅̅̅̅̅̅̅̅̅̅̅̅̅̅̅̅̅̅̅̅̅̅̅̅̅̅̅̅̅̅̅̅̅̅̅̅̅̅̅̅̅
( ) ̅ + b cos
2
(4)
2 − 1 2
1 − sin α1 ℓcos(θ/2)cos αi
√̅̅̅̅̅̅̅̅̅̅̅̅̅̅̅̅̅̅̅̅̅̅̅̅̅̅̅̅̅̅̅̅̅̅̅̅̅̅̅̅̅̅̅̅̅̅̅̅̅̅̅̅̅̅̅̅̅̅̅̅̅̅̅̅
N = n1 + n2 = (b1 + b2 ) 1 − sin2 α1 sin ℓcos(θ/2)cos− 1 α1
H i = ai ℓi tanαi cos(θ/2)

unconventional properties is an ongoing challenge. Miura-ori structures where s = sin α2 / sin α1 and j = a2 /a1 .
are origami patterns formed by a Mosaic arrangement of repeated units, Miura-ori metamaterials are formed by repeated stacking of unit cell.
the basic unit of which is shown in Fig. 1(a). It is composed of four If the geometric parameters of the unit cells in different layers are
identical parallelograms, so its basic shape can be determined by the different, in and out-of-plane gradient Miura-ori metamaterials can be
length of the side a1 , a2 , b1 , b2 , and Angle α1 and α2 . Generally, unit cells obtained. However, due to the changing geometric parameters of the
with different topological angles exhibit different mechanical Miura-ori gradient structure, it is necessary to constrain the geometric
properties. parameters of the unit cell in different layers to ensure the perfect
By extending the unit cell along the X direction, it can be found that connection between layers. To coordinate the deformation of the
two adjacent Miura-ori units share the same parameters including side structure, the adjacent elements should be guaranteed to have the same
length a1 and a2 and side Angle γ. Changing the topological Angle α1 can side length a and the same side Angle γ, and to ensure the coherence of
obtain the in-plane gradient structure. Miura-ori structure can complete the panel without affecting its motion. Changing the Angle α does not
the continuous superposition along the Z direction by mirroring. In the affect the movement of the structure, but it will affect the mechanical
connection process, different layers are connected by the same param­ properties of the structure.
eters b1 and b2 , and angles γ. Moreover, the structure can be completely In contrast to the existing methods of adjusting stiffness by changing
folded and expanded because the whole structure still maintains a single thickness and density, the stiffness of origami structures can be sys­
degree of freedom. By extending and assembling the unit cell along X, Y tematically changed through geometric design. The mechanical prop­
and Z directions, the miura-ori metamaterial structures can be obtained erties of the unit cells can be regulated by changing the topological
as shown in Fig. 1(b). parameters (See Supporting Information, S1, Fig. S1-S3). Therefore, by
The geometry of the element embodies the basic elements of all the rational arrangement of the unit cell, we can obtain the homoge­
origami structures-mountain or valley folds, where four edges (pleats) neous Miura-ori and gradient Miura-ori metamaterials. By changing the
are joined together at a single vertex. The key parameters are the topological parameters of Miura origami, and doing superposition or
