Effect of Thickness of Nanofiber Separator Membrane PAN/PVDF on Supercapacitor’s Performance

Silvia Nurlaili Agustina, Markus Diantoro, Hartatiek Hartatiek, Nasikhudin Nasikhudin

Abstract


Separators in supercapacitors have an important role as intermediaries for ions that pass during the charge-discharge process and affect the performance of supercapacitors. Therefore, a comprehensive study is needed related to separator characteristics, including morphology, pore size, diameter, functional group, and electrochemical performance of separator membranes from PAN/PVDF composites. The separator membrane was synthesized using the electrospinning method with thickness variation (2, 4, 6, 8, and 10 layers), followed by supercapacitor fabrication with coin cell device. The resulting membrane was then characterized by Scanning Electron Microscope (SEM) and Fourier Transform Infrared (FTIR). For the result of supercapacitor fabrication with coin cells, Galvanostatic Charge-Discharge (GCD), Cyclic Voltammetry (CV), and Electrochemical Impedance Spectroscopy (EIS) were carried out to determine supercapacitor performance. FTIR results showed that the PAN/PVDF membrane was successfully composites with the addition of new peaks identified as PVDF and PAN at wave numbers 2243.21 and 881 cm-1. The nanofibers formed have diameters ranging from 319.7 to 339.95 nm. The optimum percentage of electrolyte uptake is obtained at membranes that have 6 layers, which is 318.18% and decreases to 173.68% the thickness is 10 layers. In this study, the optimum supercapacitor performance was obtained in the 6 layers variation with a thickness of 75.91 x 103 nm with a gravimetric capacitance value is 53.36 F/g, the capacity retention is 88.96% after being tested for 500 cycles, the largest curve area of CV, and an ionic conductivity value is 54 x 10-5 S/cm.

Keywords


Membrane, nanofiber, PAN/PVDF, separator, supercapacitor, thickness.

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References


M. Mirzaeian, Q. Abbas, A. Ogwu, P. Hall, M. Goldin, and M. Mirzaeian et al., “Electrode and electrolyte materials for electrochemical capacitors,” Int. J. Hydrogen Energy, vol. 42, no. 40, pp. 25565–25587, 2017, doi: 10.1016/j.ijhydene.2017.04.241.

M. Y. Bhat, S.A. Hashmi, M. Khan, D. Choi, and A. Qurashi, “Frontiers and recent developments on supercapacitor’s materials, design, and applications: Transport and power system applications,” J. Energy Storage, vol. 58, p. 106104, Feb. 2023, doi: 10.1016/J.EST.2022.106104.

M. Diantoro, I. Istiqomah, Y. Al Fath, N. Mufti, N. Nasikhudin, and W. Meevasana et al., “Hierarchical activated carbon–MnO2 composite for wide potential window asymmetric supercapacitor devices in organic electrolyte,” Micromachines, vol. 13, no. 11, 2022, doi: 10.3390/mi13111989.

E.K. Addo, A.T. Kabo-Bah, F.A. Diawuo, and S.K. Debrah, “The role of nuclear energy in reducing greenhouse gas (GHG) emissions and energy security: A systematic review,” Int. J. Energy Res., 2023, doi: 10.1155/2023/8823507.

R. Arthi, V. Jaikumar, and P. Muralidharan, “Development of electrospun PVdF polymer membrane as separator for supercapacitor applications,” Energy Sources, Part A Recover. Util. Environ. Eff., vol. 44, no. 1, pp. 2294–2308, 2022, doi: 10.1080/15567036.2019.1649746.

O. Hubert, N. Todorovic, and A. Bismarck, “Towards separator-free structural composite supercapacitors,” Compos. Sci. Technol., vol. 217, p. 109126, Jan. 2022, doi: 10.1016/J.COMPSCITECH.2021.109126.

D. Xu, G. Teng, Y. Heng, Z. Chen, and D. Hu, “Eco-friendly and thermally stable cellulose film prepared by phase inversion as supercapacitor separator,” Mater. Chem. Phys., vol. 249, no. December 2019, p. 122979, 2020, doi: 10.1016/j.matchemphys.2020.122979.

C. Zhao, J. Niu, C. Xiao, Z. Qin, X. Jin, and W. Wang et al., “Separator with high ionic conductivity and good stability prepared from keratin fibers for supercapacitor applications,” Chem. Eng. J., vol. 444, p. 136537, Sep. 2022, doi: 10.1016/J.CEJ.2022.136537.

