Abstract
Polymer-based separators for energy storage applications are being developed to ensure the high safety, high performance, light weight, and low cost of the device. In this regard, poly(vinylidene fluoride-co-hexafluoropropylene) PVDF-HFP which is a co-polymer of PVDF is an excellent host polymer for energy storage applications as it possess both the crystalline PVDF and the amorphous HFP groups leading to both mechanical stability and ionic conductivity. Though the lithium-ion-conducting PVDF-HFP membranes are successfully utilized as the polymer electrolyte for lithium ion batteries, the enhanced ionic conductivity by usage of plasticizers often degrade their mechanical and thermal stability. Where else, when incorporated with graphene oxide (GO) as the filler, the membrane electrolytes show good ionic conducting nature, with no compromise on thermal stability and mechanical stability. Incorporation of GO results in porous nature and helps in the high electrolyte retention and electrochemical stability even at high potential window. In this review article, the influence of GO with respect to structural changes, thermal stability, and electrical properties is discussed in detail, which will pave way for further new aspects in membrane modification.
This is a preview of subscription content, log in via an institution to check access.
Similar content being viewed by others
Data availability
Not applicable.
References
Ahmad AL, Farooqui UR, Hamid NA (2018a) Effect of graphene oxide (GO) on poly(vinylidene fluoride-hexafluoropropylene) (PVDF- HFP) polymer electrolyte membrane. Polymer (guildford) 142:330–336. https://doi.org/10.1016/j.polymer.2018.03.052
Ahmad AL, Farooqui UR, Hamid NA (2018b) Synthesis and characterization of porous poly(vinylidene fluoride-co-hexafluoro propylene) (PVDF-co-HFP)/poly(aniline) (PANI)/graphene oxide (GO) ternary hybrid polymer electrolyte membrane. Electrochim Acta 283:842–849. https://doi.org/10.1016/j.electacta.2018.07.001
Ahmad AL, Farooqui UR, Hamid NA (2018c) Porous (PVDF-HFP/PANI/GO) ternary hybrid polymer electrolyte membranes for lithium-ion batteries. RSC Adv 8:25725–25733. https://doi.org/10.1039/c8ra03918f
Brodie BC (1859) On the atomic weight of graphite. Philos Trans R Soc Lond 149:249–259. https://doi.org/10.1098/rstl.1859.0013
Chen YT, Chuang YC, Su JH et al (2011) High discharge capacity solid composite polymer electrolyte lithium battery. J Power Sources 196:2802–2809. https://doi.org/10.1016/j.jpowsour.2010.11.058
Chen G, Zhang F, Zhou Z et al (2018) A flexible dual-ion battery based on PVDF-HFP-modified gel polymer electrolyte with excellent cycling performance and superior rate capability. Adv Energy Mater 8:1–7. https://doi.org/10.1002/aenm.201801219
Choi JW, Cheruvally G, Kim YH et al (2007) Poly(ethylene oxide)-based polymer electrolyte incorporating room-temperature ionic liquid for lithium batteries. Solid State Ion 178:1235–1241. https://doi.org/10.1016/j.ssi.2007.06.006
Choi Y, Zhang K, Chung KY et al (2016) PVdF-HFP/exfoliated graphene oxide nanosheet hybrid separators for thermally stable Li-ion batteries. RSC Adv 6:80706–80711. https://doi.org/10.1039/c6ra15062d
Dastbaz A, Karimi-Sabet J, Ahadi H, Amini Y (2017) Preparation and characterization of novel modified PVDF-HFP/GO/ODS composite hollow fiber membrane for Caspian Sea water desalination. Desalination 424:62–73. https://doi.org/10.1016/j.desal.2017.09.030
