pp 1–9 | Cite as

Mastering high ion conducting of room-temperature all-solid-state lithium-ion batteries via safe phthaloyl starch-poly(vinylidene fluoride)–based polymer electrolyte

  • Ming Xie
  • Libo LiEmail author
  • Yonghong Zhang
  • Jintian Du
  • You Li
  • Yuhang Shan
  • Huanyu ZhengEmail author
Original Paper


In this work, an all-solid-state biomaterial electrolyte derived from phthaloyl starch and poly(vinylidene fluoride) (PVDF) was introduced. Phthaloyl starch (PS) was prepared with the starch and the phthalic anhydride via a chemical method. The introduction of C=O group through the starch esterification improved the migration of the lithium ions in the all-solid-state electrolyte membrane. The AC impedance test revealed that the addition of the phthaloyl starch promoted the conductivity of electrolytes, which can reach up to 2.04 × 10−4 S cm−1 at room temperature, and the electrochemical stability window (ESW) can achieve 4.20 V. Herein, the phthaloyl starch-PVDF–based electrolyte membrane possessed the lithium-ion transference number of 0.396. The half-cell Li/SPE/LiFePO4 had a better charge and discharge performance, that is, 93.9 mAh g−1 and 92.2 mAh g−1 after the 50th cycle at 0.5 C and at room temperature.

Graphical abstract


All-solid-state battery Electrolyte membrane Starch-PVDF Lithium migration 


Funding information

This work was supported financially by the National Natural Science Foundation of China (grant number 21706043) and Synthesis and application of novel electrochemical biofunctional materials (grant number P183008061).

Compliance with ethical standards

Conflict of interest

There authors declare that they have no conflicts of interest.


