Supplementary Information Mechanical energy harvesting via plasticizer modified electrostrictive polymer

Supplementary Information

Mechanical energy harvesting via plasticizer modified electrostrictive polymer

Xunqian Yin, Jean-Fabien Capsal^a) , Mickaël Lallart, Pierre-Jean Cottinet and Daniel Guyomar

Laboratoire de Génie Electrique et Ferroélectricité (LGEF), Université de Lyon, INSA de Lyon, EA682, 8 Rue de la Physique, 69100, Villeurbanne, France

1. 
   Preparation of plasticizer DEHP modified terpolymer
   

The all-organic composite of P(VDF-TrFE-CTFE) terpolymer modified with plasticizer DEHP was prepared by a simple solution-casting method.

Terpolymer was first dissolved in methyl ethyl ketone (MEK) with help of the electromagnetic stirrer at a temperature of 70 °C for 4 h. The mass fraction of P(VDF-TrFE-CTFE)/MEK solution is 10 wt.%. DEHP with desired mass was secondly added into the solution and stirred for another 4 h. The mass fraction of DEHP in the all-organic composite is 2.5 wt.%.

The as-prepared solution was cooled to room temperature and put into a refrigerator for 48 h to stabilize the solution and to move the air within the solution. Solution with desired mass was poured into a petri dish with a diameter of 10 mm. A teflon cover was used to cover the petri dish 3 h to get a well distributed liquid within the petri dish. And then, teflon cover was taken off and the solvent MEK evaporated and finally we got the P(VDF-TrFE-CTFE)/DEHP composite film.

The solution-casted film was taken from the petri dish and put into an oven to remove the residual solvent at 70 °C for 2 h. And continuously, the film was annealed at 110 °C for 2 h to improve its crystallinity. The thickness of as-prepared film is in the range of 70-80 μm.

2. 
   Properties characterization of DEHP modified terpolymers
   

1. 
   Dielectric properties
   

For dielectric measurement, circular gold electrodes with a diameter of 8 mm were sputtered on both sides of the P(VDF-TrFE-CTFE)/DEHP composite film samples. The dielectric properties were measured with a SI1260 (Solartron) impedance analyzer system in a frequency range 0.1 Hz to 1 MHz.

2. 
   Mechanical properties
   

The uniaxial tensile measurement was performed using a load (force) sensor cell and a Newport table micro-controller (XMS50) system (Fig. S1), in which a 4 cm × 1 cm film sample was stretched in length direction with a maximum strain of 1 % at 0.1 Hz. The Young’s modulus was derived from the slope of stress versus strain curve.



Figure S1. Schematic illustration of the equipment for the measurement of mechanical properties for P(VDF-TrFE-CTFE)/DEHP composite.

3. 
   Electromechanical properties
   

The electromechanical properties of DEHP modified terpolymers films were evaluated via a dedicated test bench based on a cantilever theory. After deposition of gold electrode by sputtering (Cressington 208 HR) through a designed mask (Fig. S2), the electroactive film was bonded to a 100 µm-thick PET film using a pressure sensitive adhesive (25 µm-thick Scotch 3M ATG 924). The samples were then laminated at room temperature for 15 minutes using a D&K 4468H laminator machine in order to optimize the bonding of the polymer on the substrate. As shown in Fig S2b, the as-prepared cantilever was assembled by three layers, i.e., electroactive films with electrodes, adhesive and polyethylene terephthalate (PET) substrate.



Figure S2. Schematic illustration of (a) the mask used for gold electrode sputtering on the polymers, (b) the assembled cantilever polymer bender and (c) the measurement system for electromechanical characterization.

To perform the electromechanical measurement, the cantilever was hold on a test bench (see Fig. S3), in which aluminum profiles were used to fabricate the test bench scaffold on a breadboard. The cantilever was attached to a home-made sample holder comprising a pocket to hold the cantilever and a spring contact to apply the electric field. After being clamped, the effective length of the cantilever for electromechanical measurement was 41 mm (as shown in Fig S2c). A laser (BAUMER CH8501) was mounted on the scaffold to record the deflection at the end of the cantilever. And a Labview program was developed to generate and control the applied electric field signal which was amplified by a TREK 609D-6 high-voltage amplifier, and to collect and process the data of the deflection which was measured by the laser and recorded by a National Instrument NIDAQ-9174 test system. Subsequently, the deflection and transverse strain could be directly exported from this program.

Figure S3. Schematic illustration of test bench developed for the electromechanical characterization.

The strain can be deduced from the deflection measurements of a unimorph under quasi-static condition using the following expression^S1:

, (S1)

where δ₀ is the cantilever tip deflection, L and e are respectively the effective length and thickness of the electrostrictive polymer samples, A = Y_substrate/Y_polymer and B = e_substrate/e_polymer with Y_substrate, Y_polymer, e_substrate, e_polymer giving the Young’s modulus of electrostrictive polymer, Young’s modulus of substrate, thickness of electrostrictive polymer and thickness of substrate, respectively. The Young’s modulus of PET used as the substrate in our experiment is 4.5 GPa, and the electromechanical measurements were carried out at 0.1 Hz and 1 Hz.

3. 
   Films used for mechanical energy harvesting
   

The film thickness of pure and modified terpolymer film used for short-circuit current measurement are 76.6 µm and 65 µm, respectively, while for power characterization, they are 75.6 µm and 60.1 µm, respectively. The length and width of all polymer films with electrode are 5 cm and 1 cm. For all of the samples, 1 cm is clamped for electrical contact, and thus the effective length of films used for energy harvesting is 4 cm.

4. 
   The definition of applied strain for energy harvesting
   

As shown in Fig. S1, the polymer film was clamped by two ends: one end was clamped to a fixed clamp (left side), and the other side was clamped to a mobile side (right side) with an electrically precisely controlled motor (1mm/100 mV). To apply the desired strain, 1% for example, we first measured the effective length of the polymer film between the two clamps, 4 cm for example, and secondly, a sinus electrical signal with amplitude of 2 mV (min voltage 0 mV) generated by a function generator was applied on the motor.
References
^S1 Z. Y. Cheng, V. Bharti, T. B. Xu, Haisheng Xu, T. Mai, and Q. M. Zhang, Sensors and Actuators A: Physical 90 (1–2), 138 (2001).

a)^a) Author to whom correspondence should be addressed. Electronic mail: [e-mail]