PIEZOELECTRIC CERAMIC-POLYMER COMPOSITE FOR ENERGY STORAGE AND

HARVESTING APPLICATIONS
By
HAOCHEN LYU
A thesis submitted to the
School of Graduate Studies
Rutgers, The State University of New Jersey
In partial fulfillment of the requirements
For the degree of
Master of Science
Graduate Program in Materials Science and Engineering
Written under the direction of
Ahmad Safari
And approved by

New Brunswick, New Jersey

October, 2021
 ABSTRACT OF THE THESIS

PIEZOELECTRIC CERAMIC-POLYMER COMPOSITE FOR ENERGY STORAGE

AND HARVESTING APPLICATIONS
by HAOCHEN LYU

Thesis Director:
Ahmad Safari

Recently, the application of piezoelectric materials in energy storage and energy

harvesting has received considerable attention. Among them, piezoelectric ceramic-

polymer composites have good dielectric and piezoelectric properties as well as high

flexibility, thus making them an outstanding candidate in energy-related applications. In

this study, we investigated the preparation and electromechanical properties and

simulations of the composites: 1. PbTiO3-PVDF composites with 70% ceramic powder; 2.

the design of a two-degree-of-freedom (2-DOF) cantilever beam energy harvester and the

optimization of the design by COMSOL simulation; 3. PVDF/Al2O3 thick films, and three

layers of pure PVDF/Composite/pure PVDF composite, and the evaluation for energy

storage application.

PVDF composite with 70 vol% PbTiO3 showed d33 of 45 pC/N. 2-DOF cantilever

with micro-fiber composite (MFC) sheet could generate power of 1.08 mW and output

voltage of 28 V. Multilayer composite PVDF thick films with Al2O3 fillers showed

recovery energy density of 1.08 J/cm2 and efficiency of 71%.

ii
 Acknowledgments

First of all, I would like to thank my supervisor, Prof. Ahmad Safari, who has given

me a lot of help and guidance during these three years, both in my life and in my research.

And he lab, Gleen Howatt electronic materials lab, where I have worked for 3 years.

Secondly, I would like to thank my senior, Jack Laber, who was like a brother to me in the

group and helped me with some very trivial or complicated but very important things. I

would also like to thank my college, the School of Materials Science and Engineering at

Rutgers University, where I have had access to a lot of resources, taken a lot of great

courses, and met a lot of great professors who have taught me a lot. Of course, my friends,

Wenhao Zhou, who has graduated, and my roommates Lingjun Xie, Weiting Lyu, Siwei

Mai and Yimei Li, who have helped me and encouraged me. They are my motivation to go

forward. Last but not least, I would like to thank my family for loving me so much even

though they are in the midst of a lot of trouble, and I love you all forever. Finally, I would

like to thank the professors and students in our department who have helped me. Thank

you to Dr. Haber and his student Frank Manucci for the tape casting instrument and

tarinning, to DrLynch and Dr. Nosker for the warm pressing instrumentequiment, and to

Dr. Horvath for helping me with the cantilever beam. Thanks to all of you, without your

help this thesis would not have been possible.

iii
 Table of Contents

ABSTRACT OF THE THESIS .......................................................................................... ii

Acknowledgments.............................................................................................................. iii

Table of Contents ............................................................................................................... iv

List of Figures .................................................................................................................... vi

List of Tables ................................................................................................................. viii

CHAPTER 1 INTRODUCTION .........................................................................................1

CHAPTER 2 BACKGROUND ...........................................................................................4

2.1 Piezoelectricity .......................................................................................................... 4

2.2 Piezoelectric Materials .............................................................................................. 6

2.2.1 Single Crystal ..................................................................................................... 7

2.2.2 Piezoelectric ceramics ........................................................................................ 9

2.2.3 Piezoelectric Polymers ..................................................................................... 10

2.2.4 Ceramic-polymer Composites .......................................................................... 12

CHAPTER 3 OBJECTIVE AND RESEARCH PLAN .....................................................16

CHAPTER 4 EXPERIMENT ............................................................................................18

4.1 Materials .................................................................................................................. 18

iv
 4.2 Characterization method ......................................................................................... 18

4.3 Experiment .............................................................................................................. 22

4.3.1 Colloidal Process .............................................................................................. 22

4.3.2 Energy Harvesting Evaluation .......................................................................... 24

4.3.3 Tape Casting ..................................................................................................... 25

4.3.4 Fabrication of the (Ba0.95Ca0.05)(Ti0.92Sn0.08)O3 Ceramics ................................... 26

CHAPTER 5 RESULT ......................................................................................................28

5.1 Colloidal Process Composite .................................................................................. 28

5.2 Energy Harvester Cantilever ................................................................................... 32

5.2.1 Finite Element Model of Piezoelectric Cantilever in Comsol Multiphysics .... 32

4.2.2 Voltage output measured from cantilever ........................................................ 36

4.3 Al2O3/PVDF composite prepared by tape casting................................................... 41

CHAPTER 5 CONCLUSION............................................................................................49

CHAPTER 6 FUTURE STUDY .......................................................................................51

Reference ...........................................................................................................................52

v
 List of Figures

Figure 1 Hysteresis loop of Rocelle Salt..............................................................................4

Figure 2. Scheme of Piezoelectric Effects ...........................................................................5

Figure 3. Categories of piezoelectric materials....................................................................7

Figure 4. Lead-based piezoelectric material manufacturing method: Bridgman (BM),

Solid State Crystal Growth (SSCG) and Top Seed Solution Growth (TSSG) ....................8

Figure 5. Lead-free piezoelectric ceramics ..........................................................................9

Figure 6. Comparison of different phase of PVDF. ...........................................................11

Figure 7. Different method forming β phase. ....................................................................12

Figure 8. Scheme of different structure of 2-componenet composites ..............................13

Figure 9. (a) d33 P1 type and (b) d31 P2 type of MFC plate ...............................................14

Figure 10. Instruments of Energy Harvesting research .....................................................20

Figure 11. Berlin Court d33 piezo-meter at 100 Hz. ...........................................................21

Figure 12. 4194A Impedance/Gain-Phase Analyzer .........................................................21

Figure 13. Flow chart of Colloidal process composite process. ........................................23

Figure 14. shematic of 2-DOF cantilever ..........................................................................24

Figure 15. Tape casting Instrument ...................................................................................26

Figure 16. Scheme of the multilayer composite. ...............................................................26

Figure 17. FEM of 2-DOF piezoelectric cantilever (a) geometric design and boundary

conditions; (b) meshes of FEM ..........................................................................................34

Figure 18. Voltage output from MFCs on the cutoff cantilever design with m1 = 7.2 g; (a)

m2 = 8.8 g, (b) m2 = 11.2 g, (c) m2 = 14.2 g, and (d) m2 = 16.8 g. ....................................35

vi
Figure 19. Voltage outputs from MFC on the secondary beam of cutoff cantilever design

............................................................................................................................................35

Figure 20. Power output from cutoff cantilever under (a) different external resistances;

(b) different external resistances in log ..............................................................................37

Figure 21. Voltage output measured by oscilloscope (a) screen shot; (b) data read in csv.

