Classifications

• • H—ELECTRICITY
  • H01—ELECTRIC ELEMENTS
  • H01M—PROCESSES OR MEANS, e.g. BATTERIES, FOR THE DIRECT CONVERSION OF CHEMICAL ENERGY INTO ELECTRICAL ENERGY
  • H01M10/00—Secondary cells; Manufacture thereof
  • H01M10/05—Accumulators with non-aqueous electrolyte
  • H01M10/056—Accumulators with non-aqueous electrolyte characterised by the materials used as electrolytes, e.g. mixed inorganic/organic electrolytes
• • H—ELECTRICITY
  • H01—ELECTRIC ELEMENTS
  • H01M—PROCESSES OR MEANS, e.g. BATTERIES, FOR THE DIRECT CONVERSION OF CHEMICAL ENERGY INTO ELECTRICAL ENERGY
  • H01M10/00—Secondary cells; Manufacture thereof
  • H01M10/05—Accumulators with non-aqueous electrolyte
  • H01M10/054—Accumulators with insertion or intercalation of metals other than lithium, e.g. with magnesium or aluminium
• • C—CHEMISTRY; METALLURGY
  • C01—INORGANIC CHEMISTRY
  • C01B—NON-METALLIC ELEMENTS; COMPOUNDS THEREOF; METALLOIDS OR COMPOUNDS THEREOF NOT COVERED BY SUBCLASS C01C
  • C01B6/00—Hydrides of metals including fully or partially hydrided metals, alloys or intermetallic compounds ; Compounds containing at least one metal-hydrogen bond, e.g. (GeH3)2S, SiH GeH; Monoborane or diborane; Addition complexes thereof
  • C01B6/06—Hydrides of aluminium, gallium, indium, thallium, germanium, tin, lead, arsenic, antimony, bismuth or polonium; Monoborane; Diborane; Addition complexes thereof
  • C01B6/10—Monoborane; Diborane; Addition complexes thereof
  • C01B6/13—Addition complexes of monoborane or diborane, e.g. with phosphine, arsine or hydrazine
  • C01B6/15—Metal borohydrides; Addition complexes thereof
  • C01B6/19—Preparation from other compounds of boron
  • C01B6/21—Preparation of borohydrides of alkali metals, alkaline earth metals, magnesium or beryllium; Addition complexes thereof, e.g. LiBH4.2N2H4, NaB2H7
• • H—ELECTRICITY
  • H01—ELECTRIC ELEMENTS
  • H01M—PROCESSES OR MEANS, e.g. BATTERIES, FOR THE DIRECT CONVERSION OF CHEMICAL ENERGY INTO ELECTRICAL ENERGY
  • H01M10/00—Secondary cells; Manufacture thereof
  • H01M10/05—Accumulators with non-aqueous electrolyte
  • H01M10/056—Accumulators with non-aqueous electrolyte characterised by the materials used as electrolytes, e.g. mixed inorganic/organic electrolytes
  • H01M10/0564—Accumulators with non-aqueous electrolyte characterised by the materials used as electrolytes, e.g. mixed inorganic/organic electrolytes the electrolyte being constituted of organic materials only
  • H01M10/0566—Liquid materials
  • H01M10/0567—Liquid materials characterised by the additives
• • H—ELECTRICITY
  • H01—ELECTRIC ELEMENTS
  • H01M—PROCESSES OR MEANS, e.g. BATTERIES, FOR THE DIRECT CONVERSION OF CHEMICAL ENERGY INTO ELECTRICAL ENERGY
  • H01M10/00—Secondary cells; Manufacture thereof
  • H01M10/05—Accumulators with non-aqueous electrolyte
  • H01M10/056—Accumulators with non-aqueous electrolyte characterised by the materials used as electrolytes, e.g. mixed inorganic/organic electrolytes
  • H01M10/0564—Accumulators with non-aqueous electrolyte characterised by the materials used as electrolytes, e.g. mixed inorganic/organic electrolytes the electrolyte being constituted of organic materials only
  • H01M10/0566—Liquid materials
  • H01M10/0568—Liquid materials characterised by the solutes
• • H—ELECTRICITY
  • H01—ELECTRIC ELEMENTS