dihedral Angle θ ∈ [0, π], η ∈ [0, π ] and angle α ∈ [0, π/2]. The length, repetition in different directions of space, a series of origami meta­
width, and height of the single cell are m, n and d, respectively. Three materials with gradual mechanical properties can be designed (Sup­
parameters remain the same whether folded or not, and they are the porting Information, Fig. S4, S5 and S6). As shown in Fig. 1(c) and (d),
lengths of the two creases, a and b, and the angles between the two sides the Miura-ori structures are composed of multiple elements embedded
of the unit cell. Therefore, we chose the dihedral angle η as the only in and out of the plane and combined in a certain sequence to form
freedom degree to characterize the geometrical parameter of the unit gradient Miura-ori metamaterials.
cell. During the folding process, the ridges of length, a1 , a2 , b1 , b2 , and
the angles α1 and α2 between the ridges are constant. Therefore, we
2.2. Mechanical tests of the Miura-ori metamaterials
select the dihedral Angle θ as the control variable to characterize the ori
cell. The geometrical relationship satisfies:
If mechanical metamaterials are reconfigured to replace traditional
η = 2sin− 1 [ℓsin(θ/2)], mi = ai ℓi (1) materials with stimulation-responsive materials, they will be able to
automatically deform, move and change their structural properties or
ni = bi ℏi , hi = ai ℓi tanαi cos(θ/2) (2) functions in response to external stimuli (See Movie S-I). Furthermore,
[ ] they will be endowed with richer functional characteristics, including
χ i = sin− 1
ℓcos(θ/2)cos− 1 αi , sin α1 sinχ 1 = sin α2 sinχ 2 (3) reconfigurable and programmable, etc. In this work, the Miura-ori
metamaterial structures are fabricated by shape memory polymer and
where ℏi and ℓi represent dimensionless width and length, and can be
4D printing technology(Details see Supporting Information, Section S4,
further expressed as ℏi = sinαi sin(θ/2) and ℓi = cos αi (1 − ℏi 2 )− 1/2 . In
Fig. S7). The quasi-static compression experiment is conducted to
addition, the value range of each Angle is: η ∈ [0, π], θ ∈ [0, π], β ∈ [0, α1 +
investigate the mechanical properties. The compression rate is set as
α2 ],M′ = (m1 + m2 ) ∈ [a1 cosα1 + a2 cosα2 ,a1 + a2 ], γ ∈ [π − (α1 + α2 ), π ], 2 mm/min to avoid the influence of inertia force and kinetic energy as
hi ∈ [0, ai ], i = 1, 2... much as possible. The final compression displacement is selected as
It is assumed that the Miura-ori metamaterials are consisting of the about 75% of the overall height of the structures. The structure is
same periodic diagonal lattice connected by elastic hinges on the edges. crushed in this compression distance, and the load response shows a
The structure can be evenly expanded on a plane. In the folding process, tendency for a dramatic increase. In addition, the finite element soft­
the rigid surface rotates around the ridge. Miura-ori plates are defined ware ABAQUS/explicit is used to simulate the mechanical properties of