J. Xing, S. Bliznakov, L. Bonville, M. Oljaca, and R. Maric, “A review of nonaqueous electrolytes, binders, and separators for Lithium-ion batteries,” Electrochemical Energy Reviews., vol. 5, no. 4, 2022, doi: 10.1007/s41918-022-00131-z.

S. Wu, J. Ning, F. Jiang, J. Shi, and F. Huang, “Ceramic nanoparticle-decorated melt-electrospun PVDF nanofiber membrane with enhanced performance as a Lithium-ion battery separator,” ACS Omega, vol. 4, no. 15, pp. 16309–16317, 2019, doi: 10.1021/acsomega.9b01541.

L. Li and Y. Duan, “Engineering Polymer-Based Porous Membrane for Sustainable Lithium-Ion Battery Separators,” Polymers (Basel)., vol. 15, no. 18, 2023, doi: 10.3390/polym15183690.

M. Beg, K.M. Alcock, A. Titus Mavelil, D. O’Rourke, D. Sun, and K. Goh et al., “Paper supercapacitor developed using a manganese dioxide/carbon black composite and a water hyacinth cellulose nanofiber-based bilayer separator,” ACS Appl. Mater. Interfaces, vol. 15, no. 44, pp. 51100–51109, 2023, doi: 10.1021/acsami.3c11005.

M. Yaseen, M.A.K. Khattak, M. Humayun, M. Usman, S.S. Shah, and S. Bibi et al., “A review of supercapacitors: Materials design, modification, and applications,” Energies, vol. 14, no. 22, pp. 1–40, 2021, doi: 10.3390/en14227779.

G. Qi, S. Nguyen, D.B. Anthony, A.R.J. Kucernak, M.S.P. Shaffer, and E.S. Greenhalgh, “The influence of fabrication parameters on the electrochemical performance of multifunctional structural supercapacitors,” Multifunct. Mater., vol. 4, no. 3, 2021, doi: 10.1088/2399-7532/ac1ea6.

M. Ma, H. Zhou, S. Gao, N. Li, W. Guo, and Z. Dai, “Analysis and prediction of electrospun nanofiber diameter based on artificial neural network,” Polymers (Basel)., vol. 15, no. 13, 2023, doi: 10.3390/polym15132813.

X. Cao, W. Chen, P. Zhao, Y. Yang, and D.G. Yu, “Electrospun porous nanofibers: pore−forming mechanisms and applications for photocatalytic degradation of organic pollutants in wastewater,” Polymers (Basel), vol. 14, no. 19, 2022, doi: 10.3390/polym14193990.

A.I. Yardimci, M. Kayhan, A. Durmus, M. Aksoy, and O. Tarhan, “Synthesis and air permeability of electrospun PAN/PVDF nanofibrous membranes,” Res. Eng. Struct. Mater., vol. 8, no. 2, pp. 223–231, 2022, doi: 10.17515/resm2022.357na1027.

A.W. Jatoi, P.K. Gianchandani, I.S. Kim, and Q.Q. Ni, “Sonication induced effective approach for coloration of compact polyacrylonitrile (PAN) nanofibers,” Ultrason. Sonochem., vol. 51, pp. 399–405, 2019, doi: 10.1016/j.ultsonch.2018.07.035.

P. Mandake and P.B. Karandikar, “Effect of separator thickness variation for supercapacitor with polyethylene separator material,” J. Sci. Res. Sci. Eng. Technol., vol. 2, no. 2, pp. 967–971, 2016.

J. Wen, K. Xu, R. Li, D. Lv, Y. Cui, and Y. Chen et al., “Electrospun flexible aluminum silicate nanofibers as a flame-resistant separator for the high performance supercapacitor,” Ionics (Kiel)., vol. 28, no. 1, pp. 433–442, 2022, doi: 10.1007/s11581-021-04329-x.

Y. Zheng, R. Zhou, H. Zhao, and F. Ye, “Oriented PAN/PVDF/PAN laminated nanofiber separator for lithium-ion batteries,” Text. Res. J., vol. 92, 2022, doi: 10.1177/00405175211005027.

E.P. Gilshteyn, D. Amanbayev, A.S. Anisimov, T. Kallio, and A.G. Nasibulin, “All-nanotube stretchable supercapacitor with low equivalent series resistance,” Sci. Rep., vol. 7, no. 1, pp. 1–9, 2017, doi: 10.1038/s41598-017-17801-4.

