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Photo-rechargeable Organic-Inorganic Dye Integrated Polymeric Power Cell with Superior Performances and Durability Farha Khatun, Pradip Thakur, Arpan Kool, Swagata Roy, Nur Amin Hoque, Prosenjit Biswas, Biswajoy Bagchi, and Sukhen Das Langmuir, Just Accepted Manuscript • DOI: 10.1021/acs.langmuir.9b00622 • Publication Date (Web): 18 Apr 2019 Downloaded from http://pubs.acs.org on April 22, 2019

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Photo-rechargeable Organic-Inorganic Dye Integrated Polymeric Power Cell with Superior Performances and Durability Farha Khatun1, Pradip Thakur*2, Arpan Kool3, Swagata Roy1, Nur Amin Hoque1, Prosenjit Biswas1, Biswajoy Bagchi4, Sukhen Das*1 1Department

of Physics, Jadavpur University, Kolkata-700032, India.

Email address: [email protected], Mobile: +919433091337 2Department

of Physics, Netaji Nagar College for Women, Kolkata-700092, India.

Email address: [email protected], Mobile: +919830366215 3Department

of Physics, Techno India University, Kolkata-700091, India.

4Department

of Medical Physics and Biomedical Engineering, University College London, London, United Kingdom *Corresponding

authors.

ABSTRACT: In present work, we propose a simple and unique approach to design a light-weight, low-cost, self-charging power cell with considerable capacity to generate and store photo-charges named as self-charged photo-power cell (SCPPC). Initially, highly electroactive sodium dodecyl sulphate (SDS) incorporated poly (vinylidene fluoride) (PVDF) composite thin films with a large dielectric constant ~ 525 are synthesized via simplistic solution casting process. Then asprepared high dielectric SDS/PVDF thin film has been used as a charge storage medium in combination with a inorganic-organic dye film i.e. ZnO NPs-Eosin Y- polyvinyl pyrrolidone film as photoelectrons generator in our SCPPC. An open circuit voltage ~ 1.2 V is attained after charging SCPPC under illumination light with intensity ~110 mW /cm2 and then discharge fully with a constant current density ~ 4.5 mA/cm2. Specific areal capacitance ~ 450 F/m2 is obtained with a large energy and power density of ~ 90 mWh/m2 and 54 W/m2. The improved overall efficiency ~3.78 % along with 89 % storage efficiency leads to promising application possibilities of our rechargeable photo-power cell. The recyclability i.e. recharge-ability and storage durability of the photo-power cell are also checked for 35 days without no such reduction in voltage generation and storage. Also multi-coloured light emitting diodes have been lighten up using the photo-power cell as power source.

Keywords: PVDF; SDS; dielectric; self-charging; storage

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1. INTRODUCTION Investigation of the clean energies such as mechanical, solar, chemical etc. and its application to the global development for overall environmental security is one of the most intense research topics for the modern society. So our target should be redirected to overcome these critical issues by establishing new development in the technologies and devices for clean energy conversion, storage and conservation. On the basis of this concept, development of piezoelectric nanogenerators, Li-ion batteries, supercapacitors, dye-sensitized solar cells are already got the attention for the clean energy conversion and storage. [1-11] As a fresh and sustainable energy supply, solar energy may be considered as one of the most prosperous choice to replace regular fossil fuels like petroleum, coal etc.[1-3] Due to the increasing requirement of the clean energy to reduce the green house effect and to obtain multifunctional operation in single device, researchers and engineers are highly focused to construct different type of energy harvesting devices.[4, 5, 11] Currently, electrical energy harvesting using the photovoltaic effect with high conversion and storage efficiency is the dominant technology in the electronics industry. So the most essential demand of the scientists is to integrate energy in a single “harvesting-storage” unit with improved performance.[1] At very recent, solar electricity or photovoltaic technology is earning heightened attention for the production of sustainable energy.[1, 8-11] But till now the reports of the various type of photo-power cell with high conversion efficiency and as well as storage is limited. Few photovoltaic units based on perovskite structure and dye-sensitized solar cell are reported by some researchers.[12-15] Different type of polymer based solar device and TiO2 nanotubefunctionalized dye sensitized solar cells were also recommended by Ma et al. and Guo at al.[15] Integration of solar cells with energy storage part (Li ion cell, capacitor etc.) through external circuit also proposed by some scientists.[16-17] But the output characteristics of such integrated hybrid power cell reduce due to increase of the total impedance of the systems as well as some difficulties of light exposure.[18] Such shortcomings might be overcome by integrating solar part and energy storage part in a single unit.[13, 19] The initial idea of selfcharging photo-capacitor was also proposed by Miyasaka et al.[13] So for any photo power unit the most essential fact is to improve the solar energy conversion, high power storage, good stability with ultralow cost capture. Combination of high dielectric polymeric film with the dye-sensitized solar cell function is basically a combined form of a photo power unit with high potential to overcome the power related limitations.[20] In our earlier work, we have reported some such type of high dielectric polymeric nanocomposite based photovoltaic energy storage device with superior storage capability and stability. But, the solar to electrical energy conversation efficiency is quite low which somehow restrict the possibilities of utilization in large scale applications. [21-23] Electroactive polymers based high dielectric material are very useful for designing piezoelectric nanogenerators, capacitors, thin film transistors, grid levelling, rail runs, nonvolatile memories, sensors, actuators and also in biomedical fields.[24-28] Poly(vinylidene fluoride)(PVDF),([-CH2-CF2-]n) and its copolymers are very well known flexible and cost


