Nonaqueous redox-flow batteries: organic solvents, supporting electrolytes, and redox pairs

As members of the redox-flow battery (RFB) family, nonaqueous RFBs can offer a wide range of working temperature, high cell voltage, and potentially high energy density. These key features make nonaqueous RFBs an important complement of aqueous RFBs, broadening the spectrum of RFB applications. The development of nonaqueous RFBs is still at its early research stage and great challenges remain to be addressed before their successful use for practical applications. As such, it is essential to understand the major components in order to advance the nonaqueous RFB technology. In this perspective, three key major components of nonaqueous RFBs: organic solvents, supporting electrolytes, and redox pairs are selectively focused and discussed, with emphasis on providing an overview of those components and on highlighting the relationship between structure and properties. Urgent challenges are also discussed. To advance nonaqueous RFBs, the understanding of both components and systems is critically needed and it calls for inter-disciplinary collaborations across expertise including electrochemistry, organic chemistry, physical chemistry, cell design, and system engineering. In order to demonstrate the key features of nonaqueous RFBs, herein we also present an example of designing a 4.5 V ultrahigh-voltage nonaqueous RFB by combining a BP/BP˙− redox pair and an OFN˙+/OFN redox pair.

[1]  A. Sacco,et al.  The conductance of tetrabutylammonium salts in water-sulfolane mixtures at 30°C , 1976 .

[2]  Victor M.M. Lobo,et al.  Handbook of electrolyte solutions , 1989 .

[3]  G. J. Hoijtink,et al.  Electron transfer to aromatic hydrocarbons at the dropping mercury electrode , 1959 .

[4]  Hye Ryung Byon,et al.  High‐Performance Lithium‐Iodine Flow Battery , 2013 .

[5]  J. Reardon.  Ionic association and mobility in propylene carbonate , 1987 .

[6]  Charles W. Monroe,et al.  Electrode kinetics in non-aqueous vanadium acetylacetonate redox flow batteries , 2011 .

[7]  T. Yamamura,et al.  Enhancements in the Electron-Transfer Kinetics of Uranium-Based Redox Couples Induced by Tetraketone Ligands with Potential Chelate Effect , 2007 .

[8]  Shi Xue Dou,et al.  A hybrid electrolyte energy storage device with high energy and long life using lithium anode and MnO2 nanoflake cathode , 2013 .

[9]  M. Salomon.  Conductance of solutions of lithium bis(trifluoromethanesulfone)imide in water, propylene carbonate, acetonitrile and methyl formate at 25°C , 1993 .

[10]  S. Moon,et al.  Pore-filled anion-exchange membranes for non-aqueous redox flow batteries with dual-metal-complex redox shuttles , 2014 .

[11]  Seok-Gwang Doo,et al.  Non-Aqueous Redox Flow Batteries with Nickel and Iron Tris(2,2′-bipyridine) Complex Electrolyte , 2012 .

[12]  Kevin G. Gallagher,et al.  Pathways to Low Cost Electrochemical Energy Storage: A Comparison of Aqueous and Nonaqueous Flow Batteries , 2014 .

[13]  M. H. Chakrabarti,et al.  Ruthenium based redox flow battery for solar energy storage , 2011 .

[14]  C. Ponce de León,et al.  Redox flow cells for energy conversion , 2006 .

[15]  Qinghua Liu,et al.  Tetrabutylammonium hexafluorophosphate and 1-ethyl-3-methyl imidazolium hexafluorophosphate ionic liquids as supporting electrolytes for non-aqueous vanadium redox flow batteries , 2012 .

[16]  Ke Gong,et al.  A multiple ion-exchange membrane design for redox flow batteries , 2014 .

[17]  O. Kalugin,et al.  Electrical conductivity and ionic association of lithium and sodium perchlorates in tetrahydrofuran , 2008 .

[18]  Bin Li,et al.  Recent Progress in Redox Flow Battery Research and Development , 2012 .

[19]  B. Chachulski,et al.  Electrical conductance and ionic association of the bivalent transition metal tetrafluoroborates in acetonitrile solution , 1980 .

[20]  M. Chauhan,et al.  Conductance and viscosity measurements of tetrabutylammonium tetraphenylboride in non-aqueous solvents at 25 °C , 1982 .

[21]  Hiroyuki Nishide,et al.  Redox-active polyimide/carbon nanocomposite electrodes for reversible charge storage at negative potentials: expanding the functional horizon of polyimides , 2010 .

[22]  G. G. Stokes.  "J." , 1890, The New Yale Book of Quotations.

