Skip to main content

Thank you for visiting nature.com. You are using a browser version with limited support for CSS. To obtain the best experience, we recommend you use a more up to date browser (or turn off compatibility mode in Internet Explorer). In the meantime, to ensure continued support, we are displaying the site without styles and JavaScript.

  • Review Article
  • Published:

Ionic-liquid materials for the electrochemical challenges of the future

Abstract

Ionic liquids are room-temperature molten salts, composed mostly of organic ions that may undergo almost unlimited structural variations. This review covers the newest aspects of ionic liquids in applications where their ion conductivity is exploited; as electrochemical solvents for metal/semiconductor electrodeposition, and as batteries and fuel cells where conventional media, organic solvents (in batteries) or water (in polymer-electrolyte-membrane fuel cells), fail. Biology and biomimetic processes in ionic liquids are also discussed. In these decidedly different materials, some enzymes show activity that is not exhibited in more traditional systems, creating huge potential for bioinspired catalysis and biofuel cells. Our goal in this review is to survey the recent key developments and issues within ionic-liquid research in these areas. As well as informing materials scientists, we hope to generate interest in the wider community and encourage others to make use of ionic liquids in tackling scientific challenges.

This is a preview of subscription content, access via your institution

Access options

Buy this article

Prices may be subject to local taxes which are calculated during checkout

Figure 1: Ionic liquids, that is, salts with melting points below 100 °C, are potential candidates to be new 'green' reaction media with a number of important properties.
Figure 2: Processes that are impossible in water baths become viable if an ionic liquid solvent is used.
Figure 3: Deposits of photoluminescent semiconductors, for example GexSi1−x obtained from ionic liquid baths.
Figure 4: In their basic structure, lithium batteries are formed by two lithium-exchanging electrodes separated by a lithium-ion-conducting electrolyte.
Figure 5: Although polymer-electrolyte-membrane fuel cells have been known for a long time, they have not yet reached large-scale development as some issues are still unresolved.
Figure 6: There are several strategies to solubilize proteins into ionic liquids.
Figure 7: Sketch for a biofuel cell, that is, a device capable of generating energy with the aid of enzymes.
Figure 8: An electromechanical actuator produces a mechanical bending or axial motion in response to an electrical stimulus.

Similar content being viewed by others

References

  1. Earle, M. J. et al. The distillation and volatility of ionic liquids. Nature 439, 831–834 (2006).

    Article  CAS  Google Scholar 

  2. Wasserscheid, P. & Welton, T. (eds). Ionic Liquids in Synthesis (Wiley-VCH, 2007).

    Book  Google Scholar 

  3. Endres, F., Abbott, A. & MacFarlane, D. R. (eds). Electrodeposition from Ionic Liquids (Wiley-VCH, 2008).

    Book  Google Scholar 

  4. Abbott, A. P. & McKenzie, K. J. Application of ionic liquids to the electrodeposition of metals. Phys. Chem. Chem. Phys. 8, 4265–4279 (2006).

    Article  CAS  Google Scholar 

  5. Ziegler, K. & Lehmkuhl, H. Die elektrolytische Abscheidung von Aluminium aus organischen Komplexverbindungen. Z. Anorg. Allg. Chem. 283, 414–424 (1956).

    Article  CAS  Google Scholar 

  6. Kautek, W. & Birkle, S. Aluminum-electrocrystallization from metal organic electrolytes. Electrochim. Acta 34, 1213–1218 (1989).

    Article  Google Scholar 

  7. Caporali, S. et al. Aluminium electroplated from ionic liquids as protective coating against steel corrosion. Corros. Sci. 50, 534–539 (2008).

    Article  CAS  Google Scholar 

  8. Zein El Abedin, S. Coating of mild steel by aluminium in the ionic liquid [EMIm]Tf2N and its corrosion performance. Z. Phys. Chem. 220, 1293–1308 (2006).

    Article  CAS  Google Scholar 

  9. Liu, Q. X., Zein El Abedin, S. & Endres, F. Electroplating of mild steel by aluminium in a first generation ionic liquid: a green alternative to commercial Al-plating in organic solvents. Surf. Coat. Tech. 201, 1352–1356 (2006).