Djian D, Alloin F, Martinet S et al (2007) Lithium-ion batteries with high charge rate capacity: influence of the porous separator. J Power Sources 172:416–421. https://doi.org/10.1016/j.jpowsour.2007.07.018
Eftekhari A, Shulga YM, Baskakov SA, Gutsev GL (2018) Graphene oxide membranes for electrochemical energy storage and conversion. Int J Hydrogen Energy. https://doi.org/10.1016/j.ijhydene.2017.12.012
Farooqui UR, Ahmad AL, Hamid NA (2018) Graphene oxide: a promising membrane material for fuel cells. Renew Sustain Energy Rev 82:714–733. https://doi.org/10.1016/j.rser.2017.09.081
Fattah NFA, Ng HM, Mahipal YK et al (2016) An approach to solid-state electrical double layer capacitors fabricated with graphene oxide-doped, ionic liquid-based solid copolymer electrolytes. Materials (basel). https://doi.org/10.3390/ma9060450
Hofmann U, König E (1937) Untersuchungen über Graphitoxyd. Zeitschrift für Anorg und Allg Chemie 234:311–336. https://doi.org/10.1002/zaac.19372340405
Huang YF, Wu PF, Zhang MQ et al (2014) Boron cross-linked graphene oxide/polyvinyl alcohol nanocomposite gel electrolyte for flexible solid-state electric double layer capacitor with high performance. Electrochim Acta 132:103–111. https://doi.org/10.1016/j.electacta.2014.03.151
Huang X, Liu F, Jiang P, Tanaka T (2013) Is graphene oxide an insulating material? In: 2013 IEEE international conference on solid dielectrics (ICSD), pp 904–907
Hummers WS, Offeman RE (1958) Preparation of graphitic oxide. J Am Chem Soc 80:1339. https://doi.org/10.1021/ja01539a017
Hwang K, Kwon B, Byun H (2011) Preparation of PVdF nanofiber membranes by electrospinning and their use as secondary battery separators. J Memb Sci 378:111–116. https://doi.org/10.1016/j.memsci.2011.06.005
Il KJ, Cho JS, Wang DH, Park JH (2020) Highly dispersible graphene oxide nanoflakes in pseudo-gel-polymer porous separators for boosting ion transportation. Carbon N Y 166:427–435. https://doi.org/10.1016/j.carbon.2020.05.003
Jeong HS, Hong SC, Lee SY (2010) Effect of microporous structure on thermal shrinkage and electrochemical performance of Al2O3/poly(vinylidene fluoride-hexafluoropropylene) composite separators for lithium-ion batteries. J Memb Sci 364:177–182. https://doi.org/10.1016/j.memsci.2010.08.012
Jie J, Liu Y, Cong L et al (2020) High-performance PVDF-HFP based gel polymer electrolyte with a safe solvent in Li metal polymer battery. J Energy Chem 49:80–88. https://doi.org/10.1016/j.jechem.2020.01.019
Khan DM, Kausar A, Salman SM (2016a) Exploitation of nanobifiller in polymer/graphene oxide–carbon nanotube, polymer/graphene oxide–nanodiamond, and polymer/graphene oxide–montmorillonite composite: a review. Polym Plast Technol Eng 55:744–768. https://doi.org/10.1080/03602559.2015.1103266
Khan ZU, Kausar A, Ullah H et al (2016b) A review of graphene oxide, graphene buckypaper, and polymer/graphene composites: properties and fabrication techniques. J Plast Film Sheeting 32:336–379. https://doi.org/10.1177/8756087915614612
Khan ZU, Kausar A, Ullah H (2016c) A review on composite papers of graphene oxide, carbon nanotube, polymer/GO, and polymer/CNT: processing strategies, properties, and relevance. Polym Plast Technol Eng 55:559–581. https://doi.org/10.1080/03602559.2015.1098693
Khatmullina KG, Baimuratova GR, Lesnichaya VA et al (2018) Mechanical and electrochemical properties of new nanocomposite polymer electrolytes based on poly(vinylidene fluoride-co-hexafluoropropylene) and SiO2 addition. Polym Sci Ser A 60:222–228. https://doi.org/10.1134/S0965545X18020074