[23]  J. Dahn,et al.  Computational Estimates of Stability of Redox Shuttle Additives for Li-Ion Cells , 2006 .

[24]  Charles W. Monroe,et al.  Non-aqueous manganese acetylacetonate electrolyte for redox flow batteries , 2011 .

[25]  M. H. Chakrabarti,et al.  Charge–Discharge Performance of a Novel Undivided Redox Flow Battery for Renewable Energy Storage , 2010 .

[26]  Huamin Zhang,et al.  Ion exchange membranes for vanadium redox flow battery (VRB) applications , 2011 .

[27]  Dennis H. Evans.  One-electron and two-electron transfers in electrochemistry and homogeneous solution reactions. , 2008, Chemical reviews.

[28]  Dapeng Zhang,et al.  The application of a non-aqueous bis(acetylacetone)ethylenediamine cobalt electrolyte in redox flow battery , 2012 .

[29]  Makoto Ue,et al.  Electrochemical Properties of Organic Liquid Electrolytes Based on Quaternary Onium Salts for Electrical Double‐Layer Capacitors , 1994 .

[30]  Min‐Sik Park,et al.  Development of metal-based electrodes for non-aqueous redox flow batteries , 2011 .

[31]  Hiroyuki Nishide,et al.  Electron-Transfer Kinetics of Nitroxide Radicals as an Electrode-Active Material , 2004 .

[32]  Hye Ryung Byon,et al.  High-performance rechargeable lithium-iodine batteries using triiodide/iodide redox couples in an aqueous cathode , 2013, Nature Communications.

[33]  A. R. Forrester,et al.  Stable Nitroxide Radicals , 1964, Nature.

[34]  B. Krumgalz.  Separation of limiting equivalent conductances into ionic contributions in non-aqueous solutions by indirect methods , 1983 .

[35]  E. Plichta,et al.  Conductivities and ion association of 1:1 electrolytes in aprotic solvents , 1983 .

[36]  Yunhong Zhou,et al.  Anthraquinone based polymer as high performance cathode material for rechargeable lithium batteries. , 2009, Chemical communications.

[37]  Y. Takeda,et al.  Ion Pair Formation of Alkylimidazolium Ionic Liquids in Dichloromethane , 2008 .

[38]  Charles W. Monroe,et al.  Degradation mechanisms in the non-aqueous vanadium acetylacetonate redox flow battery , 2012 .

[39]  Zhenguo Yang,et al.  Membrane development for vanadium redox flow batteries. , 2011, ChemSusChem.

[40]  Charles W. Monroe,et al.  Non-aqueous chromium acetylacetonate electrolyte for redox flow batteries , 2009 .

[41]  M. Morita,et al.  Electrochemical Oxidation of Ruthenium and Iron Complexes at Rotating Disk Electrode in Acetonitrile Solution , 1988 .

[42]  B. Carré,et al.  Ion transport theory of nonaqueous electrolytes. LiClO4 in γ-butyrolactone: the quasi lattice approach , 2001 .

[43]  Youngsik Kim,et al.  Lithium–liquid battery: harvesting lithium from waste Li-ion batteries and discharging with water , 2012 .

[44]  B. Dunn,et al.  Electrical Energy Storage for the Grid: A Battery of Choices , 2011, Science.

[45]  Pritam Singh.  Application of non-aqueous solvents to batteries , 1984 .

[46]  Jae-Hun Kim,et al.  Novel catalytic effects of Mn3O4 for all vanadium redox flow batteries. , 2012, Chemical communications.

[47]  W. Geiger,et al.  Comparison of the conductivity properties of the tetrabutylammonium salt of tetrakis(pentafluorophenyl)borate anion with those of traditional supporting electrolyte anions in nonaqueous solvents. , 2004, Analytical chemistry.

[48]  Lu Zhang,et al.  Molecular engineering towards safer lithium-ion batteries: a highly stable and compatible redox shuttle for overcharge protection , 2012 .

[49]  Fikile R. Brushett,et al.  An All‐Organic Non‐aqueous Lithium‐Ion Redox Flow Battery , 2012 .

[50]  Neil G. Connelly,et al.  Chemical Redox Agents for Organometallic Chemistry. , 1996, Chemical reviews.

[51]  Seung-Hyeon Moon,et al.  A review of current developments in non-aqueous redox flow batteries: characterization of their membranes for design perspective , 2013 .

[52]  G. Whitesides,et al.  Membraneless vanadium redox fuel cell using laminar flow. , 2002, Journal of the American Chemical Society.

[53]  Kang Xu,et al.  Nonaqueous liquid electrolytes for lithium-based rechargeable batteries. , 2004, Chemical reviews.