............................................................................................................................................37

Figure 22. Characterization of open-circuit voltage (a) Ceramic (b) Composite ..............39

Figure 23. Guideline of the tape casting research. .............................................................41

Figure 24. Plot of energy density with change of the ceramic volume percent. ................44

Figure 25. Plot of the energy density with different multilayer design. ............................45

Figure 26. Scheme of the energy storage. ..........................................................................47

Figure 27. Hysteresis loop of (a) PVDF with DMF solvent. (b) PVDF with

DMF+Acetone (c) 1vol% Al2O3/PVDF composite (d) 3 vol% PVDF composite (e) 0-1-0

composite (f) 0-3-0 composite ...........................................................................................48

vii
 List of Tables

Table 1. Properties of BT-CT-BS ceramics ...................................................................... 27

Table 2. Result of BT/PVDF composite (65 vol%) .......................................................... 28

Table 3. Result of PMN-PT/PVDF composite (70 vol%) ................................................ 30

Table 4. Result of PT/PVDF composite (70 vol%) .......................................................... 30

Table 5. Key material parameters used in this 2-DOF piezoelectric cantilever ............... 34

Table 6. Comparison of simulation and experiment result ............................................... 38

Table 7. Open circuit result of the ceramic and composite............................................... 40

Table 8. Result of PVDF film made by tape casting. ....................................................... 42

Table 9. Result of Al2O3/PVDF composite ..................................................................... 43

Table 10. Result of multilayer composite ......................................................................... 45

viii
 1

CHAPTER 1 INTRODUCTION

Piezoelectricity was discovered in 1880 and has been widely investigated by

scientists for over 130 years. In the past few decades, researchers focused on the energy

harvesting application of piezoelectric materials in view of concern on environment and

resources[1]. Several energy harvesting methods including wind and solar energy

harvesting were limited by environmental condition. However, piezoelectric energy

harvesters remain unaffected by these limitations as long as ambient force or vibration

exists.

According to the Figure of Merit of Energy Harvester, d*g, materials should have

high piezoelectric charge coefficient and relative low dielectric permittivity. To obtain

energy harvester with high performance, composite with high volume percent of ceramic

loading was prepared and characterized. 2-degree-of-freedom(2-DOF) cantilever was

designed and vibration energy harvesting performance was characterized, the design was

simulated and optimized by COMSOL Multiphysics Software.

Piezoelectric materials are not only good materials for energy harvesting, but they

can also be used for energy storage especially with the increasing demand for dielectric

capacitors with higher energy-storage capacity. The main advantage of the dielectric

capacitors over alternatives such as electrochemical capacitors and traditional batteries is

the power density available, which could be charged up and then discharged within 1ms to

deliver stored energy[2].

Resembling piezoelectric sensors, piezoelectric energy storage also need high

permittivity. But device for these applications must consider other factors to evaluate the
 2

energy storage capacity[3]. Dissipation factor is one of the parameters which was defined

as the reciprocal of the ratio between the insulating materials capacitive reactance to its

resistance at a specified frequency. Dielectric loss(tan𝛿) is another parameter need to be

considered, which measures how much energy is lost in AC operation because of charge

dissipating to the material[4]. Another parameter is breakdown strength, which the

maximum electrical potential that a material can resist before the electrical current breaks

through the material[5]. The figure of merit of energy density performance is:

𝑊 = ∫ 𝐸𝑑𝐷

It is obvious that energy density is related to both breakdown strength and

permittivity. But unfortunately, ceramics have high permittivity but low electrical

breakdown strength. As a result, piezoelectric polymer and composites are characterized

and evaluated.

Energy-storage efficiency is energy storage capacity combined with energy

density[6]. The hysteretic loss is the main reason of low energy-storage efficiency, which

arises due to the inertia resistance from the inelastic movement of particles. Typically

polymers has larger dielectric loss than ceramics[7]. Clearly developing materials with high

permittivity and breakdown strength and low dielectric loss is necessary, and composite is

naturally the best choice to obtain the desire properties[8]. Composite films were widely

investigated in the past few decades, piezoelectric or dielectric ceramics such as BaTiO3,

Al2O3 and PZT were introduced into the polymer matrix such as PVDF and epoxy. To

obtain films with good energy storage performance, thick 0-3 composite films were

investigated. PVDF was selected as the polymer matrix due to its high piezoelectric
 3

performance and good flexibility. Al2O3 was added to improve the energy storage

performance by decreasing the loss.

 4

CHAPTER 2 BACKGROUND

2.1 Piezoelectricity

Piezoelectricity was discovered in 1880 by Curie Brothers in Paris, and was focused

by researchers for the following centuries. In 1919, Joseph Valasek investigated physical

properties of Rocelle Salt single crystal with the guidance of Professor W F G Swan at the

University of Minnesota[9]. Dielectric response, non-linear dielectric properties,

piezoelectric properties of Rocelle Salt was published in that year. The first figure of

hysteresis loop was born in Conference of American Physics Society in 1920 as it was

shown in Fig 1. In 1935[10], Busch and Steulmann tested dielectric properties of K3PO4,

K2HPO4 and KH2PO4 by conducting low-temperature experiment. After that the discovery

of PZT and BaTiO3 in 1950s, is viewed as a significant breakthrough in the field of

piezoelectric sensors application. These ceramics exhibit very high dielectric and

piezoelectric properties and find full applications as sensor and actuator devices. Nowadays,

piezoelectric materials are widely used in the fields of life, medicine, communication, and

military. And after more than 100 years, there is still a lot of research waiting to be explored.

Figure 1 Hysteresis loop of Rocelle Salt

The piezoelectric effect means that by application of pressure to a material could

produce an electric potential difference, and similarly by applying voltage could produce a
 5

certain amount of mechanical energy, these phenomena are called direct and converse

piezoelectric effects.

Natural single-crystal materials such as quartz, tourmaline and Rochelle salts have

relatively small piezoelectric effects, while polycrystalline ferroelectric ceramics such as

barium titanate (BaTiO3) and lead zirconate titanate (Pb(ZrxTi1-x)O3) exhibit larger

displacements or produce higher voltages. PZT piezoelectric ceramic materials come in

many varieties and are widely used in actuator or sensor applications. Doping of PZT

ceramics with nickel, bismuth, lanthanum, neodymium, niobium ions specially optimized

piezoelectric and dielectric parameters for specific applications.

Figure 2. Scheme of Piezoelectric Effects

The properties of piezoelectric materials are determined by many parameters such

as dielectric loss, permittivity and coupling factor, etc. The dielectric constant or relative

permittivity(εr) is the ratio of the absolute dielectric constant of a material (ε) to its

dielectric constant at vaccum (ε0). The difference between the dielectric constants of

ceramic and polymer materials is very large, with conventional piezoelectric ceramics such
 6

as BaTiO3 having a dielectric constant of about 1000 to 5000, while piezoelectric polymers

such as PVDF have a dielectric constant of only 10.

Piezoelectric coefficient is an important parameter to measure the energy

conversion ability of piezoelectric materials. The piezoelectric coefficient is the ratio of

the volume change and or polarization generated when a piezoelectric material subjected

to an applied electric field or mechanical stress. For example, for d33 it mainly represents

the strain per unit applied electric field in the polarization direction (V/m), or the charge

density that can be generated by the material per unit pressure(pC/N). The piezoelectric

voltage coefficient, g, represents the ratio of the electric field strength to the applied stress.

g can be obtained by dividing the piezoelectric coefficient, d, by the relative permittivity:

𝑑
𝑔=
𝜀𝑟 𝜀0

The electromechanical coupling coefficient, k, is a parameter that measures the

degree of piezoelectric effect. It indicates the ability of the piezoelectric material to convert

electrical to mechanical energy or mechanical to electrical energy. The coupling coefficient

is determined by the square of the ratio of the stored mechanical energy to the total

absorbed energy.

