Tunable reaction potentials in open framework nanoparticle battery electrodes for grid-scale energy storage.

The electrical energy grid has a growing need for energy storage to address short-term transients, frequency regulation, and load leveling. Though electrochemical energy storage devices such as batteries offer an attractive solution, current commercial battery technology cannot provide adequate power, and cycle life, and energy efficiency at a sufficiently low cost. Copper hexacyanoferrate and nickel hexacyanoferrate, two open framework materials with the Prussian Blue structure, were recently shown to offer ultralong cycle life and high-rate performance when operated as battery electrodes in safe, inexpensive aqueous sodium ion and potassium ion electrolytes. In this report, we demonstrate that the reaction potential of copper-nickel alloy hexacyanoferrate nanoparticles may be tuned by controlling the ratio of copper to nickel in these materials. X-ray diffraction, TEM energy dispersive X-ray spectroscopy, and galvanostatic electrochemical cycling of copper-nickel hexacyanoferrate reveal that copper and nickel form a fully miscible solution at particular sites in the framework without perturbing the structure. This allows copper-nickel hexacyanoferrate to reversibly intercalate sodium and potassium ions for over 2000 cycles with capacity retentions of 100% and 91%, respectively. The ability to precisely tune the reaction potential of copper-nickel hexacyanoferrate without sacrificing cycle life will allow the development of full cells that utilize the entire electrochemical stability window of aqueous sodium and potassium ion electrolytes.

[1]  Yi Cui,et al.  Copper hexacyanoferrate battery electrodes with long cycle life and high power. , 2011, Nature communications.

[2]  Yi Cui,et al.  Nickel hexacyanoferrate nanoparticle electrodes for aqueous sodium and potassium ion batteries. , 2011, Nano letters.

[3]  G. Soloveichik.  Battery technologies for large-scale stationary energy storage. , 2011, Annual review of chemical and biomolecular engineering.

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

[5]  Yi Cui,et al.  The Effect of Insertion Species on Nanostructured Open Framework Hexacyanoferrate Battery Electrodes , 2011 .

[6]  P. He,et al.  Raising the cycling stability of aqueous lithium-ion batteries by eliminating oxygen in the electrolyte. , 2010, Nature chemistry.

[7]  J. Whitacre,et al.  Na4Mn9O18 as a positive electrode material for an aqueous electrolyte sodium-ion energy storage device , 2010 .

[8]  Yi Cui,et al.  Electrochemical behavior of LiCoO2 as aqueous lithium-ion battery electrodes , 2009 .

[9]  J. Eto,et al.  Understanding the cost of power interruptions to U.S. electricity consumers , 2004 .

[10]  J. Yakhmi,et al.  Structure, insertion electrochemistry, and magnetic properties of a new type of substitutional solid solutions of copper, nickel, and iron hexacyanoferrates/hexacyanocobaltates. , 2002, Inorganic chemistry.

[11]  R. Mortimer,et al.  New Electrochromic Materials , 2002, Science progress.

[12]  M. Berrettoni,et al.  Electrochemical preparation and characterization of electrodes modified with mixed hexacyanoferrates of nickel and palladium , 2000 .

[13]  U. Schröder,et al.  Solid state electrochemistry, X-ray powder diffraction, magnetic susceptibility, electron spin resonance, Mössbauer and diffuse reflectance spectroscopy of mixed iron(III)-cadmium(II) hexacyanoferrates , 1999 .

[14]  F. Scholz,et al.  Solid State Electrochemical Studies of Mixed Nickel‐Iron Hexacyanoferrates with the Help of Abrasive Stripping Voltammetry. , 1996 .

[15]  F. Scholz,et al.  Lattice contractions and expansions accompanying the electrochemical conversions of Prussian blue and the reversible and irreversible insertion of rubidium and thallium ions , 1996 .

[16]  F. Scholz,et al.  The Formal Potentials of Solid Metal Hexacyanometalates , 1996 .

[17]  D. Stilwell,et al.  Electrochemical studies of the factors influencing the cycle stability of Prussian Blue films , 1992 .

[18]  E. Grabner,et al.  A secondary cell based on thin layers of zeolite-like nickel hexacyanometallates , 1989 .

[19]  A secondary battery composed of multilayer Prussian Blue and its reaction characteristics , 1988 .

[20]  J. McCargar,et al.  Thermodynamics of mixed-valence intercalation reactions: the electrochemical reduction of Prussian blue , 1988 .

[21]  K. Honda,et al.  Prussian Blue Containing Nafion Composite Film as Rechargeable Battery , 1987 .

[22]  E. Grabner,et al.  Hexacyanoferrate layers as electrodes for secondary cells , 1987 .

[23]  V. Neff.  Some Performance Characteristics of a Prussian Blue Battery , 1985 .

[24]  Vernon D. Neff,et al.  Electrochemical Oxidation and Reduction of Thin Films of Prussian Blue , 1978 .

[25]  D. Schwarzenbach,et al.  THE CRYSTAL STRUCTURE OF PRUSSIAN BLUE- FE4(FE(CN)6)3.XH2O , 1978 .