Ionic liquids and reactions at the electrochemical interface.

Ionic liquids (ILs) represent a fascinating, and yet to be fully understood, medium for a variety of chemical, physical and biological processes. Electrochemical processes form an important subset of these that are particularly of interest, since ILs tend to be good electrochemical solvents and exhibit other properties which make them very useful as electrolytes in electrochemical devices. It is important therefore to understand the extent to which electrochemical reactions and processes behave in a relatively "normal", for example aqueous solution, fashion as opposed to exhibiting phenomena more uniquely the product of their organic ionic nature. This perspective examines a range of electrochemical reactions in ionic liquids, in many cases in the context of real world applications, to highlight the phenomena as far as they are understood and where data gaps exist. The important areas of lithium and conducting polymer electrochemistry are discussed in detail.

[1]  Wen Lu,et al.  Stable Conducting Polymer Electrochemical Devices Incorporating Ionic Liquids , 2003 .

[2]  D. Macfarlane,et al.  Liquids intermediate between "molecular" and "ionic" liquids: liquid ion pairs? , 2007, Chemical communications.

[3]  D. Macfarlane,et al.  The effect of potential bias on the formation of ionic liquid generated surface films on Mg alloys , 2010 .

[4]  Doron Aurbach,et al.  Behavior of Graphite Electrodes in Solutions Based on Ionic Liquids in In Situ Raman Studies , 2008 .

[5]  S. Passerini,et al.  Effect of water and oxygen traces on the cathodic stability of N-alkyl-N-methylpyrrolidinium bis(trifluoromethanesulfonyl)imide , 2008 .

[6]  F. Leermakers,et al.  Room-temperature ionic liquids: excluded volume and ion polarizability effects in the electrical double-layer structure and capacitance. , 2009, Physical review letters.

[7]  F. Endres,et al.  Electrodeposition of metals and semiconductors in air- and water-stable ionic liquids. , 2006, Chemphyschem : a European journal of chemical physics and physical chemistry.

[8]  D. Macfarlane,et al.  Broadband dielectric response of the ionic liquid N-methyl-N-ethylpyrrolidinium dicyanamide. , 2006, Chemical communications.

[9]  Nam-Soon Choi,et al.  Electrochemical and thermal properties of graphite electrodes with imidazolium- and piperidinium-based ionic liquids , 2009 .

[10]  R. Atkin,et al.  AFM and STM Studies on the Surface Interaction of [BMP]TFSA and [EMIm]TFSA Ionic Liquids with Au(111) , 2009 .

[11]  F. Endres,et al.  Probing Lithium and Alumina Impurities in Air- and Water Stable Ionic Liquids by Cyclic Voltammetry and In Situ Scanning Tunneling Microscopy , 2006 .

[12]  Maria Forsyth,et al.  On the concept of ionicity in ionic liquids. , 2009, Physical chemistry chemical physics : PCCP.

[13]  Kikuko Hayamizu,et al.  Quaternary Ammonium Room-Temperature Ionic Liquid/Lithium Salt Binary Electrolytes: Electrochemical Study , 2008 .

[14]  D. Macfarlane,et al.  Solid state NMR analysis of polypyrrole grown in a phosphonium ionic liquid , 2005 .

[15]  S. Passerini,et al.  The influence of air and its components on the cathodic stability of N-butyl-N-methylpyrrolidinium bis(trifluoromethanesulfonyl)imide , 2007 .

[16]  D. Aurbach,et al.  In Situ Raman Spectroscopy Study of Different Kinds of Graphite Electrodes in Ionic Liquid Electrolytes , 2008 .

[17]  D. Macfarlane,et al.  CdS thin-film electrodeposition from a phosphonium ionic liquid. , 2009, Physical chemistry chemical physics : PCCP.

[18]  S. Maximovitch,et al.  Phosphate coatings on magnesium alloy AM60 part 1: study of the formation and the growth of zinc phosphate films , 2004 .

[19]  Chun’an Ma,et al.  A novel electrolyte 1-ethylimidazolium trifluoroacetate used for electropolymerization of aniline , 2005 .

[20]  F. Endres,et al.  Electrodeposition of Ge, Si and Si x Ge 1-x from an air- and water-stable ionic liquid. , 2008, Physical chemistry chemical physics : PCCP.

