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Preparation, properties, and Li-ion battery application of EC + PC-modified PVdF-HFP gel polymer electrolyte films

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Abstract

Based on poly(vinylidene fluoride-co-hexafluoropropylene) (PVdF-HFP) and lithium tetrafluoroborate (LiBF4) salt along with blending plasticizers, ethylene carbonate (EC) and propylene carbonate (PC), high Li-ion-conducting gel polymer electrolyte films are developed. Their properties are characterized by various techniques. The ambient temperature ionic conductivity of the 85PVdF-HFP:15LiBF4 + 150(EC + PC) electrolyte film has a high value of 8.1 × 10−4 S cm−1. Its crystallinity, melting point, and electrochemical stability window are 9.5%, 115 °C, and 4.6 V, respectively. The mechanical testing shows that the Young’s modulus, yield strength, and breaking strain of this electrolyte film are 36.8 MPa, 3.4 MPa, and 320%, respectively. Lithium-ion batteries based on the gel polymer electrolyte film exhibit remarkable charge–discharge and cycling performances. The initial discharge capacity of this battery is as high as 165.1 mAh g−1 at 0.1 C and just shows a small capacity fading of 4.8% after 120 cycles, indicating that the 85PVdF-HFP:15LiBF4 + 150(EC + PC) system is an excellent electrolyte candidate for lithium-ion battery applications. The charge–discharge performance of the Li-ion cell fabricated with this gel polymer electrolyte film is apparently better than that of the previously reported Li-ion cells fabricated with other PVdF-HFP-based gel polymer electrolyte films.

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References

  1. Armand M, Tarascon JM (2008) Building better batteries. Nature 451:652–657

    Article  CAS  Google Scholar 

  2. Meyer W (1998) Polymer electrolytes for lithium-ion batteries. Adv Mater 10:439–448

    Article  CAS  Google Scholar 

  3. Scrosati B, Garche J (2010) Lithium batteries: status, prospects and future. J Power Sources 195:2419–2430

    Article  CAS  Google Scholar 

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

    Article  CAS  Google Scholar 

  5. Tian Z, He XM, Pu WH, Wan CR, Jiang CY (2006) Preparation of poly(acrylonitrile–butyl acrylate) gel electrolyte for lithium-ion batteries. Electrochim Acta 52:688–693

    Article  CAS  Google Scholar 

  6. Pu WH, He XM, Wang L, Tian Z, Jiang CY, Wan CR (2008) Preparation of P(AN-MMA) gel electrolyte for Li-ion batteries. Ionics 14:27–31

    Article  CAS  Google Scholar 

  7. Osman Z, Ansor N, Chew K, Kamarulzaman N (2005) Infrared and conductivity studies on blends of PMMA/PEO based polymer electrolytes. Ionics 11:431–435

    Article  CAS  Google Scholar 

  8. Osman Z, Md Isa KB, Ahmad A, Othman L (2010) A comparative study of lithium and sodium salts in PAN-based ion conducting polymer electrolytes. Ionics 16:431–435

    Article  CAS  Google Scholar 

  9. Rodríguez J, Navarrete E, Dalchiele EA, Sánchez L, Ramos-Barrado JR, Martín F (2013) Polyvinylpyrrolidone–LiClO4 solid polymer electrolyte and its application in transparent thin film supercapacitors. J Power Sources 237:270–276

    Article  Google Scholar 

  10. Deka M, Kumar A (2010) Enhanced electrical and electrochemical properties of PMMA–clay nanocomposite gel polymer electrolytes. Electrochim Acta 55:1836–1842

    Article  CAS  Google Scholar 

  11. Li WL, Xing YJ, Wu YH, Wang JW, Chen LZ, Yang G, Tang BZ (2015) Study the effect of ion-complex on the properties of composite gel polymer electrolyte based on electrospun PVdF nanofibrous membrane. Electrochim Acta 151:289–296

    Article  CAS  Google Scholar 

  12. Isa KBM, Osman Z, Arof AK, Othman L, Zainol NH, Samin SM, Chong WG, Kamarulzaman N (2014) Lithium ion conduction and ion–polymer interaction in PVdF-HFP based gel polymer electrolytes. Solid State Ionics 268:288–293

    Article  CAS  Google Scholar 

  13. Miao R, Liu B, Zhu Z, Liu Y, Li J, Wang X, Li Q (2008) PVDF-HFP-based porous polymer electrolyte membranes for lithium-ion batteries. J Power Sources 184:420–426

    Article  CAS  Google Scholar 

  14. Senthil RA, Theerthagiri J, Madhavan J, Arof AK (2016) Performance characteristics of guanine incorporated PVDF-HFP/PEO polymer blend electrolytes with binary iodide salts for dye-sensitized solar cells. Opt Mater 58:357–364