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effective electroactive polymers for the above mentioned applications as well as very suitable for designing the storage part in integrated photo-power bank. [28] PVDF has attracted considerable interest due to its piezoelectricity, pyroelectric property, ferroelectric coefficient, excellent thermal stability and chemical resistance. PVDF is a semicrystalline polymer with five different crystalline phases 𝛼, 𝛽, 𝛾,𝛿 𝑎𝑛𝑑 𝜀.[29-32] Out of these phases, 𝛽 phase is the most electroactive due to the all trans (TTTT) planar zigzag configuration with the presence of an orthorhombic unit cell matrix and attained paramount importance over the other phases due to its excellent piezoelectric, ferroelectric and pyroelectric properties.[32, 33] So the enhancement of the 𝛽 phase content in the PVDF matrix with simultaneous improvement of the dielectric constant by incorporating different fillers is the key point and highly appreciated by modern researchers.[30, 31, 33] Here, we have chosen sodium dodecyl sulphate (SDS) as organic filler to upgrade electroactive β phase as well as dielectric behaviour of the modified PVDF/SDS (PDS) films. SDS is very well known and environmentally safe anionic surfactant which is very applicable as a detergent material. It is widely used in the cleaning, cosmetic and personal care products. After that, we are trying to achieve improving the conversion efficiency as well as storage ability of our simple prototype photo-power cell. A very simple way has been followed to design a low-cost, light weight, very active and stable two electrode self-charged photo-power cell (SCPPC) introducing the high dielectric PDS composite thin film and organic dye, eosin Y (EY) along with inorganic zinc oxide (ZnO) NPs as a solar part (Figure 1).

2. EXPERIMENTAL: 2.1. Materials: The materials that are used in our present work are poly(vinylidene fluoride) (PVDF) pellets (Aldrich, Germany . 𝑀𝑤: 275,000 GPC, 𝑀𝑛 : 71,000), sodium dodecyl sulphate (SDS) (Sisco Research Laboratories Pvt. Ltd., India), polyvinyl pyrrolidone (PVP) (Loba Chemie), ZnO nanoparticles, Ortho-phosphoric acid (H3PO4) (Merck, India), Eosin Y (EY) (Loba Chemie, India), FTO coated glass (Sigma Aldrich, Germany). 2.2. Synthesis of SDS-modified PVDF (PDS) thin films: At the beginning, 0.2 g PVDF was added in 5 ml DMSO to prepare 4 mass % PVDF solution. Then different amounts of SDS (1–25 mass%) was added to the PVDF solution (the preparation of which is described in the Supporting Information). A homogeneous mixture was obtained after stirring the mixture magnetically for 2.5 h followed by 30 min ultra-sonication. The mixture was then placed in a dust-free hot air oven at 80oC for 12 h to obtain the SDS modified PVDF thin films of average thickness ~ 20 𝜇m by the complete evaporation of the solvent. Pure PVDF film was also prepared without the addition of SDS under the same conditions. All the films are stored in a vacuum desiccator to characterize further. The sample designation is tabulated in Table S1.


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2.3 SCPPC Fabrication: Initially to prepare the solar part of the SCPPC, 20 mg/ml EY, 100 mg/ml ZnO NPs, PVP (10% mass) and H3PO4 were added to the distilled water. Then this mixture is magnetically stirred for 12 hours at room temperature at dark atmosphere. Thereafter, to form the working electrode 20 𝜇L mixed solution was casted on the previously cleaned FTO coated glass and the casted dye solution was allowed to stand for 20 min under ambient conditions to get a thick and sticky gel. Then, the counter electrode of Al foil containing previously casted PDS25 (25 mass %) or pure PVDF thin film was placed on the thick and sticky gel layer of the dye solution and dried at 60 °C for complete evaporation of the water. Two Cu wires are connected with the acting electrode FTO and counter Al electrode and extended out to study the device characteristics. We have fabricated two SCPPC using PDS25 (SCPPC1) and pure PVDF (SCPPC2) thin film as storage part without altering the solar part to compare the performances (Figure-1a).