𝑠𝑡𝑜𝑟𝑒𝑑 𝑚𝑒𝑐ℎ𝑎𝑛𝑖𝑐𝑎𝑙 𝑒𝑛𝑒𝑟𝑔𝑦

𝑘2 =
𝑇𝑜𝑡𝑎𝑙 𝑎𝑏𝑠𝑜𝑟𝑏𝑒𝑑 𝑒𝑛𝑒𝑟𝑔𝑦

2.2 Piezoelectric Materials

In general, piezoelectric materials should have the following main characteristics:

(1) require a high piezoelectric coefficient (2) according to the application of the
 7

corresponding mechanical properties, such as piezoelectric ceramics to have greater

mechanical strength and stiffness, and for flexible electronic devices to have a certain

flexbility (3) requires a high voltage breakdown strength (4) requires a relatively high Tc

to adapt to a wider range of operating temperatures.

Piezoelectric materials are mainly divided into piezoelectric single crystals,

piezoelectric ceramics, polymer piezoelectric materials and polymer-ceramic composites.

They have different process and application characteristics and therefore have different

applications, as it is shown in Fig 3[11].

Figure 3. Categories of piezoelectric materials

2.2.1 Single Crystal

Research on piezoelectric single crystals began in 1958 when Kobayashi in Japan

grew PbTiO3 single crystals[12]. However, it was not until 1967 that researchers were able

to grow 15 mm PMN single crystals by the TSSG method[13]. The most important result

was the Pb(Zn1/3Nb2/3)O3-PT (PZN-9PT) single crystal prepared by Dr. Kuwata in Japan,

which could reach a piezoelectric coefficient of 1500 pC/N[14]. However, the phase
 8

transition temperature of the single crystal was below 100 degrees, which greatly limited

its application. Toshiba Japan used the TSSG method to increase the phase transition

temperature to 230 degrees by developing PMN-PT-PIN system, and the properties of the

single crystal were significantly improved. Figure 4 shows the comparison of different

single crystal preparation methods[14].

At present, the research of single crystal is still one of the popular directions in this

field, and the single crystal components, polarization methods and crystal growth processes

are widely concerned. Among them, AC polarization (ACP) is undoubtedly the most

popular one. AC polarization is the application of an AC electric field during the

polarization process. The direction of polarization is regulated by adjusting the frequency

and period. Compared with direct current polarization, ACP can eliminate the pegging

effect and make the polarization complete. The best single crystal studied so far is the

ternary single crystal material with composition of Pb(Mg1/3Nb2/3)O3-Pb(Yb1/2Nb1/2)O3-

PbTiO3 (52PMN-5PYbN-33PT) prepared by the group from Toyama University, Japan in

2019. d33 can reach 2750pC/N[15].

Figure 4. Lead-based piezoelectric material manufacturing method: Bridgman (BM), Solid State Crystal

Growth (SSCG) and Top Seed Solution Growth (TSSG)

 9

2.2.2 Piezoelectric ceramics

Piezoelectric ceramics are the most versatile piezoelectric materials. From 1946,

when BaTiO3 was discovered, until now, lead-free ceramic components such as KNN and

BNT have been widely studied. Various high performance piezoelectric ceramics have

been produced by changing the ceramic compositions, sintering process, and heat treatment.

Lead-based ceramics such as (Pb,Zr)TiO3 have outstanding electromechanical properties,

but the use of lead is restricted because of its toxicity. Some important lead-free ceramics

are shown in Fig 5[16].

Figure 5. Lead-free piezoelectric ceramics

BaTiO3 ceramics prepared by conventional solid-state processing with a

longitudinal piezoelectric coefficient, d33, of about 190 pC/N and Tc of 120 °C[17]. Higher

piezoelectric coefficient of 460 pC/N is reported using high-quality hydrothermally

synthesis method[18]. However, due to low Curie temperature (Tc) and low depolarization
 10

temperature (Td), the effective application of BT is restricted. Bi0.5Na0.5TiO3–Bi0.5K0.5TiO3

(BNT-BKT) system has been investigated for several years and the piezoelectric

coefficient (d33) could reach 190 pC/N and Tc is about 300 °C[19]. The piezoelectric

properties of this system could be further improved by adding BT, BZT etc[20]. Xiao et al.

by adding BLT((Bi0.5 Li0.5)TiO3) in 0.85BNT-0.15BKT system could obtain dense ceramic

with d33 of 230 pC/N[21,22]. KNN based ceramics has relatively high Curie Temperature at

about 400 °C, so it has no limitation on higher temperature applications compared to BT[23].

However, poor densification of this composition makes limitations on the effective

utilization of this material. Saito improved the processability and densification of this

composition by incorporating with LiTaO3 and LiSbO3 and piezoelectric coefficient to

over 400 pC/N was reported in textured ceramic[24]. Gao et al. doped KNN system with Li,

Ta and Sb with composition of (K0.45Na0.55)0.98Li0.02(Nb0.86 Ta0.10Sb0.04)O3 and obtaining

high d33 of 413 pC/N in dense ceramic[25]. Jingfeng Li’ s group prepared fine-grained

(Na0.535K0.485)1xLix(Nb0.8Ta0.2)O3 ceramics by spark plasma sintering with d33 of 243 pC/N

and high coupling coefficient (kp) of 46.1%[26].

2.2.3 Piezoelectric Polymers

Piezoelectric polymers are widely used for flexible electronics. PVDF is one of the

most important piezoelectric polymers. PVDF is mainly a homopolymer of vinylidene

fluoride or a copolymer with other small amounts of fluorinated vinyl monomers. It has

good chemical resistance, high temperature resistance, oxidation resistance, reasonable

piezoelectricity and dielectric and thermoelectric properties. PVDF mainly consists of α, β,

γ, ε and ρ phases[27]. Among them, α-phase is the most stable, and PVDF films are usually

prepared by tape casting or solution casting.

 11

Figure 6. Comparison of different phase of PVDF.

As shown in Figure 6, the main phases studied in PVDF are phases α, β and γ. Phase

a was the dominant phase for most PVDF films, but it has poor piezoelectricity and high

loss. Phase β has excellent piezoelectric properties, which is suitable for sensor and energy

harvesting applications. The γ phase is always applied for energy storage application due

to its low loss and high electrical breakdown strength. A lot of research work has been

focused on the transformation from α to β and γ phase. The β phase could be transformed

by means of stretching, polarization or doping, as shown in Figure 7[27]. Unlike the β-phase,

the γ-phase is more complicated to obtain and requires strict preparation conditions. The

most efficient way to obtain the γ-phase is to dissolve PVFD using a mixture of solvent

and non-solvent and to heat treat the sample at 160-170 °C[42].

 12

Figure 7. Different method forming β phase.

