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WO2014140700A1 - Procédés de production de borure de vanadium et utilisations associées - Google Patents

Procédés de production de borure de vanadium et utilisations associées Download PDF

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Publication number
WO2014140700A1
WO2014140700A1 PCT/IB2013/054119 IB2013054119W WO2014140700A1 WO 2014140700 A1 WO2014140700 A1 WO 2014140700A1 IB 2013054119 W IB2013054119 W IB 2013054119W WO 2014140700 A1 WO2014140700 A1 WO 2014140700A1
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Prior art keywords
vanadium
boride
oxide
metal
lithium
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English (en)
Inventor
Nilanjan DEB
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University of Calcutta
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University of Calcutta
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Priority to CN201380076562.8A priority Critical patent/CN105228955B/zh
Publication of WO2014140700A1 publication Critical patent/WO2014140700A1/fr
Anticipated expiration legal-status Critical
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    • C—CHEMISTRY; METALLURGY
    • C01—INORGANIC CHEMISTRY
    • C01G—COMPOUNDS CONTAINING METALS NOT COVERED BY SUBCLASSES C01D OR C01F
    • C01G31/00—Compounds of vanadium
    • C01G31/02—Oxides
    • C—CHEMISTRY; METALLURGY
    • C01—INORGANIC CHEMISTRY
    • C01B—NON-METALLIC ELEMENTS; COMPOUNDS THEREOF; METALLOIDS OR COMPOUNDS THEREOF NOT COVERED BY SUBCLASS C01C
    • C01B35/00—Boron; Compounds thereof
    • C01B35/02—Boron; Borides
    • C01B35/04—Metal borides
    • C—CHEMISTRY; METALLURGY
    • C01—INORGANIC CHEMISTRY
    • C01P—INDEXING SCHEME RELATING TO STRUCTURAL AND PHYSICAL ASPECTS OF SOLID INORGANIC COMPOUNDS
    • C01P2002/00—Crystal-structural characteristics
    • C01P2002/70—Crystal-structural characteristics defined by measured X-ray, neutron or electron diffraction data
    • C01P2002/72—Crystal-structural characteristics defined by measured X-ray, neutron or electron diffraction data by d-values or two theta-values, e.g. as X-ray diagram
    • C—CHEMISTRY; METALLURGY
    • C01—INORGANIC CHEMISTRY
    • C01P—INDEXING SCHEME RELATING TO STRUCTURAL AND PHYSICAL ASPECTS OF SOLID INORGANIC COMPOUNDS
    • C01P2002/00—Crystal-structural characteristics
    • C01P2002/80—Crystal-structural characteristics defined by measured data other than those specified in group C01P2002/70
    • C01P2002/82—Crystal-structural characteristics defined by measured data other than those specified in group C01P2002/70 by IR- or Raman-data
    • C—CHEMISTRY; METALLURGY
    • C01—INORGANIC CHEMISTRY
    • C01P—INDEXING SCHEME RELATING TO STRUCTURAL AND PHYSICAL ASPECTS OF SOLID INORGANIC COMPOUNDS
    • C01P2004/00—Particle morphology
    • C01P2004/01—Particle morphology depicted by an image
    • C01P2004/02—Particle morphology depicted by an image obtained by optical microscopy
    • H—ELECTRICITY
    • H01—ELECTRIC ELEMENTS
    • H01M—PROCESSES OR MEANS, e.g. BATTERIES, FOR THE DIRECT CONVERSION OF CHEMICAL ENERGY INTO ELECTRICAL ENERGY
    • H01M12/00—Hybrid cells; Manufacture thereof
    • H01M12/04—Hybrid cells; Manufacture thereof composed of a half-cell of the fuel-cell type and of a half-cell of the primary-cell type
    • H—ELECTRICITY
    • H01—ELECTRIC ELEMENTS
    • H01M—PROCESSES OR MEANS, e.g. BATTERIES, FOR THE DIRECT CONVERSION OF CHEMICAL ENERGY INTO ELECTRICAL ENERGY
    • H01M4/00—Electrodes
    • H01M4/02—Electrodes composed of, or comprising, active material
    • H01M4/36—Selection of substances as active materials, active masses, active liquids
    • H01M4/58—Selection of substances as active materials, active masses, active liquids of inorganic compounds other than oxides or hydroxides, e.g. sulfides, selenides, tellurides, halogenides or LiCoFy; of polyanionic structures, e.g. phosphates, silicates or borates
    • 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

  • Electrochemical energy represents a dependable energy source and has utility as a replacement for depleting oil resources.
