Plasticized solid polymer electrolyte based on triblock copolymer poly(vinylidene chloride-co-acrylonitrile-co-methyl methacrylate) for magnesium ion batteries

Polymer Bulletin volume 78, pages35–57(2021)Cite this article

Abstract

Limited global resources of lithium lead to the consideration of magnesium ion batteries as potential energy storage devices. Magnesium ion batteries have potential for high energy density but require new types of electrode and electrolytes for practical applications. Solid polymer electrolytes offer the opportunity for increased safety and broader electrochemical stability relative to traditional electrolytes. Herein, we report the development of solid polymer electrolyte for magnesium ion batteries based on triblock copolymer poly(vinylidene chloride-co-acrylonitrile-co-methyl methacrylate) (poly(VdCl-co-AN-co-MMA)). The polymer electrolytes are prepared by solution-casting technique using poly(VdCl-co-AN-co-MMA) with various concentrations (10 wt%, 20 wt%, 30 wt%, and 40 wt%) of magnesium chloride (MgCl2) salt. Among the prepared polymer electrolytes, the highest magnesium-ion-conducting polymer electrolyte is 70 wt% poly(VdCl-co-AN-co-MMA):30 wt% MgCl2 polymer–salt composition by electrochemical impedance measurements, and the obtained value of ionic conductivity is found to be in the order of 10−5 S cm−1. Addition of plasticizer succinonitrile in various concentrations (0.1 wt%, 0.2 wt%, 0.3 wt% and 0.4 wt%) with the identified polymer electrolyte of highest conductivity shows increased values of conductivity up to the order of 10−3 S cm−1. Observable changes in crystalline/amorphous nature of the polymer are analyzed using X-ray diffraction pattern. Glass transition temperature of polymer electrolytes has been found using differential scanning calorimetric studies. Transference number measurements have been made to confirm the ionic conductivity. The electrochemical stability for highest conducting plasticized polymer electrolyte is obtained from linear sweep voltammetry as 3.3 V. A primary magnesium ion battery has been constructed with prepared electrolyte of highest conductivity, and its performance and discharge characteristics are also analyzed. The open-circuit voltage of 2.18 V is obtained with the constructed primary magnesium ion battery.

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References

  1. 1.

    Tan Y-H, Yao W-T, Zhang T, Ma T, Lei-Lei L, Zhou F, Yao H-B, Shu-Hong Yu (2018) High voltage magnesium-ion battery enabled by nanocluster Mg3Bi2 alloy anode in noncorrosive electrolyte. ACS Nano. https://doi.org/10.1021/acsnano.8b01847

    Article  PubMed  PubMed Central  Google Scholar 

  2. 2.

    Huie MM, Bock DC, Takeuchi ES, Marschilok AC, Takeuchi KJ (2015) Cathode materials for magnesium and magnesium-ion based batteries. Coord Chem Rev 287:15–27

    CAS  Google Scholar 

  3. 3.

    Zhou L, Liu Q, Zhang Z, Zhang K, Xiong F, Tan S, An Q, Kang Y-M, Zhou Z, Mai L (2018) Interlayer-spacing-regulated VOPO4 nanosheets with fast kinetics for high-capacity and durable rechargeable magnesium batteries. Adv Mater 30:1801984

    Google Scholar 

  4. 4.

    Bančič T, Bitenc J, Pirnat K, Lautar AK, Grdadolnik J, Vitanova AR, Dominko R (2018) Electrochemical performance and redox mechanism of naphthalene-hydrazinediimide polymer as a cathode in magnesium battery. J Power Sour 395:25–30

    Google Scholar 

  5. 5.

    Penki TR, Valurouthu G, Shivakumara S, Sethuraman VA, Munichandraiah N (2018) In-situ synthesis of bismuth (Bi)/reduced graphene oxide (RGO) nanocomposites as high capacity anode materials for Mg-ion battery. https://doi.org/10.1039/x0xx00000x

  6. 6.

    Saha P, Kanchan Datta M, Velikokhatnyi OI, Manivannan A, Alman D, Kumta PN (2014) Rechargeable magnesium battery: current status and key challenges for the future. https://doi.org/10.1016/j.pmatsci.2014.04.001

  7. 7.

    Zhao X, Zhao Z, Miao Y (2018) Chloride ion-doped polypyrrole nanocomposite as cathode material for rechargeable magnesium battery. https://doi.org/10.1016/j.materresbull.2018.01.012

    Article  Google Scholar 

  8. 8.

    Mesallam M, Sheha E, Kamar EM, Sharma N (2018) Graphene and magnesiated graphene as electrodes for magnesium ion batteries. https://doi.org/10.1016/j.matlet.2018.08.080

  9. 9.