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W. Zhao et al. Nano Energy 115 (2023) 108697

Fig. 2. Mechanical properties testing of Miura-ori metamaterials (a) Mechanical properties of structure M-III-2 under in-plane compression (b) Mechanical properties
of structure M-III-3 under in-plane compression (c) Compression performance test of in-plane gradient structures with γ = 135 (d) Mechanical properties of structure
◦

M-III-2 under out-of-plane compression (e) Mechanical properties of structure M-III-3 under out-of-plane compression (f) Compression performance test of out-of-
plane gradient structures with β = 15 Comparison of mechanical properties of metamaterials before and after programming under in-plane compression (g) M-
◦

II-2 (h) M-II-3 (i) M-III-2; Comparison of mechanical properties of metamaterials before and after programming under out-of-plane compression (j) M-III-1 (k) M-III-2
(l) M-III-3.

the structures. and the law of deformation modes. In the first stage, the load increases
Supplementary material related to this article can be found online at rapidly to a peak value with the increase of the deformation, which is the
doi:10.1016/j.nanoen.2023.108697. elastic deformation stage, and all elements maintain consistent defor­
The movement of the structure is mainly rigid rotation around the mation. Subsequently, the displacement continues to increase and the
fold, the smaller the folding Angle, the easier the deformation of the load decreases gradually or remains unchanged until the deformation
unit. The Mechanical properties testing of structures M-III-2 and M-III-3 reaches a certain point, which is the second stage. The mechanical
under in-plane compression and in-plane gradient structures with γ = properties of the structure with different topological parameters show
135 are shown in Fig. 2(a)-(c). The Mechanical properties testing of obvious differences in this stage. The final stage is the compaction stage,
◦

structures M-III-2 and M-III-3 under out-of-plane compression and in- where the load rises sharply with the deformation.
plane gradient structures with β = 15 are shown in Fig. 2(d)-(f). For
◦
The deformation of the gradual multilayer structure with γ =
the conventional structure, the compression process can be roughly 135 presents a step-change rule as shown in Fig. 2(c). The deformation
◦

divided into three stages according to the load-displacement changes process can roughly be divided into four stages. In the elastic