R.M. Ahmed, “Surface characterization and optical study on electrospun nanofibers of PVDF/PAN blends,” Fiber Integr. Opt., vol. 36, no. 1–2, pp. 78–90, 2017, doi: 10.1080/01468030.2017.1280098.

P. Deb, T. Haldar, S.M. Kashid, S. Banerjee, S. Chakrabarty, and S. Bagchi, “Correlating nitrile IR frequencies to local electrostatics quantifies noncovalent interactions of peptides and proteins,” J. Phys. Chem. B, vol. 120, no. 17, pp. 4034–4046, 2016, doi: 10.1021/acs.jpcb.6b02732.

A. Anvari, A.A. Yancheshme, F. Rekaabdar, M. Hemmati, M. Tavakolmoghadam, and A. Safekordi, “PVDF/PAN blend membrane: Preparation, characterization and fouling analysis,” J. Polym. Environ., vol. 25, no. 4, pp. 1348–1358, 2017, doi: 10.1007/s10924-016-0889-x.

H. Zhu, X. Deng, V.V. Yakovlev, and D. Zhang, “Dynamics of CH/n hydrogen bond networks probed by time-resolved CARS spectroscopy,” Chem. Sci., pp. 14344–14351, 2024, doi: 10.1039/d4sc03985h.

Y.A.Y.A. Mohammed, F. Ma, L. Liu, C. Zhang, H. Dong, and Q. Wang et al., “Preparation of electrospun polyvinylidene fluoride/amidoximized polyacrylonitrile nanofibers for trace metal ions removal from contaminated water,” J. Porous Mater., vol. 28, no. 2, pp. 383–392, 2021, doi: 10.1007/s10934-020-00995-w.

B.E.K. Dewi, Pranoto, O.A. Saputra, and E. Pramono, “Performance improvement polyvinylidene fluoride (PVDF) mordenite membranes for oil-in-water emulsion separation,” ALCHEMY, vol. 20, no. 2, pp. 226–237, 2024, doi: 10.20961/alchemy.20.2.82146.226-237.

H. Gade, S. Nikam, G.G. Chase, and D.H. Reneker, “Effect of electrospinning conditions on β-phase and surface charge potential of PVDF fibers,” Polymer (Guildf)., vol. 228, no. February, p. 123902, 2021, doi: 10.1016/j.polymer.2021.123902.

J. Liu, J. Wang, L. Zhu, X. Chen, Q. Ma, and L. Wang et al., “A high-safety and multifunctional MOFs modified aramid nanofiber separator for lithium-sulfur batteries,” Chem. Eng. J., vol. 411, no. December 2020, p. 128540, 2021, doi: 10.1016/j.cej.2021.128540.

Z. Wang, H. Ren, B. Wang, S. Yang, B. Wu, and Y. Zhou et al., “Microfiber/nanofiber/attapulgite multilayer separator with a pore-size gradient for high-performance and safe lithium-ion batteries,” Molecules, vol. 29, no. 14, 2024, doi: 10.3390/molecules29143277.

J. Bates, F. Markoulidis, C. Lekakou, and G.M. Laudone, “Design of porous carbons for supercapacitor applications for different organic solvent-electrolytes,” J. Carbon Res., vol. 7, no. 1, p. 15, 2021, doi: 10.3390/c7010015.

J. Lee, J. Yoon, J. Jeon, Y. Hong, S.G. Oh, and H. Huh, “Electrospun PVDF-HFP/PAN bicomponent nanofibers as separators in lithium-ion batteries with high thermal stability and electrolyte wettability,” Korean J. Chem. Eng., vol. 40, no. 8, pp. 1901–1911, 2023, doi: 10.1007/s11814-023-1486-z.

H. Wu, H. Huang, Y. Xu, F. Xu, and X. Zhang, “Ultrathin separator with efficient ion transport and superior stability prepared from cotton cellulose for advanced supercapacitors,” Chem. Eng. J., vol. 470, no. 35, p. 144089, 2023, doi: 10.1016/j.cej.2023.144089.

I. Falina, N. Loza, M. Brovkina, E. Titskaya, S. Timofeev, and N. Kononenko, “Electrotransport properties of perfluorinated cation-exchange membranes of various thickness,” Membranes (Basel), vol. 13, no. 11, 2023, doi: 10.3390/membranes13110873.

M.A.A. Mohamed, M. Adel, and J. El Nady, “Evaluation of the electrochemical energy storage performance of symmetric supercapacitor devices based on eco-friendly synthesized nitrogen-doped graphene-like derivative electrodes from the perspective of their nanostructural characteristics,” Energy Adv., pp. 2947–2964, 2024, doi: 10.1039/d4ya00526k.