2.2.4 Ceramic-polymer Composites

Piezoelectric Ceramics such as PZT and PMN-PT have excellent piezoelectric

coefficient. However, their dielectric loss is moderate and dielectric breakdown of the

electric field is significantly too low, which restricts their usage in nowadays advanced

technology[28]. Compared with these piezoelectric ceramics, polymers such as PVDF and

epoxy have a much lower dielectric loss and high breakdown strength. Yet their

permittivity is much lower compared with those of ceramics. The negative relationship

between permittivity and dielectric loss is conflict with each other in a specific application,

so the ceramic-polymer composite is naturally developed to solve the problem of

ceramic[29].

Ceramic-polymer composites are classified according to the self-continuity of

components in 3 directions which are shown in Fig 8. Newnham et al first reported the

connectivity of the composites.[30-32]

Above all designs, composites with 0-3 connectivity offer excellent characteristics

such as low-temperature process ability, flexibility, machinability, chemical resistance, and

 13

tailored dielectric and piezoelectric properties. Such composites consist of polymer matrix

as the body and ceramic fillers with high piezoelectric and dielectric properties dispersed

in the polymer[33-35].

Figure 8. Scheme of different structure of 2-componenet composites

Ploss et al studied PVDF-TrFE/PZT composites with 50 vol% of ceramic.

Composite poled under an electric field of over 50 kV/mm for 1 h[36]. However, the

composite remained unpoled. In most of the previous literatures, the volume fraction of

ceramic powders for composites remain below 55%. Many approaches have been tried to

increase ceramic loading in the composite. Tang et al. introduced 10 wt.% graphene plates

into PZT/PVDF (50vol%/50 vol%) composites. However, piezoelectric properties of the

material didn’t improve considerably due to a lower volume fraction of the ceramic filler,

and the loss of the composite increased. Wei et al. used Hyperbranched polymer (HBP)

and Polydiacetylene (PDA) to coat BaTiO3 spherical ceramic powders to introduce

 14

physical contact between ceramic fillers within the PVDF matrix. Ceramic loading

increased from 50 vol% to about 53 vol%, and d33 increased from 18 pC/N to 36 pC/N.

However, it appears that saturation poling was still not achieved[37]. To solve poling issue

of 0-3 composites and enhance the ceramic loading, innovated processes need to be

considered. Colloidal process is one of the processes successfully applied. Kwon Han et

al. at Rutgers prepared (Pb0.5,Bi0.5)(Ti0.5,(Fe1-xMnx)0.5)O3 (x=0.00 to 0.02) and PVDF co-

polymer composite by colloidal process[38]. Polymer-ceramic solution was precipitated by

introducing methanol solvent. This method could achieve 65 vol% ceramic loading and d33

could reach to about 70 pC/N.

Composite with 2-2 connectivity is also a promising design which attract

researcher’s attention for a variety of applications including sensor, medical ultrasonic

image and energy applications. In the case of the 2-2 composite, both the ceramic and

polymer phases are 2-dimensional self-connected pattern throughout the composite. The

stiff ceramic phase supports most of the stress applied in the parallel direction, yielding a

high piezoelectric charge coefficient. The Macro Fiber Composite (MFC) is the leading 2-

2 composite offering high performance, flexibility and reliability for a variety of

applications. It could be used in both d33 and d31 modes by arranging electrodes into

different directions, as is shown in Fig 3.

(a) (b)

Figure 9. (a) d33 P1 type and (b) d31 P2 type of MFC plate
 15

The P1 type MFCs utilize the effective d33 for actuation, and they are also very

excellent strain sensors. The P2 type MFCs utilize the d31 effect for actuation and are mostly

used for energy harvesting and as strain sensors. Wu et al. applied MFC plates to a 2

degree-of-freedom cantilever and it generated power of 1.2 mW in 1 m/s2 acceleration at

18 Hz[39].

In general, piezoelectric materials have received a great deal of attention for energy

storage and energy harvesting applications. And piezoelectric ceramic-polymer composites

have suitable dielectric and piezoelectric properties as well as high elasticity, thus making

it very promising candidate for energy applications. In this study, we investigated:

1. the preparation and characterization of PbTiO3-PVDF composites with 70%

ceramic content.

2. the design of a two-degree-of-freedom cantilever beam energy harvester and the

optimization of the design by COMSOL simulation.

3. the preparation of PVDF/Al2O3 thick films, the design of multilayer composite

structures, and the evaluation of energy storage properties.

 16

CHAPTER 3 OBJECTIVE AND RESEARCH PLAN

The objective of this work is to develop and investigate the properties of ceramic-

polymer composites, which utilize PVDF as polymer matrix. Both bulk and thin film

composite are prepared and characterized for different applications including energy

storage and energy harvesting.

To investigate the energy harvesting performance of the composite, 0-3 composite

are designed. Colloidal process method is applied to prepare the samples. Process

parameters such as pressing temperature, duration time and poling condition are

researched. The properties such as permittivity, piezoelectric coefficient and dielectric loss

are characterized.

Materials utilized in this work are:

• Ceramics: PbTiO3, BaTiO3, 0.7Pb(Mg1/3Nb2/3)O3-0.3PbTiO3, designated as PT, BT

and PMN-PT.

• Polymer matrix: Epoxy, PVDF.

Composite with high ceramic loading (more than 60 vol%) are focused. 0-3

composite developed in this study composed of above materials are shown below:

• 0.65BT/PVDF and 0.65BT/Epoxy

• 0.7PMN-PT/PVDF

• 0.7PT/PVDF

Energy harvester are also investigated. Cantilever was designed. 2 degree-of-

freedom (designated as 2-DOF) cantilever are designed which will be discussed in the next

chapter. Output voltage and power of the harvester are characterized. Different parameters
 17

such as beam size and weight of the mass are investigated by COMSOL Multi-physics

software. Some energy harvesters with good simulation result will be made in the lab and

tested, then compared to the simulation results. Materials in this part are:

• Micro-Fiber Composite (MFC) plate (PZT/Epoxy 2-2 composite)

• 0.7PT/PVDF composite (0-3 composite)

• (Ba0.95Ca0.05)(Ti0.92Sn0.08)O3 (BT-CT-BS Ceramic)

For Energy storage, thick film with thickness of about 6 µm are prepared and

evaluated. Tape casting method are selected to prepare the films. Process parameters such

as ceramic content, solvents, heat treatment are studied. Parameters such as permittivity,

dissipation factor, recovery energy density (Wr) and efficiency are evaluated. Materials in

this part are:

• PVDF (Mw~540000)

• Al2O3 nano particles. (particle size 200 nm)

Multilayer composites with sandwich structure are designed. Top and bottom layers

consist of pure PVDF, and middle layers are ceramic-polymer composite with 1vol%-5

vol% ceramic loading. Energy density and efficiency of the multilayer composite are

characterized and compared to single layer film.

 18

CHAPTER 4 EXPERIMENT

4.1 Materials

The ceramic-polymer composite was prepared by colloidal process. PVDF with

Mw (molecular weight) of 180000 was purchased from Sigma Aldrich. Ceramic powders

including BT and PMN-PT were obtained from TRS Ceramic Inc. PT was prepared by co-

precipitation method by previous student.

In 2 degree-of-freedom energy harvester research, 2-2 composite micro-fiber

composite (MFC) sheets were purchased from Smart Materials corp. (M-2814-P2).

