Supplementary Information

Biobased Piezoelectric Nanogenerator for Mechanical Energy Harvesting using Nanohybrid ofPoly(vinylidene fluoride)

Anupama Gaur1, Shivam Tiwari1, Chandan Kumar2, Pralay Maiti1*

1 School of Materials Science and Technology, Indian Institute of Technology(Banaras Hindu University), Varanasi 221005, India

2 School of Biomedical Engineering, Indian Institute of Technology(Banaras Hindu University), Varanasi 221005, India

Chemical compositions of Egg shell membrane:

Schematic: Schematic of egg layers indicating egg shell membrane (ESM).

A hen’s egg typically weighs almost 60 gm with a surface area of 53 cm2. It consists of 0.3-0.4

mm thick shell weighing 6 gm, egg white 34 gm and egg yolk 19 gm. The egg shell membrane is

one of the layers present in egg shell and has a total weight of 140 mg [1].

Electronic Supplementary Material (ESI) for Nanoscale Advances.This journal is © The Royal Society of Chemistry 2019

ESM is a fibrous structure which is situated between egg shell and the egg white (Figure S1). It

is a bi-polymeric fibrous net, which is critical for the egg shell formation and prevent the

mineralization of egg white from inside and provides non-mineralized platform for the outer

mineralization of egg shell [2, 3].

The ESM fibers are 80-85% protein, of which ~10% is collagen (type I, V and X) and 70-75%

are the secondary protein components including osteopontin, keratin, proteoglycans and

glycoproteins [4-13]. The ESM and egg shell together contains more than 500 proteins, which is

much higher than other egg parts like: egg white has 148 proteins, vitelline membrane 137 and

egg yolk has 316 proteins [9-14]. The presence of 62 proteins is reported recently [15]. Wong et

al. [16] reported the ration between collagen I and V is 100:1. The detail of proteins in egg shell

matrix can be found in literature [3, 17-20].

Each fiber of ESM has a collagen-rich core and a glycoprotein rich core [3, 25]. The outer ESM

fibers’ core contains mainly type I collagen and inner fibers’ core contain type I and V collagen

[21]. Collagen type X is present in both the membranes [22]. The inner ESM is not calcified but

the outer ESM fibers are partially mineralized [2, 3].

Figure S1:Deconvolution of X-ray diffraction pattern of egg shell membrane.

The X-ray diffraction (XRD) pattern of ESM is shown in Figure S1.XRD pattern shows the

crystalline nature of the ESM due to the presence of highly ordered collagen fibrils. The

deconvolution of XRD pattern shows the crystalline phases present. The crystalline peakssuggest

the presence of collagen, osteopontin, keratin, proteoglycans and glycoproteins [23, 24]. The

amount of crystallinity through XRD deconvolution is around 40 %, which indicates the

semicrystalline nature of the ESM.

Figure S2: X ray- diffraction pattern for (a) PVDF-ESM nanohybrids and (b) PVDF-nanoclay-ESM nanohybrids.

Figure S3: (a, b) FTIR spectra of Egg shell membrane.

Figure S3shows the FTIR spectra of ESM; the spectra have two regions higher 2500 to 3750 cm-

1 wavelength region (Figure S3a) and lower below 1700 cm-1 region. In the higher wavelength

region (Figure S3b) peak at 3440 cm-1 corresponds to stretching mode of O-H and N-H groups.

Peaks at 2932, 2869 cm-1 corresponds to stretching vibration of C-H bond present in the =CH2

groups [25, 26]. In lower wavelength region, peaks at 1630 cm-1 (C=O), 1530 cm-1 (CN

stretching/ NH bending modes) and 1234 cm-1 (CN stretching / NH bending modes) can be

assigned to amide I, amide II and amide III vibrations of the glycoprotein, respectively [27-30].

The peaks at 1448, 1073 and 620 cm-1 is due to stretching modes of C=C, C-O and C-S bonds,

respectively [27, 31-36].

The ESM fibers are structurally stable due to their chemical bonding and crystallinity. As ESM

have carbonyl, amide and –OH moieties, they are strongly associated with each other by

Hydrogen bonding and dipoles present in the fibers facilitate the piezoelectric properties. So, the

application of external force on the lattice crystal of the material changes its dipole arrangement,

which have the key role in the piezoelectric effect [37].

Figure S4: (a) Scanning electron microscope image at different magnifications of (a) ESM, (b) PVDF-nanoclay and (c) PVDF-nanoclay-ESM nanohybrids (d) EDX analysis of eggshell membrane.