2.4. Characterization 2.4.1. X-ray diffraction (XRD) The X-ray diffractometer (Model-D8,BrukerAXS Inc, Madison, WI) is used to verify the formation of β phase of in pure PVDF and SDS/PVDF samples with scan speed of 0.3s/step by using Cu-Kα irradiation working under a voltage of 40kV in 2θ range from 15° to 50°. 2.4.2. Fourier transform infrared spectroscopy (FTIR) The electroactive β phase nucleation of the pure and doped films is further investigated by FTIR (FTIR-8400S, Shimadzu). The samples are scanned 50 times in the wavenumber range from 400cm−1 to 1100cm−1 with a resolution of 4cm−1to collect the absorbance data. Lambert– Beer law F(𝜷) =

𝑨𝜷

( )𝑨 𝑲𝜷 𝑲𝜶

𝜶

(1)

+ 𝑨𝜷

has been used to calculate the β-phase fraction (F(β) %) in the samples. Here, Aα and Aβ are the absorbance at 764cm−1 and 840cm−1 respectively and Kβ (7.7×104 cm2 mol−1) and Kα (6.1×104 cm2 mol−1) are the absorption coefficients at the respective wavenumber [28]. 2.4.4. Differential scanning calorimetry (DSC) We have used differential scanning calorimeter (DSC-60, Shimadzu (Asia Pacific) Pte. Ltd., Singapore) to investigate the thermal behavior the films. All the films have been heated from 30℃ to 200℃ at the heating rate of 10 ℃ /min using ceramic crucibles of capacity 70𝜇l under N2 atmosphere. 2.4.5. Field emission scanning electron microscopy (FESEM)


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Field emission electron microscope (FESEM) (INSPECT F50, Netherland) has been used to study the morphology and microstructure of the pure PVDF and PSDS films. The films are gold coated through plasma spraying and placed within a vacuum chamber (Pressure∼5×10−3 Pa).Then FESEM images of the samples are captured under operating voltage of 20kV, emission current 170 μA and with beam spot size of 3 mm. 2.4.5. Dielectric properties measurements Initially, the capacitance (C) and tangent loss (tanδ) are measured within the frequency range 20Hz to 2MHz to study the dielectric properties of the films, with the help of a digital LCR meter (Agilent, E4980A). The measurement is performed at room temperature by applying 1 V ac voltage across the two opposite surfaces of the samples. We have used the following equations, 𝜺 = 𝑪.𝒅/𝜺𝟎𝑨

(2)

𝝈𝒂𝒄 = 𝟐𝝅𝒇𝜺𝟎𝜺 𝒕𝒂𝒏𝜹

(3)

dielectric constant (ε) and the ac conductivity (σ) of the samples are calculated, where d and A are the thickness and area of the samples respectively and f is the frequency in Hz applied across the samples and ε0 is the permittivity of the free space with value 8.854 × 10− 12 Fm−1 [28, 30]. 2.4.6. Investigation of device performances A digital multi-meter (Agilent U1252A) and an electrometer (Keysight-B2985A) used to measure the output characteristics of our fabricated photo power cell (SCPPC) by making a connection of two copper wires attached with the electrodes under light illumination and dark condition. No external bias voltage is applied across the electrode of the devices.

3. RESULTS AND DISCUSSIONS Figure-1a is illustrates the schematic representation of our SCPPC. The digital image of the both faces of our fabricated device is shown in Figure-1b. Here, we have used SDS associated PVDF (PDS25) or pure PVDF thin films as an energy storage part and PVP-EY-ZnO composite dye material as the photo sensitive part. This dye material is placed on the FTO by attaching the storage film casted on Al foil. Initially, we incorporate SDS to PVDF films and characterized the composite films. Thereafter, the self-charging photo power cell is developed in a very simple fashion by integrating our optimized large dielectric PDS25 thin film with a popular inorganic-organic composite dye film. The novelty resolves around the fabrication and optimization of electroactive and high dielectric SDS/PVDF thin film and its proper integration with the organic-inorganic dye (EY-ZnO) i.e. solar part to achieve a photo-rechargeable power cell or supercapacitor for portable and large scale energy compensation of our modern electronic gadgets.


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3.1. Characterization and optimization of PDS composite thin film for SCPPC: 3.1.1. X-Ray diffraction analysis: Figure 2a shows the X-ray diffraction (XRD) patterns of the pure PVDF and SDS incorporated PVDF thin films. The crystalline nature of all the films are inspected from the diffraction pattern. The XRD diffraction peaks around 17.6° (100), 18.3° (020), 19.9° (021) and 26.6° ((201), (310)) confirm the presence of non-crystalline 𝛼 phase in pure PVDF films. The existence of one prominent peak at 20.8° ((110), (200)) for PDS samples implies the formation of crystalline β polymorph.[29, 30, 34] Interesting fact is that the peaks related to the 𝛼 phase for the pure PVDF have completely disappeared in the diffraction pattern of the SDS modified PVDF samples. Gradual increment of the electroactive 𝛽 crystal with the increase of the SDS concentration for the doped PDS films is also observable. We have calculated the intensity ratio of the peaks I20.8 and I18.2 (Figure-2b) to quantify the 𝛼 𝑎𝑛𝑑 𝛽 phase content in the pure and PDS thin films and the highest value of the ratio is attained to be 17 for 25 mass % loading of SDS in PVDF.[35, 36] Further SDS loading in PVDF has not reported as for higher percentage of SDS content leads to formation of void and pore in the film.