Alumina sheets with the dimension of 10 cm*10 cm were purchased from Yodaoke

fulfilled by Amazon. 2-component silver epoxy paste (8331-14G) applied to connect wires

and was purchased from MG Chemicals Inc. PT/PVDF composite were prepared by

colloidal process. BT-CT-BS ceramics were prepared by solid state reaction.

In PVDF thin film research, PVDF with Mw of 540000 was purchased from Sigma

Aldrich. Al2O3 nano-powders with particle size of 200 nm were purchased from US

Research Nanomaterials, Inc.

4.2 Characterization method

In this work, dielectric properties, piezoelectric properties and energy harvesting

and storage performance were investigated.

Piezoelectric coefficient was characterized by Berlin Court d33 By the Berlincourt

Piezo-Meter at 100 Hz at room temperature, as it was shown in Fig 11. The Piezo-Meter

was calibrated by standard samples before use.

 19

Dielectric properties including permittivity and dielectric loss were obtained by

4194A Impedance/Gain-Phase Analyzer at 1kHz at room temperature, as it was shown in

Fig 12. Dielectric loss could be directly characterized by the instrument. The permittivity

of the sample was calculated by getting capacitance and calculated by the following

equation:

𝐶𝑡
𝜀𝑟 =
𝐴𝜀0

Where C is the capacitance obtained from the test. A is the top or bottom area of

the sample and t is the thickness of the sample.

Energy harvesting performance including output voltage, resonant frequency and

output power were simulated by COMSOL Multi-physics. In the lab, output voltage was

obtained from oscilloscope. Resonant frequency was set by shaker and decided by the

peak voltage. The setup of the experiment are shown in Fig 10.

Energy Storage performance including hysteresis loop, recovery energy density

and efficiency were characterized by high power supply and Vision Pro Software.

Hysteresis loop and recovery energy density were directly obtained by the software.

Efficiency was calculated by:

𝑅𝑒𝑐𝑜𝑣𝑒𝑟𝑦 𝐸𝑛𝑒𝑟𝑔𝑦 𝐷𝑒𝑛𝑠𝑖𝑡𝑦

𝜂=
𝑇𝑜𝑡𝑎𝑙 𝐸𝑛𝑒𝑟𝑔𝑦 𝐷𝑒𝑛𝑠𝑖𝑡𝑦
 20

Figure 10. Instruments of Energy Harvesting research

 21

Figure 11. Berlin Court d33 piezo-meter at 100 Hz.

Figure 12. 4194A Impedance/Gain-Phase Analyzer

 22

4.3 Experiment

4.3.1 Colloidal Process

Colloidal process is the process in which the composite was formed by precipitation

of the ceramic and polymer powders from solvents, and then pressed at 140-200 °C.

Procedures in this work are shown as Fig 13.

In this work, BT, PMN-PT and PT powders were used as ceramic fillers, and PVDF

powders were used as the polymer matrix. First, each batch consists of which 1g of PVDF

was dissolved into 10 ml Dimethylformamide solvents (designated as DMF). After

dissolving PVDF in DMF, ceramic fillers were added to have ceramic with 65-70 vol%

loading. The mixture was fully stirred for 24 h, and then DI water was drop-wised with the

speed of 2 ml/min. After adding 14 ml of DI water, the PVDF and fillers were fully

precipitated. The composite was pressed at room temperature at 15 psi to remove the liquid

phase. Finally, the condensed sample was warm pressed at 160-200 °C.
 23

Figure 13. Flow chart of Colloidal process composite process.

 24

4.3.2 Energy Harvesting Evaluation

In this work, 2-Degree of Freedom cantilever was designed for vibration energy

harvesting. As it was shown in Fig 13. Piezoelectric materials including MFC, PT/PVDF

composite and BT-CT-BS ceramic were attached on the inner beam. 2-component silver

epoxy paste was applied to connect wires. The output voltage is shown by oscilloscope or

computer.

Figure 14. Design of 2-DOF cantilever

Laboratory testing system on the energy harvesting performance of piezoelectric

cantilever has been built. Major testing devices selected in this system contain an APS 400

Electro-SEIS Long Stroke Shaker to simulate the base vibration, an APS Power Amplifier

to drive the shaker, an IEPE data acquisition system to control the shaker by input signals

from a computer and to collect the output signal from the accelerometer on the shaker, a

computer installed with a software to generate signals and to receive the acceleration

information measured from the accelerometers, and an EDUX1002A oscilloscope to

measure the voltage output from the piezoelectric cantilevers on the shaker.

Once the piezoelectric cantilever was fabricated and the laboratory devices were

setup, the voltage output from cantilever was then measured by the EDUX1002A
 25

oscilloscope. The measurement was further saved by the USB flash drive in the format of

“csv.” for further analysis use.

COMSOL Multiphysics was applied to simulate and optimize the design.

Cantilever was designed by SolidWorks Software. Piezoelectric device was selected.

Transient analysis was applied to obtain output voltage in different frequency. Output

power at resonant frequency was also simulated by COMSOL for different resistance.

4.3.3 Tape Casting

In this work, PVDF with Mw of 540000 was selected. Al2O3 nanoparticles with an

average particle size of 200 nm was used as fillers. A tape casting method was used to

prepare the films. Before tape casting, every 1 g PVDF was dissolved in 10ml of solvent.

PVDF was gradually added in the solvent, the temperature was set to 60 °C and the Teflon

film was covered on the beaker during the stirring to help dissolving. Here DMF and

DMF+Acetone (3:1) chemicals were selected as solvents. For composite films,

nanoparticles were added gradually and kept stirred to obtain uniform distribution.

Tape casting instrument was shown in Fig 15, the tape caster was supplied by The

Tape Casting Warehouse, Inc. The temperature of the carrier was set to 60 °C and casting

speed to 0.5 mm/s. First, the solution was poured on the blade, and the instrument was

turned on to cast the film. Then the mixture was dried in the chamber to form the film.

When all liquid phase disappeared, the film was moved to furnace at 140-160 °C for heat

treatment. The films were cut into square samples with 1 to 2 cm side lengths and then

electroded by sputtering.
 26

Multilayer design was shown in Fig 16, top and bottom layers were PVDF films,

the middle layer was doped by Al2O3 with 1 to 5 vol% loading. The bottom films were

casted, then the second and third layers were casted layer by layer after the last layers were

fully dried.

Figure 15. Tape casting Instrument

Pure PVDF
PVDF/Al2O3 composite

Pure PVDF
Figure 16. Scheme of the multilayer composite.

4.3.4 Fabrication of the (Ba0.95Ca0.05)(Ti0.92Sn0.08)O3 Ceramic

The BT-CT-BS ceramic composition used for energy harvesting was prepared by

conventional solid-state reaction using BaCO3, CaCO3, TiO2 and SnO2 as raw materials.

The raw materials were mix in stoichiometric proportionaccording the composition

(Ba0.95Ca0.05)(Ti0.92Sn0.08)O3. Then the mixture of the staring oxides and carbonate powder

was ball milled for 12 h. After drying, the powder was calcinated at 1100 °C for 4h, and

the calcined powder ball milled again for 12 h. The powder was mixed with 10 wt.% of
 27

10% polyvinyl alcohol (PVA) solution and then pressed into disc. The binder was removed

at 550 °C for 4h and the ceramic disc was sintered at 1480-1500°C for 2h.