  • H01M—PROCESSES OR MEANS, e.g. BATTERIES, FOR THE DIRECT CONVERSION OF CHEMICAL ENERGY INTO ELECTRICAL ENERGY
  • H01M10/00—Secondary cells; Manufacture thereof
  • H01M10/05—Accumulators with non-aqueous electrolyte
  • H01M10/056—Accumulators with non-aqueous electrolyte characterised by the materials used as electrolytes, e.g. mixed inorganic/organic electrolytes
  • H01M10/0564—Accumulators with non-aqueous electrolyte characterised by the materials used as electrolytes, e.g. mixed inorganic/organic electrolytes the electrolyte being constituted of organic materials only
  • H01M10/0566—Liquid materials
  • H01M10/0569—Liquid materials characterised by the solvents
• • H—ELECTRICITY
  • H01—ELECTRIC ELEMENTS
  • H01M—PROCESSES OR MEANS, e.g. BATTERIES, FOR THE DIRECT CONVERSION OF CHEMICAL ENERGY INTO ELECTRICAL ENERGY
  • H01M2220/00—Batteries for particular applications
  • H01M2220/20—Batteries in motive systems, e.g. vehicle, ship, plane
• • 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
• • 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
• • 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
  • H01M2300/0045—Room temperature molten salts comprising at least one organic ion
• • Y—GENERAL TAGGING OF NEW TECHNOLOGICAL DEVELOPMENTS; GENERAL TAGGING OF CROSS-SECTIONAL TECHNOLOGIES SPANNING OVER SEVERAL SECTIONS OF THE IPC; TECHNICAL SUBJECTS COVERED BY FORMER USPC CROSS-REFERENCE ART COLLECTIONS [XRACs] AND DIGESTS
  • Y02—TECHNOLOGIES OR APPLICATIONS FOR MITIGATION OR ADAPTATION AGAINST CLIMATE CHANGE
  • Y02E—REDUCTION OF GREENHOUSE GAS [GHG] EMISSIONS, RELATED TO ENERGY GENERATION, TRANSMISSION OR DISTRIBUTION
  • Y02E60/00—Enabling technologies; Technologies with a potential or indirect contribution to GHG emissions mitigation
  • Y02E60/10—Energy storage using batteries

Definitions

• the invention relates to electrolytes and more particularly to electrolytes for magnesium batteries.
• Rechargeable batteries such as lithium-ion batteries
• Capacity density is an important characteristic, and higher capacity densities are desirable for a variety of applications.
• a magnesium ion in a magnesium or magnesium-ion battery carries two electrical charges, in contrast to the single charge of a lithium ion. Improved electrolyte materials would be very useful in order to develop high capacity density batteries.
• the electrolyte also includes a solvent, the magnesium salt being dissolved in the solvent.
• solvents including aprotic solvents and molten salts such as ionic liquids may be utilized.
• the electrolyte also includes a solvent, the magnesium salt being dissolved in the solvent.
• solvents including aprotic solvents and molten salts such as ionic liquids may be utilized.
• the electrolyte also includes a solvent, the magnesium salt being dissolved in the solvent.
• solvents including aprotic solvents and molten salts such as ionic liquids may be utilized.
• a magnesium battery that includes a magnesium metal containing anode.
• the electrolyte also includes a solvent. The magnesium salt being dissolved in the solvent.
• the battery also includes a cathode separated from the anode. Magnesium cations are reversibly stripped and deposited between the anode and cathode.
• a magnesium battery that includes a magnesium metal containing anode.
• the electrolyte also includes a solvent.
• the magnesium salt being dissolved in the solvent.