Figure 1: (a) Symbolical representation of the fabricated SCPPC. (b) Digital photograph of the SCPPC.

3.1.2. Fourier transform infrared spectroscopy: Figure – 2c represents the Fourier transform infrared (FTIR) spectra of pure PVDF and SDS loaded PVDF films. The absorbance bands in pure PVDF at 489 cm-1(CF2 waging), 533 cm-1 (CF2 bending), 615 and 764 cm-1 (CF2 bending and skeletalbending),795and 975 cm-1 (CH2 rocking) ensure about the existence of the 𝛼-phase. The characteristic absorbance bands related to the 𝛽 phase at 475 cm-1 (CF2 deformation), 510 cm-1 (CF2 stretching), 600 cm-1 (CF2 wag) and 840 cm-1 (CH2 rocking, CF2 stretching and skeletal C–C stretching) are clearly intensified in the spectra of PDS samples and the absorbance bands related to the 𝛼 phase are faded with the increment of the SDS content.[29, 30, 34] We have calculated the electroactive fraction of 𝛽 phase content (F(𝛽)) in composite films by Eq. (1) and plotted the variation of F(𝛽) (%) with dopant concentration (mass %) in the Figure-2d.[37-39 ] We have achieved maximum ~ 90% F(𝛽) value for highest concentrated doped sample PDS25. This results is well agreed with the XRD data.


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Figure 2: (a) XRD patterns of pure PVDF and SDS/PVDF composite thin films, (b) Ratio of I20.7 and I18.3 of the samples estimated from XRD pattern, (c) FTIR spectra of pure PVDF and PDS thin films, (d) Variation of β-phase content with increasing SDS content evaluated form IR spectra.

3.1.3. Differential scanning calorimetry: We have used the thermal technique i.e. differential scanning calorimetry (DSC) for the further verification of phase transition behavior and β polymorph nucleation in the films. Figure-3a represents the DSC thermographs of SDS modified PVDF and pure PVDF thin films. According to DSC thermographs the melting temperature of the PDS films is shifted to higher temperature (~7-8 oC) for SDS modified PVDF films with respect to the melting temperature for pure PVDF film (~ 163 oC). Shifting of the melting temperature is due to some change in the degree of crystallinity and homogeneity in the molecular configuration of the composite films which may be attributed to the formation of 𝛽 phase in the composite samples.[34, 3941] Electroactive 𝛽 phase nucleation is already confirmed by the two techniques i.e. XRD and FTIR and increase of the melting temperature in the DSC thermographs is also another justification with XRD and FTIR data obtained previously. Here, SDS molecules acts as a nucleating or catalytic reagent for transformation of electroactive β-phase in the SDS/PVDF samples. Strong electrostatic attraction between the negative head of SDS molecules (-SO4-) and the positive –CH2 dipoles of PVDF chains leads to formation of all trans i.e. longer TTTT conformation in the composite samples. As a result electroactive β crystals have been crystalized in SDS doped PVDF samples. Possible interaction between the SDS molecules and PVDF matrix has been schematically illustrated in Figure 3b.


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Figure 3: (a) DSC thermographs of pure PVDF and SDS incorporated PVDF thin films and (b) Schematic presentation of possible electroactive β-phase nucleation in PDS samples.

3.1.4. Field emission scanning electron microscopy (FESEM): Figure-4 shows the FESEM micrographs of the SDS loaded PVDF (PDS5, PDS15 and PDS25) and neat PVDF samples. We have used FESEM image to examine the microstructure and surface grain texture before and after addition of the dopant within the polymer matrix. According to the captured FESEM images, larger grains with diameter in the range of ~ 50-70 𝜇m have been observed for pure PVDF film. The extra stretching diameter of the grains for the unblended PVDF film are mainly for the occupation of the non-crystalline 𝛼 polymorph.[41, 43] Whereas, crystallization of smaller size spherulites with diameter ~ 5-8 𝜇m are clearly observed with distinct and smooth boundary after incorporation of SDS in PVDF matrix (PDS5, PDS15 and PDS25). The spherulites with lesser diameter are actually indication of nucleation of β polymorphs in the SDS modified PVDF thin films. [42, 43] The FESEM micrographs of the PDS thin films also displays a clear view of fine and uniform distribution of the SDS molecules within the polymer matrix. The homogeneous dispersion of SDS indicates the intimate interaction between the SDS molecules and the polymer chains and leads to nucleation of piezoelectric β polymorphs (Figure 3b). The interaction becomes stronger with the augmentation of the SDS in the polymer matrix and this contributes to the maximum electroactive β phase for the highest concentration i.e. PDS25 (25 mass %) thin film.