  • Metal borides can be used to create batteries or fuel cells, which can be alternative energy sources to oil resources.
  • Electrochemical energy storage technology with multi-electron oxidation of metal borides such as vanadium boride can be promising to replace existing batteries that are based on single electron charge storage.
  • the multiple electron oxidation of a vanadium boride anode coupled with a carbon air cathode can provide extraordinary electrochemical energy storage capacities due to its multi- electron charge storage capabilities.
  • Vanadium can be found in vanadium-bearing ores, such as titaniferous magnetite ore, where the vanadium pentoxide content may range from about 0.63 weight percent to about 1.38 weight percent. Vanadium can also be found in iron slag after smelting, where the vanadium pentoxide content may range from about 6 weight percent to about 25 weight percent. It will therefore be desirable to provide a simple method of producing vanadium boride directly from a vanadium-bearing ore or slag, and it will also be desirable that the method can be performed under ambient temperatures and pressures.
  • Embodiments described herein are directed to methods of producing metal borides, including, but are not limited to, vanadium boride.
  • a method of producing vanadium boride may comprise reducing vanadium pentoxide contained in vanadium-bearing ore, vanadium-bearing iron slag, or both, to produce vanadium (III) oxide; reducing the vanadium (III) oxide to vanadium (II) oxide; forming a vanadium nanoparticle; and forming vanadium boride from the vanadium nanoparticle.
  • a method of producing vanadium boride may comprise: reducing vanadium pentoxide contained in vanadium-bearing ore, vanadium-bearing iron slag, or both, to produce a vanadium nanoparticle; and forming vanadium boride from the vanadium nanoparticle.
  • a method of producing a metal boride may comprise: reducing a metal oxide contained in metal bearing ore, metal bearing iron slag, or both, to produce a metal nanoparticle; and forming a metal boride from the metal nanoparticle.
  • Figure 1 depicts the X-ray diffraction (XRD) of vanadium boride produced from vanadium chloride.
  • Figure 2 depicts the X-ray diffraction (XRD) of vanadium boride produced from vanadium bearing magnetite ore.
  • Figure 3 depicts the X-ray diffraction (XRD) of vanadium boride produced from vanadium bearing iron slag.
  • Figure 4 depicts the Fourier transform infrared spectroscopy (FTIR) of vanadium boride produced from vanadium chloride.
  • FTIR Fourier transform infrared spectroscopy
  • Figure 5 depicts the Fourier transform infrared spectroscopy (FTIR) of vanadium boride produced from vanadium bearing magnetite ore.
  • FTIR Fourier transform infrared spectroscopy
  • Figure 6 depicts the Fourier transform infrared spectroscopy (FTIR) of vanadium boride produced from vanadium bearing iron slag.
  • FTIR Fourier transform infrared spectroscopy
  • Figure 7 depicts the in-situ formation of vanadium boride crystals from vanadium bearing iron slag
  • Figure 8 depicts various shapes and sizes of vanadium boride crystals produced by the methods described herein.
  • Figure 9 depicts iron oxide coated vanadium boride crystals.
  • Embodiments described herein are directed to methods of producing metal borides including, but are not limited to, vanadium boride from metal-containing ores and iron slag.
  • the metal oxides produced by the methods described herein can have multiple applications including, but are not limited to, their uses in batteries.
  • components may be added in a single batch, in multiple portions, or continuously.
  • a method of producing vanadium boride may include: reducing vanadium pentoxide contained in vanadium-bearing ore, vanadium-bearing iron slag, or both, to produce vanadium (III) oxide; reducing the vanadium (III) oxide to vanadium (II) oxide; forming a vanadium nanoparticle; and forming vanadium boride from the vanadium nanoparticle.
  • the vanadium-bearing ore may generally be any vanadium-bearing ore, and for example can be titaniferous magnetite ore, oxidized patronite, vanadinite, carnotite, or a combination thereof.
  • Vanadium is naturally found in a number of vanadium-bearing ores in the form of vanadium pentoxide (V 2 O 5 ).
  • the amount of vanadium pentoxide in titaniferous magnetite ore may often range from about 0.63% to about 1.38% by weight, and the amount of vanadium pentoxide in iron slag after smelting may often range from about 6% to about 25% by weight.
  • the ore and slag may generally contain any concentration of vanadium and vanadium pentoxide.
  • the vanadium-bearing ore may contain less than about 2% vanadium pentoxide by weight.
  • the vanadium-bearing iron slag may contain less than about 25% vanadium pentoxide by weight.
  • the reducing of the vanadium pentoxide to vanadium (III) oxide can be performed using a catalytic reduction process or a non-catalytic reduction process.
