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Sensors 2020, 20, 506 7 of 14 Sensors 2020, 20, x FOR PEER REVIEW 8 of 14 PA6, PVDF and BaTiO . The mid-band is ideally a small 45◦ line segment, indicating the diffusion of 3 since the ion migration transmission rate cannot be consistent with the current density increase ions into the pore structure of the friction layer. The slope changes due to the Warburg impedance amplitude. As the current density increases, the frictional capacitance of each friction layer first region. It can be seen from the difference of the slope of the EIS curve that the difficulty of charge decreases sharply and then tends to be stable. In addition, after adding PA6, PVDF, and BaTiO3, the transfer in each friction layer system is different, and the slope of the EIS curve of the Cel friction internal arrangement structure of each friction layer is different and lead to different permeability, so layer is small, indicating that it has a large impedance charge transfer capability. The slope of the the electrochemical parameters are different at each current density. The energy density E is EIScurveofthefrictionlayersafteraddingPA6,PVDFandBaTiO increased,whichindicatesthat 3 calculated according to Equation (5), and the result is plotted as Figure 4c. It can be found that the it has a small impedance value. W combines the high frequency and low frequency to obtain the energy density has a similar change0trend with the specific capacitance. Since this experiment uses a overall transmission impedance value Rct. The charge transfer resistance Rct reflects the difficulty potential-based charge and discharge test method. By simplifying the calculation formula, it is known of transferring charge (electrons and ions) into the friction layer. The size can be obtained from the that the current density is the larger than the energy density, so it tends to decrease as the current high frequency band. The difficulty of transfer is inversely related −t1o the size. The small diameter can density increases. Among them, at the current density of 1 A g , after adding PVDF, the energy causeasmalltransferresist−a1nce,andthereisacertainrelationshipwiththefrequencybandinthe density reaches 8.85 Wh Kg (up to 112.78% of the pure cellulose friction layer). It can be found that test segment. The ideal low frequency band is a straight line parallel to the vertical axis, but due to the specific capacitance and energy density decrease after adding PA6, PVDF and BaTiO3. Although thecontinuouscurrentimpact,therewillbeacertainleakageresistanceR inthedriver.Becauseitis 1 the number of internal conductive particles increases, but the permeability decreases, and the ion rate small, it is usually ignored. The slope of the overall curve can reflect the speed of the ion diffusion rate of transmission also decreases at low current densities. It is manifested that the specific capacitance of the whole process, and the conductivity σ can be obtained by formula calculation. and energy density are reduced at this current density. 5 −22 Figure 4. (a) EIS curve at 10 Hz-10 Hz and GCD curves at difffferent current densities: (b) speciffiic capacitance, (c) energy density.. The electric double layer capacitor C reflects the internal charge capacity. As can be seen from 3.4. Single Open Circuit Voltage/Short Circuidtl Current Test Table 2, the value increases after adding PA6 and PVDF. After the addition of BaTiO3, the Cdl value The performance of different types of friction layer and PTFE film is tested, and the extrusion further increases. The ionic conductivity σ is calculated by Equation (2). Combined with Table 2, frequency was 1 Hz. The open circuit output voltage and short circuit current values of different it can be found that the σ value increases after adding PA6, PVDF and BaTiO3. After adding PA6, types of friction layers in the 50 s are tested experimentally. By eliminating the cluttered data and PVDF and BaTiO3, the increase of Cdl and σ indicates that the charge capacity and the charge transfer fitting the curve, the open circuit output voltage curve of a single different type of friction layer is rate of the cellulose layer increase. Based on strategies to develop efficient TENG through increasing shown in Figure 5, and the short circuit output current curve is shown in Figure 6. It can be seen that dielectric constant, optimization of internal resistance, and surface modification, the internal resistance the peak output voltage of the pure cellulose friction layer is 7.925 V, and the peak value of the short- of the cellulose friction film changes, and the electrical performance of the friction generator will be circuit output current is 1.095 μA. After adding PA6, the output voltage increased to 14.279 V (up improved [34]. Thus it is estimated that the electrical output performance of TENG after assembly 180.17%) and the output current increased to 2.917 μA (up 266.30%). After adding PVDF, the output also increases. voltage increased to 15.755 V (up 198.80%) and the output current increased to 3.239 μA (up 295.63%). Due to the different electTraobnleg2a.tPivaritaymeotferdsioffedrieffnetremntattyepreisalosf,ftrhicetioenlelcatyreirc.al output performance is different. The greater different in electronegativity between the two materials, the better the electrical Reagent Cel + PA6 + Cel + PVDF output performance of the nano-generaCteolr. TheCreflo+rPeA, t6he electrical outpuCtelp+erPfVoDrmF ance after PVDF EIS Parameter BaTiO3 + BaTiO3 is better than that with PA6. After adding BaTiO3 based on the addition of PA6, the output voltage Re (Ω) 1.455 1.553 1.571 1.922 1.731 was further increased to 18.798 V (up 131.65%), and the output current was increased to 5.129 μA (up Rct (Ω) 7.194 3.876 5.986 6.794 4.324 C (mF) 0.439 0.453 0.572 0.504 0.792 192.59%). After addl ding BaTiO3 to the PVDF, the output voltage is further increased to 20.155 V (up σ (ms/cm) 3.029 10.423 7.947 8.613 14.738 127.93%), and the output current is increased to 6.001 μA (up 185.30%). This is because BaTiO3 is a ferroelectric compound with high dielectric constant and low dielectric loss, and has a strong charge Specific capacitance C and energy density E can be obtained by using Equations (4) and (5), storage capacity. where m is the mass of active substances on the electrode, I is the charging current, ∆V is the charging By using its high dielectric constant property, strong charge storage capacity and piezoelectric potential difference, and ∆t is the charging time: effect, its incorporation into the original friction layer can increase its dielectric constant and further improve the output performance of the nano-generator. At the same time, since the BaTiO3 crystal I·∆t has no symmetry center, the charge distribuCti=on changes when the pressure is applied, the dipo(4le) m·∆V moment is generated, and the piezoelectric effect is generated. The piezoelectric effect furtherPDF Image | Green Triboelectric Nano-Generator Composite of Degradable Cellulose, Piezoelectric Polymers of PVDF PA6
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