WO2008105916A2 - Agents dissociants, formulations et procédés fournissant une solubilité augmentée des fluorures - Google Patents

Agents dissociants, formulations et procédés fournissant une solubilité augmentée des fluorures Download PDF

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WO2008105916A2
WO2008105916A2 PCT/US2007/075697 US2007075697W WO2008105916A2 WO 2008105916 A2 WO2008105916 A2 WO 2008105916A2 US 2007075697 W US2007075697 W US 2007075697W WO 2008105916 A2 WO2008105916 A2 WO 2008105916A2
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crown
solvents
solution
group
dissociating agent
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PCT/US2007/075697
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WO2008105916A3 (fr
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Rachid Yazami
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California Institute Of Technology
Centre National De La Recherche Scientifique (C.N.R.S.)
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Priority claimed from US11/681,493 external-priority patent/US8377586B2/en
Application filed by California Institute Of Technology, Centre National De La Recherche Scientifique (C.N.R.S.) filed Critical California Institute Of Technology
Priority to CA002660449A priority Critical patent/CA2660449A1/fr
Priority to JP2009524011A priority patent/JP2010500725A/ja
Priority to EP07873790A priority patent/EP2054961A4/fr
Publication of WO2008105916A2 publication Critical patent/WO2008105916A2/fr
Publication of WO2008105916A3 publication Critical patent/WO2008105916A3/fr

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    • H—ELECTRICITY
    • H01—ELECTRIC ELEMENTS
    • H01M—PROCESSES OR MEANS, e.g. BATTERIES, FOR THE DIRECT CONVERSION OF CHEMICAL ENERGY INTO ELECTRICAL ENERGY
    • H01M6/00—Primary cells; Manufacture thereof
    • H01M6/04—Cells with aqueous electrolyte
    • H—ELECTRICITY
    • H01—ELECTRIC ELEMENTS
    • H01M—PROCESSES OR MEANS, e.g. BATTERIES, FOR THE DIRECT CONVERSION OF CHEMICAL ENERGY INTO ELECTRICAL ENERGY
    • H01M6/00—Primary cells; Manufacture thereof
    • H01M6/14—Cells with non-aqueous electrolyte
    • H01M6/16—Cells with non-aqueous electrolyte with organic electrolyte
    • H01M6/162—Cells with non-aqueous electrolyte with organic electrolyte characterised by the electrolyte
    • H01M6/168—Cells with non-aqueous electrolyte with organic electrolyte characterised by the electrolyte by additives
    • H—ELECTRICITY
    • H01—ELECTRIC ELEMENTS
    • H01M—PROCESSES OR MEANS, e.g. BATTERIES, FOR THE DIRECT CONVERSION OF CHEMICAL ENERGY INTO ELECTRICAL ENERGY
    • H01M6/00—Primary cells; Manufacture thereof
    • H01M6/14—Cells with non-aqueous electrolyte
    • H—ELECTRICITY
    • H01—ELECTRIC ELEMENTS
    • H01M—PROCESSES OR MEANS, e.g. BATTERIES, FOR THE DIRECT CONVERSION OF CHEMICAL ENERGY INTO ELECTRICAL ENERGY
    • H01M6/00—Primary cells; Manufacture thereof
    • H01M6/14—Cells with non-aqueous electrolyte
    • H01M6/16—Cells with non-aqueous electrolyte with organic electrolyte
    • H01M6/162—Cells with non-aqueous electrolyte with organic electrolyte characterised by the electrolyte
    • H01M6/166—Cells with non-aqueous electrolyte with organic electrolyte characterised by the electrolyte by the solute
    • H—ELECTRICITY
    • H01—ELECTRIC ELEMENTS
    • H01M—PROCESSES OR MEANS, e.g. BATTERIES, FOR THE DIRECT CONVERSION OF CHEMICAL ENERGY INTO ELECTRICAL ENERGY
    • H01M2300/00—Electrolytes
    • H01M2300/0017—Non-aqueous electrolytes
    • H01M2300/0025—Organic electrolyte
    • H01M2300/0028—Organic electrolyte characterised by the solvent
    • H01M2300/0037—Mixture of solvents

Definitions

  • electrochemical storage and conversion devices have significantly expanded the capabilities of these systems in a variety of fields including portable electronics, aerospace technologies, communications and biomedical instrumentation.
  • State of the art electrochemical storage and conversion devices are specifically engineered to have designs and performance attributes supporting specific target application requirements and operating environments.
  • Such advanced electrochemical storage systems include high energy density batteries exhibiting low self discharge rates and high discharge reliability for implanted medical devices; inexpensive light weight rechargeable batteries for portable electronics, and high capacity batteries capable of providing high discharge rates over short time intervals for military and aerospace applications.
  • Lithium battery technology continues to rapidly develop, at least in part, due to the discovery of novel electrode and electrolyte materials for these systems. From the pioneering identification of intercalation host materials for positive and negative electrodes to the development of high performance non-aqueous electrolytes, the discovery and optimization of novel materials for lithium battery systems have revolutionized their design and performance capabilities. As a result of these advances, lithium based battery technology is currently preferred for certain commercially significant applications including primary and secondary electrochemical cells for portable electronic systems.
  • primary and secondary lithium batteries are widely employed as power sources for many portable electronic devices, such as cellular telephones and portable computers, and for other important device applications in the fields of biomedical engineering, sensing, military communications, and lighting.
  • Primary lithium battery systems typically utilize a lithium metal negative electrode for generating lithium ions.
  • lithium ions are transported from the negative electrode through a liquid phase or solid phase electrolyte and undergo intercalation reaction at a positive electrode comprising an intercalation host material.
  • Dual intercalation lithium ion secondary batteries have also been developed, wherein lithium metal is replaced with a second lithium ion intercalation host material providing the negative electrode.
  • simultaneous lithium ion insertion and de-insertion reactions allow lithium ions to migrate between the positive and negative intercalation electrodes during discharge and charging cycles.
  • incorpora lithium ion intercalation host material for the negative electrode has the significant advantage of avoiding the use of metallic lithium which is susceptible to safety problems upon recharging attributable to the highly reactive nature and non- epitaxial deposition properties of lithium.
  • Useful intercalation host materials for electrodes in lithium cells include carbonaceous materials (e.g., graphite, cokes, subfluorinated carbons etc.), metal oxides, metal sulfides, metal nitrides, metal selenides and metal phosphides.
  • Electrolytes for lithium electrochemical cells are limited to nonaqueous materials given the extremely reactive nature of lithium with water.
  • Several classes of nonaqueous electrolytes have been successfully implemented for lithium electrochemical cells including: (i) solutions of lithium salts dissolved in organic or inorganic solvents, (ii) ionically conducting polymers, (iii) ionic liquids and (iv) fused lithium salts.
  • Nonaqueous electrolyte solutions comprising lithium salts dissolved in polar organic solvents are currently the most widely adopted electrolytes for primary and secondary lithium cells.