• the battery also includes a cathode separated from the anode. Magnesium cations are reversibly stripped and deposited between the anode and cathode.
• a magnesium battery that includes a magnesium metal containing anode.
• the electrolyte also includes a solvent.
• the magnesium salt being dissolved in the solvent.
• the battery also includes a cathode separated from the anode. Magnesium cations are reversibly stripped and deposited between the anode and cathode.
• the electrolyte also includes a solvent, the magnesium salt being dissolved in the solvent.
• Various solvents including aprotic solvents and molten salts such as ionic liquids may be utilized.
• a magnesium battery that includes a magnesium metal containing anode.
• the electrolyte also includes a solvent.
• the magnesium salt being dissolved in the solvent.
• the battery also includes a cathode separated from the anode. Magnesium cations are reversibly stripped and deposited between the anode and cathode.
• a method of forming an electrolyte material for a magnesium battery that includes the steps of: providing a borane material; providing a magnesium borohydride material; combining the borane and magnesium borohydride material forming a combined mixture; adding an aprotic solvent to the combined mixture forming a combined solvent mixture; heating the combined solvent mixture under reflux; and removing the aprotic solvent forming an electrolyte material.
• Figure 1 is a diagram of 0.5 M Mg(BH 4 ) 2 /THF showing (a) Cyclic voltammetry (8 cycles) with the inset showing deposition/stripping charge balance (3 cycle) (b) XRD results following galvanostatic deposition of Mg on a Pt working electrode, (c) Cyclic voltammetry for 0.1 M Mg(BH 4 ) 2 /DME compared to 0.5 M Mg(BH 4 ) 2 /THF with the inset showing deposition/stripping charge balance for Mg(BH 4 ) 2 /DME;
• Figure 2 is a diagram of Mg(BH 4 ) 2 in THF and DME: (a) IR Spectra, (b) U B NMR, and (c) 1H NMR;
• Figure 3 is a diagram of LiBH 4 (.6 M)/ Mg(BH 4 ) 2 (.18 M) in DME: (a) cyclic voltammetry with the inset showing deposition/stripping charge balance, (b) XRD results following galvanostatic deposition of Mg on a Pt disk and (c) IR spectra ( I ) indicates band maxima for Mg(BH 4 ) 2 /DME); [0019] Figure 4 is a diagram of Charge/discharge profiles with Mg anode/Chevrel phase cathode for 3.3:1 molar LiBH 4 / Mg(BH 4 ) 2 in DME;
• novel electrolyte for an Mg battery.
• the novel electrolyte allows electrochemical reversible Mg deposition and stripping in a halide-free inorganic salt.
• electrolytes may include magnesium salts such MgBH 4 , MgBnHn, MgBi 2 Hi 2 , MgB 2 H 8 , MgB 2 H 2 F 6 , MgB 2 H 4 F 4 , MgB 2 H 6 F 2 MgB 2 0-alkyl 8 , MgB 2 H 2 0-alkyl 6 , MgB 2 H 4 0-alkyl 4 , MgB 2 H 6 0-alkyl 2 , MgBHF 3 , MgBH 2 F 2 , MgBH 3 F and MgBO-alkyl.
• the electrolyte also includes a solvent, the magnesium salt being dissolved in the solvent.
• aprotic solvents may include, for example solvents such as tetrahydrofuran (THF) and dimethoxyethane (DME).
• aprotic solvents include: dioxane, triethyl amine, diisopropyl ether, diethyl ether, t-butyl methyl ether (MTBE), 1,2-dimethoxyethane (glyme), 2-methoxyethyl ether (diglyme), tetraglyme, and polyethylene glycol dimethyl ether.
• the magnesium salt may have a molarity of from .01 to 4 molar.
• the electrolyte may further include a chelating agent.
• a chelating agent including glymes and crown ethers may be utilized.
• the chelating agent may be included to increase the current and lower the over-potential of a battery that includes the electrolyte.