  • reducing the vanadium pentoxide may include contacting the vanadium pentoxide contained in a mixture or solution of the vanadium-bearing ore, vanadium-bearing iron slag, or both, with vanadium tetrachloride.
  • the vanadium tetrachloride may function as a catalytic reagent in the catalytic reduction process.
  • the vanadium tetrachloride may be obtained commercially, or can be prepared by various methods, including being prepared by combining vanadium pentoxide with hydrochloric acid.
  • the vanadium-bearing ore, the vanadium-bearing iron slag, or both may be combined with at least one solvent to form a mixture or solution before contacting with the vanadium tetrachloride.
  • the solvent may be added after contacting the vanadium pentoxide with the vanadium tetrachloride.
  • reducing the vanadium pentoxide may further include contacting the vanadium pentoxide and the vanadium tetrachloride with at least one solvent.
  • the vanadium- bearing ore, vanadium-bearing iron slag or both may be milled or otherwise processed into a powder followed by mixing with at least one solvent prior to being used in the methods described herein.
  • the finer the vanadium-bearing ore, vanadium- bearing iron slag or both the greater the reactivity.
  • the solvent may be water, ethanol, isopropanol, methanol, or a combination thereof.
  • the solvent may be a mixture of at least two of water, ethanol, isopropanol, and methanol.
  • the solvent may be a mixture of water and ethanol.
  • the water and ethanol may be present in the mixture in a ratio of about 1 to 2 by volume.
  • the mixture or solution may be formed by grinding titaniferous magnetite ore to a powder and mixing with deionized water to produce a 10% titaniferous magnetite ore solution by weight.
  • iron slag may be ground to a powder and mixed with deionized water to produce a 10% iron slag solution by weight. Accordingly, the titaniferous magnetite ore solution, and the iron slag solution can be made up of up to about 25% w/v of titaniferous magnetite ore, and iron slag, respectively.
  • the titaniferous magnetite ore solution, and the iron slag solution can be made up of about 1 to about 10%> titaniferous magnetite ore, and iron slag, respectively. In some embodiments, the titaniferous magnetite ore solution, and the iron slag solution can be made up of about 1 to about 25% titaniferous magnetite ore, and iron slag, respectively. In some embodiments, the titaniferous magnetite ore solution, and the iron slag solution can be made up of greater than 25% titaniferous magnetite ore, and iron slag, respectively. These ratios, amounts, concentrations, solvents, and materials can be varied.
  • the mixture or solution of vanadium-bearing ore, vanadium-bearing iron slag or both, in the solvent, and the vanadium tetrachloride may be contacted at generally any ratio, including, for example a ratio of about 2 to 1 (v/v), to about 20 to 1 (v/v).
  • the solution and the vanadium tetrachloride may be contacted at a ratio of about 2 to 1 (v/v), about 5 to 1 (v/v), about 10 to 1 (v/v), about 15 to 1 (v/v), about 20 to 1 (v/v), and any ratio between any two of these values.
  • the reducing of the vanadium pentoxide to vanadium (III) oxide may optionally further include adding at least one reducing agent after contacting the vanadium pentoxide with vanadium tetrachloride.
  • the reducing agent can be any compound that is capable of releasing hydrogen (3 ⁇ 4) and providing the boron component in the vanadium boride.
  • reducing the vanadium pentoxide may further include adding a borohydride compound, a borate compound with hydrogen (3 ⁇ 4), or both, after contacting the vanadium pentoxide with the vanadium tetrachloride.
  • the borohydride compound may be sodium borohydride, lithium borohydride, sodium cyanoborohydride, potassium borohydride, lithium triethylborohydride, or a combination thereof.
  • the borate compound may be sodium metaborate, sodium borate, lithium metaborate, lithium borate, lithium tetraborate, or a combination thereof.
  • the reducing of the vanadium (III) oxide to vanadium (II) oxide can be performed as a catalytic reduction process or as a non-catalytic reduction process.
  • the catalytic reagent in the catalytic reduction process may be vanadium tetrachloride.
  • the vanadium tetrachloride may be from an excess of the catalytic reagent that was previously contacted with the vanadium pentoxide, or can be additionally introduced.
  • the reducing of the vanadium (III) oxide to vanadium (II) oxide can also include contacting the vanadium (III) oxide with at least one reducing agent.
  • the reducing agent can be any compound that is capable of releasing hydrogen (H 2 ) and providing the boron component in the vanadium boride.
  • reducing the vanadium (III) oxide to vanadium (II) oxide may include contacting the vanadium (III) oxide with a borohydride compound, a borate compound and hydrogen (H 2 ), or both.