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Figure 4: FESEM micrographs of pure PVDF and SDS modified PVDF films (PDS5, PDS10 and PDS25).

3.1.5. Dielectric properties: Figure-5a and b represents the variation of the dielectric constant and tangent loss value of pure PVDF and SDS/PVDF composite samples at frequency 20 Hz with respect to the SDS content. Initially, the value of dielectric constant and tan 𝛿 has been increased very slowly upto 15 mass% loading of SDS but a sharp and dramatic increment has been noticed for further content of SDS (20 and 25 mass%) at 20 Hz. We have achieved the maximum dielectric constant ~ 525 at 20 Hz for PDS25. The achieved dielectric constant for the PDS25 film is ~ 65 times larger than the dielectric value of the neat PVDF film (ε ~ 8). The high dielectric response for the SDS incorporated PVDF samples can be explained with the help of Maxwell– Wagner–Sillars (MWS) interfacial polarization which occurred in heterogeneous medium in between the interface of two different phases of non-identical conductivity.[28,29, 44] When SDS has been added to PVDF matrix, a strong electrostatic interaction has been taken place due to the polarity and conductivity difference between the SDS and PVDF. As a result, a large number of charge carriers accumulate at the interfacial region of the SDS and polymer along with alignment of PVDF chains in all TTTT conformation which creates the larger dielectric value in the composite samples. With increasing concentration interfacial areas for charge accumulation as well as the nucleation of β-phase has been increased which leads to increment of dielectric value with SDS concentration and the dielectric value reaches to its maximum


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value upon attaining the percolation threshold value (i.e. 25 mass%) for SDS/PVDF composite film.[29, 45]

Figure 5: (a) SDS content (mass %) dependency of dielectric constant and tangent loss at 20 Hz of pure PVDF and PDS films. Frequency dependency of (b) dielectric constant, (c) tangent loss, (d) ac conductivities of pure PVDF and PDS films.

The characteristic deviation of the entire dielectric features i.e. dielectric constant, ac conductivity and tangent loss (tan 𝛿) for both the SDS modified and pure PVDF films with frequency are shown graphically in Figure-5b-d. The dielectric constant is almost unchanged for the pure PVDF while a reducing pattern of the dielectric value has been noticed for the SDS doped PVDF samples with increasing frequency (Figure-5b). At the lower frequency region the value of the dielectric constant is considerably large (~ 525) because of accumulation of the large number charge carriers and formation of dipoles due to MWS interfacial polarization and with increasing frequency, the dipole inadequacy has reduced the dielectric values.[29, 46, 47] When the external alternating electric field is applied to the PDS composite samples, at low frequency the charge carriers coming from the dopants are able to move freely. At this low frequency domain the free charge carriers are concentrated at the junction of the SDS and polymer due to the conductivity difference between them. Due to the continuous process of the surface charge accumulation and their free movement at low frequency, the large dielectric value has been attained. With increasing frequency, these charge carriers or dipoles is not permitted to get enough time to move freely i.e. the charge carriers are not able to follow the change of the direction of external electric field. As a result, the dielectric constant is reduced at higher frequency region.[29, 34, 48, 49] Figure-4c illustrates the frequency dependency of the tangent loss (tan 𝛿) of the neat PVDF and PDS composite samples. The graphs are showing a continuous decreasing pattern of the tan 𝛿 values of the SDS modified films with increasing


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frequency due to the reduction of the interfacial polarization. The variation property of ac conductivity of SDS incorporated PVDF and pure PVDF films with increasing frequency is depicted Figure 4d. Although a slight unchanged behaviour of ac conductivity has been observed at the low frequency region but an acute linear raise in ac conductivity values is noticed at the higher frequency zone. Nearly unchanged pattern of conductivity at the low frequency region is basically activated by the dc conductivity effect, while the sharp linear increment of the ac conductivity of the high frequency zone is affected by the fast polarization mechanism. [29, 34] 3.2. Mechanism and performances of the SCPPC: According to our above study on the basis of the intrinsic structure and dielectric property of the PDS samples it is noticeable that the maximum value of 𝛽 phase crystallization and the dielectric constant is obtained for the 25 (mass %) SDS incorporation. High dielectric value is the main reason to prefer PDS25 for fabricating SCPPC1 (Figure 1). To design the SCPPC1, we have used the FTO coated glass containing the photo charge carrier generator part i.e. composite film of EY/ZnO NPs/H3PO4/PVP connected with the photo-electrons storage material i.e. high dielectric SDS modified PVDF film (PDS25) of dimension 0.25 cm x 0.25 cm and average thickness ~ 20 𝜇m. The presence of the acidic medium (H3PO4) in dye solution is basically to supply electrons as an electrolyte.[50] By assembling the same solar materials with the replacement of the PDS25 by pure PVDF film, we have fabricated SCPPC2 to compare the performances with the SCPPC1.