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W. Zhao et al. Nano Energy 115 (2023) 108697

deformation stage, the deformation ranges from 0 to 2.8 mm, while the have advantages in the aspects of adjustable stiffness, programmable
load gradually increases and reaches the platform stage, which we label structure and mechanical properties but also have excellent energy ab­
as platform level 1. The Level 1 platform is maintained until the sorption effect (More information can be seen in Supporting Information
compression displacement is 6.4 mm. The load increases from 111 N to Fig. S8-S15).
385 N, when the compression displacement reaches 31 mm, and the
gradual stiffness is achieved through structural changes. As exemplified
2.3. Schematic of fabrication and working principle
by the structure with β = 15 as shown in Fig. 2(f), the deformation
◦

process can roughly be divided into four stages too. The first is the elastic
With the development of techniques and the economy, people are
stage from 0 to 12 mm, and the load increases rapidly to a value and
paying more and more attention to their daily lives, such as gait moni­
then drops sharply which we label as platform level 1. Subsequently, the
toring, motion sensing, etc. As smart wearable devices gradually inte­
deformation of level 2, level 3 and level 4 is 20 mm, 30 mm and 40 mm,
grate into people’s lives, the power supply problem has attracted more
respectively.
and more attention. Self-powered wearable devices can convert me­
Based on SME, the shape and mechanical properties of the 4D printed
chanical energy into electrical energy to power wearable devices, which
metamaterial can be actively adjusted in a large range and switched
has great development prospects. In this work, combined with meta­
between a variety of stable shapes. Consequently, when dealing with
materials, we develop a kind of 4D printed shoe sole with the ability of
extreme external loads, the 4D printed metamaterials can not only
self-powered and self-sensing MS-TENG for gait tracking. The design of
protect the object by adjusting the stiffness but also protect themselves
the sole originated from the Miura-origami method, which could be
from damage. Furthermore, the structure can restore to its original state
further programmed, integrated and lightened, as shown in Fig. 3(a). In
after deformation and its mechanical properties can be redefined. Fig. 2
addition, the MS-TENG can be embedded in normal shoes (Fig. 3(b)),
(g)-(i) shows the load-deformation curve before and after programming,
detecting and correcting gaits (Fig. 3(c)) and characterizing different
with good consistency. The angles β of structures M-II-1, M-II-2 and M-II-
motions (Fig. 3(d)). The flow chart of signal conversions during the self-
2 are equal to 120◦ , 90◦ and 60◦ , respectively. By applying a certain
sensing process is shown in Fig. 3(e).
deformation to M-II-1, the Angle β can gradually change from 120◦ to
As a validation, we have designed and fabricated a shoe sole using
90◦ . Similarly, by applying a certain deformation to M-II-2, the Angle β
this metamaterial. For running shoes, efficient energy absorption is an
can gradually change from 90◦ to 60◦ .
important factor in sole design. They need to be strong enough - not too
Utilizing SME, heat the 4D printed metamaterials to 90 ℃, and the
soft to cause skew - but also have efficient cushioning, energy absorption
angles β of M-II-1 and M-II-2 are changed to 90◦ and 60◦ by applying a
and shock absorption effect. Exemplified by the metamaterials M-III-2,
certain displacement, respectively. Subsequently, the configuration is
we design and fabricate a sole with 4D printing technology, and inte­
maintained and lowered the temperature to 20 ℃. After this program­
grate the sensing function to monitor the gait in real-time. Combined
ming process, the configuration of M-II-1 changes to M-II-2, and the
with the concept of triboelectric nanogenerators, the metamaterial
configuration of M-II-2 changes to M-II-3. Similarly, this programming
structure-based triboelectric nanogenerator (MS-TENG) could be
approach can be applied to other structures.
designed for converting mechanical energy into electricity. The elec­
Using the same method, the geometrical configuration of the meta­
trical signals can be used for energy storage and motion monitoring.
materials along the out-of-plane compression direction can be pro­
PDMS is considered to be one of the triboelectric materials, realizing
grammed. The angle γ of Miura-ori metamaterials of M-III series is 90◦ ,
the combination between piezoelectricity and triboelectricity. The
while M-IV series is 60◦ . By applying a certain deformation along the Z-
fabrication process of the PDMS-based piezoelectric and flexible thin
direction, the Angle γ can be changed from 60◦ to 90◦ , i.e. the geomet­
film (PFF) is shown in Fig. 4(a). The polyvinylidene fluoride (P(VDF-
rical configuration of the metamaterials of M-III series and M-IV series
TrFE)), barium titanate (BTO) and polydimethylsiloxane (PDMS) are
can switch each other by programming process. To verify whether the
mixed and cured for 3 h. It is worth noting that part of the BTO content
programmed structure can show its due mechanical properties under
can serve as the nucleating agent of P(VDF-TrFE) to facilitate the for­
this geometric parameter, we carried out mechanical experiments. The
mation of the piezoelectric phase-β phase, while the rest of BTO could
load-displacement curves before and after programming are shown in
act as piezoelectric ceramics.
Fig. 2(j)-(l). The results indicate that the programmed structure has
The fabricating diagram of MS-TENG is shown in Fig. 4(b), where the
relatively consistent mechanical properties with the original structure.
structure M-III-2 with three topological units is chosen to be the sub­
Consequently, it can be concluded that by utilizing SME, not only the
strate. Set one single cell of the structure as an example (the enlarged
structural configuration can be programmed but also the mechanical
figure in Fig. 4(b)), the aluminum foil is attached to the dark part to be
properties can be re-designed. The 4D-printed metamaterials not only
both the conductive and the positive triboelectric layer. In the opposite