    Article  CAS  Google Scholar 

  15. Stephan AM, Nahm KS, Kumar TP, Kulandainathan MA, Ravi G, Wilson J (2006) Nanofiller incorporated poly(vinylidene fluoride–hexafluoropropylene) (PVdF–HFP) composite electrolytes for lithium batteries. J Power Sources 159:1316–1321

    Article  CAS  Google Scholar 

  16. Stolarska M, Niedzicki L, Borkowska R, Zalewska A, Wieczorek W (2007) Structure, transport properties and interfacial stability of PVdF/HFP electrolytes containing modified inorganic filler. Electrochim Acta 53:1512–1517

    Article  CAS  Google Scholar 

  17. Tang JW, Muchakayala R, Song SH, Wang M, Kumar KN (2016) Effect of EMIMBF4 ionic liquid addition on the structure and ionic conductivity of LiBF4-complexed PVdF-HFP polymer electrolyte films. Polym Test 50:247–254

    Article  CAS  Google Scholar 

  18. Quartarone E, Mustarelli P (2011) Electrolytes for solid-state lithium rechargeable batteries: recent advances and perspectives. Chem Soc Rev 40:2525–2540

    Article  CAS  Google Scholar 

  19. Wu HY, Saikia D, Chao HY, Pan YC, Fang J, Tsai LD, Fey GTK, Kao H (2013) Synthesis and characterization of highly conductive plasticized double core organic–inorganic hybrid electrolytes for lithium polymer batteries. J Power Sources 238:265–273

    Article  CAS  Google Scholar 

  20. Saito Y, Okano M, Kubota K, Sakai T, Fujioka J, Kawakami T (2012) Evaluation of interactive effects on the ionic conduction properties of polymer gel electrolytes. J Phys Chem B 116:10089–10097

    Article  CAS  Google Scholar 

  21. Senthil RA, Theerthagiri J, Madhavan J, Ganesan S, Arof AK (2017) Influence of organic additive to PVDF-HFP mixed iodide electrolytes on the photovoltaic performance of dye-sensitized solar cells. J Phys Chem Solids 101:18–24

    Article  CAS  Google Scholar 

  22. Stephan AM (2006) Review on gel polymer electrolytes for lithium batteries. Eur Polym J 42:21–42

    Article  Google Scholar 

  23. Woo HJ, Majid SR, Arof AK (2013) Effect of ethylene carbonate on proton conducting polymer electrolyte based on poly(ε-caprolactone) (PCL). Solid State Ionics 252:102–108

    Article  CAS  Google Scholar 

  24. Żukowska GZ, Marcinek M, Drzewiecki S, Kryczka J, Syzdek J, Woźniak AA, Wieczorek W, Sporzyński A (2010) Studies on the influence of tris(pentafluorophenyl)borane on the properties of ethylene carbonate, dimethyl carbonate and poly(ethylene oxide) dimethyl ether lithium trifluoromethanesulfonate electrolytes. J Power Sources 195:7506–7510

    Article  Google Scholar 

  25. Senthil RA, Theerthagiri J, Madhavan J, Arof AK (2016) Enhanced performance of dye-sensitized solar cell using 2-mercaptobenzothiazole-doped poly(vinylidinefluoride-co-hexafluoropropylene) polymer electrolyte. Ionics 22:1225–1230

    Article  CAS  Google Scholar 

  26. Johan MR, Shy OH, Ibrahim S, Yassin SMM, Hui TY (2011) Effects of Al2O3 nanofiller and EC plasticizer on the ionic conductivity enhancement of solid PEO–LiCF3SO3 solid polymer electrolyte. Solid State Ionics 196:41–47

    Article  CAS  Google Scholar 

  27. Tian LY, Huang XB, Tang XZ (2004) Single-ionic gel polymer electrolyte based on polyvinylidene fluoride and fluorine-containing ionomer. Eur Polym J 40:735–742

    Article  CAS  Google Scholar 

  28. Muchakayal R, Song SH, Gao S, Wang XL, Fan YH (2017) Structure and ion transport in an ethylene carbonate-modified biodegradable gel polymer electrolyte. Polym Test 58:116–125

    Article  Google Scholar 

  29. Kim CS, Oh SM (2001) Performance of gel-type polymer electrolytes according to the affinity between polymer matrix and plasticizing solvent molecules. Electrochim Acta 46:1323–1331

    Article  CAS  Google Scholar 

  30. Nookala M, Kumar B, Rodrigues S (2002) Ionic conductivity and ambient temperature li electrode reaction in composite polymer electrolytes containing nanosize alumina. J Power Sources 111:165–172

    Article  CAS  Google Scholar 

  31. Idris NH, Rahman MM, Wang J, Liu H (2012) Microporous gel polymer electrolytes for lithium rechargeable battery application. J Power Sources 201:294–300