[21]  Maria Forsyth,et al.  Transport properties of ionic liquid electrolytes with organic diluents. , 2009, Physical chemistry chemical physics : PCCP.

[22]  Maria Forsyth,et al.  Ionic liquids in electrochemical devices and processes: managing interfacial electrochemistry. , 2007, Accounts of chemical research.

[23]  G. Baker,et al.  Sum frequency generation studies of ammonium and pyrrolidinium ionic liquids based on the bis-trifluoromethanesulfonimide anion. , 2008, The journal of physical chemistry. B.

[24]  F. Endres,et al.  Electrosynthesis of poly(para)phenylene in an ionic liquid: cyclic voltammetry and in situ STM/tunnelling spectroscopy studies. , 2008, Chemphyschem : a European journal of chemical physics and physical chemistry.

[25]  Doron Aurbach,et al.  On the application of ionic liquids for rechargeable Li batteries: High voltage systems , 2009 .

[26]  R. Compton,et al.  Kinetic and thermodynamic parameters of the Li/Li+ couple in the room temperature ionic liquid N-butyl-N-methylpyrrolidinium bis(trifluoromethylsulfonyl) imide in the temperature range 298-318 K: a theoretical and experimental study using Pt and Ni electrodes. , 2009, The journal of physical chemistry. B.

[27]  F. Endres,et al.  AFM-Assisted Investigation of the Corrosion Behaviour of Magnesium and AZ91 Alloys in an Ionic Liquid with Varying Water Content , 2007 .

[28]  D. Macfarlane,et al.  Exploring corrosion protection of Mg via ionic liquid pretreatment , 2007 .

[29]  Ugo Bardi,et al.  Interaction Between an Imidazolium Based Ionic Liquid and the AZ91D Magnesium Alloy , 2007 .

[30]  D. Macfarlane,et al.  On the components of the dielectric constants of ionic liquids: ionic polarization? , 2009, Physical chemistry chemical physics : PCCP.

[31]  B. Scrosati,et al.  Compatibility of the Py24TFSI–LiTFSI ionic liquid solution with Li4Ti5O12 and LiFePO4 lithium ion battery electrodes , 2009 .

[32]  D. Aurbach,et al.  Correlation between surface chemistry, morphology, cycling efficiency and interfacial properties of Li electrodes in solutions containing different Li salts , 1994 .

[33]  Emanuel Peled,et al.  The Anode/Electrolyte Interface , 1998 .

[34]  Anthony F. Hollenkamp,et al.  High Lithium Metal Cycling Efficiency in a Room-Temperature Ionic Liquid , 2004 .

[35]  Bruno Scrosati,et al.  Ionic-liquid materials for the electrochemical challenges of the future. , 2009, Nature materials.

[36]  Stephen X. Zhang,et al.  An Investigation of a Phosphinate-Based Ionic Liquid for Corrosion Protection of Magnesium Alloy AZ31 , 2007 .

[37]  María-Dolores Bermúdez,et al.  Study of surface interactions of ionic liquids with aluminium alloys in corrosion and erosion–corrosion processes , 2007 .

[38]  F. Endres,et al.  An experimental and theoretical study of the aluminium species present in mixtures of AlCl3 with the ionic liquids [BMP]Tf2N and [EMIm]Tf2N. , 2009, Chemistry.

[39]  B. Ocko,et al.  Molecular Layering of Fluorinated Ionic Liquids at a Charged Sapphire (0001) Surface , 2008, Science.

[40]  M. Ishikawa,et al.  Ionic liquid electrolytes compatible with graphitized carbon negative without additive and their effects on interfacial properties , 2008 .

[41]  T. Fuchigami,et al.  Electropolymerization of pyrrole in 1-ethyl-3-methylimidazolium trifluoromethanesulfonate room temperature ionic liquid , 2002 .

[42]  D. Macfarlane,et al.  An ionic liquid surface treatment for corrosion protection of magnesium alloy AZ31 , 2006 .

[43]  R. A. Marsh,et al.  Surface films of lithium: an overview of electrochemical studies , 1998 .

[44]  C. Breslin,et al.  The Formation of Polypyrrole at Iron from 1-Butyl-3-methylimidazolium Hexafluorophosphate , 2005 .