  • Useful solvents for these electrolytes include polar solvents that facilitate dissociation of lithium salts into their ionic components.
  • Polar solvents exhibiting useful properties for lithium cell electrolytes include linear and cyclic esters (e.g., methyl formate, ethylene carbonate, dimethyl carbonate and propylene carbonate), linear and cyclic ethers (e.g., dimethoxiethane, and dioxolane) acetonitrile, and ⁇ -butyrolactone.
  • Lithium salts in these electrolyte systems are typically salts comprising lithium and complex anions that have relatively low lattice energies so as to facilitate their dissociation in polar organic solvents.
  • Lithium salts that have been successfully incorporated in electrolytes for these systems include LiCIO 4 , LiBF 4 , LiAsF 6 , LiSbF 6 , LiAICI 4 and LiPF 6 provided at concentrations ranging from 0.01 M to 1 M.
  • the electrolyte must be capable of forming a stable passivation layer on the surfaces of the electrode that does not result in a significant voltage delay at the onset of discharge and is capable of rapid reformation upon high current discharge.
  • the electrolyte must be chemically stable with respect to electrolytic degradation for relevant electrode material and discharge conditions.
  • the electrolyte must exhibit a useful ionic conductivity. State of the art electrolytes for these systems, for example, exhibit ionic conductivities at 25 degrees Celsius greater than or equal to about 0.005 S cm "1 .
  • Other physical properties of electrolytes useful for providing enhanced performance in electrochemical cells include thermal stability, low viscosity, low melting point, and high boiling point.
  • Anion receptors are a class of compounds that have been recently developed as additives to increase the ionic conductivity of nonaqueous electrolyte solutions (See, e.g., U.S. Pat. Nos. 6,022,643, 6,120,941 , and 6,352,798).
  • Anion receptors enhance the ionic disassociation of lithium salts in low dielectric solvents by incorporating non- hydrogen bonded electrophilic groups that participate in complex formation reactions with anions of the lithium salt provided to the electrolyte.
  • Some anion receptor additives have been demonstrated to enhance the dissolution of specific lithium salts in a manner resulting in an increase in solubility by several orders of magnitude.
  • Anion receptor additives encompass a wide range of compounds including fluorinated boron-based anion receptors, such as boranes, boronates and borates having electron withdrawing ligands, polyammonium compounds, guanidiniums, calixarene compounds, and aza- ether compounds.
  • Successful integration of anion receptors in lithium batteries depends on a number of key factors.
  • the anion receptor must be stable with respect to electrolyte decomposition under useful discharge and charging conditions.
  • anion receptors should be capable of releasing (or de-complexing) complexed anions so as not to hinder intercalation reactions at the electrodes.
  • the anion receptor itself preferably should not participate in intercalation with the intercalation host material, and if it does participate in such intercalation reactions it should not result in mechanically induced degradation of the electrodes.
  • Additives have also been developed to impart other useful chemical and physical characteristics to polar organic solvent based electrolytes for lithium cells.
  • U.S. Patent No. 6,306,540 provides additives for improving the stability of nonaqueous electrolytes by minimizing gas formation decomposition reactions involving lithium salts and their dissociation products.
  • This reference discloses electrolyte compositions having a LiF additive provided to a solution of LiPF 6 in a nonaqueous organic solvent. At least partial dissolution of the LiF additive generates fluoride ions in the nonaqueous electrolyte which is reported to suppress gas forming decomposition reactions involving PF 6 " anions.
  • Nonaqueous electrolytes exhibiting chemical and physical properties useful for electrochemical conversion and storage systems.
  • Nonaqueous electrolytes are needed that exhibit large ionic conductivities and good stability for use in primary and secondary lithium electrochemical cells.
  • Table 1 provides a summary of solubility data for a range of inorganic fluorides in water.
  • MF n many solid state inorganic fluorides (MF n ), for example CdF 2 , CoF 2 , FeF 3 , MnF 2 , NaF, NiF 2 , ZnF 2 , ZrF 4 , AIF 3 , BaF 2 , CaF 2 , CuF 2 , FeF 2 , InF 3 , LiF, MgF 2 , PbF 2 , SrF 2 , UF 4 , VF 3 -3H 2 0, BiF 3 , CeF 3 , CrF 2 /CrF 3 , GaF 3 , LaF 3 , NdF 3 , and ThF 4 , are poorly soluble in water and many organic solvents.
  • MF n solid state inorganic fluorides
  • fluorides such as CsF, RbF, KF, SbF 3 and AgF
  • CsF, RbF, KF, SbF 3 and AgF readily dissolve into water at the ambient temperatures.
  • insoluble element fluorides can be prepared as water precipitates by halide metathesis or by the reaction of aqueous hydrofluoric acid with the appropriate element oxide, hydroxide, carbonate or with the element itself.
  • hydrofluoric acid has significant drawbacks given its highly corrosive and toxic nature.
  • insoluble fluorides are currently a great challenge in chemical science and technology. Among other advantages, it can provide fluorine rich solutions for new chemical synthesis through solution reactions or for appropriate physical properties of dissolved fluohnated species.
  • methods and compositions providing enhanced solubility of fluorides may provide an important tool for accessing solution phase fluoride compositions useful for solution phase and surface phase synthetic pathways.
  • methods and compositions providing enhanced solubility of fluorides would also enable new electrolyte solutions for many applications, including electrosynthesis, electrodeposition, and electropassivation, and in electrochemical energy storage and conversion systems such as primary and secondary batteries, electrochemical double-layer capacitors and fuel cells.
  • the present invention provides compositions, formulations and methods providing for the effective dissolution of inorganic fluorides (i.e., an inorganic salt containing one or more fluoride groups) in solvents via incorporation of a dissociating agent component.
  • Dissociating agents of the present invention participate in chemical reactions in solution, such as complex formation, acid-base reactions and adduct formation reactions, that result in enhancement in the dissolution of inorganic fluorides in a range of solvent environments.
  • Dissociating agents comprising Lewis acids, Lewis bases, anion receptors, cation receptors or combinations thereof are provided that significantly increase the extent of dissolution of a range of inorganic fluorides, particularly inorganic fluorides, such as LiF, that are highly insoluble in many solvents in the absence of the dissociating agents of present invention.
  • the compositions, formulations and methods of the present invention are versatile and, thus, are useful for making solutions containing dissolved inorganic fluorides, including aqueous solutions, nonaqueous organic solutions and nonaqueous inorganic solutions.
  • Dissociating agents, formulations and methods of the present invention are useful for producing fluoride ion rich solutions having selected chemical, electronic and physical properties.
  • the present invention provides compositions useful for providing solution phase reagents for chemical synthesis applications. Further, the present invention provides compositions useful for in electrochemical conversion and storage systems, electrosynthesis, electrodeposition (electroplating) , electropassivation, electro-etching, and electrochemical detection and analysis, such as enhanced F- ions sensors and specific electrodes applications.
  • the methods and compositions of the present are also useful for sensing systems, including electrochemical sensing systems such as fluoride ion specific electrodes.