Khurana R, Schaefer JL, Archer LA, Coates GW (2014) Suppression of lithium dendrite growth using cross-linked polyethylene/poly(ethylene oxide) electrolytes: a new approach for practical lithium-metal polymer batteries. J Am Chem Soc 136:7395–7402. https://doi.org/10.1021/ja502133j
Kim H-S, Choi G-Y, Moon S-I, Kim S-P (2003) Electrochemical properties of Li ion polymer battery with gel polymer electrolyte based on polyurethane. J Appl Electrochem 33:491–496. https://doi.org/10.1023/A:1024458513004
Kim I, Kim BS, Nam S et al (2018a) Cross-linked poly(vinylidene fluoride-cohexafluoropropene) (PVDF-co-HFP) gel polymer electrolyte for flexible li-ion battery integrated with organic light emitting diode (OLED). Materials (basel) 11:1–11. https://doi.org/10.3390/ma11040543
Kim SH, Choi KH, Cho SJ et al (2018b) Flexible/shape-versatile, bipolar all-solid-state lithium-ion batteries prepared by multistage printing. Energy Environ Sci 11:321–330. https://doi.org/10.1039/c7ee01630a
Konios D, Stylianakis MM, Stratakis E, Kymakis E (2014) Dispersion behaviour of graphene oxide and reduced graphene oxide. J Colloid Interface Sci 430:108–112. https://doi.org/10.1016/j.jcis.2014.05.033
Liang J, Deng W, Zhou X et al (2021) High Li-ion conductivity artificial interface enabled by Li-grafted graphene oxide for stable Li metal pouch cell. ACS Appl Mater Interfaces 13:29500–29510. https://doi.org/10.1021/acsami.1c04135
Lin M, Wang ZL, Yang PW, Li P (2019) Micro-structure and rheological properties of graphene oxide rubber asphalt. Nanotechnol Rev 8:227–235. https://doi.org/10.1515/ntrev-2019-0021
Liu T, Chang Z, Yin Y et al (2018a) The PVDF-HFP gel polymer electrolyte for Li-O2 battery. Solid State Ion 318:88–94. https://doi.org/10.1016/j.ssi.2017.08.001
Liu X, Song K, Lu C et al (2018b) Electrospun PU@GO separators for advanced lithium ion batteries. J Memb Sci 555:1–6. https://doi.org/10.1016/j.memsci.2018.03.027
Lu W, Henry K, Turchi C, Pellegrino J (2007) Ionic liquid-incorporated gel polymer electrolytes for ultracapacitors. ECS Trans 2:15–26. https://doi.org/10.1149/1.2409039
Luo C, Shen T, Ji H et al (2020) Mechanically robust gel polymer electrolyte for an ultrastable sodium metal battery. Small. https://doi.org/10.1002/smll.201906208
Moharana S, Mahaling RN (2017) Silver (Ag)–graphene oxide (GO)–Poly (vinylidene fluoride-co-hexafluoropropylene) (PVDF-HFP) nanostructured composites with high dielectric constant and low dielectric loss. Chem Phys Lett 680:31–36. https://doi.org/10.1016/j.cplett.2017.05.018
Moreno M, Quijada R, Santa Ana MA, et al (2011) Electrical and mechanical properties of poly(ethylene oxide)/intercalated clay polymer electrolyte. Electrochim Acta 58:112–118. https://doi.org/10.1016/j.electacta.2011.08.096
Noor MM, Buraidah MH, Careem MA et al (2014) An optimized poly(vinylidene fluoride-hexafluoropropylene)-NaI gel polymer electrolyte and its application in natural dye sensitized solar cells. Electrochim Acta 121:159–167. https://doi.org/10.1016/j.electacta.2013.12.136
Park JH, Cho JH, Park W et al (2010) Close-packed SiO2/poly(methyl methacrylate) binary nanoparticles-coated polyethylene separators for lithium-ion batteries. J Power Sources 195:8306–8310. https://doi.org/10.1016/j.jpowsour.2010.06.112
Perrozzi F, Prezioso S, Ottaviano L (2015) Graphene oxide: from fundamentals to applications. J Phys Condens Matter 27:13002. https://doi.org/10.1088/0953-8984/27/1/013002