    Article  CAS  Google Scholar 

  10. Zein El Abedin, S., Moustafa, E. M., Hempelmann, R., Natter, H. & Endres, F. Electrodeposition of nano- and microcrystalline aluminium in three different air and water stable ionic liquids. ChemPhysChem 7, 1535–1543 (2006).

    Article  CAS  Google Scholar 

  11. Deng, M. J. et al. Dicyanamide anion based ionic liquids for electrodeposition of metals. Electrochem. Commun. 10, 213–216 (2008).

    Article  CAS  Google Scholar 

  12. Zein El Abedin, S., Welz-Biermann, S. U. & Endres, F. A study on the electrodeposition of tantalum on NiTi alloy in an ionic liquid and corrosion behaviour of the coated alloy. Electrochem. Commun. 7, 941–946 (2005).

    Article  CAS  Google Scholar 

  13. Arnould, C. J., Delhalle, J. & Mekhalif, Z. Multifunctional hybrid coating on titanium towards hydroxyapatite growth: electrodeposition of tantalum and its molecular functionalization with organophosphonic acids films. Electrochim. Acta 53, 5632–5638 (2008).

    Article  CAS  Google Scholar 

  14. Endres, F. et al. On the electrodeposition of titanium in ionic liquids. Phys. Chem. Chem. Phys. 10, 2189–2199 (2008).

    Article  CAS  Google Scholar 

  15. Redel, E., Thomann, R. & Janiak, C. Use of ionic liquids (ILs) for the IL-anion size-dependent formation of Cr, Mo and W nanoparticles from metal carbonyl M(CO)6 precursors. Chem. Commun. 15, 1789–1791 (2008).

    Article  Google Scholar 

  16. Tsuda, T., Arimoto, S., Kuwabata, S. & Hussey, C. L. Electrodeposition of Al–Mo–Ti ternary alloys in the Lewis acidic aluminum chloride-1-ethyl-3-methylimidazolium chloride room-temperature ionic liquid. J. Electrochem. Soc. 155, D256–D262 (2008).

    Article  CAS  Google Scholar 

  17. Kazeminezhad, I. et al. Templated electrodeposition of silver nanowires in a nanoporous polycarbonate membrane from a nonaqueous ionic liquid electrolyte. Appl. Phys. A 86, 373–375 (2007).

    Article  CAS  Google Scholar 

  18. Yang, P. X., An, M. Z., Su, C. N. & Wang, F. P. Electrodeposition of cobalt nanowires array from an ionic liquid. Chinese J. Inorg. Chem. 23, 1501–1504 (2007).

    CAS  Google Scholar 

  19. Al-Salman, R. et al. Template assisted electrodeposition of germanium and silicon nanowires in an ionic liquid. Phys. Chem. Chem. Phys. 10, 6233–6237 (2008).

    Article  CAS  Google Scholar 

  20. Al-Salman, R., Zein El Abedin, S. & Endres, F. Electrodeposition of Ge, Si and SixGe1−x from an air- and water-stable ionic liquid. Phys. Chem. Chem. Phys. 10, 4650–4657 (2008).

    Article  CAS  Google Scholar 

  21. Armand, M. & Tarascon, J.-M. Building better batteries. Nature 451, 652–657 (2008).

    Article  CAS  Google Scholar 

  22. Matsumoto, H., Sakaebe, H. & Tatsumi, K. Preparation of room temperature ionic liquids based on aliphatic onium cations and asymmetric amide anions and their electrochemical properties as a lithium battery electrolyte. J. Power Sources 160, 1308–1313 (2006).

    Article  CAS  Google Scholar 

  23. Seki, S. et al. Lithium secondary batteries using modified-imidazolium room-temperature ionic liquid. J. Phys. Chem. B 110, 10228–10230 (2006).

    Article  CAS  Google Scholar 

  24. Shin, J.-H., Henderson, W. A. & Passerini, S. PEO-based polymer electrolytes with ionic liquids and their use in lithium metal-polymer electrolyte batteries. J. Electrochem. Soc. 152, A978–A983 (2005).