  • the present invention also provides a new class of nonaqueous electrolytes for electrochemical devices, particularly for primary and secondary lithium electrochemical cells. Electrolyte formulations of this embodiment provide for effective dissolution of lithium salts having inherently low solubilities in many nonaqueous organic solvents. This aspect of the present invention provides electrolyte compositions having chemical and physical properties, such as high ionic conductivities, good chemical and electrochemical stability and useful fluoride ion containing solution phase compositions, that are otherwise inaccessible in these systems.
  • Dissociating agents comprising Lewis acids, Lewis bases, anion receptors, cation receptors or combinations thereof are provided in electrolyte formulations of the present invention that significantly increase the extent of dissolution and solubility of lithium salts, such as LiF, in polar nonaqueous organic solvents such as polar carbonates and ⁇ -butyrolactone.
  • the present nonaqueous electrolyte compositions and dissociating agents are chemically stable in contact with metallic lithium and also exhibit high voltage stabilities over a useful range of discharge and charging potentials.
  • Nonaqueous electrolytes of the present invention enable primary and secondary electrochemical cells, including primary and secondary lithium batteries, exhibiting advanced performance characteristics relative to conventional systems, including large discharge rates and power output capabilities.
  • the present invention provides a solution having a dissociating agent for enhancing dissolution of one or more inorganic fluorides provided to a solvent or combination of solvents.
  • a solution of this aspect of the present invention is a multi- component formulation comprising: (i) one or more solvents; (ii) a dissociating agent provided to the one or more solvents; and (iii) one or more inorganic fluorides dissolved in the one or more solvents having the dissociating agent.
  • Useful dissociating agents in this aspect of the present invention include Lewis acids, Lewis bases, anion receptors, cation receptors and combinations of these.
  • This aspect of the present invention further provides methods of dissolving an inorganic fluoride in a solvent or combination of solvents comprising the steps of providing a dissociating agent to the solvent(s) and dissolving the inorganic fluoride into the solvent(s) containing the dissociating agent.
  • incorporación of a dissociating agent component in solutions of this aspect of the present invention increases the extent of dissolution of the inorganic fluoride in the solvent(s) by participating in chemical reactions in solution, including complex formation, acid-base reactions and adduct formation reactions, that affect the solubility equilibrium conditions in a manner to provide for dissolution of inorganic fluoride(s).
  • the dissociating agent and inorganic fluoride are provided in amounts sufficient to generate a concentration of inorganic fluoride dissolved in the one or more solvents greater than or equal to 0.15 M.
  • the dissociating agent and inorganic fluoride are provided in amounts sufficient to generate a concentration of the inorganic fluoride dissolved in the one or more solvents selected over the range of 0.15 M to 3M, and preferably for particular applications selected over the range of 0.5 M to 1 M.
  • Dissociating agents preferred for some applications exhibit a significant enhancement of the dissolution of the inorganic fluoride on a mole-to-mole basis.
  • [025] is greater than or equal to 0.1 , and preferably for some applications selected over the range of 0.1 to 10.
  • the present formulations, dissociating agents and methods are applicable to a broad range of inorganic fluorides, particularly those exhibiting low solubilities in pure solvent or solvent combinations.
  • Classes of inorganic fluorides useful in the present solutions, formulations and methods include alkali metal fluorides, alkaline earth metal fluorides, transition metal fluorides and ammonium fluorides.
  • the present invention provides solutions of dissolved fluorides having the formula: [027] MF n or BF y ;
  • M is a metal selected from the group consisting of Li, Na, K, Rb, Cs, Be, Mg, Ca, Sr, Ba, Sn Pb, and Sb, and n is the oxidation state of M; and wherein B is a polyatomic cation selected from the group consisting of NH 4 + (i.e., ammonium ion) and N(R-
  • B is a polyatomic cation selected from the group consisting of NH 4 + (i.e., ammonium ion) and N(R-
  • a solution of the present invention comprises an inorganic fluoride component selected from the group consisting of CdF 2 , CoF 2 , FeF 3 , MnF 2 , NaF, NiF2, ZnF 2 , ZrF 4 , AIF 3 , BaF 2 , CaF 2 , CuF 2 , FeF 2 , InF 3 , LiF, MgF 2 , PbF 2 , SrF 2 , UF 4 , VF 3 - 3H 2 O, BiF 3 , CeF 3 , CrF 2 /CrF 3 , GaF 3 , LaF 3 , NdF 3 , ThF 4 , AgF, CsF, RbF, SbF 3 , TIF, BeF 2 , KF, NH 4 F, SnF 2 , TaF 5 , VF 4 , BF 3 , BrF, BrF 3 , BrF 5 , CoF 3 , GeF 2 /
  • a solution of the present invention comprises an inorganic fluoride component selected from the group consisting of: CdF 2 , CoF 2 , FeF 3 , MnF 2 , NaF, NiF 2 , ZnF 2 , ZrF 4 , AIF 3 , BaF 2 , CaF 2 , CuF 2 , FeF 2 , InF 3 , LiF, MgF 2 , PbF 2 , SrF 2 , UF 4 , VF 3 -3H 2 0, BiF 3 , CeF 3 , CrF 2 /CrF 3 , GaF 3 , LaF 3 , NdF 3 , and ThF 4 .
  • an inorganic fluoride component selected from the group consisting of: CdF 2 , CoF 2 , FeF 3 , MnF 2 , NaF, NiF 2 , ZnF 2 , ZrF 4 , AIF 3 , BaF 2 , CaF 2 , CuF 2 , Fe
  • a solution of this aspect comprises: (i) one or more solvents; (ii) a dissociating agent provided to the one or more solvents, the dissociating agent comprising one or more compounds selected from the group consisting of a Lewis acid, a Lewis base; and a crown ether; and (iii) LiF dissolved in the one or more solvents having the dissociating agent, wherein the concentration of LiF dissolved in said one or more solvents is greater than or equal to 0.15 M.
  • this aspect of the present invention provides for the dissolution of LiF so as to generate a concentration of dissolved LiF in the solvent(s) selected over the range of 0.15 M to 3M, preferably for some applications selected over the range of 0.5 M to 1 M.
  • This aspect of the present invention further provides methods of dissolving LiF in a solvent or combination of solvents comprising the steps of providing a dissociating agent comprising a Lewis acid, a Lewis base, a crown ether or combination of these to the solvent(s) and dissolving the LiF into the solvent(s) containing the dissociating agent.
  • composition and concentration of the dissociating agent determines, at least in part, the composition, chemical properties and/or physical properties of the solutions and formulations of this aspect of the present invention.
  • the composition and concentration of dissociating agents in solutions and methods of the present invention are important parameters for achieving a desired extent of dissolution of an inorganic fluoride such as LiF.
  • Useful dissociating agents in some embodiments include Lewis acids, Lewis bases, anion receptors, cation receptors, complexing agents, adduct formation agents and combinations of these compounds.