    Nacimiento F, Cabello M, Pérez-Vicente C, Alcántara R, Lavela P, Ortiz GF, Tirado JL (2018) On the mechanism of magnesium storage in micro and nano-particulate tin battery electrodes. Nanomaterials 8:501

    PubMed Central  Google Scholar 

  10. 10.

    Zhang Z, Dong S, Cui Z, Du A, Li G, Cui G (2018) Rechargeable magnesium batteries using conversion-type cathodes: a perspective and minireview. Small Methods 1800020

  11. 11.

    Li Y, Yerian JA, Khan SA, Fedkiw PS (2006) Crosslinkable fumed silica-based nanocomposite electrolytes for rechargeable lithium batteries. J Power Sour 161:1288–1296

    CAS  Google Scholar 

  12. 12.

    Hallinan DT Jr, Balsara NP (2013) Polymer electrolytes. Annu Rev Mater Res 43:503–525

    CAS  Google Scholar 

  13. 13.

    Ahmad S (2009) Polymer electrolytes: characteristics and peculiarities. Ionics 15:309–321

    CAS  Google Scholar 

  14. 14.

    Ibrahim S, Yassin MM, Ahmad R, Johan MR (2011) Effects of various LiPF6 salt concentrations on PEO-based solid polymer electrolytes. Ionics 17:399–405

    CAS  Google Scholar 

  15. 15.

    Meyer WH (1998) Polymer electrolytes for lithium-ion batteries. Adv Mater 10(6):439

    CAS  PubMed  Google Scholar 

  16. 16.

    Pandey M, Joshi GM, Ghosh NN (2016) Ionic conductivity and diffusion coefficient of barium-chloride-based polymer electrolyte with poly(vinyl alcohol)-poly(4-styrenesulphonic acid) polymer complex. Bull Mater Sci 40:655–666

    Google Scholar 

  17. 17.

    Khutia M, Joshi GM, Deshmukh K, Pandey M (2015) Optimization of dielectric constant of polycarbonate/polystyrene modified blend by ceramic metal oxide. Polym-Plast Technol Eng 54:383–389

    CAS  Google Scholar 

  18. 18.

    Fergus JW (2010) Ceramic and polymeric solid electrolytes for lithium-ion batteries. J Power Sour 195:4554–4569

    CAS  Google Scholar 

  19. 19.

    Zhang Z, Fang S (2000) Novel network polymer electrolytes based on polysiloxane with internal plasticizer. Electrochim Acta 45:2131–2138

    CAS  Google Scholar 

  20. 20.

    Soo PP, Huang B, Jang Y-I, Chiang Y-M, Sadoway DR, Mayes AM (1999) Rubbery block copolymer electrolytes for solid-state rechargeable lithium batteries. J Electrochem Soc 146(1):32–37

    CAS  Google Scholar 

  21. 21.

    Arges CG, Kambe Y, Dolejsi M, Wu G, Segal-Pertz T, Ren J, Cao C, Craig GSW, Nealey PF (2017) Interconnected ionic domains enhance conductivity in microphase separated block copolymer electrolytes. https://doi.org/10.1039/c6ta10838e

  22. 22.

    Devaux D, Gle D, Phan TNT, Gigmes D, Giroud E, Deschamps M, Denoyel R, Bouchet R (2015) Optimization of block copolymer electrolytes for lithium metal batteries. https://doi.org/10.1021/acs.chemmater.5b01273

  23. 23.

    Saikia D, Hao-Yiang W, Pan Y-C, Lin C-P, Huang K-P, Chen K-N, Fey George TK, Kao H-M (2011) Highly conductive and electrochemically stable plasticized blend polymer electrolytes based on PVdF-HFP and triblock copolymer PPG-PEG-PPG diamine for Li-ion batteries. J Power Sourc 196:2826–2834

    CAS  Google Scholar 

  24. 24.

    Young NP, Devaux D, Khurana R, Coates GW, Balsara NP (2014) Investigating polypropylene-poly(ethylene oxide)-polypropylene triblock copolymers as solid polymer electrolytes for lithium batteries. Solid State Ionics 263:87–94

    CAS  Google Scholar 

  25. 25.

    Young W-S, Epps TH (2012) Ionic conductivities of block copolymer electrolytes with various conducting pathways: sample preparation and processing considerations. Macromolecules 45:4689–4697

    CAS  Google Scholar 

  26. 26.

    Bouchet R, Phan TNT, Beaudoin E, Devaux D, Davidson P, Bertin D, Denoyel R (2014) Charge transport in nanostructured PS–PEO–PS triblock copolymer electrolytes. Macromolecules 47:2659–2665

    CAS  Google Scholar 

  27. 27.

    Inceoglu S, Rojas AA, Didier Devaux X, Chen C, Stone GM, Balsara NP (2014) Morphology–conductivity relationship of single-ion-conducting block copolymer electrolytes for lithium batteries. ACS Macro Lett 3:510–514

    CAS  Google Scholar 

  28. 28.