  • the borate compound may be sodium metaborate, sodium borate, lithium metaborate, lithium borate, lithium tetraborate, or a combination thereof.
  • the borohydride compound may be sodium borohydride, lithium borohydride, sodium cyanoborohydride, potassium borohydride, lithium triethylborohydride, or a combination thereof.
  • the reducing agent is the borate compound and hydrogen (H 2 )
  • the borate compound and hydrogen (H 2 ) may be additionally introduced, or may formed in situ from an excess of the borohydride compound used in the reducing of the vanadium pentoxide to vanadium (III) oxide.
  • reducing the vanadium (III) oxide to vanadium (II) oxide may further include contacting the vanadium (III) oxide with hydrochloric acid, chlorine (Cl 2 ), or both.
  • the hydrochloric acid and chlorine (Cl 2 ) may be additionally introduced or may be formed in situ from the reducing of the vanadium pentoxide to vanadium (III) oxide.
  • reducing the vanadium (III) oxide to vanadium (II) oxide may include contacting the vanadium (III) oxide with sodium metaborate, hydrochloric acid, chlorine (Cl 2 ), and hydrogen (H 2 ).
  • the forming of a vanadium nanoparticle from vanadium (II) oxide may include contacting the vanadium (II) oxide with at least one reducing agent.
  • the reducing agent can be any compound that is capable of releasing hydrogen (H 2 ) and providing the boron component in the vanadium boride.
  • forming a vanadium nanoparticle may include contacting the vanadium (II) oxide with a borate compound and hydrogen (H 2 ), a borohydride compound, or both.
  • the borate compound may be sodium metaborate, sodium borate, lithium metaborate, lithium borate, lithium tetraborate, or a combination thereof.
  • the borohydride compound may be sodium borohydride, lithium borohydride, sodium cyanoborohydride, potassium borohydride, lithium triethylborohydride, or a combination thereof.
  • the reducing agent is the borate compound and hydrogen (3 ⁇ 4)
  • the borate compound and hydrogen (H 2 ) may be additionally introduced, or may formed in situ from an excess of the borohydride compound used in the reducing of the vanadium pentoxide to vanadium (III) oxide, from the reducing of the vanadium (III) oxide to vanadium (II) oxide, or both.
  • forming the vanadium nanoparticle may further include contacting the vanadium (II) oxide with hydrochloric acid, chlorine (Cl 2 ), or both.
  • the hydrochloric acid and chlorine (Cl 2 ) may be additionally introduced or may be formed in situ from the reducing of the vanadium pentoxide to vanadium (III) oxide, the reducing of the vanadium (III) oxide to vanadium (II) oxide, or both.
  • forming the vanadium nanoparticle may include contacting the vanadium (II) oxide with sodium metaborate, hydrochloric acid, chlorine (Cl 2 ), and hydrogen (H 2 ).
  • forming the vanadium boride from the vanadium nanoparticle may include contacting the vanadium nanoparticle with boric acid. In some embodiments, forming the vanadium boride from the vanadium nanoparticle may further include contacting the vanadium nanoparticle with hydrogen (H 2 ). In some embodiments, forming vanadium boride from the vanadium nanoparticle may include contacting the vanadium boride nanoparticle with boric acid and hydrogen (H 2 ).
  • the boric acid and the hydrogen (H 2 ) may be additionally introduced, or may be formed in situ from the reduction of vanadium pentoxide to vanadium (III) oxide, the reduction of vanadium (III) oxide to vanadium (II) oxide, the forming of vanadium nanoparticle from vanadium (II) oxide, or a combination thereof.
  • the vanadium nanoparticle may bond with the boron released from the boric acid to form vanadium boride in aqueous solution.
  • the method of forming vanadium boride may further include forming vanadium boride crystals.
  • forming vanadium boride crystals may include incubating the solution of the vanadium boride at about ambient temperature and pressure.
  • forming vanadium boride crystals may include incubating the solution of the vanadium boride at above ambient temperature, for example, about 40 °C to about 80 °C.
  • forming vanadium boride crystals may include incubating the solution of the vanadium boride at about 40°C to about 50°C, about 50°C to about 60°C, about 60°C to about 70°C, or about 70°C to about 80 °C. In some embodiments, forming the vanadium boride crystals may include incubating the solution of the vanadium boride at about ambient temperature and pressure for a period of time sufficient to form vanadium boride crystals.
  • forming the vanadium boride crystals may include incubating the solution of the vanadium boride at above ambient temperature, for example about 40 °C to about 80 °C, for a period of time sufficient to form vanadium boride crystals.