  • the dissociating agent is provided in the one or more solvents at a concentration selected over the range of 0.01 M to 10 M, and preferably for some applications selected over the range of 0.1 M to 5 M, and more preferably for some applications selected over the range of 0.5 M to 1.5 M.
  • Other properties of dissociating agents useful for some embodiments include chemical stability (for example in the presence of lithium metal), electrochemical stability under discharge or charge conditions in an electrochemical cell, low viscosity impact when provided to solution, thermal stability and an enhancement in ionic conductivity when provided to solution.
  • dissociating reagents do not significantly undergo intercalation reactions at the electrodes.
  • Lewis acids and Lewis bases are a particularly useful class of dissociating agents in the present solutions, formulations and methods.
  • the term "Lewis acid” refers to a substance which, in solution, is able to generate a cation or combine with an anion, and/or a molecule which can accept a pair of electrons and form a coordinate covalent bond
  • the term "Lewis base” refers to a substance which, in solution, is able to generate an anion or combine with a cation, and/or a molecule or ion that can form a coordinate covalent bond by donating a pair of electrons.
  • Useful Lewis base or Lewis acid dissociating agents provided to solutions of the present invention include, but are not limited to, inorganic fluorides, inorganic chlorides, inorganic carbonates, and inorganic oxides.
  • the dissociating agent is one or more Lewis base selected from the group consisting Of AICI 4 “ , CIO 4 “ , SnCI 6 2" , BF 4 “ , PF 6 “ , and AsF 6 " .
  • the dissociating agent is one or more Lewis acid selected from the group consisting of BF 3 , PF 5 , SbF 5 , AsF 5 , AICI 3 , SnCI 4 , FeCI 3 , NbCI 5 , TiCI 4 , and ZnCI 2 .
  • a dissociating agent comprising one or more Lewis acid and/or Lewis base is provided at a concentration in the solution selected over the range of 0.1 M to 10M, a preferably for some applications selected over the range of 0.5M to 3M.
  • Lewis acids and bases may be provided to solutions of the present invention via providing a precursor compound to the solution.
  • the term "precursor compound” refers to a substance that generates a Lewis acid, Lewis base or both in solution when provided to a solvent or combination of solvents.
  • the dissociating agent is provided by dissolving a precursor compound in the one or more solvents to generate a Lewis base, a Lewis acid or a combination of a Lewis acid and a Lewis base, wherein the precursor compound comprises an alkali metal salt, alkaline earth metal salt; a transition metal salt, a rare earth metal salt, or an ammonium salt having the formula:
  • A is selected from the group consisting of a metal, a metal cation and an ammonium group; and wherein X is selected from the group consisting of a fluohnated anion, a perchlorate group, an imide group, a carbide group, a carbonate group, an oxide group and a chloride group.
  • Lithium salts are precursors useful for generating Lewis acids and/or Lewis bases in some solutions and methods of the present invention.
  • Precursor compounds useful in the present solutions, formulations and methods include, but are not limited to, LiPF 6 , LiBF 4 , LiAsF 6 , LiCIO 4 , LiSnCI 5 , LiAICI 4 , LiFeCI 4 , LiNbCI 6 , LiTiCI 5 , LiZnCI 3 , NaPF 6 , NaBF 4 , NaAsF 6 , NaCIO 4 , NaSnCI 5 , NaAICI 4 , NaFeCI 4 , NaNbCI 6 , NaTiCI 5 , NaZnCI 3 , KPF 6 , KBF 4 , KAsF 6 , KCIO 4 , KSnCI 5 , KAICI 4 , KFeCI 4 , KNbCI 6 , KTiCI 5 , KZnCI 3 , NH 4 PF 6 , NH 4 BF 4 , NH 4 AsF 6 , NH 4 CIO 4 , NH 4 SnCI 5
  • Cation receptors are another particularly useful class of dissociating agents in the present solutions, formulations and methods.
  • the term "cation receptor" refers to a molecule or ion which can bind or otherwise take up a cation in solution.
  • Some solutions of the present invention comprise one or more cation receptors selected from the group consisting of a crown ether, a Lewis base, and a cation complexing agent.
  • a dissociating agent comprising one or more cation receptor is provided at a concentration in the solution selected over the range of 0.1 M to 10M, a preferably for some applications selected over the range of 0.3M to 5M.
  • Crown ethers are a class of cation receptor exhibiting chemical and physical properties beneficial for enhancing the dissolution of inorganic fluorides, including LiF. These compounds are useful for complexing with metal ions in solution. Crown ether cation receptors useful in the present invention include, but are not limited to, Benzo-15- crown-5, 15-Crown-5, 18-Crown-6, Cyclohexyl-15-crown-5, Dibenzo-18-crown-6, Dicyclohexyl-i ⁇ -crown-6, Di-t-butyldibenzo-18-crown-6, 4,4r(5r)-Di-tert-butyldibenzo- 24-crown-8, 4-Aminobenzo-15-Crown-5, Benzo-15-Crown-5, Benzo-18-crown-6, 4-tert- Butylbenzo-15-crown-5, 4-tert-Butylcyclohexano-15-crown-5, 18
  • Anion receptors are another particularly useful class of dissociating agents in the present solutions, formulations and methods.
  • anion receptor refers to a molecule or ion which can bind or otherwise take up an anion in solution.
  • Anion receptors useful in the present solutions, formulations and methods include, but are not limited to fluohnated and semifluorinated borate compounds, fluohnated and semifluorinated boronate compounds, fluorinated and semifluorinated boranes, phenyl boron compounds, aza-ether boron compounds, Lewis acids, cyclic polyammonium compounds, guanidinium compounds, calixarene compounds, aza-ether compounds, quaternary ammonium compounds, amines, imidazolinium based receptors, mercury metallacycle compounds, silicon containing cages, and macrocycles.
  • a dissociating agent comprising one or more anion receptor is provided at a concentration in the solution selected over the range of 0.1 M to 1 OM, a preferably for some applications selected over the range of 0.5M to 3M.
  • calixarene compounds include cobaltocenium-based receptors, ferrocene-based receptors, ⁇ -m eta Hated cationic hosts, calix[4]arenes, and calix[6]arenes.
  • aza-ether anion receptors include linear aza-ethers, multi- branched aza-ethers, and cyclic aza-crown ethers.
  • mercury metallacycle anion receptors include mercuracarborands and perfluoro-o-phenylenemercury metallacycles.
  • anion receiving silicon-containing cages and macrocycles includes silsesquioxane cages and crown silanes.
  • McBreen, L.S. Choi "The Synthesis of a New Family of Boron-Based Anion Receptors and the Study of Their Effect on Ion Pair Dissociation and Conductivily of Lithium Salts in Nonaqueous Solutions", J. Electrochem. So ⁇ , Vol. 145, No. 8, August 1998; H.S. Lee, Z. F. Ma, X.Q. Yang, X. Sun and J. McBreen, "Synthesis of a Series of Fluohnated Boronate Compounds and Their Use as Additives in Lithium Battery Electrolytes", Journal of The Electrochemical Society, 151 (9) A1429-A1435 (2004); and X. Sun, H.S. Lee, S. Lee, X.Q.