Figure 6: (a) Schematic diagram of the photo electron generation and storage mechanism of the SCPPC1 and SCPPC2. (b) HOMO and LUMO state of entire dye solution, (b) UV-Visible absorption spectrum of the dye film.

The devices are charged under illuminating four different i.e. 40 W, 60 W, 80 W and 100 W tungsten bulb with different intensities and the bulbs are totally covered with ultra-violet and


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infrared light eliminating filters. The charging behaviour i.e. charging rates seem to independent with intensity of light illumination. No such significant change in output voltage has been observed in higher intensities. So, charging characteristics of our prototype device under 40 W bulb with intensity 110 mW/cm2 have been reported in our present study. Figure-6a is the schematic representation of the working principle of the SCPPCs. The working mechanism of the devices can be explained by two connecting processes, creation of the photoelectrons by the solar part i.e. EY-PVP-ZnO with H3PO4 and reservation of that photo generated electrons by the storage substance i.e. high dielectric PDS25 or neat PVDF thin film. Figure 6b is showing the energy structure i.e. the HOMO/LUMO configuration of the dyes. The photo electrons are generated by the solar part due to the absorption of the photons by the light absorbing dye EY. The UV-Vis absorption spectrum of the EY-PVP-ZnO-H3PO4 film is shown in the Figure 6c. Two distinct absorption peaks (492 nm and 535 nm) are observed in visible region. The performance of the SCPPC is depended on the large number of photoelectrons generation by the solar composite dye and storage capacity of the high dielectric material. The casted EY-PVP-ZnO-H3PO4 film on the conducting FTO glass acting as a working electrode and Al foil is used as a counter electrode. The current-voltage (J-V curve) and the photovoltaic performance i.e. self-chargingdischarging phenomena (V-t graphs) of the SCPPC1 and SCPPC2 are graphically illustrated in Figure 7a-d. Good short circuit current density (Isc) ~ 5.9 mA/cm2 of the SCPPC1 is obtained (Figure-7a). This high value of the initial current density is obviously due to the large flow of the electrons during the charging process. When the device is placed under light i.e. the tungsten bulb filament, immediately the photons (h𝜈) absorption process has been started by the EY molecules. The excitement of the EY molecule is the main source of photo-electrons generation. These photo charge carriers reach to the higher energy state i.e. to LUMO level of the EY (~ ― 2.5eV). Then the photo-electrons immediately transfer to the FTO (~ - 4.4eV) by conducting though the ZnO NPs (~ ― 4.3 eV). So the motion of the photo-electrons is enhanced and becomes smoother due to the combination of ZnO NPs within the dye solution. The LUMO value of ZnO is lower than the LUMO level of EY and higher than that of FTO resulting a continuous and steady tunnelling of the photo electrons from EY to FTO glass. The photoelectric conversion efficiency of the SCPPC is improved due to the photoactive and catalytic behaviour of the ZnO NPs infused with EY molecules.[51, 52] As the electrodes are connected through a copper wire, photo-electrons are flowed massively from FTO to the Al counter electrode and electrons are accumulated at the interface of Al and high dielectric PDS25 thin film as well as the junction of SDS and PVDF chains forming large number of micro-capacitor structure in the composite samples. By the meantime PVP and H3PO4 fill the inadequacy of the electrons in EY molecules for further requirement. Thus, the charging process is continued up to the arrival of the overloading situation. At this moment no more photo-electrons will be produced by EY. So, the counter electrode i.e. Al terminal becomes negatively charged through reserving the photo generated electrons. Simultaneously, the deficiency of the electrons in the solar portion will make it positively charged which is comparable with the holes.


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Figure 7: J-V curve of (a) SCPPC1 and SCPPC2. (c-f) Self-charging and discharging behaviour (V-t curves) of the fabricated SCPPCs as a function of time and different dielectric films (pure PVDF and PDS films) under light illumination and dark conditions.

Finally, a potential difference will be occurred between the two electrodes. As a result a quite large open circuit voltage (Voc) is 1.2 V is obtained within 8 seconds for the SCPPC1(Fig 7c).[7, 12, 24] The charging process of the device is totally completed under this condition and due to no further photo-electrons creation, short circuit current density (Isc) will be zero (Fig 7a). The maximum open circuit voltage (Voc~ 1.034 V) and short circuited current (Isc~ 2 mA/cm2) is observed for the SCPPC2 (Fig 7b). The charge storage capacity of the SCPPC1 is enriched due to large dielectric value (~ 5.25 × 102) of the PDS25 created by the strong interaction between SDS within the PVDF chain which is already justified in the above section. During the charging process, the photo-electrons generation through the excitation of EY molecules and their recombination are explained by the following equations, EY + hν =EY+ + e-, PVP → PVP-, H3PO4 ↔ H+ + H2PO41H2PO41- ↔ H+ + HPO42-