  • the period of time can be about 1 hour, about 2 hours, about 4 hours, about 8 hours, about 12 hours, about 24 hours, about 36 hours, about 48 hours, or ranges between any two of these values (including endpoints).
  • forming the vanadium boride crystals may further include mixing or stirring the solution.
  • the vanadium boride crystals may become visible on a surface of a reaction vessel after a period of time, such as about 2 hours from initiation of the reaction.
  • the vanadium boride crystals may also continue to be formed on the surface of the reaction vessel for a period of time, such as up to about 48 hours after initiation of the reaction.
  • the size and shape of the crystals being formed can be modulated by altering stirring speed, stirring time, the concentration of reactants, the concentration of the solvent, the type of solvent used, concentration of the reducing agent, the type of reducing agent used, the ethanol to water ratio in the reaction, the ratio of vanadium tetrachloride to vanadium bearing magnetite ore, the ratio of vanadium tetrachloride to vanadium bearing iron slag, the temperature of the reaction, the size of the reaction vessel, the shape of the reaction vessel and any combination thereof.
  • the method of forming vanadium boride may further comprise coating the vanadium boride with an iron oxide.
  • the iron oxide may be iron oxide, iron (II) oxide, iron (III) oxide, iron (II, III) oxide, or any combination thereof.
  • the iron oxide may be present in the vanadium-bearing ore and the vanadium-bearing iron slag, which forms a coating on the vanadium boride crystals.
  • the iron oxide can also be additionally introduced to coat the vanadium boride. The coating may increase the vanadium boride 's resistance to corrosion.
  • Figure 9 depicts vanadium boride crystals produced by the method described herein coated with iron oxide.
  • the method of producing vanadium boride may be performed at about ambient temperature and pressure. In some embodiments, the method of producing vanadium boride may be performed at above ambient temperature, for example about 40 °C to about 80 °C. In some embodiments, the method of producing vanadium boride may be performed at about at about 40 °C to about 50 °C, about 50 °C to about 60 °C, about 60 °C to about 70 °C, or about 70 °C to about 80 °C. In some embodiments, the method may optionally be performed in a single reaction vessel.
  • the vanadium boride When the method is performed in a single reaction vessel, the vanadium boride may be formed in situ within a reaction mixture of the vanadium-bearing ore, vanadium-bearing iron slag, or both, the vanadium tetrachloride and the reducing agent.
  • Figure 7 depicts the in situ formation of vanadium boride crystals from vanadium bearing iron slag performed in a single reaction vessel.
  • Panel A shows the vanadium boride immediately after synthesis where hydrogen gas pushes the material in an upward direction.
  • Panel B shows continued production of vanadium boride and hydrogen gas after 30 minutes.
  • Panel C shows continued production of vanadium boride after 60 minutes.
  • Panel D shows the appearance of a vanadium boride crystal on the reaction vessel wall after about 90 to 120 minutes.
  • Panel E shows additional vanadium boride crystals forming on the reaction vessel wall and release of hydrogen gas.
  • Panel F shows continued production appearance of vanadium boride crystals after 4 hours of synthesis.
  • Panel G shows continued production appearance of vanadium boride crystals after 8 hours of synthesis.
  • Panel H shows continued production appearance of vanadium boride crystals after 24 hours of synthesis. At this stage, the size of the vanadium boride crystals may increase significantly.
  • Panel I shows the increasing size of the vanadium boride crystals after 36 hours of synthesis.
  • Panel J shows the increasing size of the vanadium boride crystals after 40 hours of synthesis.
  • Panel K shows the increasing size of the vanadium boride crystals after 42 hours of synthesis due to the presence of vanadium oxide (deep green in color).
  • Panel L shows the increasing size of the vanadium boride crystals after 44 hours of synthesis.
  • Panel M shows the increasing size of the vanadium boride crystals after 46 hours of synthesis.
  • Panel N shows the vanadium boride crystals after completion of synthesis. As shown in Panel N, the vanadium boride crystals after completion of the synthesis are transparent and colorless.
  • changes in the color of the reaction mixture may be observed either by eye or by using a machine, which can indicate the conversion of vanadium tetrachloride to vanadium pentoxide, vanadium pentoxide to vanadium (III) oxide, and vanadium (III) oxide to vanadium (II) oxide.
  • the vanadium (II) oxide may be further reduced to vanadium nanoparticles, which can react with the boric acid to form vanadium boride in aqueous solution. Crystals of vanadium boride may then appear through incubating the solution under conditions as described in the disclosed embodiments.
  • the color change may be from red (VC1 4 ), to yellow (V 2 O 5 ), to blue (V 2 O 3 ), and to green (VO).