[54]  T. Yamamura,et al.  Electrolytic preparation, redox titration and stability of pentavalent state of uranyl tetraketonate in dimethyl sulfoxide , 2006 .

[55]  Kosuke Izutsu.  Electrochemistry in Nonaqueous Solutions , 2002 .

[56]  Jun Liu,et al.  Materials Science and Materials Chemistry for Large Scale Electrochemical Energy Storage: From Transportation to Electrical Grid , 2013 .

[57]  John B Goodenough,et al.  Aqueous cathode for next-generation alkali-ion batteries. , 2011, Journal of the American Chemical Society.

[58]  G. R. Li,et al.  Electroactive Organic Compounds as Anode-Active Materials for Solar Rechargeable Redox Flow Battery in Dual-Phase Electrolytes , 2014 .

[59]  D. K. Hazra,et al.  Conductance of Selected Alkali Metal Salts in Aqueous Binary Mixtures of 2-Methoxyethanol at 25°C , 1998 .

[60]  A. Apelblat.  The universal curves of limiting conductances of 1:1 type electrolytes in alcohol–water-rich mixtures , 2010 .

[61]  J. Ramsey,et al.  The Free Energy, Enthalpy and Entropy of Dissociation of Some Perchlorates in Ethylene Chloride and Ethylidene Chloride , 1955 .

[62]  Using waste Li ion batteries as cathodes in rechargeable Li-liquid batteries. , 2013, Physical chemistry chemical physics : PCCP.

[63]  Ping He,et al.  Li‐Redox Flow Batteries Based on Hybrid Electrolytes: At the Cross Road between Li‐ion and Redox Flow Batteries , 2012 .

[64]  M. Morita,et al.  A rechargeable redox battery utilizing ruthenium complexes with non-aqueous organic electrolyte , 1988 .

[65]  F. Millero.  The apparent and partial molal volume of aqueous sodium chloride solutions at various temperatures , 1970 .

[66]  S. Moon,et al.  Anion exchange membrane prepared from simultaneous polymerization and quaternization of 4-vinyl pyridine for non-aqueous vanadium redox flow battery applications , 2014 .

[67]  R. Holze,et al.  Macroporous LiFePO4 as a cathode for an aqueous rechargeable lithium battery of high energy density , 2013 .

[68]  Gareth H McKinley,et al.  Polysulfide flow batteries enabled by percolating nanoscale conductor networks. , 2014, Nano letters.

[69]  M. Ue.  Mobility and Ionic Association of Lithium and Quaternary Ammonium Salts in Propylene Carbonate and γ‐Butyrolactone , 1994 .

[70]  M. Mench,et al.  Redox flow batteries: a review , 2011 .

[71]  A. Philippopoulos,et al.  Studies of ion solvation and ion association of n-tetrabutylammonium hexafluorophosphate and n-tetrabutylammonium tetraphenylborate in various solvents , 2009 .

[72]  Maria Skyllas-Kazacos,et al.  Progress in Flow Battery Research and Development , 2011 .

[73]  T. Saji,et al.  Electron-transfer Kinetics of Transition-metal Complexes in Lower Oxidation States. Part III. Electrochemical Rate Constants for the Fe(II)/Fe(I) Redox Systems , 1975 .

[74]  Hajimu Yamana,et al.  Electrochemical investigation of uranium β-diketonates for all-uranium redox flow battery , 2002 .

[75]  M. Roy,et al.  Probing subsistence of ion-pair and triple-ion of an ionic salt in liquid environments by means of conductometric contrivance , 2013 .

[76]  H. Gores,et al.  Electrolyte solutions for technology - new aspects and approaches , 1999 .

[77]  Dong Fang,et al.  Electrochemical Properties of an All-Organic Redox Flow Battery Using 2,2,6,6-Tetramethyl-1-Piperidinyloxy and N-Methylphthalimide , 2011 .

[78]  C. Monroe,et al.  Solvents and supporting electrolytes for vanadium acetylacetonate flow batteries , 2014 .

[79]  V. Koch,et al.  Conductance of Solutions of Lithium tris(trifluoromethanesulfonyl) Methide in Water, Acetonitrile, Propylene Carbonate, N,N‐Dimethylformamide, and Nitromethane at 25°C , 1996 .

[80]  Xueping Gao,et al.  A solar rechargeable flow battery based on photoregeneration of two soluble redox couples. , 2013, ChemSusChem.

[81]  Lelia Cosimbescu,et al.  Anthraquinone with tailored structure for a nonaqueous metal-organic redox flow battery. , 2012, Chemical communications.