[45]  G. Wallace,et al.  Use of Ionic Liquids for π-Conjugated Polymer Electrochemical Devices , 2002, Science.

[46]  M. Ishikawa,et al.  Ionic liquid electrolyte systems based on bis(fluorosulfonyl)imide for lithium-ion batteries , 2009 .

[47]  T. Fuchigami,et al.  Electrooxidative polymerization of aromatic compounds in 1-ethyl-3-methylimidazolium trifluoromethanesulfonate room-temperature ionic liquid , 2003 .

[48]  Kikuko Hayamizu,et al.  How ionic are room-temperature ionic liquids? An indicator of the physicochemical properties. , 2006, The journal of physical chemistry. B.

[49]  A. Lewandowski,et al.  Ferrocene as a Reference Redox Couple for Aprotic Ionic Liquids , 2009 .

[50]  G. Wallace,et al.  Electrosynthesis of novel photochemically active inherently conducting polymers using an ionic liquid electrolyte , 2006 .

[51]  A. Bond,et al.  Aluminium speciation in 1-butyl-1-methylpyrrolidinium bis(trifluoromethylsulfonyl)amide/AlCl3 mixtures. , 2009, Chemistry.

[52]  A. Ivaska,et al.  Electrochemical synthesis and in situ spectroelectrochemical characterization of poly(3,4-ethylenedioxythiophene) (PEDOT) in room temperature ionic liquids , 2004 .

[53]  D. Macfarlane,et al.  Electrochemistry at Negative Potentials in Bis(trifluoromethanesulfonyl)amide Ionic Liquids , 2006 .

[54]  Maria Forsyth,et al.  Lewis base ionic liquids. , 2006, Chemical communications.

[55]  C. Plesse,et al.  Ions transfer mechanisms during the electrochemical oxidation of poly(3,4-ethylenedioxythiophene) in 1-ethyl-3-methylimidazolium bis((trifluoromethyl)sulfonyl)amide ionic liquid , 2004 .

[56]  B. Scrosati,et al.  An advanced lithium-ion battery based on a nanostructured Sn-C anode and an electrochemically stable LiTFSi-Py24TFSI ionic liquid electrolyte , 2010 .

[57]  D. Macfarlane,et al.  New insights into the fundamental chemical nature of ionic liquid film formation on magnesium alloy surfaces. , 2009, ACS Applied Materials and Interfaces.

[58]  Doron Aurbach,et al.  A short review on surface chemical aspects of Li batteries: A key for a good performance , 2009 .

[59]  D. Aurbach,et al.  Recent studies on the correlation between surface chemistry, morphology, three-dimensional structures and performance of Li and Li-C intercalation anodes in several important electrolyte systems , 1997 .

[60]  D. Macfarlane,et al.  An Electrochemical Impedance Study of Ionic Liquid Film Formation and Aqueous Corrosion of Magnesium Alloy ZE41 , 2008 .

[61]  M. Deepa,et al.  Polypyrrole films electropolymerized from ionic liquids and in a traditional liquid electrolyte: A comparison of morphology and electro–optical properties , 2008 .

[62]  R. Lynden-Bell Can marcus theory be applied to redox processes in ionic liquids? A comparative simulation study of dimethylimidazolium liquids and acetonitrile. , 2007, The journal of physical chemistry. B.

[63]  Frank Endres,et al.  Electrodeposition of 3D ordered macroporous germanium from ionic liquids: a feasible method to make photonic crystals with a high dielectric constant. , 2009, Angewandte Chemie.

[64]  D. Macfarlane,et al.  Synthesis and physical property characterisation of phosphonium ionic liquids based on P(O)2(OR)2− and P(O)2(R)2− anions with potential application for corrosion mitigation of magnesium alloys , 2008 .

[65]  C. Hutchinson,et al.  Corrosion of magnesium alloy ZE41 : The role of microstructural features , 2009 .

[66]  Jun‐Jie Zhu,et al.  Electropolymerization of high stable poly(3,4-ethylenedioxythiophene) in ionic liquids and its potential applications in electrochemical capacitor , 2008 .

[67]  Masaki Yamagata,et al.  Electrodeposition of Metallic Lithium on a Tungsten Electrode in 1-Butyl-1-methylpyrrolidinium Bis(trifluoromethanesulfone)imide Room-temperature Molten Salt , 2003 .