  • the color of the solution may change to white.
  • the final color may sometimes be grey due to the greyish residual materials from the ore or slag.
  • a method of producing vanadium boride may include reducing vanadium pentoxide contained in vanadium-bearing ore, vanadium-bearing iron slag, or both, to produce a vanadium nanoparticle; and forming vanadium boride from the vanadium nanoparticle.
  • reaction scheme I The reduction of vanadium (III) oxide to vanadium (II) oxide may occur in situ.
  • the sodium borohydride may dissociate into sodium metaborate and hydrogen (H 2 ).
  • the vanadium (III) oxide produced in reaction scheme (I) may be reduced to vanadium (II) oxide in the presence of the sodium metaborate and hydrogen (H 2 ) according to reaction scheme (II):
  • a vanadium nanoparticle may be formed in situ according to reaction scheme
  • Figure 1 and Figure 4 depict X-ray diffraction (XRD) and Fourier transform infrared spectroscopy (FTIR) respectively, for vanadium boride produced from vanadium tetrachloride.
  • XRD X-ray diffraction
  • FTIR Fourier transform infrared spectroscopy
  • all vanadium borides are denoted as VB 2 .
  • other vanadium borides may also be present including but not limited to V 3 B 2 , VB, V 5 B 6 , V 3 B 4 , V 2 B 3 , and VB 2 .
  • the types of vanadium boride formed may be determined by the presence of vanadium bearing magnetite ore, vanadium bearing iron slag or combinations thereof.
  • Figure 2 and Figure 5 depict X-ray diffraction (XRD) and Fourier transform infrared spectroscopy (FTIR) respectively, for vanadium boride produced from vanadium bearing magnetite ore.
  • Figure 3 and Figure 6 depict X-ray diffraction (XRD) and Fourier transform infrared spectroscopy (FTIR) respectively, for vanadium boride produced from vanadium bearing iron slag respectively.
  • all vanadium borides are denoted as VB 2 or V 2 B 3 .
  • other vanadium borides may also be present including but not limited to V 3 B 2 , VB, V 5 B 6 , V 3 B 4 , V 2 B 3 , and VB 2 .
  • the types of vanadium boride formed may be determined by the presence of vanadium bearing magnetite ore, vanadium bearing iron slag or combinations thereof.
  • FTIR Fourier transform infrared spectroscopy
  • a method of producing a metal boride may include: reducing a metal oxide contained in metal bearing ore, metal bearing iron slag or both, to produce a metal nanoparticle; and forming a metal boride from the metal nanoparticle.
  • the metal bearing ore may be titaniferous magnetite ore, oxidized patronite, vanadinite, carnotite, or a combination thereof.
  • the metal oxide may be oxides of lithium, titanium, magnesium, manganese, aluminum, zinc, iron, or a combination thereof.
  • the reducing of the metal oxide can be a catalytic reduction or non-catalytic reduction of the metal oxide to one or more intermediate metal oxides having a lower metal oxidation state than that of the metal oxide.
  • titanium dioxide Ti0 2 will be reduced to its intermediate metal oxides, dititanium trioxide Ti 2 0 3 and titanium monooxide TiO, before forming titanium nanoparticle.
  • the metal oxidation state or the oxidation state of titanium reduces from +4 in titanium dioxide, to +3 in dititanium trioxide, and to +2 in titanium monooxide.
  • the series of reduction reactions may occur in situ within a single reaction vessel.
  • reducing the metal oxide may comprise contacting the metal oxide contained in metal bearing ore, metal bearing iron slag, or both, with a metal chloride.
  • the metal chloride corresponds to the metal boride being formed.
  • the metal chloride is lithium chloride.
  • the metal chloride may function as a catalytic reagent in the catalytic reduction process.
  • the metal bearing ore, the metal bearing iron slag, or both may be in mixture or solution form before contacting with the metal chloride.
  • the solvent may be added after the metal bearing ore, the metal bearing iron slag, or both, is contacted with the metal chloride.
  • reducing the metal oxide may further comprise contacting the metal oxide and the metal chloride with a solvent.
  • the metal bearing ore, metal bearing iron slag or both may be processed or milled into a powder followed by mixing with at least one solvent prior to being used in the methods described herein.
  • the solvent may be water, ethanol, isopropanol, methanol, or a combination thereof.
  • the solvent may be a mixture containing at least two of water, ethanol, isopropanol, and methanol. In some embodiments, the solvent may be a mixture of water and ethanol. In some embodiments, the water and ethanol may be present in the mixture in a ratio of about 1 to 2 by volume.