Schick C (2009) Differential scanning calorimetry (DSC) of semicrystalline polymers. Anal Bioanal Chem 395:1589–1611. https://doi.org/10.1007/s00216-009-3169-y
Senthil Kumar P, Sakunthala A, Govindan K et al (2016) Single crystalline TiO2 nanorods as effective fillers for lithium ion conducting PVdF-HFP based composite polymer electrolytes. RSC Adv 6:91711–91719. https://doi.org/10.1039/c6ra20649b
Shah R, Kausar A, Muhammad B, Shah S (2015) Progression from graphene and graphene oxide to high performance polymer-based nanocomposite: a review. Polym Plast Technol Eng 54:173–183. https://doi.org/10.1080/03602559.2014.955202
Shanmugaraj P, Swaminathan A, Ravi RK et al (2019) Preparation and characterization of porous PVdF-HFP/graphene oxide composite membranes by solution casting technique. J Mater Sci Mater Electron 30:20079–20087. https://doi.org/10.1007/s10854-019-02380-z
Singh MK, Suleman M, Kumar Y, Hashmi SA (2015) A novel configuration of electrical double layer capacitor with plastic crystal based gel polymer electrolyte and graphene nano-platelets as electrodes: a high rate performance. Energy 80:465–473. https://doi.org/10.1016/j.energy.2014.11.087
Song X, Ding W, Cheng B, Xing J (2017) Electrospun poly(vinylidene-fluoride)/POSS nanofiber membrane-based polymer electrolytes for lithium ion batteries. Polym Compos 38:629–636. https://doi.org/10.1002/pc.23621
Staudenmaier L (1898) Verfahren zur Darstellung der Graphitsäure. Berichte der Dtsch Chem Gesellschaft 31:1481–1487. https://doi.org/10.1002/cber.18980310237
Stephan AM, Nahm KS, Anbu Kulandainathan M et al (2006) Poly(vinylidene fluoride-hexafluoropropylene) (PVdF-HFP) based composite electrolytes for lithium batteries. Eur Polym J 42:1728–1734. https://doi.org/10.1016/j.eurpolymj.2006.02.006
Sui Y, Liu C, Masse RC et al (2020) Dual-ion batteries: the emerging alternative rechargeable batteries. Energy Storage Mater 25:1–32. https://doi.org/10.1016/j.ensm.2019.11.003
Tarascon J-M, Gozdz AS, Schmutz C et al (1996) Performance of Bellcore’s plastic rechargeable Li-ion batteries. Solid State Ion 86–88:49–54. https://doi.org/10.1016/0167-2738(96)00330-X
Vijayakumar G, Karthick SN, Subramania A (2011) A new class of P(VdF-HFP)-CeO2-LiClO4-based composite microporous membrane electrolytes for Li-ion batteries. Int J Electrochem 2011:1–10. https://doi.org/10.4061/2011/926383
Wang S-H, Kuo P-L, Hsieh C-T, Teng H (2014) Design of poly(acrylonitrile)-based gel electrolytes for high-performance lithium ion batteries. ACS Appl Mater Interfaces 6:19360–19370. https://doi.org/10.1021/am505448a
Wang C, Shen W, Lu J, Guo S (2017) Graphene oxide doped poly(vinylidene fluoride-co-hexafluoropropylene) gel electrolyte for lithium ion battery. Ionics (kiel) 23:2045–2053. https://doi.org/10.1007/s11581-017-2037-6
Wang X, Zhao H, Deng N et al (2022) Efficient lithium-metal battery based on a graphene oxide-modified heat-resistant gel polymer electrolyte with superior cycling stability and excellent rate capability. Sustain Energy Fuels 6:386–397. https://doi.org/10.1039/D1SE01277K
Waqas M, Ali S, Feng C et al (2019) Recent development in separators for high-temperature lithium-ion batteries. Small. https://doi.org/10.1002/smll.201901689
Xiao W, Gong Y, Wang H et al (2015) Preparation and electrochemical performance of ZrO2 nanoparticle-embedded nonwoven composite separator for lithium-ion batteries. Ceram Int 41:14223–14229. https://doi.org/10.1016/j.ceramint.2015.07.048
