Skip to main content
SpringerLink
Log in

In situ sol–gel preparation of ZrO2 in nano-composite polymer electrolyte of PVDF-HFP/MG49 for lithium-ion polymer battery

  • Original Paper: Sol-gel and hybrid materials for energy, environment and building applications
  • Published:
Journal of Sol-Gel Science and Technology Aims and scope Submit manuscript

Abstract

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 high electrochemical stability and flexible nanocomposite for lithium ion polymer battery application.

Highlights

  • 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.

This is a preview of subscription content, log in via an institution to check access.

Access this article

Log in via an institution

Price excludes VAT (USA)
Tax calculation will be finalised during checkout.

Instant access to the full article PDF.

Institutional subscriptions

Fig. 1
Fig. 2
Fig. 3
Fig. 4
Fig. 5
Fig. 6
Fig. 7
Fig. 8

Similar content being viewed by others

References

  1. Guangming Z, Feng L, Huiming C (2014) Progress in flexible lithium batteries and future prospects. Energy Environ Sci 4:1307–1338

    Google Scholar 

  2. Da QL, Chao YX, Xiao MX, Chun XZ, Ke SX, Xiaon QC, Shi BQ (2016) Sol–gel preparation of Li rich layered cathode material for lithioum ion battery with polymer polyacrylic acid+citric acid chelators. J Sol–Gel Sci Technol 78:403–410

    Article  Google Scholar 

  3. Hyunhyub K, Rehan K, Kuniharu T, Toshitake T, Xiaobo Z, Ali J (2012) Multifunctional, flexible electronic systems based on engineering nanostructured materials. Nanotechnology 23:344001

    Article  Google 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):511–517

    Article  Google Scholar 

  5. Razali I, Glasse MD, Latham RJ, Linford RG, Schlindwein WS (2001) Polymer electrolyes based on modified natural rubber for use in rechargeable lithium. Batter J Power Sources 94:206–211

    Article  Google 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 276:72–79

    Article  Google Scholar 

  7. Lee TK, Siti A, Azizan A, Dahlan HM, Rahman MYA (2012) Temperature dependence of conductivity of plasticized poly (vinyl chloride)-low molecular weight liquid 50% epoxidized natural rubber solid polymer electrolyte. J Solid State Electrochem 16:2251–2260

    Article  Google Scholar 

  8. Ferraria S, Quartaronea E, Mustarellia P, Magistrisa A, Fagnonib M, Prottib S, Gerbaldic AC (2010) Ion conducting PVdF-HFP composite gel electrolytes based on N-methoxyethyl-N-methylpyrrolidinium bis(trifluoromethanesulfonyl)-imide ionic liquid. J Power Sources 195:559–566

    Article  Google 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 8:3834–3850

    Google 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 25:1395–1400

    Google Scholar 

  11. Vickraman P, Ramamurthy S (2006) A study on the blending effect of PVDF in the ionic transport mechanism of plasticized PVC-LiBF4 polymer electrolyte. Mater Lett 60:3431–3436

    Article  Google 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 8:2154–2163

    Google 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 9:390–397

    Google Scholar 

  14. Tan C, Hackenberg K, Qiang F, Ajayan PM, Ardebili H (2012) High ion conducting polymer nanocomposite electrolytes using hybrid nanofillers. Nano Lett 3:1152–1156

    Google Scholar 

  15. Johnson P, Jacobsson P (2004) TiO2 nano particles in the polymer electrolytes: surface interactions. Solid State Ion 170:73–78

    Article  Google Scholar 

  16. Chung SH, Wang Y, Persi L (2001) Enhancement of the ion transport in polymer electrolytes by addition of nanoscale inorganic oxides. J Power Sources 98:644–648

    Article  Google Scholar 

  17. Croce F, Appetecchi GB, Persi L, Scrosati B (1998) Nanocomposite polymer electrolytes for lithium batteries. Nature 294:456–458

    Article  Google Scholar 

  18. Kühnel RS, Böckenfeld N, Passerini S, Winter M, Balducci A (2011) Mixtures of ionic liquid and organic carbonate as electrolyte with improved safety and performance for rechargeable lithium batteries. Electrochim Acta 56:4092–4099