    Renaud Bouchet, Sébastien Maria, Rachid Meziane, Abdelmaula Aboulaich, Livie Lienafa, Jean-Pierre Bonnet, Trang N. T. Phan, Denis Bertin, Didier Gigmes, Didier Devaux, Renaud Denoyel, Michel Armand (2013) Single-ion BAB triblock copolymers as highly efficient electrolytes for lithium-metal batteries, https://doi.org/10.1038/nmat3602

  29. 29.

    Inbavalli D, Selvasekarapandian S, Sanjeeviraja C, Baskaran R, Kawamura J, Masuda Y (2013) Structural, thermal, morphological and electrical conductivity analysis of proton conducting tri block copolymer P(VdCl-Co-AN-Co-MMA) based electrolytes. In. J Electroact Mater 1:71–78

    Google Scholar 

  30. 30.

    Inbavalli D, Selvasekarapandian S, Sanjeeviraja C et al (2015) Analysis of P(VdCl-co-AN-co-MMA)-LiClO4-EC triblock copolymer electrolytes. Bull Mater Sci 38:183

    CAS  Google Scholar 

  31. 31.

    Inbavalli D, Selvasekarapandian S, Sanjeeviraja C et al (2013) Analysis of lithium ion conducting P(VdCl-co-AN-co-MMA)-LiClO4-DMF tri block copolymer electrolytes. Indian J Appl Res 3(12). ISSN-2249-555X

  32. 32.

    Anbazhakan K, Selvasekarapandiyan S, Monisha S et al (2017) Lithium ion conductivity and dielectric properties of P(VdCl-co-AN-co-MMA)-LiCl-EC triblock co-polymer electrolytes. Ionics 23:2663

    CAS  Google Scholar 

  33. 33.

    Pandey M, Joshi GM, Ghosh NN (2016) Electrical performance of lithium ion based polymer electrolyte with polyethylene glycol and polyvinyl alcohol network. Int J Polym Mater Polym Biomater 65:759–768

    CAS  Google Scholar 

  34. 34.

    Eom H-C, Park H, Yoon H-S (2010) Preparation of anhydrous magnesium chloride from ammonium magnesium chloride hexahydrate. Adv Powder Technol 21:125–130

    CAS  Google Scholar 

  35. 35.

    Zhang Z, Xuchen L, Yang S, Pan F (2012) Preparation of anhydrous magnesium chloride from magnesia. Ind Eng Chem Res 51:9713–9718

    CAS  Google Scholar 

  36. 36.

    Hodge RM (1996) Water absorption and states of water in semicrystalline poly(vinyl alcohol) films. Polymer 37(8):1371–1376

    CAS  Google Scholar 

  37. 37.

    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

    CAS  Google Scholar 

  38. 38.

    Polu AR, Kumar R (2013) Ionic conductivity and discharge characteristic studies of PVA-Mg(CH3COO)2 solid polymer electrolytes. Int J Polym Mater Polym Biomater 62(2):76–80

    CAS  Google Scholar 

  39. 39.

    Polu AR, Kumar R (2013) Preparation and characterization of PVA based solid polymer electrolytes for electrochemical cell applications. Chin J Polym Sci 31(4):641–648

    CAS  Google Scholar 

  40. 40.

    Selvalakshmi S, Vijaya N, Selvasekarapandian S, Premalatha M (2016) Biopolymer agar-agar doped with NH4SCN as solid polymer electrolyte for electrochemical cell application. J Appl Polym Sci. https://doi.org/10.1002/APP.44702

    Article  Google Scholar 

  41. 41.

    Liu W, Lee SW, Lin D, Shi F, Wang S, Sendek AD, Cui Y (2017) Enhancing ionic conductivity in composite polymer electrolytes with well-aligned ceramic nanowires. Nat Energy 2. Article number: 17035

  42. 42.

    Boukamp BA (1986) A package for Impedance/Admittance data analysis. Solid State Ion 18 & 19:136–140

    Google Scholar 

  43. 43.

    Boukamp BA (1986) A Nonlinear least squares fit procedure for analysis of immittance data of electrochemical systems. Solid State Ion 20:31–44

    CAS  Google Scholar 

  44. 44.

    Osman Z, Zainol NH, Samin SM, Chong WG, Md Isa KB, Othman L, Supa’at I, Sonsudin F (2014) Electrochemical impedance spectroscopy studies of magnesium-based polymethylmethacrylate gel polymer electroytes. ElectrochimicaActa 131:148–153

    CAS  Google Scholar 

  45. 45.

    Kumudu Perera MAKL, Dissanayake PWSK Bandaranayake (2004) Ionic conductivity of a gel polymer electrolyte based on Mg(ClO4)2 and polyacrylonitrile (PAN). Mater Res Bull 39:1745–1751

    Google Scholar 

  46. 46.