Yang X, Zhang F, Zhang L et al (2013) A high-performance graphene oxide-doped ion gel as gel polymer electrolyte for all-solid-state supercapacitor applications. Adv Funct Mater 23:3353–3360. https://doi.org/10.1002/adfm.201203556
Yang T, Shu C, Hou Z et al (2019) 3D porous network gel polymer electrolyte with high transference number for dendrite-free Li[sbnd]O2 batteries. Solid State Ionics 343:115088. https://doi.org/10.1016/j.ssi.2019.115088
Zhang J, Zhao J, Yue L et al (2015) Safety-reinforced poly(propylene carbonate)-based all-solid-state polymer electrolyte for ambient-temperature solid polymer lithium batteries. Adv Energy Mater 5:1–10. https://doi.org/10.1002/aenm.201501082
Zhang Z, Antonio RG, Choy KL (2019) Boron nitride enhanced polymer/salt hybrid electrolytes for all-solid-state lithium ion batteries. J Power Sources 435:226736. https://doi.org/10.1016/j.jpowsour.2019.226736
Zhang Y, Wu F, Huang Y et al (2022) A novel gel polymer electrolyte doped with MXene enables dendrite-free cycling for high-performance sodium metal batteries. J Mater Chem A 10:11553–11561. https://doi.org/10.1039/D2TA00452F
Zhao C, Xu X, Chen J et al (2014) Highly effective antifouling performance of PVDF/graphene oxide composite membrane in membrane bioreactor (MBR) system. Desalination 340:59–66. https://doi.org/10.1016/j.desal.2014.02.022
Zhao X, Tao C, Li Y et al (2020) Preparation of gel polymer electrolyte with high lithium ion transference number using GO as filler and application in lithium battery. Ionics (kiel). https://doi.org/10.1007/s11581-020-03628-z
Zhu YS, Wang XJ, Hou YY et al (2013) A new single-ion polymer electrolyte based on polyvinyl alcohol for lithium ion batteries. Electrochim Acta 87:113–118. https://doi.org/10.1016/j.electacta.2012.08.114
Zhu G, Jing X, Chen D, He W (2020) Novel composite separator for high power density lithium-ion battery. Int J Hydrogen Energy 45:2917–2924. https://doi.org/10.1016/j.ijhydene.2019.11.125
Funding
The author Dr. A. Sakunthala thanks the Department of Science and Technology, Science and Engineering Research Board, (DST-SERB) for the financial assistance through the Project no. EMR/2017/003227dated 16 July 2018. The authors also thank the research facilities provided by Karunya Institute of Technology and Science, Coimbatore 641114, Tamil Nadu, India.
Author information
Authors and Affiliations
Contributions
SP collected the literatures, analyzed, and written the manuscript. AS guided and mentored the work. All authors discussed the results.
Corresponding author
Ethics declarations
Conflict of interest
The authors declare that they have no conflicts of interests to this work.
Additional information
Publisher's Note
Springer Nature remains neutral with regard to jurisdictional claims in published maps and institutional affiliations.
Rights and permissions
Springer Nature or its licensor (e.g. a society or other partner) holds exclusive rights to this article under a publishing agreement with the author(s) or other rightsholder(s); author self-archiving of the accepted manuscript version of this article is solely governed by the terms of such publishing agreement and applicable law.
About this article
Cite this article
Pavithra, S., Sakunthala, A., Rajesh, S. et al. Influence of graphene oxide on the membrane characteristics of PVDF-HFP as an electrolyte for lithium-based energy storage devices. Appl Nanosci 13, 4177–4192 (2023). https://doi.org/10.1007/s13204-023-02839-w
Received:
Accepted:
Published:
Issue Date:
DOI: https://doi.org/10.1007/s13204-023-02839-w