Fig. 3. Schematic illustrations of (a) structure designing (b) application potentials (c), (d) detection of gaits and motions (e) self-sensing flow diagram based on
MS-TENG.

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W. Zhao et al. Nano Energy 115 (2023) 108697

Fig. 4. Schematic diagram of the preparation and fabrication of the MS-TENG (a) Preparation of the piezoelectric and flexible thin film (PFF) (b) Fabrication of the
MS-TENG (c) Schematic of the working principle of the MS-TENG (d) Electrical simulation of the MS-TENG via COMSOL.

part, the aluminum foil is pasted first to transfer electrons and the PFF is currents and voltages. Besides, the relationship between output prop­
fixed above serving as the negative triboelectric material. Every two erties and the loading values is demonstrated under the constant fre­
parts form one hybrid nanogenerator, which contributes to the overall quency of 4 Hz, as shown in Fig. 5(d) and (e). Both the output voltage
MS-TENG. and current show increasing trends in loading values (from 5 N to 25 N)
The working principle of the MS-TENG is shown in Fig. 4(c) which and the maximum is 131.3 V and 1.10 μA, respectively. The load value is
can be classified as the contact-separation modal. In the initial state, a key factor for piezoelectric nanogenerators (PENGs), while triboelec­
both the aluminum and the PFF are in electric neutrality. Once they get tric nanogenerators depend on frequencies more. Meanwhile, TENGs are
in contact with each other, different electrical properties are excited featured with high voltages, while PENGs are characterized more by
under the attractions of the different nucleus, resulting in the aluminum current (More details can be seen in Supporting Information S8,
trend being positive and PFF being negative as shown in Fig. 4(c)-I. Fig. S19-S21). As a result, both the values and the frequencies of loading
During the separating process, the electrical potential changes owing to promote the combination between TENGs and PENGs.
the distance between the two parts increasing, leading to the trans­ In addition, the output voltage shows a linearly related to the applied
ferring of electrons and further the current in external circuits (Fig. 4(c)- loading values, and the sensitivity is calculated to be 4.68 ± 0.6 V⋅N− 1
II, III). Once the MS-TENG is pressed under external forces, the potential (R2 =0.956) as shown in Fig. 5(d), which indicates the potential in the
changes again and the electrons flow to the opposite, leading to the sensing area. The output voltages under different external load resis­
reverse current (Fig. 4(c)-IV). At the same time, piezoelectricity triggers tance are tested, and the maximum power density is calculated to be 77
once the two parts got in contact, which attributes to the output elec­ nW/cm2 under 100 MΩ as shown in Fig. 5(f). Considering that stability
trical properties apart from the triboelectricity. The electrical stimula­ is essential for the practical application of the MS-TENG, the real-time
tion obtained by COMSOL is shown in Fig. 3, and the trend of potential working cycles test is carried out under 15 N and 10 Hz, as shown in
change is consistent with the experiment and theoretical analysis. The Fig. 5(g) & (h). It is obvious that MS-TENG can output electrical signals
fundamental properties of the film can be seen in Supporting Informa­ steadily under 10,000 cycles, which proves the good robustness under
tion Fig. S16-S18. long-time contact and the capability of daily use for motion monitoring.
To verify the energy harvesting effect of the structure, the device is
connected to some LEDs that arrange to a “HIT” shape. The circuit di­
2.4. Electrical performances of MS-TENG agram and the lighted LEDs are shown in Fig. 6(a) and (b), respectively.
All LEDs are successfully lit under the action of cyclic load, which can
The fundamental electrical output properties of TENG, PENG and light up about two hundred LEDs. (Details see in Supporting Informa­
MS-TENG are investigated. The working diagram and testing methods tion, Movie S-II).
are shown in Fig. 5(a), where the MS-TENG is fixed to the linear motor Supplementary material related to this article can be found online at
and tested under different loading values and frequencies. The output doi:10.1016/j.nanoen.2023.108697.
currents increase from 0.38 μA to 1.31 μA, simultaneously, the voltages Trigger unit as a trigger signal generation mode is widely used in
grow from 27.51 V to 89.27 V constantly with frequency increasing industrial production and the Internet of Things as a sensor. If self-
from 1 Hz to 5 Hz under 10 N pressure (Fig. 5(b) and (c)). The more powered trigger units can be prepared, it will provide a more energy-
frequent the loading is, the faster the potential changes, further to higher

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W. Zhao et al. Nano Energy 115 (2023) 108697

Fig. 5. Basic electrical performance output (a) Loading schematic diagram of the MS-TENG (b), (c) Short-circuit current and open circuit voltage at different loading
frequencies (d), (e) Open circuit voltage and short-circuit current and under different pressures (f) Output power under different load resistances (g), (h) Robustness
test of open circuit voltage under 10,000 cycles.

Fig. 6. Functional application of the Miura-ori metamaterials integrating triboelectric-piezoelectric sensing function (a) The arrangement diagram of LEDs (b) The
lighted LEDs (c) The equivalent circuit diagram of the self-powered touch switch (d) The arrangement of sensors on the sole (e) Human-computer interaction
interface (f) Output characteristics of the human body tested by the triboelectric-piezoelectric sensor.

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W. Zhao et al. Nano Energy 115 (2023) 108697