    Mathew CM, Kesavan K, Rajendran S (2014) Structural and electrochemical analysis of PMMA based gel electrolyte membranes. Int J Electrochem 2015. Article ID 494308

  47. 47.

    Aravindan V, Vickraman P (2007) A novel gel electrolyte with lithium difluoro(oxalato)borate salt and Sb2O3 nanoparticles for lithium ion batteries. Solid State Sci 9:1069–1073

    CAS  Google Scholar 

  48. 48.

    Cowie JMG, Spence GH (1998) Ion conduction in macroporous polyethylene film doped with electrolytes. Solid State Ion 109:139–144

    CAS  Google Scholar 

  49. 49.

    Tsunemi K, Ohno H, Tsuchida E (1983) A mechanism of ionic conduction of poly(vinylidene fluoride) lithium perchlorate hybrid films. Electrochimica 28(6):833–837

    CAS  Google Scholar 

  50. 50.

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

    CAS  Google Scholar 

  51. 51.

    Evans J, Vincent CA, Bruce PG (1987) Electrochemical measurement of transference numbers in polymer electrolytes. Polymer 28:2324–2328

    CAS  Google Scholar 

  52. 52.

    Manjuladevi R, Thamilselvan M, Selvasekarapandian S, Mangalam R, Premalatha M, Monisha S (2017) Mg-ion conducting blend polymer electrolyte based on poly(vinyl alcohol)-poly(acrylonitrile) with magnesium perchlorate. Solid State Ion 308:90–100

    CAS  Google Scholar 

  53. 53.

    ShanmugaPriya S, Karthika M, Selvasekarapandian S, Manjuladevi R (2018) Preparation and characterization of polymer electrolyte based on biopolymer I-Carrageenan with magnesium nitrate. Solid State Ion 327:136–149

    CAS  Google Scholar 

  54. 54.

    Mokhtar M, Majlan EH, Ahmad A, Tasirin SM, Daud WRW (2018) Effect of ZnO filler on PVA-alkaline solid polymer electrolyte for aluminum-air battery applications. J Electrochem Soc 165(11):A2483–A2492

    CAS  Google Scholar 

  55. 55.

    Hallinan DT, Rausch A Jr, McGill B (2016) An electrochemical approach to measuring oxidative stability of solid polymer electrolytes for lithium batteries. Chem Eng Sci 154:34–41

    CAS  Google Scholar 

  56. 56.

    Zhang Y, Zhao Y, Gosselink D, Chen P (2014) Synthesis of poly(ethylene-oxide)/nanoclay solid polymer electrolyte for all solid-state lithium/sulfur battery. Ionics. https://doi.org/10.1007/s11581-014-1176-2

    Article  Google Scholar 

  57. 57.

    Manjuladevi R, Selvasekarapandian S, Thamilselvan M, Mangalam R, Monisha, Christopher Selvin P (2018) A study on blend polymer electrolyte based on poly(vinyl alcohol)-poly(acrylonitrile) with magnesium nitrate for magnesium battery. Ionics. https://doi.org/10.1007/s11581-018-2500-z

    Article  Google Scholar 

  58. 58.

    Chung S-H, Manthiram A (2017) Lithium–sulfur batteries with the lowest self-discharge and the longest shelf life. ACS Energy Lett 2:1056–1061

    CAS  Google Scholar 

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Affiliations

  1. Department of Physics, Government Arts College, Udumalpet, TamilNadu, India

    T. Ponraj & A. Ramalingam

  2. Department of Physics, Nallamuthu Gounder Mahalingam College, Pollachi, TamilNadu, India

    T. Ponraj

  3. Materials Research Center, Coimbatore, TamilNadu, India

    T. Ponraj & S. Selvasekarapandian

  4. Bharathiar University, Coimbatore, TamilNadu, India

    S. Selvasekarapandian

  5. Kalasalingam Academy of Research and Education, Srivilliputhur, TamilNadu, India

    S. R. Srikumar

  6. PSG College of Arts and Science, Coimbatore, TamilNadu, India

    R. Manjuladevi

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  1. T. Ponraj
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  2. A. Ramalingam
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  3. S. Selvasekarapandian
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  4. S. R. Srikumar
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  5. R. Manjuladevi
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Correspondence to S. Selvasekarapandian.

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Ponraj, T., Ramalingam, A., Selvasekarapandian, S. et al. Plasticized solid polymer electrolyte based on triblock copolymer poly(vinylidene chloride-co-acrylonitrile-co-methyl methacrylate) for magnesium ion batteries. Polym. Bull. 78, 35–57 (2021). https://doi.org/10.1007/s00289-019-03091-5

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Keywords

  • Polymer electrolyte
  • Magnesium battery
  • Triblock copolymer
  • Electrochemical device
  • Magnesium chloride
  • Succinonitrile