  • Solutions, formulations, and methods of the present invention are compatible with a range of solvents, including water, nonaqueous organic solvents and nonaqueous inorganic solvents.
  • the solvent(s) comprises one or more polar nonaqueous solvents, such as linear and cyclic esters, linear and cyclic ethers and polar carbonates.
  • Electrolytes of the present invention may comprise a single nonaqueous solvent or a combination of nonaqueous solvents provided in relative proportions useful for a given electrochemical device or application.
  • composition of nonaqueous solvents in some embodiments of the present invention is selected to provide electrolyte formulations having desired physical, electronic and chemical properties, such as ionic conductivities, viscosities, melting points, freezing points and stability with respect to electrolytic decomposition and/or reaction with lithium metal.
  • Useful solvents in the present invention include, but are not limited to, one or more of ⁇ -butyrolactone, propylene carbonate, dimethyl carbonate, ethylene carbonate, acetonitrile, 1 ,2, -dimethoxy ethane, N,N-dimethyl formamide, dimethyl sulfoxide, 1 ,3- diolane, methyl formate, nitromethane, phosphoroxichloride, thionylchlohde, sulfurylchlohde, diethyl ether, diethoxy ethane, 1 ,3 -dioxolane, tetrahydrofuran, 2- methyl-THF, diethyl carbonate, ethyl methyl carbonate, methylacetate and tratahydrofurane.
  • solutions and formulations of the present invention provide electrolyte compositions useful for electrochemical storage and conversion applications.
  • inorganic fluoride, dissociating agent and solvent components are selected to provide solution properties useful for a target electrochemical device application.
  • the composition of solution components of an electrolyte are selected to establish useful chemical and physical properties, such as large ionic conductivities, and enhanced solubility for solutions containing inorganic fluorides that are relatively insoluble in pure nonaqueous organic solvents.
  • the present invention includes electrolytes, including nonaqueous electrolytes, exhibiting a high degree of chemical and electrochemical stability.
  • an electrolyte of the present invention has a high voltage stability window over 5V vs. Li + /Li.
  • electrolyte formulations of the present invention are stable with respect to contact with Li metal under discharge or charging conditions.
  • a electrolyte of the present invention has an ionic conductivity at 25 degrees Celsius greater than or equal to 10 "4 S cm “1 , preferably for some applications greater than or equal to 10 ⁇ 3 S cm “1 , and more preferably for some applications greater than or equal to 5 x 10 ⁇ 3 S cm “1 .
  • a nonaqueous electrolyte of the present invention has a viscosity at 25 degrees Celsius less than or equal to 5 cP, more preferably for some applications less than or equal to 3 cP.
  • a preferred class of electrolytes for lithium electrochemical cells comprises LiF and a dissociating agent provided in one or more nonaqueous organic solvents.
  • the present invention provides electrolyte formulations having an inorganic fluoride component comprising LiF salt and a dissociating agent capable of significantly enhancing the dissociation and solubility of LiF in organic solvent(s).
  • Embodiments of this aspect are particularly useful for electrolytes of electrochemical cells because F is the most electronegative element and Li is the most electropositive element.
  • electrolytes of the present invention comprising LiF are particularly attractive for providing electrochemical cells having enhanced cell voltages and specific capacities relative to conventional lithium electrochemical cells.
  • Dissociating agents of the present invention are capable of increasing the conductivity of LiF in a selected nonaqueous organic solvent or combination of nonaqueous organic solvents, at 25°C, to a value equal to or greater than 10 ⁇ 4 S cm “1 , preferably equal to or greater 5 x 10 ⁇ 4 S cm "1 , and more preferably equal to or greater 10 ⁇ 3 S cm "1 .
  • dissociating agents of the present invention increase the solubility of LiF in a selected nonaqueous organic solvent (or combination of solvents) from a low value (e.g., on the order of micromolar) to 0.1 M or greater, preferably 0.5 M or greater, and preferably 1 M or greater.
  • LiF solubility at a temperature of about 25°C in an electrolyte of the present invention is increased by addition of a dissociating agent to a value greater than about 0.1 M, including between about 0.1 M to 5 M, and between about 1 M to 2 M.
  • the present invention includes electrochemical devices comprising the present electrolytes, such as nonaqueous electrolytes, including, but not limited to, primary electrochemical cells, secondary electrochemical cells, capacitors, supercapacitors and fuel cells.
  • the solutions, dissociating agents and methods of the present invention are also useful for sensing systems, including electrochemical sensing systems. Solutions and dissociating agents of the present invention, for example, are useful for reducing interference and enhancing the selectivity of fluoride ion specific electrodes.
  • the present invention provides an electrochemical cell comprising: (i) a positive electrode; (ii) a negative electrode; and (iii) an electrolyte of the present invention provided between the positive electrode and the negative electrode.
  • an electrolyte of an electrochemical device of the present invention comprises (i) one or more solvents; (ii) a dissociating agent provided to the one or more solvents; and (iii) an inorganic fluoride dissolved in the one or more solvents having the dissociating agent; wherein the dissociating agent and inorganic fluoride are provided in amounts sufficient to generate a concentration of inorganic fluoride dissolved in the one or more solvents greater than or equal to 0.15 M.
  • the negative electrode comprises lithium metal, a carbonaceous material, such as graphite, coke, multiwalled carbon nanotubes, multi-layered carbon nanofibers, multi-layered carbon nanoparticles, carbon nanowhiskers and carbon nanorods having lithium storage capability or a lithium metal alloy.
  • a carbonaceous material such as graphite, coke, multiwalled carbon nanotubes, multi-layered carbon nanofibers, multi-layered carbon nanoparticles, carbon nanowhiskers and carbon nanorods having lithium storage capability or a lithium metal alloy.
  • the positive electrode comprises a carbonaceous material, such as graphite, coke, multiwalled carbon nanotubes, multi- layered carbon nanofibers, multi-layered carbon nanoparticles, carbon nanowhiskers and carbon nanorods having fluoride ion storage capability.
  • positive electrode comprises a carbonaceous material comprises a subfluohnated carbonaceous material having an average stoichiometry CF x , wherein x is the average atomic ratio of fluorine atoms to carbon atoms and is selected from the range of about 0.3 to about 1.0; the subfluohnated carbonaceous material being a multiphase material having an unfluorinated carbon component.
  • positive electrode comprises a fluohnated element such a transition metal or a rare earth metal having reversible fluorine ion storage capability.
  • Solutions, dissociating agents and methods of the present invention providing enhanced solubility of fluorides have significant applications in addition to their use as electrolytes in electrochemical devices and systems.
  • the compositions and methods of the present invention are beneficial for accessing solution phase compositions and properties (e.g., chemical, physical and/or electrochemical) useful for enabling a broad class of surface phase and solution synthetic pathways and other processes.