• the electrolyte may further include acidic cation additives increasing the current density and providing a high coulombic efficiency.
• acidic cation additives include lithium borohydride, sodium borohydride and potassium borohydride.
• the acidic cation additives may be present in an amount of up to five times the amount in relation to MgB a H b X y.
• the magnesium salt is dissolved in the solvent.
• solvents including aprotic solvents and molten salts such as ionic liquids may be utilized.
• Aprotic solvents may include, for example solvents such as tetrahydrofuran (THF) and dimethoxyethane (DME).
• aprotic solvents include: dioxane, triethyl amine, diisopropyl ether, diethyl ether, t-butyl methyl ether (MTBE), 1,2-dimethoxyethane (glyme), 2-methoxyethyl ether (diglyme), tetraglyme, and polyethylene glycol dimethyl ether.
• the magnesium salt may have a molarity of from .01 to 4 molar.
• the electrolyte may further include a chelating agent.
• a chelating agent including glymes and crown ethers may be utilized.
• the chelating agent may be included to increase the current and lower the over-potential of a battery that includes the electrolyte.
• the electrolyte may further include acidic cation additives increasing the current density and providing a high coulombic efficiency.
• acidic cation additives include lithium borohydride, sodium borohydride and potassium borohydride.
• the acidic cation additives may be present in an amount of up to five times the amount in relation to MgB 2 H b X y.
• the magnesium salt is dissolved in the solvent.
• Various solvents including aprotic solvents and molten salts such as ionic liquids may be utilized.
• Aprotic solvents may include, for example solvents such as tetrahydrofuran (THF) and dimethoxyethane (DME) as well as the above described solvents.
• the magnesium salt may have a molarity of from .01 to 4 molar.
• the electrolyte may further include a chelating agent.
• a chelating agent including monoglyme may be utilized.
• the chelating agent may be included to increase the current and lower the over-potential of a battery that includes the electrolyte.
• the electrolyte may further include acidic cation additives increasing the current density and providing a high coulombic efficiency.
• acidic cation additives include lithium borohydride, sodium borohydride and potassium borohydride.
• the acidic cation additives may be present in an amount of up to five times the amount in relation to MgB a H b.
• the electrolyte may also include the chelating agents and acidic cation additives as described above.
• the electrolyte may also include the chelating agents and acidic cation additives as described above.
• the electrolyte may also include the chelating agents and acidic cation additives as described above.
• the anode may include magnesium metal anodes.
• the cathode may include various materials that show an electrochemical reaction at a higher electrode potential than the anode. Examples of cathode materials include transition metal oxides, sulfides, fluorides, chlorides or sulphur and Chevrel phase materials such as Mo 6 S8.
• the battery includes magnesium cations that are reversibly stripped and deposited between the anode and cathode.
• Magnesium borohydride (Mg(BH 4 ) 2 ,95%), lithium borohydride (LiBH 4 ,90%), anhydrous tetrahydrofuran (THF) and dimethoxyethane (DME) were purchased from Sigma- Aldrich. The various components were mixed to provide the specified molar electrolyte solutions. Cyclic voltammetry testing was conducted in a three-electrode cell with an Mg wire/ribbon as reference/counter electrodes. The electrochemical testing was conducted in an argon filled glove box with 0 2 and H 2 0 amounts kept below 0.1 ppm.
• Mg deposition and stripping was performed for Mg(BH 4 ) 2 in ether solvents.
• Figure la shows the cyclic voltammogram obtained for 0.5 M Mg(BH 4 ) 2 /THF where a reversible reduction/oxidation process took place with onsets at -0.6 V/0.2 V and a 40% coulombic efficiency, as shown in Figure la inset, indicating reversible Mg deposition and stripping.
• X-ray diffraction (XRD) of the deposited product following galvanostatic reduction from the above solution as shown in Figure lb denotes that the deposited product is hexagonal Mg.