  1. 1.
    Sun WW, Cai C, Tang X, Lv LP, Wang Y (2018) Carbon coated mixed-metal selenide microrod: bimetal-organic-framework derivation approach and applications for lithium-ion batteries. Chem Eng J 351:169–176. CrossRefGoogle Scholar
  2. 2.
    Hassoun J, Lee DJ, Sun YK, Scrosati B (2011) A lithium ion battery using nanostructured Sn–C anode, LiFePO4 cathode and polyethylene oxide-based electrolyte. Solid State Ionics 202:36–39. CrossRefGoogle Scholar
  3. 3.
    Guo X, Cao X, Huang G, Tian Q, Sun H (2017) Recovery of lithium from the effluent obtained in the process of spent lithium-ion batteries recycling. J Environ Manag 198:84–89. CrossRefGoogle Scholar
  4. 4.
    Polu AR, Rhee HW, Jeevan Kumar Reddy M, Shanmugharaj AM, Ryu SH, Kim DK (2017) Effect of POSS-PEG hybrid nanoparticles on cycling performance of polyether-LiDFOB based solid polymer electrolytes for all solid-state Li-ion battery applications. J Ind Eng Chem 45:68–77. CrossRefGoogle Scholar
  5. 5.
    Wang Q, Song WL, Fan LZ, Shi Q (2015) Effect of polyacrylonitrile on triethylene glycol diacetate-2-propenoic acid butyl ester gel polymer electrolytes with interpenetrating crosslinked network for flexible lithium ion batteries. J Power Sources 295:139–148. CrossRefGoogle Scholar
  6. 6.
    Cheng SHS, He KQ, Liu Y, Zha JW, Kamruzzaman M, Ma RLW, Dang ZM, Li RKY, Chung CY (2017) Electrochemical performance of all-solid-state lithium batteries using inorganic lithium garnets particulate reinforced PEO/LiClO4 electrolyte. Electrochim Acta 253:430–438. CrossRefGoogle Scholar
  7. 7.
    Shi QX, Xia Q, Xiang X, Ye YS, Peng HY, Xue ZG, Xie XL, Mai YW (2017) Self-assembled polymeric ionic liquid-functionalized cellulose nano-crystals: constructing 3D ion-conducting channels within ionic liquid-based composite polymer electrolytes. Chem-Eur J 23:11881–11890. CrossRefPubMedGoogle Scholar
  8. 8.
    Li Y, Sun Z, Shi L, Lu S, Sun Z, Shi Y, Wu H, Zhang Y, Ding S (2019) Poly(ionic liquid)-polyethylene oxide semi-interpenetrating polymer network solid electrolyte for safe lithium metal batteries. Chem Eng J 375:129925. CrossRefGoogle Scholar
  9. 9.
    Chinnam PR, Zhang H, Wunder SL (2015) Blends of pegylated polyoctahedralsilsesquioxanes (POSS-PEG) and methyl cellulose as solid polymer electrolytes for lithium batteries. Electrochim Acta 170:191–201. CrossRefGoogle Scholar
  10. 10.
    Meabe L, Lago N, Rubatat L, Li C, Müller AJ, Sardon H, Armand M, Mecerreyes D (2017) Polycondensation as a versatile synthetic route to aliphatic polycarbonates for solid polymer electrolytes. Electrochim Acta 237:259–266. CrossRefGoogle Scholar
  11. 11.
    Meabe L, Huynh TV, Lago N, Sardon H, Li C, O’Dell LA, Armand M, Forsyth M, Mecerreyes D (2018) Poly(ethylene oxide carbonates) solid polymer electrolytes for lithium batteries. Electrochim Acta 264:367–375. CrossRefGoogle Scholar
  12. 12.
    Liu Q, Li F, Lu H, Li M, Liu J, Zhang S, Sun Q, Xiong L (2018) Enhanced dispersion stability and heavy metal ion adsorption capability of oxidized starch nanoparticles. Food Chem 242:256–263. CrossRefPubMedGoogle Scholar
  13. 13.
    Lee SY, Lee KY, Lee HG (2018) Effect of different pH conditions on the in vitro digestibility and physicochemical properties of citric acid-treated potato starch. Int J Biol Macromol 107:1235–1241. CrossRefPubMedGoogle Scholar
  14. 14.
    Yadav M, Nautiyal G, Verma A, Kumar M, Tiwari T, Srivastava N (2019) Electrochemical characterization of NaClO4–mixed rice starch as a cost-effective and environment-friendly electrolyte. Ionics 25:2693–2700. CrossRefGoogle Scholar
  15. 15.
    Hazarika BJ, Sit N (2016) Effect of dual modification with hydroxypropylation and cross-linking on physicochemical properties of taro starch. Carbohydr Polym 140:269–278. CrossRefPubMedGoogle Scholar
  16. 16.