[82]  Nicholas S. Hudak,et al.  Application of Redox Non‐Innocent Ligands to Non‐Aqueous Flow Battery Electrolytes , 2014 .

[83]  Jun Liu,et al.  Electrochemical energy storage for green grid. , 2011, Chemical reviews.

[84]  T. Yamamura,et al.  Electrochemical and spectroscopic investigations of uranium(III) with N,N,N′,N′-tetramethylmalonamide in DMF , 2006 .

[85]  Jianji Wang,et al.  Ionic association of the ionic liquids [C4mim][BF4], [C4mim][PF6], and [Cnmim]Br in molecular solvents. , 2009, Chemphyschem : a European journal of chemical physics and physical chemistry.

[86]  C. Low,et al.  Progress in redox flow batteries, remaining challenges and their applications in energy storage , 2012 .

[87]  John B. Goodenough,et al.  Rechargeable alkali-ion cathode-flow battery , 2011 .

[88]  N. Holy.  Reactions of the radical anions and dianions of aromatic hydrocarbons , 1974 .

[89]  S. Wawzonek,et al.  Polarographic Studies in Acetonitrile and Dimethylformamide. IV. Stability of Anion-free Radicals1,2 , 1959 .

[90]  Michael P. Marshak,et al.  A metal-free organic–inorganic aqueous flow battery , 2014, Nature.

[91]  M. Ue,et al.  Electrochemical Properties of Quaternary Ammonium Salts for Electrochemical Capacitors , 1997 .

[92]  H. Høiland,et al.  SOLVENT PROPERTIES OF DICHLOROMETHANE. III. CONDUCTIVITY STUDIES OF SOME TETRAALKYLAMMONIUM-, TETRAPHENYLARSONIUM- AND BIS(TRIPHENYLPHOSPHINE)IMINIUM SALTS IN DICHLOROMETHANE , 1985 .

[93]  T. Yamamura,et al.  Characterization of tetraketone ligands for active materials of all-uranium redox flow battery , 2004 .

[94]  Richard S. Nicholson,et al.  Theory and Application of Cyclic Voltammetry for Measurement of Electrode Reaction Kinetics. , 1965 .

[95]  M. H. Chakrabarti,et al.  Evaluation of electrolytes for redox flow battery applications , 2007 .

[96]  Guihua Yu,et al.  A 3.5 V lithium-iodine hybrid redox battery with vertically aligned carbon nanotube current collector. , 2014, Nano letters.

[97]  Bin Li,et al.  Capacity decay and remediation of nafion-based all-vanadium redox flow batteries. , 2013, ChemSusChem.

[98]  M. Roy,et al.  Conductance, a contrivance to explore ion association and solvation behavior of an ionic liquid (tetrabutylphosphonium tetrafluoroborate) in acetonitrile, tetrahydrofuran, 1,3-dioxolane, and their binaries. , 2012, The journal of physical chemistry. B.

[99]  Richard L. C. Wang,et al.  Correlation between the Stability of Redox Shuttles in Li Ion Cells and the Reactivity Defined by the Binding Energy of Redox Shuttle Cations with Ethyl Radical , 2012 .

[100]  C. A. Kraus,et al.  Properties of Electrolytic Solutions. XLVII. Conductance of Some Quaternary Ammonium and Other Salts in Water at Low Concentration1 , 1951 .

[101]  Martin Z Bazant,et al.  Membrane-less hydrogen bromine flow battery , 2013, Nature Communications.

[102]  Yarong Wang,et al.  A Li-liquid cathode battery based on a hybrid electrolyte. , 2011, ChemSusChem.

[103]  P. Fischer,et al.  1,3-Dioxolane, tetrahydrofuran, acetylacetone and dimethyl sulfoxide as solvents for non-aqueous vanadium acetylacetonate redox-flow-batteries , 2013 .

[104]  Qiang Sun,et al.  Interactions of uranium atom with tetraketone complexes , 2005 .

[105]  Victor E. Brunini,et al.  Semi‐Solid Lithium Rechargeable Flow Battery , 2011 .

[106]  Jeff Dahn,et al.  Studies of aromatic redox shuttle additives for LiFePO4-based Li-ion cells , 2005 .

[107]  Pierre-Louis Taberna,et al.  Non-Aqueous Li-Based Redox Flow Batteries , 2012 .

[108]  T. Yamamura,et al.  Electrodeposition of uranium in dimethyl sulfoxide and its inhibition by acetylacetone as studied by EQCM , 2006 .

[109]  Youngsik Kim,et al.  Li-Water Battery with Oxygen Dissolved in Water as a Cathode , 2014 .