efficient way of human-computer interaction. In this paper, a simple SME, the structure can adjust its configuration to another with different
self-powered touch switch is designed and prepared by combining the topological parameters. Accordingly, its mechanical properties can be
three-stage amplifier circuit. The trigger module can be extended to switched between structures with different topological parameters,
meet the requirement in different application fields. Connect the pre­ which greatly expands its application range. Experiments indicate that
pared energy harvesting device to the three-stage amplifying circuit the metamaterials with the same topological parameter obtained by the
which is used to amplify the electrical signal output as shown in Fig. 6 initial design and after the programming process exhibits similar me­
(c). The signal lamp can blink by pressing the energy harvesting device, chanical properties. Further, we investigate the compression perfor­
the demonstration video can be found in Supporting Information, Movie mance of the structure with different topological parameters and
S-II. analyze the energy absorption properties of each structure. By inte­
In the field of life medicine, step frequency signals can be used to grating the TENG and PENG functions into the structure, we explore and
detect the motion state of patients. The motion state of patients can be find that this class of structures exhibits excellent energy harvesting
obtained by analyzing the electric signals generated by the triboelectric- ability, and proves good robustness under long-time contact. Finally,
piezoelectric unit, which has a good early warning function for the utilizing M-III-2 with excellent energy absorption capacity, we fabricate
pathological characteristics of non-strenuous exercise. At present, most a sole, and the gait monitoring function is successfully realized by
of the step frequency sensors are electronic products, which not only integrating the sensing and self-powered functions. 4D printing tech­
cause high costs but also cause certain damage to the human body due to nology has unique advantages in structure fabrication and reprogram­
the radiation effect of electronic products themselves. Consequently, we ming after structure fabrication, which will bring more possibilities for
extend the functionality of the structure as a trigger unit and sensor the functional integration and application of TENG.
function and integrate it into the sole to monitor the gait and forces at
different positions. The realization of the monitoring function is based CRediT authorship contribution statement
on the conversion between mechanical and electrical signals. Voltage
data sets of different actions are collected through the response mech­ Wei Zhao and Nan Li: Conceptualization, Methodology, Wei Zhao,
anism of mechanical compression and voltage signal. In this work, the Nan Li, Xu Liu, Chengbin Yue and Chengjun Zeng: Data curation,
triboelectric-piezoelectric unit generates electrical signals by taking Writing- Original draft preparation. Wei Zhao, Xu Liu and Nan Li::
advantage of the difference between the gain and loss of electronic ca­ Visualization, Investigation. Liwu Liu, Yanju Liu anf Jinsong Leng:Su­
pabilities of the two materials. The materials selected in this paper, such pervision. Wei Zhao and Nan Li, Yanju Liu:Writing- Reviewing and
as PDMS and Al, have no damage to the human body. Their thickness is Editing.
extremely thin, their plasticity is in line with human characteristics, and
they are comfortable to wear. The possible physiological characteristics Declaration of Competing Interest
of the human body can be predicted through the feedback of human step
frequency signals. The sensor location and the human-computer inter­ The authors declare that they have no known competing financial
action interface set by programming language are shown in Fig. 6(d) and interests or personal relationships that could have appeared to influence
(e), which can be used to monitor the position of force (Supporting In­ the work reported in this paper.
formation, Movie S-III).
Supplementary material related to this article can be found online at Data Availability
doi:10.1016/j.nanoen.2023.108697.
Further, the output performance of the device is used to evaluate the Data will be made available on request.
movement condition, including slow walking, fast walking, jogging and
fast running. To evaluate the applying effect, we conduct a series of Acknowledgment
experiments by testing four kinds of human movements, such as slow
walking, fast walking, jogging and fast running. The monitoring of the This work was supported by the National Natural Science Foundation
exercise experiment is done on a treadmill by the subjects wearing smart of China (Grant No. 12072094), China Postdoctoral Science Foundation
sole with integrated sensing functions. (No. 2022M720962), and Postdoctoral Science Foundation of Hei­
Step frequency is often affected by human body differences. The slow longjiang Province (No. LBH-Z22114).
walking of normal adults is 60–80 steps/min, the fast walking is
100–120 steps/min, the jogging is 120–140 steps/min, and the fast Appendix A. Supporting information
running is 180–600 steps/min. Signals from the Miura-ori metamaterials
sensors are recorded for 8 s to obtain data sets. The output character­ Supplementary data associated with this article can be found in the
istics of the human body are tested by the triboelectric-piezoelectric online version at doi:10.1016/j.nanoen.2023.108697.
sensor as shown in Fig. 6(f). It can be seen from the figure that the
frequency of slow walking, fast walking, jogging and fast running is 60 References
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