    Article  CAS  Google Scholar 

  25. Garcia, B., Lavallée, S., Perron, G., Michot, C. & Armand, M. Room temperature molten salts as lithium battery electrolyte. Electrochim. Acta 49, 4583–4588 (2004).

    Article  CAS  Google Scholar 

  26. Howlett, P. C., MacFarlane, D. R. & Hollenkamp, A. F. High lithium metal cycling efficiency in a room-temperature ionic liquid. Electrochem. Solid-State Lett. 7, A97–A101 (2004).

    Article  CAS  Google Scholar 

  27. Fernicola, A. et al. LiTFSI-BEPyTFSI as an improved ionic liquid electrolyte for rechargeable lithium batteries. J. Power Sources 174, 342–348 (2007).

    Article  CAS  Google Scholar 

  28. Seki, S. et al. Reversibility of lithium secondary batteries using a room-temperature ionic liquid mixture and lithium metal. Electrochem. Solid-State Lett. 8, A577–A578 (2005).

    Article  CAS  Google Scholar 

  29. Ogasawara, T. et al. Rechargeable Li2O2 electrode for lithium batteries. J. Am. Chem. Soc. 128, 1390–1393 (2006).

    Article  CAS  Google Scholar 

  30. Kordeesch, K. & Simader, G. (eds). Fuel Cells and Their Applications (VCH, 1996).

    Book  Google Scholar 

  31. Kreur, K. D. Handbook of Fuel Cells: Fundamental, Technology & Applications Vol. 3 (eds Vielstich, W., Lamm, A. & Gasteiger, H. A.) (Wiley, 2003).

    Google Scholar 

  32. Fuller, J., Breda, A. C. & Carlin, R. T. Ionic liquid-polymer gel electrolytes. J. Electrochem. Soc. 144, L67–L70 (1997).

    Article  CAS  Google Scholar 

  33. Navarra, M. A., Panero, S. & Scrosati, B. Novel, ionic-liquid-based, gel-type proton membranes. Electrochem. Solid-State Lett. 8, A324–A327 (2005).

    Article  CAS  Google Scholar 

  34. Susan, M. A. B. H., Kaneko, T., Noda, A. & Watanabe, M. Ion gels prepared by in situ radical polymerization of vinyl monomers in an ionic liquid and their characterization as polymer electrolytes. J. Am. Chem. Soc. 127, 4976–4983 (2005).

    Article  CAS  Google Scholar 

  35. Winther-Jensen, B., Winther-Jensen, O., Forsyth, M. & MacFarlane, D. R. High rates of oxygen reduction over a vapor phase-polymerized PEDOT electrode. Science 321, 671–674 (2008).

    Article  CAS  Google Scholar 

  36. Simon, P. & Gogotsi, Y. Materials for electrochemical capacitors. Nature Mater. 7, 845–854 (2008).

    Article  CAS  Google Scholar 

  37. Sato, T., Masuda, G. & Takagi, K. Electrochemical properties of novel ionic liquids for electric double layer capacitor applications. Electrochim. Acta 49, 3603–3611 (2004).

    Article  CAS  Google Scholar 

  38. Arbizzani, C. et al. Safe high-energy supercapacitors based on solvent-free ionic liquid electrolytes ionic liquid electrolytes. J. Power Sources 185, 1575–1579 (2008).

    Article  CAS  Google Scholar 

  39. Fukaya, Y., Sugimoto, A. & Ohno, H. Superior solubility of polysaccharides in low viscosity, polar, and halogen-free 1,3-dialkylimidazolium formates. Biomacromolecules 7, 3295–3297 (2006).

    Article  CAS  Google Scholar 

  40. Hermanutz, F. et al. New developments in dissolving and processing of cellulose in ionic liquids. Macromol. Symp. 262, 23–27 (2008).

    Article  CAS  Google Scholar 

  41. Swatloski, R. P., Spear, S. K., Holbrey, J. D. & Rogers, R. D. Dissolution of cellulose with ionic liquids. J. Am. Chem. Soc. 124, 4974–4975 (2002).