    Article  Google Scholar 

  19. Xiang HF, Yin B, Wang H, Lin HW, Ge XW, Xie S, Chen CH (2010) Improving electrochemical properties of room temperature ionic liquid (RTIL) based electrolyte for Li-ion batteries. ‎Electrochim Acta 55:5204–5209

    Article  Google Scholar 

  20. GuangSun X, Dai S (2010) Electrochemical investigation of ionic liquid with vinylene carbonate for applications in rechargeable lithium ion batteries. ‎Electrochim Acta 5:4618–4626

    Google Scholar 

  21. Yan C, Zaijun L, Hailang Z, Yinjun F, Xu F, Junkang L (2010) 1-Alkyl-2,3-dimethylimidazolium bis(trifluoromethanesulfonyl)imide ionic liquids as highly safe electrolyte for Li/LiFePO4 battery. ‎Electrochim Acta 55:4728–4733

    Article  Google Scholar 

  22. Padbury R, Xiangwu Z (2010) Lithium–oxygen batteries—limiting factors that affect performance. J Power Sources 196:4436–4444

    Article  Google Scholar 

  23. Xiao J, Jianzhi H, Deyu W, Dehong H, Xu W, Graff GL, Zimin N, Liu J, GuangZhang J (2011) Investigation of the rechargeability of Li–O2 batteries in non-aqueous electrolyte. J Power Sources 196:5674–5678

    Article  Google Scholar 

  24. Fernando P, Mariano R, Ricardo F, Álvaro WM (2017) Experimental and theoretical study of ionic pair dissociation in a lithium ion−linear polyethylenimine−polyacrylonitrile blend for solid polymer electrolytes. J Phys Chem B 121:6759–6765

    Article  Google Scholar 

  25. Dan Z, Rui Z, Chuanxiang C, Wu-Aik Y, Junhua K, Guoqiang D, Xuehong L (2013) Non-volatile polymer electrolyte based on poly(propylene carbonate), ionic liquid, and lithium perchlorate for electrochromic devices. J Phys Chem B 117:7783–7789

    Article  Google Scholar 

  26. Miller TF, Wang ZG, Coates GW, Balsara NP (2017) Designing polymer electrolytes for safe and high capacity rechargeable lithium batteries. Acc Chem Res 50:590–593

    Article  Google Scholar 

  27. Rahman MYA, Ahmad A, Lee TK, Farina Y, Dahlan HM (2012) LiClO4 salt concentration effect on the properties of PVC-modified low molecular weight LENR50-based solid polymer electrolyte. J Appl Polym Sci 124:2227–2233

    Article  Google Scholar 

  28. Peng C, Xiaoping L, Jun W, Di Z, Shanmin Y, Weishan W, Wei Z, Xiaowei F, Dequan Y (2017) PEO/PVDF-based gel polymer electrolyte by incorporating nano-TiO2 for electrochromic glass. J Sol–Gel Sci Technol 81:850–858

    Article  Google Scholar 

  29. Zou H, Lin YS (2014) Structural and surface chemical properties of Sol–Gel derived TiO2-ZrO2 oxides. Appl Catal A 265:35–42

    Article  Google Scholar 

  30. Perez-Hernandez R, Mendoza-Anaya D, Fernandez ME, Gomez-Cortes A (2008) Synthesis of mixed ZrO2-TiO2 oxides by Sol–Gel: microstructural characterization and infrared spectroscopy studies of NOx. J Mol Catal A 281:200–206

    Article  Google Scholar 

  31. Manriquez ME, Lopez T, Gomez R, Navarrete J (2004) Preparation of TiO2-ZrO2 mixed oxides with controlled acid-basic properties. J Mol Catal A 220:229–237

    Article  Google 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 87:779–787

    Article  Google Scholar 

  33. Tyagi B, Sidhpuria K, Shaik B, Jasra RV (2006) Synthesis of nanocrystalline zirconia using Sol–Gel and precipitation techniques. Ind Eng Chem Res 45:8643–8650

    Article  Google Scholar 

  34. Park MS, Ma SB, Lee DJ, Im D, Doo SG, Yamamoto O (2013) Highly reversible lithium metal anode. Sci Rep 4:3815–3822

    Article  Google Scholar 

  35. Becke AD (1988) Density-functional exchange-energy approximation with correct asymptotic behavior. Phys Rev A 38:3098–3100