Sintering temperature of this composition was investigated, as it was shown in Table 1.

Ceramics sintered at 1500 °C has optimum dielectric permittivity and piezoelectric

coefficient. As a result, composites sintered at 1500°C was used for the future energy

harvesting application.

Table 1. Properties of BT-CT-BS ceramics

(Ba0.95Ca0.05) (Ba0.95Ca0.05)
Composition
(Ti0.92Sn0.08)O3 (Ti0.92Sn0.08)O3

Sintering Temperature 1480°C 1500°C

Piezoelectric coefficient
422 368
d33 (pC/N)

Permittivity at room
~2800 ~3000
temperature

% Theoretical Density 95.3 93

 28

CHAPTER 5 RESULT

5.1 Colloidal Process Composite

In this section, dielectric and piezoelectric properties of the samples were

characterized. Piezoelectric coefficient, permittivity and dielectric loss were tested and

compared. Process parameters including press temperature, duration time and poling

conditions were investigated to further improve the performance.

BaTiO3/Epoxy and BaTiO3/PVDF composites were first prepared and

characterized. The average particle size of BT powder was 200 nm. The molecular weight

of PVDF was 180000. The results of the dielectric and piezoelectric measurements are

shown as Table 1.

Table 2. Result of BT/PVDF composite (65 vol%)

Sample BT/Epoxy BT/PVDF BT/PVDF BT/PVDF

Applied 14 kV/mm 14kV/mm 14 kV/mm 16kV/mm

Voltage
Keeping 30 min 30 min 30 min 30 min
time
d33 9 14 14 10
(10-12pC/N)
Permittivity 76 72 80 74
at 1 kHz
Dielectric 0.092 0.037 0.035 0.038
loss at 1
kHz

The piezoelectric coefficient of the composites ranges from 9 to 14, which

resembles the d33 of pure PVDF. The reason for this is that the dielectric constant of

ceramic materials is very different from that of polymers, and this difference changes the

flow of voltage. Permittivity of PVDF and BaTiO3 are 10 and 5000, respectively, at room
 29

temperature. During poling of the samples, most of the voltage will pass through the

polymer matrix instead of the ceramic fillers, which results in poor polarization of BT

particles. The composite was poled at 14 kV/mm and would breakthrough at about 16

kV/mm. Traditionally high temperature poling of piezoelectric samples could improve the

polarization of filler materials, due to the low Curie temperature of barium titanate, the

temperature of the oil bath should not be higher than the Curie temperature of barium

titanate.

To further investigate the influence of the ceramic fillers in the composite,

0.7PMN-0.3PT powder was introduced. Compared with BT, PMN-PT has a higher d33 of

about 700 pC/N and lower permittivity at room temperature of about 2000. The results of

the dielectric and piezoelectric properties of the composite are shown in Table 2.

Compared with BT/PVDF composites, PMN-PT/PVDF composites shows improvement

in both properties with similar dielectric loss. Samples pressed at 200 °C was better than

those pressed at 175°C, which suggests that the press temperature has pronounced effect

on the improvement of the dielectric and piezoelectric properties of the composite.

 30

Table 3. Result of PMN-PT/PVDF composite (70 vol%)

Sample PMN-PT/PVDF PMN-PT/PVDF PMN-PT/PVDF PMN-PT/PVDF

Applied Voltage 10kV/mm 10kV/mm 15kV/mm 15kV/mm

Press 175°C 200°C 175°C 200°C

Temperature

d33 10 12 16 25
(10-12pC/N)
Permittivity 80 98 88 78
(at 1kHz)
Dielectric loss 0.062 0.047 0.044 0.049
(at 1kHz)

To furtherly mitigate the difference of the permittivity of the composite, ceramic

fillers with lower permittivity was investigated. PbTiO3 has permittivity of about 200 at

room temperature. Also, PT powders used in this research was prepared by solution-based

co-precipitation method[41]. The result of piezoelectric and dielectric properties of the PT-

PVDF composite was shown in Table 3.

Table 4. Result of PT/PVDF composite (70 vol%)

Sample PT/Epoxy PT/PVDF PT/PVDF PT/PVDF

Applied Voltage 10 kV/mm 15kV/mm 16kV/mm 16kV/mm

Press 200°C 200°C 175°C 200°C

Temperature
d33 22 35 38 45
(10-12pC/N)
Permittivity 66 69 75 81
(at 1kHz)
 31

Dielectric loss 0.062 0.077 0.025 0.040

(at 1kHz)

Compared to the all 0-3 composites, prepared PT/PVDF had much higher

piezoelectric coefficient with 45 pC/N, which was about 5 times of that of pure PVDF.
 32

5.2 Energy Harvester Cantilever

5.2.1 Finite Element Model of Piezoelectric Cantilever in Comsol Multiphysics

Based on the previous research on the design of cantilevers for energy harvesting

through piezoelectric materials under base vibration, a 2 degree-of-freedom cantilever

being able to create a power output level of 1 mW under pavement vibration frequencies

with two resonant frequencies is searched out and compared with previous result [40].

The double-degree-of-freedom cantilever beam structure is shown in the figure 17.

A pathway is cut out of the middle of the aluminum plate, thus forming two cantilever

beams inside and outside, which were designated as secondary and main beam. When both

beams vibrate simultaneously, one beam attached by piezoelectric materials drives them to

generate electrical energy, while the vibration of the other beam affects the vibration of the

inner cantilever beam resulting in a pronounced change in resonant frequency and output

electrical energy. The detailed design of this cutout 2 degree-of-freedom was consistent

with the one built in the laboratory. The material properties of each component in this

cutout cantilever used in this study are listed in Table 4.

The design of the cantilever was evaluated and optimized by Comsol Multi-physics.

First, the influence of the mass combination was investigated, mass 1 and mass 2 were set

on the main and secondary beam, respectively. (m1 = 7.2 g; m2 = 8.8 g, 11.2 g, 14.2 g, and

16.8 g). Fig 18 shows the result of the voltage output from MFCs on the cantilever with

different mass design. The output voltage of the cantilever of which the MFC sheets was

attached on the main beam was shown as the black line and red on the secondary beam.

For all the 4 mass distributions the peaks of the red line are higher than that of the black

line, means it is better to set the piezoelectric materials on the secondary beam. The voltage
 33

from MFCs on the secondary beam with different mass distribution were compared, as it

was shown in Fig 19. Cantilever with the mass 2 of 16.8g could generate output voltage of

28.8 V at 16 Hz.
 34

Figure 17. FEM of 2-DOF piezoelectric cantilever (a) geometric design and boundary conditions; (b) meshes of FEM

Table 5. Key material parameters used in this 2-DOF piezoelectric cantilever

Material Properties
Components Cantilever MFC
Density (kg/m3) 2700 5440
Poisson's ratio 0.33
ν12 0.31
ν13 0.31
ν23 0.44
Young's modulus
(Pa) 7.00×1010
E1 3.03×1010
E2 1.59×1010
E3 5.52×109
Capacitance (nF) 30.8
Structural loss
factor 0.007
 35

Figure 18. Voltage output from MFCs on the cutoff cantilever design with m1 = 7.2 g; (a) m2 = 8.8 g, (b) m2 = 11.2 g,
(c) m2 = 14.2 g, and (d) m2 = 16.8 g.