    Article  CAS  Google Scholar 

  42. Wu, J. et al. Homogeneous acetylation of cellulose in a new ionic liquid. Biomacromolecules 5, 266–268 (2004).

    Article  CAS  Google Scholar 

  43. Anderson, J. L., Ding, J., Welton, T. & Armstrong, D. W. Characterizing ionic liquids on the basis of multiple solvation interactions. J. Am. Chem. Soc. 124, 14247–14254 (2002).

    Article  CAS  Google Scholar 

  44. Fukaya, Y., Hayashi, K., Wada, M. & Ohno, H. Cellulose dissolution with polar ionic liquids under mild conditions: required factors for anions. Green Chem. 10, 44–46 (2008).

    Article  CAS  Google Scholar 

  45. Ohno, H., Suzuki, C., Fukumoto, K., Yoshizawa, M. & Fujita, K. Electron transfer process of poly(ethylene oxide) modified cytochrome c in imidazolium type ionic liquid. Chem. Lett. 32, 450–451 (2003).

    Article  CAS  Google Scholar 

  46. Nakashima, K., Maruyama, T., Kamiya, N. & Goto, M. Comb-shaped poly(ethylene glycol)-modified subtilisin Carlsberg is soluble and highly active in ionic liquids. Chem. Commun. 4297–4299 (2005).

  47. Shimojo, K., Nakashima, K., Kamiya, N. & Goto, M. Crown ether-mediated extraction and functional conversion of cytochrome c in ionic liquids. Biomacromolecules 7, 2–5 (2006).

    Article  CAS  Google Scholar 

  48. Fujita, K., MacFarlane, D. R. & Forsyth, M. Protein solubilising and stabilising ionic liquids. Chem. Commun. 4804–4806 (2005).

  49. Fujita, K. et al. Unexpected improvement in stability and utility of cytochrome c by solution in biocompatible ionic liquids. Biotechnol. Bioeng. 94, 1209–1213 (2006).

    Article  CAS  Google Scholar 

  50. Fujita, K. et al. Solubility and stability of cytochrome c in hydrated ionic liquids: effect of oxo acid residues and kosmotropicity. Biomacromolecules 8, 2080–2086 (2007).

    Article  CAS  Google Scholar 

  51. Tamura, K. & Ohno, H. Solubility of cytochrome c in ionic liquids and redox response at high temperature. 2nd Internat. Congr. Ionic Liquids, abstr. 2P09-090, 306 (2007).

  52. DiCarlo, C. M., Compton, D. L., Evans, K. O. & Laszlo, J. A. Bioelectrocatalysis in ionic liquids. Examining specific cation and anion effects on electrode-immobilized cytochrome c. Bioelectrochemistry 68, 134–143 (2006).

    Article  CAS  Google Scholar 

  53. Turner, M. B. et al. Ionic liquid salt-induced inactivation and unfolding of cellulase from Trichoderma reesei. Green Chem. 5, 443–447 (2003).

    Article  CAS  Google Scholar 

  54. Motoyama, Y., Nakamura, N. & Ohno, H. An ethanol/dioxygen biofuel cell using hydrophobic ionic liquid as electrolyte. 2nd Internat. Congr. Ionic Liquids, abstr. 1P09-091, 213 (2007).

  55. Lu, W. et al. Use of ionic liquids for pi-conjugated polymer electrochemical devices. Science 297, 983–987 (2002).

    Article  CAS  Google Scholar 

  56. Ding, J. et al. Use of ionic liquids as electrolytes in electromechanical actuator systems based on inherently conducting polymers. Chem. Mater. 15, 2392–2398 (2003).

    Article  CAS  Google Scholar 

  57. Zhou, D. Z. et al. Solid state actuators based on polypyrrole and polymer-in-ionic liquid electrolytes. Electrochim. Acta 48, 2355–2359 (2003).

    Article  CAS  Google Scholar 

  58. Xi, B. B. et al. Poly(3-methylthiophene) electrochemical actuators showing increased strain and work per cycle at higher operating stresses. Polymer (Guildf.) 47, 7720–7725 (2006).