    Article  CAS  Google Scholar 

  32. Ulaganathan M, Rajendran S (2011) Novel Li-ion conduction on poly(vinyl acetate)-based hybrid polymer electrolytes with double plasticizers. J Appl Electrochem 41:83–88

    Article  CAS  Google Scholar 

  33. Li Y, Xiao W, Li XH, Miao C, Guo HJ, Wang ZX (2014) Study on performance of a novel P(VDF-HFP)/SiO2 composite polymer electrolyte using urea as pore-forming agent. Ionics 20:1217–1224

    Article  CAS  Google Scholar 

  34. Krebs H, Yang L, Shirshova N, Steinke JHG (2012) A new series of cross-linked (meth)acrylate polymer electrolytes for energy storage. React Funct Polym 72:931–938

    Article  CAS  Google Scholar 

  35. Wu N, Cao Q, Wang XY, Li XY, Deng HY (2011) A novel high-performance gel polymer electrolyte membrane basing on electrospinning technique for lithium rechargeable batteries. J Power Sources 196:8638–8643

    Article  CAS  Google Scholar 

  36. Ravi M, Song SH, Wang JW, Wang T, Nadimicherla R (2016) Ionic liquid incorporated biodegradable gel polymer electrolyte for lithium ion battery applications. J Mater Sci Mater Electron 27:1370–1377

    Article  CAS  Google Scholar 

  37. Kim J, Manuel J, Lee M, Scheers J, Lim D, Johansson P, Ahn J, Matic A, Jacobsson P (2012) Towards flexible secondary lithium batteries: polypyrrole-LiFePO4 thin electrodes with polymer electrolytes. J Mater Chem 22:15045–15049

    Article  CAS  Google Scholar 

  38. Li ZQ, Li B, Yin LW, Qi YX (2014) Prussion blue-supported annealing chemical reaction route synthesized double-shelled Fe2O3/Co3O4 hollow microcubes as anode materials for lithium-ion battery. ACS Appl. Mater. Inter. 6:8098–8107

    Article  CAS  Google Scholar 

  39. Prasanth R, Shubha N, Hng HH, Srinivasan M (2014) Effect of poly(ethylene oxide) on ionic conductivity and electrochemical properties of poly(vinylidenefluoride) based polymer gel electrolytes prepared by electrospinning for lithium ion batteries. J Power Sources 245:283–291

    Article  CAS  Google Scholar 

  40. Padhi A, Nanjundaswamy K, Goodenough J (1997) Phospho-olivines as positive-electrode materials for rechargeable lithium batteries. J Electrochem Soc 144:1188–1194

    Article  CAS  Google Scholar 

  41. Ferrari S, Quartarone E, Mustarelli P, Magistris A, Fagnoni M, Protti S, Gerbaldi C, Spinella A (2010) Lithium 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  CAS  Google Scholar 

  42. Wang SH, Hou SS, Kuo PL, Teng H (2013) Poly(ethylene oxide)-co-poly(propylene oxide)-based gel electrolyte with high ionic conductivity and mechanical integrity for lithium-ion batteries. ACS Appl Mater Inter 5:8477–8485

    Article  CAS  Google Scholar 

  43. Kim J, Niedzicki L, Scheers J, Shin C, Lim D, Wieczorek W, Johansson P, Ahn J, Matic A, Jacobsson P (2013) Characterization of N-butyl-N-methyl-pyrrolidinium bis(trifluoromethanesulfonyl)imide-based polymer electrolytes for high safety lithium batteries. J Power Sources 224:93–98

    Article  CAS  Google Scholar 

  44. Kang DW, Kim JK (2016) Characterization of fibrous gel polymer electrolyte for lithium polymer batteries with enhanced electrochemical properties. J Electroanal Chem 775:37–42

    Article  CAS  Google Scholar 

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Acknowledgments

This work was supported by the International S&T Cooperation Program of China (No. 2014DFA53020) and Guangdong Innovative and Entrepreneurial Research Team Program (No. 2013C099).

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Authors and Affiliations

  1. Shenzhen Key Laboratory of Advanced Materials, Department of Materials Science and Engineering, Shenzhen Graduate School, Harbin Institute of Technology, Shenzhen, 518055, China

    Shenhua Song, Jingwei Wang, Jiwu Tang & Ravi Muchakayala

  2. College of Chemistry and Environmental Engineering, Shenzhen University, Shenzhen, 518060, China

    Rui Ma

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  1. Shenhua Song
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  2. Jingwei Wang
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  4. Ravi Muchakayala
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Correspondence to Shenhua Song or Rui Ma.

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Song, S., Wang, J., Tang, J. et al. Preparation, properties, and Li-ion battery application of EC + PC-modified PVdF-HFP gel polymer electrolyte films. Ionics 23, 3365–3375 (2017). https://doi.org/10.1007/s11581-017-2130-x

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  • DOI: https://doi.org/10.1007/s11581-017-2130-x

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