  • the reducing of the metal oxide may occur stepwise to form one or more intermediate metal oxides, before forming the metal nanoparticle.
  • the reducing of the metal oxide to the one or more intermediate metal oxides may include contacting the metal oxide with at least one reducing agent after contacting the metal oxide with the metal chloride.
  • the reducing agent can be any compound that is capable of releasing hydrogen (H 2 ) and providing the boron component in the resulting metal boride.
  • reducing the metal oxide may further comprise adding a borohydride compound, a borate compound and hydrogen (H 2 ), or both, after contacting the metal oxide with the metal chloride.
  • the borohydride compound may be sodium borohydride, lithium borohydride, sodium cyanoborohydride, potassium borohydride, lithium triethylborohydride, or combinations thereof.
  • the borate compound may be sodium metaborate, sodium borate, lithium metaborate, lithium borate, lithium tetraborate, or a combination thereof.
  • the reducing agent is the borate compound and hydrogen (H 2 )
  • the borate compound and hydrogen (H 2 ) may be additionally introduced or may be formed in situ from an excess of the borohydride compound used in the reducing of the metal oxide to the one or more intermediate oxides.
  • reducing the metal oxide to the one or more intermediate metal oxides may further comprise contacting the metal oxide with hydrochloric acid, chlorine, or both.
  • the hydrochloric acid and chlorine (Cl 2 ) may be additionally introduced or may be formed in situ from the reducing of the metal oxide to the one or more intermediate oxides.
  • reducing the metal oxide to the one or more intermediate metal oxides may further comprise contacting the metal oxide with sodium metaborate, hydrochloric acid, chlorine (Cl 2 ), and hydrogen (H 2 ).
  • the reducing of the intermediate metal oxide to metal nanoparticle may include contacting the intermediate metal oxide with at least one reducing agent.
  • the reducing agent can be any compound that is capable of releasing hydrogen (H 2 ) and providing the boron component in the resulting metal boride.
  • reducing the intermediate metal oxide to the metal nanoparticle may further include contacting the intermediate metal oxide with a borohydride compound, a borate compound with hydrogen (H 2 ), or both.
  • the borohydride compound may be sodium borohydride, lithium borohydride, sodium cyanoborohydride, potassium borohydride, lithium triethylborohydride, or a combination thereof.
  • the borate compound may be sodium metaborate, sodium borate, lithium metaborate, lithium borate, lithium tetraborate, or a combination thereof.
  • the reducing agent is the borate compound and hydrogen (H 2 )
  • the borate compound and hydrogen (H 2 ) may be additionally introduced or may be formed in situ from an excess of the borohydride compound used in the reducing of the metal oxide to the one or more intermediate metal oxides.
  • reducing the intermediate metal oxide to the metal nanoparticle may further include contacting the intermediate metal oxide with hydrochloric acid, chlorine (Cl 2 ), or both.
  • the hydrochloric acid and chlorine (Cl 2 ) may be additionally introduced or may be formed in situ from the reducing of the metal oxide to the one or more intermediate metal oxides.
  • reducing the intermediate metal oxide to the metal nanoparticle may further include contacting the intermediate metal oxide with sodium metaborate, hydrochloric acid, chlorine (Cl 2 ), and hydrogen (H 2 ).
  • forming metal boride from the metal nanoparticle may include contacting the metal nanoparticle with boric acid.
  • forming the metal boride may further include contacting the metal nanoparticle with hydrogen (H 2 ).
  • forming the metal boride may include contacting the metal nanoparticle with boric acid and hydrogen (H 2 ).
  • the boric acid and the hydrogen (H 2 ) may be additionally introduced, or may be formed in situ from the reduction of the metal oxide to the one or more intermediate metal oxides.
  • the metal nanoparticle may bond with the boron released from the boric acid to form metal boride in aqueous solution.
  • the method of forming metal boride may further include forming metal boride crystals.
  • forming metal boride crystals may include incubating a solution of the metal boride at about ambient temperature and pressure.
  • forming metal boride crystals may include incubating a solution of the metal boride at above ambient temperature, for example about 40 °C to 80 °C.
  • forming metal boride crystals may include incubating a solution of the metal boride at about 40 °C to about 50 °C, about 50 °C to about 60 °C, about 60 °C to about 70 °C, or about 70 °C to about 80 °C.
  • forming metal boride crystals may include incubating a solution of the metal boride at about ambient temperature and pressure for any period of time sufficient to obtain metal boride crystals, such as up to about 24 hours or more. In some embodiments, forming metal boride crystals may include incubating a solution of the metal boride at above ambient temperature, for example about 40 °C to about 80 °C, for any period of time sufficient to obtain metal boride crystals, such as up to about 24 hours or more. In some embodiments, forming metal boride crystals may include incubating a solution of the metal boride at ambient temperature and pressure for up to about 48 hours.