    Article  CAS  Google Scholar 

  59. Lu, W., Norris, I. D. & Mattes, B. R. Electrochemical actuator devices based on polyaniline yarns and ionic liquid electrolytes. Aust. J. Chem. 58, 263–269 (2005).

    Article  CAS  Google Scholar 

  60. MacFarlane, D. R. et al. Lewis base ionic liquids. Chem. Commun. 1905–1917 (2006).

  61. Pringle, J. et al. The influence of the monomer and the ionic liquid on the electrochemical preparation of polythiophene. Polymer (Guildf.) 47, 2047–2058 (2005).

    Article  Google Scholar 

  62. Lim, H. T., Lef, J. W. & Yoo, Y. T. Actuation behavior of a carbon nanotube/nafion IPMC actuator containing an ionic liquid. J. Korean Phys. Soc. 49, 1101–1106 (2006).

    CAS  Google Scholar 

  63. Barisci, J. N., Wallace, G. G., MacFarlane, D. R. & Baughman, R. H. Investigation of ionic liquids as electrolytes for carbon nanotube electrodes. Electrochem. Commun. 6, 22–27 (2004).

    Article  CAS  Google Scholar 

  64. Vidal, F., Plesse, C., Teyssie, D. & Chevrot, C. Long-life air working conducting semi-IPN/ionic liquid based actuator. Synth. Met. 142, 287–291 (2004).

    Article  CAS  Google Scholar 

  65. Vidal, F., Juger, J., Chevrot, C. & Teyssie, D. Interpenetrating polymer networks from polymeric imidazolium-type ionic liquid and polybutadiene. Polym. Bull. 57, 473–480 (2006).

    Article  CAS  Google Scholar 

  66. Vidal, F. et al. Long-life air working semi-IPN/ionic liquid: new precursor of artificial muscles. Mol. Cryst. Liq. Cryst. 448, 95–102 (2006).

    Article  Google Scholar 

  67. Cho, M. S. et al. A solid state actuator based on the PEDOT/NBR system. Sens. Actuators B 119, 621–624 (2006).

    Article  CAS  Google Scholar 

  68. Cho, M. S. et al. A solid state actuator based on the PEDOT/NBR system: effect of anion size of imidazolium ionic liquid. Mol. Cryst. Liq. Cryst. 464, 633–638 (2007).

    CAS  Google Scholar 

  69. MacFarlane, D. R. & Forsyth, M. Plastic crystal electrolyte materials: new perspectives on solid state ionics. Adv. Mater. 13, 957–966 (2001).

    Article  CAS  Google Scholar 

  70. Long, S., MacFarlane, D. R. & Forsyth, M. Fast ion conduction in molecular plastic crystals. Solid State Ionics 161, 105–112 (2003).

    Article  CAS  Google Scholar 

  71. Bennett, M. D. & Leo, D. J. Ionic liquids as stable solvents for ionic polymer transducers. Sens. Actuators A 115, 79–90 (2004).

    Article  CAS  Google Scholar 

  72. Wang, J., Xu, C. Y., Taya, M. & Kuga, Y. A. Flemion-based actuator with ionic liquid as solvent. Smart Mater. Struct. 16, S214–S219 (2007).

    Article  CAS  Google Scholar 

  73. Ohno, H. (ed). Electrochemical Aspects of Ionic Liquids (Wiley, 2005).

    Book  Google Scholar 

Download references

Acknowledgements

We thank M. Mastragostino for discussions and information concerning supercapacitors.

Author information

Authors and Affiliations

Authors

Corresponding author

Correspondence to Bruno Scrosati.

Rights and permissions

Reprints and permissions

About this article

Cite this article

Armand, M., Endres, F., MacFarlane, D. et al. Ionic-liquid materials for the electrochemical challenges of the future. Nature Mater 8, 621–629 (2009). https://doi.org/10.1038/nmat2448

Download citation

  • Published:

  • Issue Date:

  • DOI: https://doi.org/10.1038/nmat2448

This article is cited by

Search

Quick links

Nature Briefing

Sign up for the Nature Briefing newsletter — what matters in science, free to your inbox daily.

Get the most important science stories of the day, free in your inbox. Sign up for Nature Briefing