J.H. Bang, B.H. Lee, Y.C. Choi, H.M. Lee, and B.J. Kim, “A study on superior mesoporous activated carbons for ultra power density supercapacitor from biomass precursors,” Int. J. Mol. Sci., vol. 23, no. 15, 2022, doi: 10.3390/ijms23158537.

M.S. Islam, S.M. Hoque, M. Rahaman, M.R. Islam, A. Irfan, and A. Sharif, “Superior cyclic stability and capacitive performance of cation- and water molecule-preintercalated δ-MnO2/h-WO3 Nanostructures as supercapacitor electrodes,” ACS Omega, vol. 9, no. 9, pp. 10680–10693, 2024, doi: 10.1021/acsomega.3c09236.

A. Azizpour, N. Bagovic, N. Ploumis, K. Mylonas, D. Hoxha, and F. Kienberger et al., “Electrochemical analysis of carbon-based supercapacitors using finite element modeling and impedance spectroscopy,” Energies, vol. 18, no. 6, pp. 1–20, 2025, doi: 10.3390/en18061450.

K. Gajewska, A. Moyseowicz, D. Minta, and G. Gryglewicz, “Effect of electrolyte and carbon material on the electrochemical performance of high-voltage aqueous symmetric supercapacitors,” J. Mater. Sci., vol. 58, no. 4, pp. 1721–1738, 2023, doi: 10.1007/s10853-023-08148-5.

H. Wang, H. Niu, H. Wang, W. Wang, X. Jin, and H. Wang et al., “Micro-meso porous structured carbon nanofibers with ultra-high surface area and large supercapacitor electrode capacitance,” J. Power Sources, vol. 482, no. June 2020, p. 228986, 2021, doi: 10.1016/j.jpowsour.2020.228986.

G. Singh, Y. Kumar, and S. Husain, “Improved electrochemical performance of symmetric polyaniline/activated carbon hybrid for high supercapacitance: Comparison with indirect capacitance,” Polym. Adv. Technol., vol. 32, no. 11, pp. 4490–4501, 2021, doi: 10.1002/pat.5451.

P. De, J. Halder, C.C. Gowda, S. Kansal, S. Priya, and S. Anshu et al., “Role of porosity and diffusion coefficient in porous electrode used in supercapacitors – Correlating theoretical and experimental studies,” Electrochem. Sci. Adv., vol. 3, no. 1, pp. 1–15, 2023, doi: 10.1002/elsa.202100159.

L. Stolz, M. Winter, and J. Kasnatscheew, “Practical relevance of charge transfer resistance at the Li metal electrode|electrolyte interface in batteries?,” J. Solid State Electrochem., no. 0123456789, pp. 11–14, 2024, doi: 10.1007/s10008-023-05792-4.

J. Tang, R. Muchakayala, S. Song, M. Wang, and K.N. Kumar, “Effect of EMIMBF4 ionic liquid addition on the structure and ionic conductivity of LiBF4-complexed PVdF-HFP polymer electrolyte films,” Polym. Test., vol. 50, pp. 247–254, 2016, doi: 10.1016/j.polymertesting.2016.01.023.

N. Hidayati and Munasir, “Study of electrical and thermal properties of PVA-nanosilica as a candidate for supercapacitor separators,” J. Phys. Conf. Ser., vol. 2110, no. 1, pp. 0–6, 2021, doi: 10.1088/1742-6596/2110/1/012012.

Y. Zilong, T. Dachuan, L. Jian, and N. Zhongming, “Dependence of Li-ion Battery energy density on separator thickness,” Chinese Phys. C, vol. 45, p. 124107, 2021.

N. Flores-Diaz, F. De Rossi, A. Das, M. Deepa, F. Brunetti, and M. Freitag, “Progress of photocapacitors,” Chem. Rev., vol. 123, no. 15, pp. 9327–9355, 2023, doi: 10.1021/acs.chemrev.2c00773.

T. He, R. Jia, X. Lang, X. Wu, and Y. Wang, “Preparation and Electrochemical performance of PVdF ultrafine porous fiber separator-cum-electrolyte for supercapacitor,” J. Electrochem. Soc., vol. 164, no. 13, pp. E379–E384, 2017, doi: 10.1149/2.0631713jes.




DOI: http://dx.doi.org/10.17977/um016v9i12025p228

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