    Article  Google Scholar 

  36. Becke AD (1993) Density functional thermochemistry III: the role of exact exchange. J Chem Phys 98:5648–5652

    Article  Google Scholar 

  37. Davidson ER, Feller D (1986) Basis set selection for molecular calculations. Chem Rev 86:681–696

    Article  Google Scholar 

  38. Hehre WJ, Radom L, Schleyer PVR, Pople JA (1986) Ab initio molecular orbital theory. Acc Chem Res 9:399–406

    Article  Google Scholar 

  39. Lee C, Yang W, Parr R (1988) Development of the Colle-Salvetti correlation energy formula into a functional of the electron density. Phys Rev B 37:785–789

    Article  Google Scholar 

  40. Croce F, Persi L, Scrosati B, Serraino-Fiory F, Plichta E, Hendrickson MA (2001) Role of the ceramic fillers in enhancing the transport properties of composite polymer electrolytes. Electrochim Acta 46:2457–2461

    Article  Google Scholar 

  41. Croce F, Curini R, Martinelli A, Persi L, Ronci F, Scrosati B, Caminiti R (1999) Physical and chemical properties of nanocomposite polymer electrolytes. J Phys Chem B 103:10632–10638

    Article  Google Scholar 

  42. Puthirath AB, Patra S, Pal S, Manoj M, Balan AP, Jayalekshimi S, Tharangatu NN (2017) Transparent flexible lithium ion conducting solid polymer electrolyte. J Mater Chem A 5:11152–11162

    Article  Google Scholar 

  43. Miyamoto T, Shibayama K (1973) Free-volume model for ionic conductivity in polymers. J Appl Phys 44:5372–5376

    Article  Google Scholar 

  44. Arun KS, Vignesh M, Subramania A (2017) Dimensional stability and electrochemical behaviour of ZrO2 incorporated electrospun PVdF-HFP based nanocomposite polymer membrane electrolyte for Li-ion capacitors. Sci Rep 7:45390–45399

    Article  Google Scholar 

  45. Paneroa S, Scrosati B, Sumathipalaa HH, Wieczorek W (2007) Dual-composite polymer electrolytes with enhanced transport properties. J Power Sources 167:510–514

    Article  Google Scholar 

  46. Xing L, Guohua G, Yindan L, Zeyuan G, Pengliang L, Guangming W (2017) Carbon nanotubes/vanadium oxide composites as cathode materials for lithium-ion batteries. J Sol–Gel Sci Technol 82:224–232

    Article  Google Scholar 

  47. Ying T, Danqing Y, Baojun Z (2018) Synthesis of LiNiPO4 via citrate sol–gel route. J Sol–Gel Sci Technol 87:240–244

    Article  Google Scholar 

  48. Croce F, Persi L, Ronci F, Scrosati B (2000) Nanocomposite polymer electrolytes and their impact on the lithium battery technology. Solid State Ion 135:47–52

    Article  Google 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 7:6693–6703

    Google Scholar 

  50. Wu CG, Lu MI, Tsai CH, Chuang HJ (2006) PVDF-HFP/metal oxide nanocomposite: the matrices for high-conducting, low leakage porous polymer electrolytes. J Power Sources 159:295–300

    Article  Google Scholar 

  51. TianKhoon L, Ataollahi N, Hassan NH, Ahmad A (2016) Studies of porous solid polymeric electrolytes based on poly (vinylidene fluoride) and poly (methyl methacrylate) grafted natural rubber for applications in electrochemical devices. J Solid State Electrochem 20:203–213

    Article  Google Scholar 

  52. Mahmood WAK, Khan MMR, Azarian MH (2013) Sol–gel synthesis and morphology, thermal and optical properties of epoxidized natural rubber/zirconia hybrid films. J Non-Cryst Solids 378:152–157

    Article  Google Scholar 

  53. Chuanglong W, Monica S, James AK, Leon LS (2015) Roles of processing, structural defects and ionic conductivity in the electrochemical performance of Na3MnCO3PO4 cathode material. J Electrochem Soc 162(8):1601–1609