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HPO42- ↔ H+ + PO43EY+ + PVP- = EY + PVP+ EY+ + HPO42- = EY + H2PO41EY+ + H2PO41- = EY + H3PO4

The self-charging and stability performance of the devices are illustrated in Figure 7c-7d. The curves prominently show a very good and steady storage capacity of the photo-power cell made by PDS25 i.e. SCPPC1. It is also observable (Fig 7c) that the charge storing capability of SCPPC1 is better than that of the pure PVDF based photo-power cell or SCPPC2. The variation of photovoltage with respect to time is nearly unchanged for a long time for SCPPC1. To study the stability i.e. self-recombination behaviour of the photo-power cells, devices are placed in a complete dark atmosphere. In the absence of light there is no excitement of EY molecules and generation of photo-electrons. The prevention of the electrons recombination by the high dielectric medium (PDS25 thin film) is the main criteria of storing the photo charge carriers and improve the storage efficiency of the SCPPC1. So, the internal recombination of electrons and holes occurs very slowly which causes a small drop in voltage during self-discharging for SSPPC1. When the light is turned off, the voltage has been dropped to 0.930 V after 4 hours observation (Figure 7c) for SSPPC1. So, the self-discharging rate for SSPPC1 is approximately ~ 1.125 mV/min after turn off the light. In case of SCPPC2, electrons-holes recombination process is accelerated as the dielectric value of neat PVDF is almost 50 times less than that of the PDS25. As a result, a steep voltage drop is observed (Fig 7d) and the pure PVDF based device is mostly discharged within 50 minutes that signifies definitely a smaller storage capability of the photo-power cell SCPPC2. A further test is also performed to verify the discharging phenomenon, of the SDS doped polymer based device. SCPPC1 is discharged with a constant discharge current density (~ 4.5mA/cm2) under dark condition. We have also discharged the photo-power cell with different discharge current density (~ 3.75 mA/cm2) and~ 3 mA/cm2). We proceed all parameter calculations with the highest current density value (~ 4.5mA/cm2) for both devices. Discharging phenomenon of SCPPC1 with different constant current density is graphically depicted in Figure-7e. To compare the result of SCPPC1 with pure PVDF based device, we move on with the constant discharge current density (~ 3.75mA/cm2) of SCPPC2 (Figure 7f). the SCPPC1 is discharged by 10 seconds whereas PVDF based SCPPC2 is discharged within 5 seconds. The photovoltaic performances of the two prototype devices SCPPC1 and SCPPC2 are explained by evaluating the related parameters like charge storage density, specific areal capacitance, energy density and power density of our SCPPCs. To calculate the above mentioned quantities the successive equations have been used: Q = ∫Idisdt

(4)


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C = Q/dV

(5)

Eoutput = ½ CV2

(6)

P = VIdis

(7)

Q= the stored charge density, C = specific areal capacitance Eoutput= output energy density P = power density Idis = discharge current density dt = discharge time dV = the difference between the maximum output voltage and the voltage after complete discharge of the SCPPCs. After evaluating all the values, the maximum capacity of the SCPPC1 to store the charge is found to be ~ 450 C/m2 with higher energy density ~ 90 mWh/m2 whereas SCPPC2 the corresponding values are ~ 180 C/m2 and ~ 28 mWh/m2 respectively. Power density ~ 54 W/m2 and areal specific capacitance ~ 450 F/m2 have been found for the SCPPC1 but in case of pure PVDF based SCPPC2 respective parameters are found to be~ 38 W/m2 and ~ 200 F/m2 respectively. To verify the potentiality of the device, photo-electric conversion efficiency is calculated by the equation ɳ𝐜𝐨𝐧𝐯𝐞𝐫𝐬𝐢𝐨𝐧 % =

𝐏𝐨𝐮𝐭 𝐏𝐢𝐧

× 100 =

𝐕𝐎𝐂 × 𝐈𝐒𝐂 × 𝐅𝐅 𝐏𝐢𝐧

× 100

(8)

Vsc= open circuit voltage, ISC= short circuit current, FF = fill factor, Pin= the incident light power (110 mW/cm2). [17, 53 - 54] Where,

𝐕𝐩𝐩 × 𝐈𝐏𝐏

FF = 𝐕𝐎𝐂 × 𝐈𝐒𝐂

(9)

Vpp= voltage power point, IPP = current power point, where ISC and IPP are in mA/cm2,VOCand Vppare in V, Pin and Pout are in mW. To determine the storage strength of the SCPPCs, initially we have calculated the overall efficiency of the device by using equation 6, Overall efficiency,

ɳ𝐨𝐯𝐞𝐫𝐚𝐥𝐥% =

𝐄𝐨𝐮𝐭𝐩𝐮𝐭 𝐄𝐢𝐧𝐩𝐮𝐭

× 100


(10)

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Where the input energy density Einput = Pin × dť, dť is the charging time.[8, 55] Now, by utilizing the conversion efficiency (equation 8) and overall efficiency (equation 10), the storage efficiency of the SCPPCs is approximated such as ɳ𝐨𝐯𝐞𝐫𝐚𝐥𝐥%

ɳ𝐬𝐭𝐨𝐫𝐚𝐠𝐞=ɳ𝐜𝐨𝐧𝐯𝐞𝐫𝐬𝐢𝐨𝐧 %

(11)

These obtained values of various parameters including with the conversion, storage and overall efficiencies of both SCPPC1 and SCPPC2 are highlighted graphically in Figure 8a-b.