[68]  F. Endres,et al.  Electropolymerization of benzene in a room temperature ionic liquid , 2004 .

[69]  C. Plesse,et al.  Electrochemical behaviour of poly(3,4-ethylenedioxythiophene) in a room-temperature ionic liquid , 2003 .

[70]  H. Steinrück,et al.  Surface Studies on the Ionic Liquid 1-Ethyl-3-Methylimidazolium Ethylsulfate Using X-Ray Photoelectron Spectroscopy (XPS) , 2006 .

[71]  Stefano Passerini,et al.  Lithium insertion in graphite from ternary ionic liquid-lithium salt electrolytes. I. Electrochemical characterization of the electrolytes , 2009 .

[72]  F. Endres,et al.  Template-assisted electrodeposition of SixGe1−xnanowires with varying length and composition from two different ionic liquids , 2009 .

[73]  A. Bond,et al.  Voltammetric studies on the reduction of polyoxometalate anions in ionic liquids. , 2005, Inorganic chemistry.

[74]  Douglas R. MacFarlane,et al.  The madelung constant of organic salts , 2009 .

[75]  W. Henderson,et al.  Electrochemical and Physicochemical Properties of PY[sub 14]FSI-Based Electrolytes with LiFSI , 2009, Journal of The Electrochemical Society.

[76]  S. Baldelli,et al.  Surface structure at the ionic liquid-electrified metal interface. , 2008, Accounts of chemical research.

[77]  R. Lynden-Bell Redox potentials and screening in ionic liquids: effects of sizes and shapes of solute ions. , 2008, The Journal of chemical physics.

[78]  M. Forsyth,et al.  A Potential Novel Rapid Screening NMR Approach to Boundary Film Formation at Solid Interfaces in Contact with Ionic Liquids , 2008 .

[79]  A. Bond,et al.  Prospects for a widely applicable reference potential scale in ionic liquids based on ideal reversible reduction of the cobaltocenium cation , 2008 .

[80]  G. Wallace,et al.  Electrochemical polymerization of pyrrole in BMIMPF6 ionic liquid and its electrochemical response to dopamine in the presence of ascorbic acid , 2009 .

[81]  C. Plesse,et al.  Charging/discharging kinetics of poly(3,4-ethylenedioxythiophene) in 1-ethyl-3-methylimidazolium bis-(trifluoromethylsulfonyl)imide ionic liquid under galvanostatic conditions , 2005 .

[82]  G. Shi,et al.  Electrochemical synthesis, characterization, and electrochromic properties of poly(3-chlorothiophene) and its copolymer with 3-methylthiophene in a room temperature ionic liquid , 2006 .

[83]  D. Macfarlane,et al.  Characterization of the Lithium Surface in N-Methyl-N-alkylpyrrolidinium Bis(trifluoromethanesulfonyl)amide Room-Temperature Ionic Liquid Electrolytes , 2006 .

[84]  A. Bund,et al.  An EQCM study of the electropolymerization of benzene in an ionic liquid and ion exchange characteristics of the resulting polymer film. , 2005, The journal of physical chemistry. B.

[85]  G. Wallace,et al.  Electrochemical synthesis of polypyrrole in ionic liquids , 2004 .

[86]  D. Macfarlane,et al.  The influence of the monomer and the ionic liquid on the electrochemical preparation of polythiophene , 2005 .

[87]  P. Pickup,et al.  Electrochemical Polymerization of Pyrrole and Electrochemistry of Polypyrrole Films in Ambient Temperature Molten Salts. , 1984 .

[88]  D. Macfarlane,et al.  High Frequency Dielectric Response of the Ionic Liquid N-Methyl-N-ethylpyrrolidinium Dicyanamide , 2007 .

[89]  F. Endres,et al.  Ionic liquids: the link to high-temperature molten salts? , 2007, Accounts of chemical research.

[90]  D. Macfarlane,et al.  Investigation of the Electropolymerisation of EDOT in Ionic liquids , 2005 .

[91]  Hajime Matsumoto,et al.  N-Methyl-N-propylpiperidinium bis(trifluoromethanesulfonyl)imide (PP13–TFSI) – novel electrolyte base for Li battery , 2003 .