    Article  Google Scholar 

  54. Chuanglong W, Monica S, Satya E, Caihong L, Leon LS (2015) Na3MnCO3PO4—a high capacity, multi-electron transfers redox cathode material for sodium ion batteries. Electrochim Acta 161:322–328

    Article  Google Scholar 

  55. Kim DW, Noh KA, Chun JH, Kim SH, Ko JM (2011) Highly conductive polymer electrolytes supported by microporous membrane. Solid State Ion 144:329–337

    Article  Google Scholar 

  56. Fang S, Zhang Z, Jin Y, Yang L, Hirano S, Tachibana K, Katayama S (2011) New functionalized ionic liquids based on pyrrolidinium and piperidinium cations with two ether groups as electrolytes for lithium battery. J Power Sources 196:5637–5644

    Article  Google Scholar 

  57. Appetecchi GB, Kim GT, Montanino M, Alessandrini F, Passerini S (2011) Room temperature lithium polymer batteries based on ionic liquids. J Power Sources 196:6703–6709

    Article  Google Scholar 

Download references

Acknowledgements

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.

Author information

Authors and Affiliations

  1. Fuel Cell Institute (FCI), Universiti Kebangsaan Malaysia, 43600, Bangi, Selangor D. E., Malaysia

    Lee Tian Khoon & Loh Kee Shyuan

  2. School of Chemical Sciences and Food Technology, Faculty of Science and Technology, Universiti Kebangsaan Malaysia, 43600, Bangi, Selangor D. E., Malaysia

    Mark-Lee Wun Fui, Nur Hasyareeda Hassan, Mohammad Bin Kassim & Azizan Ahmad

  3. Solar Energy Research Institute (SERI), Universiti Kebangsaan Malaysia, 43600, Bangi, Selangor, Malaysia

    Mohd Sukor Su’ait

  4. International Advanced Research Centre for Powder Metallurgy and New Materials (ARCI), Balapur P.O., Hyderabad, Telangana, 500005, India

    Raman Vedarajan

  5. School of Materials Science, Japan Advanced Institute of Science and Technology, MS, Building III, 3F, 1-1 Asahidai, Nomi, Ishikawa, 923-1292, Japan

    Noriyoshi Matsumi

Authors
  1. Lee Tian Khoon
    View author publications

    You can also search for this author in PubMed Google Scholar

  2. Mark-Lee Wun Fui
    View author publications

    You can also search for this author in PubMed Google Scholar

  3. Nur Hasyareeda Hassan
    View author publications

    You can also search for this author in PubMed Google Scholar

  4. Mohd Sukor Su’ait
    View author publications

    You can also search for this author in PubMed Google Scholar

  5. Raman Vedarajan
    View author publications

    You can also search for this author in PubMed Google Scholar

  6. Noriyoshi Matsumi
    View author publications

    You can also search for this author in PubMed Google Scholar

  7. Mohammad Bin Kassim
    View author publications

    You can also search for this author in PubMed Google Scholar

  8. Loh Kee Shyuan
    View author publications

    You can also search for this author in PubMed Google Scholar

  9. Azizan Ahmad
    View author publications

    You can also search for this author in PubMed Google Scholar

Corresponding authors

Correspondence to Lee Tian Khoon or Azizan Ahmad.

Ethics declarations

Conflict of interest

The authors declare that they have no conflict of interest.

Additional information

Publisher’s note: Springer Nature remains neutral with regard to jurisdictional claims in published maps and institutional affiliations.

Supplementary information

Rights and permissions

Reprints and permissions

About this article

Check for updates. Verify currency and authenticity via CrossMark

Cite this article

Khoon, L.T., Fui, ML.W., Hassan, N.H. et al. In situ sol–gel preparation of ZrO2 in nano-composite polymer electrolyte of PVDF-HFP/MG49 for lithium-ion polymer battery. J Sol-Gel Sci Technol 90, 665–675 (2019). https://doi.org/10.1007/s10971-019-04936-1

Download citation

  • Received:

  • Accepted:

  • Published:

  • Issue Date:

  • DOI: https://doi.org/10.1007/s10971-019-04936-1

Keywords

Search

Navigation