In situ sol–gel preparation of ZrO2 in nano-composite polymer electrolyte of PVDF-HFP/MG49 for lithium-ion polymer battery
- 37 Downloads
Nano-composite polymer electrolyte (NCPE), poly(vinylidenefluoride-hexafluoropropylene)-poly(methylmethacrylate) grafted natural rubber with lithium tetrafluoroborate and zirconia (PVdF-HFP/MG49-LiBF4-ZrO2) was prepared by a facile one-pot in situ sol–gel method. The influence of zirconia nano-fillers on the electrochemical, chemical and structural properties of polymer electrolyte was investigated. The interaction of polymer electrolyte and zirconia was explored via density functional theory (DFT). Electrochemical impedance spectroscopy study showed that the optimum ionic conductivity is 2.39 × 10−3 S cm−1 (6 wt% zirconia). X-ray diffractogram results revealed a decreasing trend of crystalline phases and no lithium salt peaks were observed upon the addition of zirconia. As a result, the LiBF4 salt was well-solvated in the polymer matrix with a one-fold increase in lithium transference number. Remarkably, a good electrochemical stability was achieved at 6.9 V from a linear sweep voltammetry (LSV) analysis. Observations from the infrared spectra indicate that chemical interactions occurred at the carbonyl and fluoride functional groups and is further corroborated by DFT studies. Micrograph images showed that the zirconia nano-particles were successfully produced (7–15 nm). The nanocomposite polymer electrolyte possesses promising charge/discharge performance and has the potential to be applied in lithium-ion polymer battery.
The sizes of ZrO2 nano-particles are in the range of 7–15 nm.
High ionic conductivity (2.39 × 10−3 S cm−1) and electrochemical stability (6.9 V) was achieved for the nanocomposite polymer electrolyte sample.
Nano-particle zirconia improved the lithium transference number by a fold from 0.103 to 0.216.
The nanocomposite polymer electrolyte was able to maintain a good ionic conductivity (~10−5 S cm−1) at a high temperature of 200 °C.
KeywordsNanocomposite polymer electrolyte Zirconia In situ sol–gel One pot preparation Lithium-ion polymer battery DFT
The authors would like to acknowledge National University of Malaysia for the research facilities and sponsoring this project under Modal Insan UKM (MI-2018-002 and MI-2018-012) and INOVASI-2017-011. We would also like to thank UKM and Mr. Patrick Tan Sang Hup from KGC Resources Sdn. Bhd. for providing part of the financial support under INOVASI-2017-011. Special thanks to the Japan Student Services Organization (JASSO) for sponsoring the internship program in Japan. Many thanks to Prof. Hideaki Kasai, Prof. Wilson Agerico Diño and Osaka University, Japan for supporting us with the quantum computational facilities.
Compliance with ethical standards
Conflict of interest
The authors declare that they have no conflict of interest.
- 1.Guangming Z, Feng L, Huiming C (2014) Progress in flexible lithium batteries and future prospects. Energy Environ Sci 4:1307–1338Google Scholar
- 4.Dae-Hyeong K, Jonathan V, Jason JA, Jianliang X, Leif V, Yun-Soung K, Justin AB, Bruce P, Eric SF, Diego C, David LK, Fiorenzo GO, Yonggang H, Keh-Chih H, Mitchell RZ, Brian L, John AR (2010) Dissolvable films of silk fibroin for ultrathin conformal bio-integrated electronics. Nat Mater 9(6):511–517CrossRefGoogle Scholar
- 6.TianKhoon L, Hassan NH, Rahman MYA, Vedarajan R, Matsumi N, Ahmad A (2015) One-pot synthesis nano-hybrid ZrO2–TiO2 fillers in 49% poly (methyl methacrylate) grafted natural rubber (MG49) based nano-composite polymer electrolyte for lithium ion battery application. Solid State Ion 276:72–79CrossRefGoogle Scholar
- 9.Kuo CW, Huang CW, Chen BK, Li WB, Chen PR, Ho TH, Tseng CG, Wu TY (2013) Enhanced ionic conductivity in PAN–PEGME-LiClO4-PC composite polymer electrolytes. Int J Electrochem Sci 8:3834–3850Google Scholar
- 10.HyeKil E, HoChoi K, JeongHa H, Xu S, Rogers JA, RiKim M, GiLee Y, ManKim K, YoungCho K, YoungLee S (2013) Imprintable, bendable, and shape-conformable polymer electrolytes for versatile-shaped lithium-ion batteries. Mater 25:1395–1400Google Scholar
- 12.Yap YL, You AH, Teo LL, Hanapei H (2013) Inorganic filler sizes effect on ionic conductivity in polyethylene oxide (PEO) composite polymer electrolyte. Int J Electrochem Sci 8:2154–2163Google Scholar
- 13.Kedi C, Haijing J, Weihua P (2014) Comparative investigation of organic solution and ionic liquid as electrolyte under lithium-air battery. Int J Electrochem Sci 9:390–397Google Scholar
- 14.Tan C, Hackenberg K, Qiang F, Ajayan PM, Ardebili H (2012) High ion conducting polymer nanocomposite electrolytes using hybrid nanofillers. Nano Lett 3:1152–1156Google Scholar
- 20.GuangSun X, Dai S (2010) Electrochemical investigation of ionic liquid with vinylene carbonate for applications in rechargeable lithium ion batteries. Electrochim Acta 5:4618–4626Google Scholar
- 32.Wetjen M, Kim G, Joost M, Winter M, Passerini S (2013) Temperature dependence of electrochemical properties of cross-linked poly(ehtylne oxide) -lithium bis(trifluoromethanesulfonyl) imide - N-buty l-N-methylprrolidinium bis (trifluoromethanesulfonyl) imide solid polymer electrolytes for lithium batteries. Electrochim Acta 87:779–787CrossRefGoogle Scholar
- 49.Ataollahi N, Ahmad A, Hamzah H, Rahman MYA, Mohamed NS (2012) Preparation and characterization of PVDF-HFP/MG49 based polymer blend electrolyte. Int J Electrochem Sci 7:6693–6703Google Scholar