  • Fluoride containing solutions of the present invention may provide solution phase reagents for important synthetic chemistries, including organic and inorganic fluohnation, for example by soft chemistry methods, and surface fluorination reactions.
  • Fluoride containing solutions of the present invention may also be useful for accessing solution properties (e.g., ionic conductivities, ionic strength, etc.) critical for accessing important solution phase processes, including electrosynthesis, electrodeposition, and electropassivation.
  • the present invention provides a method for dissolving an inorganic fluoride in one or more solvents comprising the steps of: (i) providing the one or more solvents; (ii) providing a dissociating agent to the one or more solvents; and (iii) dissolving the inorganic fluoride in the one or more solvents having the dissociating agent; wherein the dissociating agent and inorganic fluoride are provided in amounts sufficient to generate a concentration of inorganic fluoride dissolved in the one or more solvents greater than or equal to 0.15 M, thereby dissolving the inorganic fluoride into the one or more solvents.
  • the present invention provides a method for dissolving LiF in one or more solvents, comprising the steps of: (i) providing the one or more solvents; (ii) providing a dissociating agent to the one or more solvents, the dissociating agent comprising one or more compound selected from the group consisting of a Lewis acid, a Lewis base; and a crown ether; and dissolving LiF in the one or more solvents having the dissociating agent, wherein the concentration of LiF dissolved in said one or more solvents is greater than or equal to 0.15 M, and optionally greater than or equal to 0.5M.
  • the present invention provides a method of making an electrolyte for an electrochemical device, the method comprising the steps of: (i) providing one or more solvents; (ii) providing a dissociating agent to the one or more solvents; and (iii) dissolving an inorganic fluoride in the one or more solvents having the dissociating agent; wherein the dissociating agent and inorganic fluoride are provided in amounts sufficient to generate a concentration of inorganic fluoride dissolved in the one or more solvents greater than or equal to 0.15 M, thereby making the electrolyte for the electrochemical device.
  • the present invention provides a method of making an electrolyte for an electrochemical device, the method comprising the steps of: (i) providing one or more solvents; (ii) providing a dissociating agent to the one or more solvents, the dissociating agent comprising one or more compounds selected from the group consisting of a Lewis acid, a Lewis base; and a crown ether; and (iii) dissolving LiF in the one or more solvents having the dissociating agent, thereby making the electrolyte for the electrochemical device.
  • the present invention provides a solution having LiF dissolved in one or more solvents, said solution comprising: (i) said one or more solvents; and (ii) LiF dissolved in said one or more solvents; wherein the concentration of LiF dissolved in said one or more solvents is greater than or equal to 0.15 M.
  • Figure 1 Comparative (normalized) discharge profile of Li/electrolyte/graph ite- based electrode cells with LiF-containing and LiF-free electrolytes consisting of 1 M LiPF 6 solution in EC-DMC.
  • Figure 2 Shows the cyclic voltammogram obtained with the LiF containing electrolyte cell between 2.1 and 4.8V under 15mV/mn sweeping rate. It shows oxidation and reduction peaks corresponding to negatively charged species intercalation and de- intercalation into graphite.
  • Figure 3 Comparative (normalized) discharge profile of Li/electrolyte/graphite fluoride (CF 0 53 )-based electrode cells with LiF-containing and LiF-free electrolytes consisting of 1 M LiPF 6 solution in EC-DMC.
  • Figure 4 depicts the current provided by the cell containing LiPF 6 during a charge/discharge cycle.
  • Figure 5 depicts the current provided by the cell containing LiF and 12-crown-4 during a charge/discharge cycle.
  • Intercalation refers to refers to the process wherein an ion inserts into a host material to generate an intercalation compound via a host/guest solid state redox reaction involving electrochemical charge transfer processes coupled with insertion of mobile guest ions, such as fluoride ions. Major structural features of the host material are preserved after insertion of the guest ions via intercalation.
  • intercalation refers to a process wherein guest ions are taken up with interlayer gaps (e.g., galleries) of a layered host material.
  • Examples of intercalation compounds include fluoride ion intercalation compounds wherein fluoride ions are inserted into a host material, such as a layered fluoride host material or carbon host material.
  • Host materials useful for forming intercalation compounds for electrodes of the present invention include, but are not limited to, CF x , FeFx, MnFx, NiFx, CoFx, LiC ⁇ , LixSi, and LJxGe.
  • Electrochemical cell refers to devices and/or device components that convert chemical energy into electrical energy or electrical energy into chemical energy. Electrochemical cells have two or more electrodes (e.g., positive and negative electrodes) and an electrolyte, wherein electrode reactions occurring at the electrode surfaces result in charge transfer processes. Electrochemical cells include, but are not limited to, primary batteries, secondary batteries and electrolysis systems. General cell and/or battery construction is known in the art, see e.g., U.S. Pat. Nos. 6,489,055, 4,052,539, 6,306,540, Seel and Dahn J. Electrochem. Soc. 147(3) 892-898 (2000).
  • Capacity is a characteristic of an electrochemical cell that refers to the total amount of electrical charge an electrochemical cell, such as a battery, is able to hold. Capacity is typically expressed in units of ampere-hours.
  • specific capacity refers to the capacity output of an electrochemical cell, such as a battery, per unit weight. Specific capacity is typically expressed in units of ampere-hours kg “1 .
  • discharge rate refers to the current at which an electrochemical cell is discharged.
  • Discharge current can be expressed in units of ampere-hours.
  • discharge current can be normalized to the rated capacity of the electrochemical cell, and expressed as C/(X t), wherein C is the capacity of the electrochemical cell, X is a variable and t is a specified unit of time, as used herein, equal to 1 hour.
  • open circuit voltage refers to the difference in potential between terminals (i.e. electrodes) of an electrochemical cell when the circuit is open (i.e. no load conditions). Under certain conditions the open circuit voltage can be used to estimate the composition of an electrochemical cell.
  • the present methods and system utilize measurements of open circuit voltage for thermochemically stabilized conditions of an electrochemical cell to determine thermodynamic parameters, materials properties and electrochemical properties of electrodes, electrochemical cells and electrochemical systems.
  • state of charge is a characteristic of an electrochemical cell or component thereof (e.g. electrode - cathode and/or anode) referring to its available capacity, such as a battery, expressed as a percentage of its rated capacity.
  • Electrode refers to an electrical conductor where ions and electrons are exchanged with electrolyte and an outer circuit.
  • Positive electrode and “cathode” are used synonymously in the present description and refer to the electrode having the higher electrode potential in an electrochemical cell (i.e. higher than the negative electrode).
  • Negative electrode and “anode” are used synonymously in the present description and refer to the electrode having the lower electrode potential in an electrochemical cell (i.e. lower than the positive electrode).
  • Cathodic reduction refers to a gain of electron(s) of a chemical species
  • anodic oxidation refers to the loss of electron(s) of a chemical species.