Figure 19. Voltage outputs from MFC on the secondary beam of cutoff cantilever design
 36

Secondly, the output power of the designed cantilever was investigated. The output

power changing with the resistance estimated by FEMs is shown in Figure 20. As can be

seen, the maximum power output from the MFC on secondary beam occurs at external

resistance of 250 kΩ, which was 1.08 mW.

4.2.2 Voltage output measured from cantilever

The Energy harvester was fabricated according to the simulation to verify the

simulation result. As an example, the voltage output from the 2-DOF cantilever in a length

of 13.5 cm with a mass of 17.2 g under a vibration of 0.15 g acceleration at 7 Hz is shown

in Figure 21.
 37

Figure 20. Power output from cutoff cantilever under (a) different external resistances; (b) different external
resistances in log

Figure 21. Voltage output measured by oscilloscope (a) screen shot; (b) data read in csv.
 38

The result of the laboratory evaluation with various applied mass distribution at

resonant frequency was compared with the FEM simulation, as it was shown in Table 5.

Mass distributions of the lab evaluation was the same as those of FEM simulation

mentioned above.

Table 6. Comparison of simulation and experiment result

Mass 2 (g) 8.8 11.2 14.2 16.8

FEM (V) 24.7 25.2 20.8 28.8

Lab Result (V) 19.2 21.5 15.4 23.7

It was found that the result of the experiment was lower than FEM result. The

reason was investigated. It could be due to an unsteady vibration from the shaker or a

loosen connection between cantilever and the shaker. The connection between MFC and

cantilever was not fully considered which also might cause vibration loss.

Also, the composite prepared by colloidal process mentioned before was used on

the designed cantilever to investigate the energy harvesting performance. To meet with the

FOM of energy harvesting(d*g), 70 vol% PT/PVDF composite with d33 of 45 was studied

and compared with (Ba0.95Ca0.05)(Ti0.92Sn0.08)O3 ceramic prepared by conventional solid

state process, which has d33 of 422 pC/N and permittivity of about 3000 at room

temperature.

The 70 vol% PT/PVDF composite and (Ba0.95Ca0.05)(Ti0.92Sn0.08)O3 ceramics were

pressed into disc shape with diameter of 15 mm and thickness of 6 mm. The samples were
 39

attached on the 2-DOF beam. Two different masses were introduced into the beam to

optimize the open-circuit performance.

Two cantilevers were separately attached on the beam and set on the accelerator

and connected with the oscilloscope. The voltage could be characterized by wave

amplitude, as it was shown in Fig 22.

(a) (b)
Figure 22. Characterization of open-circuit voltage (a) Ceramic (b) Composite

The results of the output voltage of the piezoelectric materials at resonant frequency

are shown in Table 6. The frequency was tried from 1 Hz to 25 Hz to obtain the resonant

frequency. According to the result, 15 Hz and 22 Hz shows voltage peaks. the 70 vol%

PT/PVDF composites show the better open-circuit performance, which meet with the

figure of merit of energy harvesting.

 40

Table 7. Open circuit result of the ceramic and composite

Frequency
15Hz 22Hz
Materials

(Ba0.95Ca0.05)(Ti0.92Sn0.08)O3 0.52V 0.94V

0.7PbTiO3/0.3PVDF 1.37V 0.51V

Composite
 41

4.3 Al2O3/PVDF composite prepared by tape casting

The flow chart of this study is shown in Fig 23. As described earlier, the γ phase of

PVDF has high breakdown strength, low dielectric loss. The use of solvent and non-solvent

mixtures to dissolve PVDF combining with the heat treatment of the film can effectively

facilitate the conversion of the α-phase to the γ-phase [42]. This study was focused on

influence of solvents and heat treatment of the film, Acetylacetone was applied as non-solvent.

For composite research, 1 to 5 vol% Al2O3 nanoparticles were introduced into the PVDF

to prepare the film with the thickness of 6 μm. For multilayer composite, low-high-low k

design was designed. Top and bottom layers consist of pure PVDF, and middle layers

consist of composite film with 1 to 5 vol% Al2O3, as it is shown in Fig 16.

Figure 23. Guideline of the tape casting research.

To investigate the influence of the process to the PVDF, pure PVDF films were

prepared by tape casting. DMF with acetylacetone in volume ratio of 3:1 was selected as

solvent, and the prepared film was kept at different temperature ranging from 140°C to
 42

160 °C. The result of the energy storage performance of films prepared by different

solvents, kept temperature and duration time were shown in Table 7.

The PVDF films prepared by DMF solvents were lossy even kept at 160 °C for 12h.

PVDF films prepared by DMF and Acetylacetone solvents were still lossy when kept at

140 °C. the films prepared by mixed solvents and kept at 160°C which was slightly lower

than melting temperature of the PVDF (170 °C) obtained high recovery energy of 0.66

J/cm2 and the efficiency of 62%. These results mean γ phase should be formed by

combination of DMF/Acetylacetone solvents and heat treatment at 160 °C.

Table 8. Result of PVDF film made by tape casting.

Process Tape Tape Tape casting Tape casting Tape casting Tape casting
casti casti
ng ng
Solvent DM DM DMF+Acetyla DMF+Acetyla DMF+Acetyla DMF+Acetyla
F F cetone cetone cetone cetone
Duration 6 12 6 12 6 12
time(h)
Temperat 160 160 140 140 160 160
ure(°C)
Permittivi 9 11 14 13 13 14
ty
(1 kHz)
Dielectric 0.04 0.09 0.06 0.09 0.06 0.06
loss
(1 kHz)
Breakdow 1600 1800 >2000 >2000 >2000 >2000
n Strength
(kV/mm)
Energy loss Loss Lossy Lossy Wr=0.57 Wr=0.66
Storage y y Efficiency=66 Efficiency=62
% %

After pure PVDF work, Al2O3 nano-powder/PVDF polymer composite was

prepared. Here the permittivity of Al2O3 resembles that of PVDF, which means the voltage
 43

applied especially to both PVDF and Al2O3 phases. In the composites, Al2O3 with 1-5 vol%

loading was prepared, Higher ceramic concentrations can lead to uneven distribution of

ceramic powders and possible precipitation. Thickness of the samples ranged from 5 to 7

micrometers by setting the thickness of the tape casting blade. The result of the energy

storage performance of the Al2O3/PVDF composite was shown in Table 8, the energy

density and the efficiency were plotted in Fig 24. The energy density of the films increases

with increasing Al2O3 content, reaching a maximum value of 0.98 J/cm2 at about 3 vol%,

but significantly decrease at about 5 vol%. It means additive of Al2O3 could help forming

γ phase thus improve the energy storage performance of the composite. However, the

excessive ceramic loading will make the composite inhomogeneous and deteriorate the

properties of the composite.