The ESM is located just under the egg shell; it is actually two shell membranes, mostly tightly

bound together. The outer shell membrane has a thickness of 50-70 µm and has fibers of

diameter 1 to 7 µm [38, 39]. The inner egg shell membrane has smaller diameter fibers of 0.1 to

0.3 µm range and has a thickness of 15 to 26 µm [38, 39]. Figure S4ashow the scanning electron

microscopy (SEM) images of egg shell membranes. A detailed study about these fibrous

diameters has been done [40, 41]. We can see the 4-5 μm size pores around the fibers, which

supports the fibrous nature of ESM. This highly ordered fibrous structure is responsible for the

piezoelectric property of the ESM. Figure S4b and c shows the SEM images of PVDF-nanoclay

and PVDF-nanoclay-ESM hybrids respectively.The EDX analysis (Figure S4d) shows the

presence of elements C, O, S and N in egg shell membrane. These elements support the presence

of carbonyl, carboxyl and amino groups present in the egg shell membrane as shown in FTIR

spectra.

Figure S5:KPFM images and corresponding profile for pure PVDF, P-ESM40 and PC-ESM40 nanohybrids.

0 2 4 6 8 10

-0.001

0.000

0.001

piez

ores

pons

e / a

.u.

m

PC-ESM40 P-ESM40 P

0 V

0 2 4 6 8 10

-0.001

0.000

0.001

piez

ores

pons

e /a.

u.

m

PC-ESM40 P-ESM40 P

10 V

0 2 4 6 8 10-0.30

-0.15

0.00

0.15

0.30

phas

e / o

m

PC-ESM40 P-ESM40 P

0 V

0 2 4 6 8 10-0.30

-0.15

0.00

0.15

0.30

phas

e / o

m

PC-ESM40 P-ESM40 P

10 V

a)

b)

Figure S6:Comparison of average profile at 0 V and 10 V for pure PVDF and nanohybrids.

Note S1: Calculation of applied pressure under Finger pressing.

The imparting pressure from finger can be calculated by combining pulse and gravity [42]. When

an object falls on the device surface, two phenomena occur: First the object touches the surface

of the device and secondly, completely acts on device. In first process, the objects decending

velocity increases to maximum and in second process, it decreases to zero. So, based on the

kinetic energy and momentum equation, we can write:

(1)𝑚𝑔h =

12

𝑚𝑣2

(2)(𝐹 - 𝑚.𝑔).∆𝑡 = 𝑚.𝑣

(3)𝜎 =

𝐹𝐴

Where, m is the mass of the object, is the acceleration due to gravity, h is falling height of the 𝑔

object, σ is the applied pressure, is the falling velocity, A is the effective area of the device, F 𝑣

is contact force and ∆t is the time span during the second impact.

The effective area can be measured by the contact area of the falling object (fingers) ≈350 mm2.

The estimated mass of the object is measured by an electronic balance as ≈0.9 kg. The average

time span ∆t is≈0.22 sec the difference between two consecutive voltage peaks [42]. The average

falling height is ≈0.075 m and = 9.8 m/s2. Using these values the estimated force is calculated 𝑔

as F ≈13.77 N and estimated pressure as σ ≈ 40kPa.

Figure S7: Variation in output voltage with resistance.

Table S1: Different bio-based piezoelectric devices and their power density.

Bio-based materials Output Voltage Maximum power

density

Reference

M13 bacteriophage (Virus) 0.4 V --- [43]

Fish scale 4 V 1.14 μW/cm2 [44]

Bio Waste onion skin 18 V 1.7 μW/cm2 [45]

Fish swim bladder 10 V 4.15 μW/cm2 [46]

Cellulose-ZnO 0.08 V 5 ×10-2μW/cm2 [47]

Paper/BaTiO3/ Bacterial cellulose 14 V 0.64 μW/cm2 [48]

Cellulose/ZnOnanocoating 500 mV [49]

Vertically aligned M13

bacteriophage (phage) nanopillars

140.8 mV ~8.7×10-5μW/cm2 [50]

Prawn shell 4V 0.76 μW/cm2 [51]

DNA/ PVDF 6 V 11.5 μW/cm2 [52]

Egg shell membrane 26.4 V 11.91 μW/cm2 [23]

Spider silk 21.3 V 4.56 μW/cm2 [53]

PVDF + nanoclay + Egg shell

membrane

56.78 V 55μW/cm2 Present

work

Figure S8: Synergism PVDF and ESM nanohybrid.

Figure S9: Power density of nanogenerator on different modes (a) twisting, bending, coin dropping and (b) walking, tapping and hand slapping.

Figure S10: Repeated charging and discharging of the capacitor.

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