    Simi CK, Emilia Abraham T (2007) Hydrophobic grafted and cross-linked starch nanoparticles for drug delivery. Bioprocess Biosyst Eng 30:173–180. CrossRefPubMedGoogle Scholar
  17. 17.
    Lewicka K, Siemion P, Kurcok P (2015) Chemical modifications of starch: microwave effect. Int J Polym Sci 2015:1–10. CrossRefGoogle Scholar
  18. 18.
    Teaca CA, Bodirlau R, Spiridon I (2013) Effect of cellulose reinforcement on the properties of organic acid modified starch microparticles/plasticized starch bio-composite films. Carbohydr Polym 93:307–315. CrossRefPubMedGoogle Scholar
  19. 19.
    Lawal OS, Ogundiran OO, Awokoya K, Ogunkunle AO (2008) The low-substituted propylene oxide etherified plantain (Musa paradisiaca normalis) starch: characterization and functional parameters. Carbohydr Polym 74:717–724. CrossRefGoogle Scholar
  20. 20.
    Ren L, Wang Q, Yan X, Tong J, Zhou J, Su X (2016) Dual modification of starch nanocrystals via crosslinking and esterification for enhancing their hydrophobicity. Food Res Int 87:180–188. CrossRefPubMedGoogle Scholar
  21. 21.
    Raina CS, Singh S, Bawa AS, Saxena DC (2006) Some characteristics of acetylated, cross-linked and dual modified Indian rice starches. Eur Food Res Technol 223:561–570. CrossRefGoogle Scholar
  22. 22.
    Tizzotti MJ, Sweedman MC, Tang D, Schaefer C, Gilbert RG (2011) New 1H NMR procedure for the characterization of native and modified food-grade starches. J Agric Food Chem 59:6913–6919. CrossRefPubMedGoogle Scholar
  23. 23.
    Namazi H, Fathi F, Dadkhah A (2011) Hydrophobically modified starch using long-chain fatty acids for preparation of nanosized starch particles. Sci Iran 18:439–445. CrossRefGoogle Scholar
  24. 24.
    Selvanathan V, Azzhari A, Halim AAA, Yahya R (2017) Ternary natural deep eutectic solvent (NADES) infused phthaloyl starch as cost efficient quasi-solid gel polymer electrolyte. Carbohydr Polym 167:210–218. CrossRefPubMedGoogle Scholar
  25. 25.
    Zhang G, Li Y, Gao A, Zhang Q, Cui J, Zhao S, Zhan X, Yan Y (2019) Bio-inspired underwater superoleophobic PVDF membranes for highly-efficient simultaneous removal of insoluble emulsified oils and soluble anionic dyes. Chem Eng J 369:576–587. CrossRefGoogle Scholar
  26. 26.
    Liu Y, Xie H, Shi M (2016) Effect of ethanol-water solution on the crystallization of short chain amylose from potato starch. Starch 68:683–690. CrossRefGoogle Scholar
  27. 27.
    Surendra Babu A, Parimalavalli R, Jagannadham K (2015) Chemical and structural properties of sweet potato starch treated with organic and inorganic acid. J Food Sci Technol 52:5745–5753. CrossRefPubMedGoogle Scholar
  28. 28.
    Dankar I, Haddarah A, Omar FEL, Pujolà M, Sepulcre F (2018) Characterization of food additive-potato starch complexes by FTIR and X-ray diffraction. Food Chem 260:7–12. CrossRefPubMedGoogle Scholar
  29. 29.
    Singh HH, Khare N (2019) Improved performance of ferroelectric nanocomposite flexible film based triboelectric nanogenerator by controlling surface morphology, polarizability, and hydrophobicity. Energy 178:765–771. CrossRefGoogle Scholar
  30. 30.
    Kabir E, Khatun M, Nasrin L, Raihan MJ, Rahman M (2017) Pure β-phase formation in polyvinylidene fluoride (PVDF)-carbon nanotube composites. J Phys D Appl Phys 50:163002–1630018. CrossRefGoogle Scholar
  31. 31.
    Lanceros-Mendez S, Mano JF, Costa AM, Schmidt VH (2001) FTIR and DSC studies of mechanically deformed β-PVDF films. J Macromol Sci Phys B40:517–527. CrossRefGoogle Scholar
  32. 32.
    Tiwar S, Gaur A, Kumar C, Maiti P (2019) Enhanced piezoelectric response in nanoclay induced electrospun PVDF nanofibers for energy harvesting. Energy 171:485–492. CrossRefGoogle Scholar
  33. 33.
    Sun Y, Rohan R, Cai W, Wan X, Pareek K, Lin A, Yunfeng Z, Cheng H (2014) A Polyamide single-ion electrolyte membrane for application in lithium-ion batteries. Energy Technol 2:698–704. CrossRefGoogle Scholar
  34. 34.