• the deposition of the hexagonal magnesium demonstrates the compatibility of the electrolyte, Mg(BH 4 ) 2 with Mg metal.
• the electrochemical oxidative stabilities measured on platinum, stainless steel and glassy carbon electrodes were 1.7, 2.2 and 2.3 V, respectively. These results denote that Mg(BH 4 ) 2 is electrochemically active in THF such that ionic conduction and reversible magnesium deposition and stripping utilizing the electrolyte occurs.
• IR and NMR spectroscopic analyses as shown in Figure 2 were conducted for 0.5 M Mg(BH 4 ) 2 /THF and 0.1 M Mg(BH 4 ) 2 /DME to characterize the magnesium electroactive species.
• the IR B-H stretching region (2000-2500 cm “1 ) reveals two strong widely separated vibrations (Mg(BH 4 ) 2 /THF: 2379 cm “1 , 2176 cm “1 and Mg(BH 4 ) 2 /DME: 2372 cm “1 , 2175 cm “ l ).
• the spectra for 0.1M DME and 0.5 M in THF are similar.
• Mg ⁇ -H ⁇ BH ⁇ may further dissociate:
• the electrolyte may include an acidic cation additive.
• the acidic cation additive may include the following characteristics: (1) a reductive stability comparable to Mg(BH 4 ) 2 , (2) non-reactive, (3) halide free and (4) soluble in DME.
• One such material that includes these properties is LiBH 4 .
• Mg deposition and stripping was performed in DME using various molar ratios of LiBH 4 to Mg(BH 4 ) 2. As shown in Figure 3a cyclic voltammetry data was obtained for 3.3:1 molar LiBH 4 to Mg(BH 4 ) 2 .
• a magnesium battery was tested using an electrolyte for 3.3:1 molar LiBH 4 to
• the cathode of the test battery included a cathode active material having a
• the anode for the test battery included an Mg metal anode.
• the test battery demonstrated reversible cycling capabilities at a 128.8 mA g "1 rate.
• the charge and discharge curves indicate reversible cycling of a magnesium ion.
• a mixture of 5.0 g (0.0409 mol) decaborane (B10H14) and 2.43 g (0.0450 mol, 1.1 eq.) magnesium borohydride (Mg(BH 4 ) 2 ) is prepared in a 100 ml Schlenk flask inside an argon filled glovebox. The flask is transferred from the glovebox to a nitrogen Schlenk- line and fitted with a reflux condenser. To this is added 50 ml Diglyme (C 6 H 14 O 3 ) via cannula transfer. Upon solvent addition, vigorous gas evolution begins, and a yellow homogeneous solution is formed. When gas evolution has ceased, the mixture is slowly heated to reflux using a silicon oil bath.
• Mg(BH 4 ) 2 magnesium borohydride
• the mixture is held at reflux for 5 days before being allowed to cool to room temperature. Following cooling, the solvent is removed under vacuum to give a pale yellow solid.
• the crude product obtained at this stage may be purified by dissolving in a minimal amount of hot (120 C) DMF. The resulting solution is allowed to cool to room temperature, and a colorless precipitate is observed which is isolated by filtration.
• the product as synthesized was subjected to electrochemical testing.
• the electrochemical testing procedure included cyclic voltammetry collected using a 3-electrode cell in which the working electrode was platinum and both the counter and reference electrodes were magnesium.
• a plot of the electrochemical testing data is shown in Figure 6 as a plot of the current density as a function of the Potential.
• the synthesized product is stable against both electrochemical reduction (> -2 V vs. Mg) and oxidation (> 3 V vs. Mg).
• the synthesized compound will allow a magnesium battery utilizing the synthesized compound as an electrolyte to operate at a high voltage necessary to achieve sufficient energy density for use in numerous applications such as in automotive applications.

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  • 2013-08-01 US US13/956,993 patent/US20140038037A1/en not_active Abandoned
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