Figure 8: (a) The comparative values of energy density, power density and storage density and (b) The conversion, overall and storage efficiencies of SCPPC2 and SCPPC1 respectively. (c) Charge−discharge repeat cycle of SCPPC1, (d) Self-charging (V-t) curve of three serially connected SCPPC1 under light illumination with schematic diagram as well as digital image of the glowing of the blue, red and green LEDs by serially connected three SCPPC1 as a power bank.

We have achieved large storage potentiality of high dielectric polymer based SCPPC1 and obtained value is ~ 89 %. Simultaneously, the energy conversion and overall efficiency of SCPPC1 are improved up to 4.12 % and 3.68 % respectively (Figure 8b). According to our study, photo-electrons generation process is bettered by improving the energy conversion efficiency. A comparing study of the overall performance of our device with the earlier reported different type of photo-supercapacitors is displayed in a tabulated form in supporting information (Table S2). The utilization of the SDS incorporated high dielectric PDS25 to fabricate the SCPPC1 is really promising since the efficiency parameters are much better than the pure PVDF based SCPPC2. Especially the storage efficiency for SCPPC2 is found to be 46% that is much lower than that of SCPPC1. The evaluated values of the conversion and overall efficiencies of SCPPC2 are 0.92 % and 0.43 % respectively (Figure 8b). To detect the long lastingness i.e. recyclability of our present device i.e. SCPPC1, we have performed a continuous observation of the entire characteristics of the photo-power cell for nearly 35 days. No such fall is noticed in the output characteristics (storage ability, efficiency parameters etc.)


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of the device which confirms about the reproducible nature of our SCPPC1 (Figure-8c). The excellent charge storing capability and recyclability is further verified by making a series connection of three SCPPC1s and we have used the stored energy to light up 4 different coloured LEDs. This combined photo-power bank is charged up to ~ 3 volt within 8 seconds (Figure 8d) and the illumination of the LEDs with constant intensity for long time justifies the remarkable performance of SCPPC1 which is schematically and digitally presented in Figure 8d and Video S1, S2 and S3 (Supplied as supporting data). In the energy storage fields, our unique photo-power cell with remarkable photo-electric conversion and storage efficiency is highly applicable for the future sustainable development. 4. CONCLUSIONS Based on the present work, we have prepared a high dielectric and electroactive 𝛽 phase crystallized SDS doped PVDF thin film by a very simple solution casting method. Maximum electroactive β phase is reached ~ 90 % along with a large dielectric value ~525 at 20 Hz for 25 mass % doping of SDS molecules due to the interfacial polarization via strong electrostatic interaction between SDS and PVDF chains. After that we develop a cost-effective, very light, portable self-charging photo-power cell (SCPPC) with high power density to convert solar energy into the form of electricity and storage. SCPPC has been fabricated in a very simplified way by using ZnO NPs mixed with EY in PVP solution as a source of the sufficient amount of photoelectrons and PDS25 dielectric thin film as a storage medium to reserve the photo generated electrons. The utilization of the high dielectric medium (PDS25) enhance the charge storing property of the photo-power cell (SCPPC1) and the storage efficiency is reached upto ~ 89%. The stability of the overall performance and realistic application of our device is also examined by the glowing different commercially available LEDs. SUPPORTING INFORMATION The SDS content in the PVDF matrix as tabulated format, Preparation and characterization of ZnO NPs, a comparative study of output characteristics of our SCPPC1 with previously reported photo-supercapacitors are supplied as supporting information. SUPPORTING VIDEO Demonstration of glowing different commercially available LEDs using our SCPPC supplied as Video S1, S2 and S3. ACKNOWLEDGEMENT Authors are thankful to Department of Higher Education, Science & Technology and Biotechnology, Government of West Bengal, India and University Grants Commission (UGC) India for providing financial assistances.

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55. Kobayashi, E.; Watabe, Y.; Hao, R.; Ravi, T. S. High efficiency heterojunction solar cells on n-type kerfless mono crystalline silicon wafers by epitaxial growth. APPLIED PHYSICS LETTERS 2015, 106, 223504.

Table of Contents Graphic: Designing of photo-rechargeable printable polymeric power cell based on electroactive and large dielectric SDS/PVDF film. Achievement of large conversion and storage efficiency of the photo-power cell which is able to drive different coloured LEDs. Potential possibilities for large-scale portable applications in electronics.


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