    Liu B, Huang Y, Cao H, Zhao L, Huang Y, Song A, Lin Y, Li X, Wang M (2018) A novel porous gel polymer electrolyte based on poly(acrylonitrile-polyhedral oligomeric silsesquioxane) with high performances for lithium-ion batteries. J Membr Sci 545:140–149. CrossRefGoogle Scholar
  35. 35.
    He C, Liu J, Cui J, Li J, Wu X (2018) A gel polymer electrolyte based on polyacrylonitrile/organic montmorillonite membrane exhibiting dense structure for lithium ion battery. Solid State Ionics 315:102–110. CrossRefGoogle Scholar
  36. 36.
    Shi J, Yang Y, Shao H (2018) Co-polymerization and blending based PEO/PMMA/P(VDF-HFP) gel polymer electrolyte for rechargeable lithium metal batteries. J Membr Sci 547:1–10. CrossRefGoogle Scholar
  37. 37.
    Takenaka N, Fujie T, Bouibes A, Yamada Y, Yamada A, Nagaoka M (2018) Microscopic formation mechanism of solid electrolyte interphase film in lithium-ion batteries with highly concentrated electrolyte. Phys Chem C 122:2564–2571. CrossRefGoogle Scholar
  38. 38.
    Wang A, Kadam S, Li H, Shi S, Qi Y (2018) Review on modeling of the anode solid electrolyte interphase (SEI) for lithium-ion batteries. Comput Mater 3:15–43. CrossRefGoogle Scholar
  39. 39.
    Ohta N, Takada K, Zhang L, Ma R, Osada M, Sasaki T (2006) Enhancement of the high-rate capability of solid-state lithium batteries by nanoscale interfacial modification. Adv Mater 18:2226–2229. CrossRefGoogle Scholar
  40. 40.
    Sakuda A, Hayashi A, Tatsumisago M (2010) Interfacial observation between LiCoO2 electrode and Li2S-P2S5 solid electrolytes of all-solid-state lithium secondary batteries using transmission electron microscopy. Chem Mater 22:949–956. CrossRefGoogle Scholar
  41. 41.
    Aurbach D, Markovsky B, Levi MD, Levi E, Schechter A, Moshkovich CY (1999) New insights into the interactions between electrode materials and electrolyte solutions for advanced nonaqueous batteries. J Power Sources 81:95–111. CrossRefGoogle Scholar
  42. 42.
    Winter M (2009) The solid electrolyte interphase-the most important and the least understood solid electrolyte in rechargeable Li batteries. Z Fur Phys Chem 223:1395–1406. CrossRefGoogle Scholar
  43. 43.
    Verma P, Maire P, Novak P (2010) A review of the features and analyses of the solid electrolyte interphase in Li-ion batteries. Electrochim Acta 55:6332–6341. CrossRefGoogle Scholar
  44. 44.
    Vetter J, Novak P, Wagner MR, Veit C, Besenhard JO MKC, Winter M, Wohlfahrt-Mehrens M (2005) Ageing mechanisms in lithium-ion batteries. J Power Sources 147:269–281. CrossRefGoogle Scholar
  45. 45.
    Aurbach D, Ein-Ely Y, Zaban A (1994) The surface chemistry of lithium electrodes in alkyl carbonate solutions. J Electrochem Soc 141:L1–L3. CrossRefGoogle Scholar
  46. 46.
    Herstedt M, Abraham DP, Kerr JB, Edström K (2004) X-ray photoelectron spectroscopy of negative electrodes from high-power lithium-ion cells showing various levels of power fade. Electrochim Acta 49:5097–5110. CrossRefGoogle Scholar
  47. 47.
    Lin J, Xu Y, Wang J, Zhang B, Wang C, He S, Wu J (2019) Preinserted Li metal porous carbon nanotubes with high coulombic efficiency for lithium-ion battery anodes. Chem Eng J 373:78–85. CrossRefGoogle Scholar

Copyright information

© Springer-Verlag GmbH Germany, part of Springer Nature 2019

Authors and Affiliations

  1. 1.Key Laboratory of Green Chemical Engineering and Technology of College of Heilongjiang Province, College of Chemical and Environmental EngineeringHarbin University of Science and TechnologyHarbinPeople’s Republic of China
  2. 2.Department of ChemistryThe University of Texas Rio Grande ValleyEdinburgUSA
  3. 3.Harbin Research Institute of Electrical InstrumentsHarbinPeople’s Republic of China
  4. 4.College of Food ScienceNortheast Agricultural UniversityHarbinPeople’s Republic of China
  5. 5.Heilongjiang Green Food Science Research InstituteHarbinChina

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