Table 9. Result of Al2O3/PVDF composite

Process Pure PVDF 1 vol% Al2O3 3 vol% Al2O3 5 vol% Al2O3

Temperature(°C) 160 160 160 160

Permittivity 9 14 12 18
(1 kHz)
Dielectric loss 0.06 0.08 0.08 0.07
(1 kHz)
Energy Density Wr=0.57J/cm2 Wr=0.68J/cm2 Wr=0.98J/cm2 Wr=0.54J/cm2
Efficiency=66% Efficiency=57% Efficiency=65% Efficiency=55%

Thickness(μm) 6 7 6 5
 44

(J/cm2) Energy Density

1.2

0.8

0.6

0.4

0.2

0
0 1 vol% 3 vol% 5 vol%

Figure 24. Plot of energy density with change of the ceramic volume percent.

The result of the energy storage performance of the multilayer composite was

shown in Table 9. The multilayer consists of 3 layers, the top and the bottom layers were

pure PVDF, and the middle layers were Al2O3/PVDF composites with ceramic loading of

1 to 5 vol%. Similar to the single layer composite, the energy performance of the multilayer

composite improved with the increasement of the ceramic loading and reach maximum at

3 vol% loading, then dropped at about 5 vol%. But the energy density of the multilayer

composite increases about 20% and the efficiency increases about 15% compared with

those of single layer composite. The reason is the multilayer design. The difference of the

permittivity between outer layers and the middle layer could help decrease the loss of the

energy storage and increase the breakdown strength, thus improve the energy storage

performance. The Al2O3/PVDF composite with the ceramic loading of 3 vol% could

generate recovery energy density of 1.08 J/cm2 with the efficiency of 71%, which is nearly

twice of the pure PVDF.

 45

Table 10. Result of multilayer composite

Process Pure PVDF 0-1-0 0-3-0 0-5-0

Keeping 160 160 160 160

Temperature(°C)

Thickness(μm) 6 16 18 16

Permittivity 9 13 14 13
(1 kHz)
Dielectric loss 0.06 0.04 0.03 0.04
(1 kHz)
Energy Density Wr=0.57J/cm2 Wr=0.77J/cm2 Wr=1.08J/cm2 Wr=0.86J/cm2
Efficiency=66% Efficiency=62% Efficiency=71% Efficiency=54%

1.2

1
Energy Density (J/cm2)

0.8

0.6

0.4

0.2

0
Pure PVDF 0-1-0 0-3-0 0-5-0
multilayer Design

Figure 25. Plot of the energy density with different multilayer design.
 46

To furtherly compare the difference between PVDF, composite and multilayer

thin film, the hysteresis loop of three materials were shown as Fig 24. The energy density

of the materials could be calculated by:

𝑊 = ∫ 𝐸𝑑𝐷

As it is indicated in the blue area in Fig 26[43]. Therefore, the hysteresis loop of

the material can also observe the energy performance of the material. Figure 27 shows

the hysteresis loop of some of the films studied above. Figures 27 a and 27 b show films

dissolved with DMF and stored at 140 degrees for 12 hours, and films dissolved with a

mixture of DMF and Acetylacetone and stored at 160 degrees for 12 hours, respectively.

It can be seen that the shape of the hysteresis loop of the latter is significantly thinner and

the upper space area is larger, thus the energy storage performance should be better,

which is also consistent with the measured data, the former one is lossy and the latter one

generates energy density of 0.57 J/cm2. Fig 27 c and d show the hysteresis loop of the

single layer composite with 1 vol% and 3 vol% ceramic loading. Composites with 3 vol%

loading has slimmer loop thus relative higher area, the energy density of them are 0.68

J/cm2 and 0.98 J/cm2, which accord with the difference of the hysteresis loop. Fig 27 d

and e are hysteresis loop of 0-1-0 and 0-3-0 multilayer composite films. The loop

becomes thinner compared with single layer film, cause the 20% increasement of the

energy density.
 47

Figure 26. Scheme of the energy storage.

 48

a b

c d

e f

Figure 27. Hysteresis loop of (a) PVDF with DMF solvent. (b) PVDF with DMF+Acetone (c) 1vol% Al 2O3/PVDF
composite (d) 3 vol% PVDF composite (e) 0-1-0 composite (f) 0-3-0 composite
 49

CHAPTER 5 CONCLUSION

In this study, 0-3 piezoelectric ceramic-polymer composites with various fillers

were prepared by several different methods. Cantilevers was designed and fabricated, the

PZT-Polymer composite with 2-2 connectivity was applied to the designed cantilever. The

PVDF/Al2O3 composite films were prepared by tape casting and the three layers of

PVDF/alumina powder composite/PDVF composite were designed for energy storage

application. The followings are a summary of the achievements.

(1) PVDF/PbTiO3 powder composite with 70% ceramic loading was prepared and

processing parameters such as pressing temperature, pressure, and heat treatment time and

temperature were investigated. The composite was processed at 200 °C pressing

temperature and 5000 psi pressure. showed the best piezoelectric coefficient, d33, of 45

pC/N and dielectric constant of 80 at 1 kHz

(2) 2-DOF cantilevers were designed. 2-2 composite MFC sheet was used to the

cantilever for energy harvesting application. The design was optimized and simulated by

COMSOL Multiphysics Software. In the simulation, the cantilever with mass distribution

of 7.2g and 16.8g for mass 1 and mass 2, respectively, showed the highest voltage of 28.8V

and the highest output power of 1.08 mW at resonant frequency. The simulated cantilever

was fabricated in the physical experiment and could generate the highest output voltage of

23.7V, which is comparable to the simulation result.

(3) PVDF/Al2O3 flexible thick film composite with 1 to 5 vol% Al2O3 nano-powder

were successfully fabricated by tape casting method. Process parameters such as solvents,

post fabricated temperature, and time was investigated. The recovery energy density of

0.98 J/cm2 and efficiency of 65% at 500 kV/cm was obtained from the composite with 3
 50

vol% Al2O3. Multilayer composite of PVDF/ 3vol%alumina composite/PVDF provided

the highest recovery energy density of 1.08 J/cm2 and efficiency of 71%.
 51

CHAPTER 6 FUTURE STUDY

In the future, the study will focus on the energy harvesting and energy storage

application of the 0-3 composite:

(1) Different lead-free ceramic fillers such as Bi0.5Na0.5TiO3, BiFeO3-Bi0.5K0.5TiO3

compositions will be used to prepare the 0-3 composite to meet with the environmental

requirements. Alternating current poling (ACP) will be applied to help poling the prepared

composite.

(2) For cantilevers for energy harvesting, different designs of the cantilevers will

be researched to meet with the application for low frequency. Different composites will be

applied to the cantilevers to obtain the materials with promising energy harvesting

performance.

(3) For PVDF composite thick film research, influence of the morphology of the

fillers such as nanotube, nano-plate structures will be investigated. Different multilayer

composites will be designed with the consideration of the number of layers, distribution of

the ceramic fillers and layout of each layers.

 52

Reference

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Devices and Applications: Chapter (1988).
[2] Dang, Zhi‐Min, et al. "Flexible nanodielectric materials with high permittivity for
power energy storage." Advanced Materials 25.44 (2013): 6334-6365.
[3] Yao, Zhonghua, et al. "Homogeneous/inhomogeneous‐structured dielectrics and
their energy‐storage performances." Advanced Materials 29.20 (2017): 1601727.
[4] Luo, Qu, et al. "The role of dielectric permittivity in the energy storage
performances of ultrahigh-permittivity (SrxBa1− x)(Ti0. 85Sn0. 15) O3
ceramics." Ceramics International 44.5 (2018): 5304-5310.
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