  • Positive electrodes and negative electrodes of the present electrochemical cell may further comprise a conductive diluent, such as acetylene black, carbon black, powdered graphite, coke, carbon fiber, and metallic powder, and/or may further comprises a binder, such as a polymer binder.
  • a conductive diluent such as acetylene black, carbon black, powdered graphite, coke, carbon fiber, and metallic powder
  • a binder such as a polymer binder.
  • Useful binders for positive electrodes in some embodiments comprise a fluoropolymer such as polyvinylidene fluoride (PVDF).
  • PVDF polyvinylidene fluoride
  • Positive and negative electrodes of the present invention may be provided in a range of useful configurations and form factors as known in the art of electrochemistry and battery science, including thin electrode designs, such as thin film electrode configurations. Electrodes are manufactured as disclosed herein and as known in the art, including as disclosed in, for example
  • the electrode is typically fabricated by depositing a slurry of the electrode material, an electrically conductive inert material, the binder, and a liquid carrier on the electrode current collector, and then evaporating the carrier to leave a coherent mass in electrical contact with the current collector.
  • Electrode potential refers to a voltage, usually measured against a reference electrode, due to the presence within or in contact with the electrode of chemical species at different oxidation (valence) states.
  • Electrode refers to an ionic conductor which can be in the solid state, the liquid state (most common) or more rarely a gas (e.g., plasma). In the context of an electrochemical cell, the electrolyte provides ionic conductivity between two or more electrodes of an electrochemical cell.
  • Lewis acid refers to a substance which, in solution, is able to generate a cation or combine with an anion, and/or a molecule which can accept a pair of electrons and form a coordinate covalent bond.
  • Useful classes of Lewis acids include, but are not limited to, inorganic fluorides, inorganic chlorides, inorganic carbonates, and inorganic oxides. Examples of inorganic fluoride Lewis acids are BF 3 , PF 5 , SbF 5 , and AsF 5 . Examples of inorganic chloride Lewis acids are AICI 3 , SnCI 4 , FeCI 3 , NbCI 5 , TiCI 4 , and ZnCI 2 .
  • Lewis base refers to a substance which, in solution, is able to generate an anion or combine with a cation, and/or a molecule or ion that can form a coordinate covalent bond by donating a pair of electrons.
  • Useful classes of Lewis bases include, but are not limited to, inorganic fluorides, inorganic chlorides, inorganic carbonates, and inorganic oxides. Examples of inorganic chloride Lewis bases are AICI 4 " , CIO 4 " , and SnCI 6 2" . Examples of inorganic fluoride Lewis bases are BF 4 " , PF 6 " , and AsF 6 " .
  • Lewis acid precursor or “precursor” and “Lewis base precursor” or “precursor” refers to a substance which is able to generate Lewis acids and/or Lewis bases when introduced into a solvent and/or solution.
  • Lewis acid/base precursors are LiPF 6 , LiBF 4 , LiAsF 6 , LiCIO 4 , LiSnCI 5 , LiAICI 4 , LiFeCI 4 , LiNbCI 6 , LiTiCI 5 , LiZnCI 3 , NaPF 6 , NaBF 4 , NaAsF 6 , NaCIO 4 , NaSnCI 5 , NaAICI 4 , NaFeCI 4 , NaNbCI 6 , NaTiCI 5 , NaZnCI 3 , KPF 6 , KBF 4 , KAsF 6 , KCIO 4 , KSnCI 5 , KAICI 4 , KFeCI 4 , KNbCI 6 , KTiCI 5 ,
  • anion receptor refers to a molecule or ion which can bind or otherwise take up an anion.
  • useful classes of anion receptors include, but are not limited to, fluorinated and semifluorinated borate compounds, fluorinated and semifluorinated boronate compounds, fluorinated and semifluorinated boranes, Lewis acids, cyclic polyammonium compounds, guanidiniums, calixarene compounds, aza-ether compounds, quaternary ammonium, amine, and imidazolinium based receptors, mercury metallacycles, and silicon containing cages and macrocycles.
  • Examples of cyclic polyammonium anion receptors include polyammonium macrocycles, polyammonium macrobicycles, polyammonium macrothcycles, azacrown compounds, protonated tetra-, penta- and hexaamines.
  • Examples of calixarene compounds include cobaltocenium-based receptors, ferrocene-based receptors, ⁇ -metallated cationic hosts, calix[4]arenes, and calix[6]arenes.
  • Examples of aza-ether anion receptors include linear aza-ethers, multi- branched aza-ethers, and cyclic aza-crown ethers.
  • mercury metallacycle anion receptors include mercuracarborands and perfluoro-o-phenylenemercury metallacycles.
  • anion receiving silicon-containing cages and macrocycles include silsesquioxane cages and crown silanes.
  • Other examples of useful anion receptors can generally be found in the art [See, e.g., Dietrich, Pure & Appl. Chem., VoI 65, No. 7, pp. 1457-1464, 1993; U.S. Pat. No. 5,705,689; U.S. Pat. No. 6,120,941 ; Matthews and Beer, Calixarene Anion Receptors, in Calixarenes 2001 , pp.
  • cation receptors include, but are not limited to, crown ethers, Lewis bases, and other cation complexing agents.
  • crown ether cation receptors include, but are not limited to, Benzo-15-crown-5, 15-Crown-5, 18-Crown-6, Cyclohexyl-15-crown-5, Dibenzo-18-crown-6, Dicyclohexyl-15-crown-6, Di-t- butyldibenzo-18-crown-6, 4,4r(5r)-Di-tert-butyldibenzo-24-crown-8, 4-Aminobenzo-15- Crown-5, Benzo-15-Crown-5, Benzo-18-crown-6, 4-tert-Butylbenzo-15-crown-5, 4-tert- Butylcyclohexano-15-crown-5, 18-Crown-6, Cyclohexano-15-crown-5, Di-2,3-naph
  • Dissociating agent and “dissociation agent” are used synonymously and refer to a compound added to a solution, solvent, and/or electrolyte to increase the solubility and/or dissolution of a salt.
  • Dissociating agents of the present invention are useful for increasing the dissolution of inorganic fluorides, particularly inorganic fluorides, generally regarded to be relatively insoluble, such as LiF.
  • the present invention provides methods for generating solutions containing large concentrations of dissolved fluoride salts which are generally regarded as insoluble.
  • the present invention provides solutions, solvents, and electrolytes containing large concentrations of dissolved fluoride salts which are generally regarded as insoluble.
  • compounds are provided to the solutions, solvents, and electrolytes which facilitate dissolution of the fluoride salts. These compounds can be regarded as dissolution, dissolving, dissociating, or dissociation agents, since they provide a means for dissolving normally insoluble compounds.
  • the fluoride salts are present as solutes in solution at concentrations much larger than that which occurs at a natural equilibrium in a solution that does not contain the dissociating agents.
  • the fluoride salts are a minor solute component. In another embodiment, the fluoride salts are the most abundant solute present in the solution, solvent, or electrolyte.
  • the present invention provides additives and methods for dissolving element fluorides (MF n ) such as LiF.
  • MF n element fluorides
  • organic solutions of lithium salts (LiX), such as LiPF 6 , LiBF 4 , LiAsF 6 and LiCIO 4 , in carbonate or gamma butyro- lactone ( ⁇ -BL) based liquid solvents dissolve a significant amount LiF, whereas, the same solvents without the presence of the LiX salt do not appreciably dissolve LiF.
  • compositions of the present invention also provide a new family of electrolytes for lithium batteries applications containing LiF dissolved at significant solubilities in nonaqueous organic solvents.
  • Example 1 Electrolytes and Dissociating Agents for Electrochemical Cells
  • electrolytes of the present invention were prepared and integrated into lithium electrochemical cells.
  • the electrolytes evaluated comprise LiF and an appropriate dissociating agent dissolved in a selected nonaqueous organic solvent or combination of nonaqueous organic solvents.
  • the electronic performance of the electrochemical cells was evaluated to demonstrate the beneficial chemical and physical properties of electrolytes of the present invention.
  • Electrochemical tests Coin cells were created in a dry box, consisting of a metallic lithium disc (negative pole), a polypropylene microporous separator wet with 'electrolyte', and a composite electrode (positive pole). Two types of composite cathode electrodes were used: a graphite based electrode and a graphite fluoride based electrode.
  • the 'electrolyte' is either the LiPF 6 in EC-DMC mother solution or the LiF dissolved in LiPF 6 in EC-DMC mother solution.
  • [083] 3a) graphite based cells The cells were first discharged under a constant current of 10 mA/g-graphite to 250 mV. The 250 mV vs. Li + /Li Potential was chosen between that of the first passivation (solid electrolyte interphase: SEI formation usually at >500 mV vs. Li + /Li) and that of the lithium intercalation (usually at ⁇ 200 mV vs. Li7U). The cells were then charged to 5V vs. Li + /Li under the same 10 mA/g-graphite rate. A constant 5V was then applied for several hours to further charge. The cells were then allowed to rest for several hours and were then discharged to 3V under the same 10 mA/g-graphite rate. Following this, the cells were cycled between 3V and 5V several times under the same procedure described above.
  • solid electrolyte interphase SEI formation usually at >500 mV vs. Li + /Li
  • the cells were then charged to 4.8V and to 5.0V and allowed to rest for several hours the same constant voltage was applied ( 4.8 or 5.0V) for several hours to further charge.
  • the cells were discharged to 3V and then recharged to 4.8 V or 5.0 V following the same procedure described above.
  • Figure 1 provides a comparative (normalized) discharge profile of Li/electrolyte/graphite-based electrode cells with LiF-containing and LiF-free electrolytes consisting of 1 M LiPF 6 solution in EC-DMC.
  • Figure 1 shows the voltage versus discharge/charge ratio of the graphite based cells using mother solution electrolyte (no LiF) and LiF dissolved in mother electrolyte (LiF) with charge voltage up to 4.8V.
  • Figure 2 shows a cyclic voltammogram obtained with the Li/0.5M LiF+1 M LiPF 6 in EC-DMC/graphite cell, obtained between 2.1 and 4.8 V under a 15mV/min sweeping rate. Visible in Figure 2 are oxidation and reduction peaks corresponding to the intercalation and de-intercalation of the negatively charged species into graphite. These positive current (oxidation) peaks and negative current peaks (reduction) peaks correspond to reversible charging and discharging of the cell. The peaks may be associated with negatively charged species (or anions) intercalation and de- intercalation, respectively.
  • LiF containing electrolyte solutions show enhanced electrochemical performances of electrode materials for batteries applications such as those based on pure graphite or graphite fluoride positive electrodes. Dissolution of many insoluble element fluorides can be achieved using the same principle of 'mother solution' electrolytes.
  • FIG. 1 Two fluorinated carbon electrode (CF 0 125) lithium half cells were prepared.
  • One cell contained an electrolyte of 1 M LiPF 6 in propylene carbonate (PC); the other cell contained an electrolyte of 1 M LiF and 1 M 12-crown-4 in PC.
  • the crown ether acts as a cation receptor to allow LiF to dissolve in the PC.
  • the cells were cycled between about 3.2V and 5.5V at a rate of 1 mV/s.
  • Figure 4 depicts the current provided by the cell containing LiPF 6 during a charge/discharge cycle and shows no clear oxidation or reduction peaks. This cell has a much higher charge capacity than discharge, indicating a large irreversibility.
  • Figure 5 depicts the current provided by the cell containing LiF during a charge/discharge cycle and shows oxidation peaks at about 3.6V and 4.15V and a reduction peak at about 4 V. This cell has similar charge and discharge capacities, indicating good reversibility.
  • Table 2 provides a summary of experimental conditions useful for making fluorides solutions of the present invention from a variety of fluoride salts, including NH 4 F, NaF, KF, MgF 2 and AIF 3 .
  • isotopic variants of compounds disclosed herein are intended to be encompassed by the disclosure.
  • any one or more hydrogens in a molecule disclosed can be replaced with deuterium or tritium.
  • Isotopic variants of a molecule are generally useful as standards in assays for the molecule and in chemical and biological research related to the molecule or its use. Methods for making such isotopic variants are known in the art. Specific names of compounds are intended to be exemplary, as it is known that one of ordinary skill in the art can name the same compounds differently.
  • ionizable groups [groups from which a proton can be removed (e.g., -COOH) or added (e.g., amines) or which can be quaternized (e.g., amines)]. All possible ionic forms of such molecules and salts thereof are intended to be included individually in the disclosure herein.
  • salts of the compounds herein one of ordinary skill in the art can select from among a wide variety of available countehons those that are appropriate for preparation of salts of this invention for a given application. In specific applications, the selection of a given anion or cation for preparation of a salt may result in increased or decreased solubility of that salt.

Abstract

La présente invention concerne des compositions, des formulations et des procédés fournissant une dissolution efficace de fluorures inorganiques dans des solvants par l'incorporation d'un composant agent dissociant. Les agents dissociants de la présente invention participent à des réactions chimiques en solution, telles que la formation de complexes, à des réactions acido-basiques et à des réactions de formation d'adduits, qui résultent en une augmentation de la dissolution de fluorures inorganiques dans une variété d'environnements de solvants. L'invention concerne également des agents dissociants comprenant les acides de Lewis, les bases de Lewis, les récepteurs d'anions, les récepteurs de cations ou des combinaisons de ceux-ci qui augmentent significativement la portée de la dissolution d'une variété de fluorures inorganiques, en particulier les fluorures inorganiques, tels que le LiF, qui sont hautement insolubles dans nombre de solvants en l'absence des agents dissociants de la présente invention.
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EP2054961A2 (fr) 2009-05-06
EP2054961A4 (fr) 2012-02-29
JP2010500725A (ja) 2010-01-07
KR20090064382A (ko) 2009-06-18
CA2660449A1 (fr) 2008-09-04

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