  • forming metal boride crystals may include incubating a solution of the metal boride at above ambient temperature, for example about 40 °C to 80 °C, for up to about 48 hours. In some embodiments, forming the metal boride crystals may further include mixing or stirring the solution. The metal boride crystals may become visible on a surface of the reaction vessel after a period of time, such as about 2 hours from initiation of the reaction. The metal boride crystals may also continue to be formed on the surface of the reaction vessel for a period of time, such as up to about 48 hours after initiation of the reaction. In some embodiments, the formation of the metal boride results in the formation of transparent colorless crystals.
  • the method of forming metal boride may further include coating the metal boride with an iron oxide.
  • the iron oxide can also be additionally introduced to coat the metal boride.
  • the coating may increase the metal boride's resistance to corrosion.
  • the iron oxide may be present in the titaniferous magnetite ore, oxidized patronite, vanadinite, carnotite, iron slag or combination thereof as a raw material in the methods described herein.
  • the iron oxide can also be additionally introduced to coat the metal boride.
  • the method of producing metal boride may be performed at about ambient temperature and pressure. In some embodiments, the method of producing metal boride may be performed at above ambient temperature, for example, about 40 °C to about 80 °C. In some embodiments, the method of producing metal boride may be performed at above ambient temperature, for example, about 40 °C to about 50 °C, about 50 °C to about 60 °C, about 60 °C to about 70 °C, or about 70 °C to about 80 °C. In some embodiments, the method of producing metal boride may be performed in a single reaction vessel.
  • the costs of producing metal borides including, but are not limited to vanadium boride, using the methods described herein can be significantly lower than currently practiced commercial methods of production.
  • the cost of producing vanadium boride by the methods disclosed herein may be as much as one hundred times less expensive than currently practiced commercial manufacturing methods.
  • the vanadium boride that is produced by the methods disclosed herein can have physical characteristics including but are not limited to hardness, electrical conductivity, a high melting point and the ability to break down in strong oxidizing or alkaline agents.
  • the hardness of the vanadium boride is determined by the hammer process.
  • vanadium boride produced from magnetite ore or iron slag is at least two times harder than vanadium boride produced from vanadium tetrachloride.
  • the vanadium boride produced by the methods disclosed herein can have multiple applications including but are not limited to automotive batteries with improved storage and discharge potentials, any application where electrical energy is used or can be used, and as a replacement for lithium and zinc electrodes in traditional fuel cells and batteries.
  • the vanadium boride produced by the methods disclosed herein can be suitable for use in vanadium boride air cells.
  • the vanadium boride produced by the methods disclosed herein, when used in such cells, can have high energy storage capacity.
  • the energy storage capacity can be equivalent to or greater than that of gasoline, lithium ion, or zinc air cell.
  • the vanadium boride produced by the methods disclosed herein can be used as an anode in a battery.
  • the vanadium boride produced by the methods disclosed herein can also be used as an anode in a rechargeable battery.
  • Such rechargeable batteries can have a rapid recharge rate and greater energy storage capacity than lithium ion batteries.
  • the vanadium boride produced by the methods disclosed herein can confer a superior charge storage density.
  • Vanadium tetrachloride was freshly prepared from 1M vanadium pentoxide dissolved in concentrated hydrochloric acid (11.65M). The vanadium pentoxide was combined with the hydrochloric acid at a ratio of 1 : 10 by volume.
  • Vanadium tetrachloride was freshly prepared by combining 0.182 g of vanadium pentoxide with 4 mL of concentrated hydrochloric acid (11.65M), followed by mixing and a 10-minute incubation at ambient temperature and pressure.
  • Example 5 In situ Preparation of vanadium boride from titaniferous magnetite ore [0056] 10 mL of titaniferous magnetite ore solution from Example 1 was mixed with
  • a vanadium nanoparticle was formed from the vanadium (II) oxide in situ according to the following reaction scheme:
  • reaction mixture was allowed to incubate at ambient temperature and pressure for about 48 hours resulting in the formation of vanadium boride crystals.
  • the reaction mixture was stirred continuously during the incubation as well as during the process of adding the reactants.
  • Example 6 In situ Preparation of vanadium boride from iron slag
  • 10 mL of iron slag solution from Example 1 was mixed with 30 mL of a 2: 1 (v/v) ethanol and water mixture in a reaction vessel at ambient temperature and pressure.
  • 1 mL of freshly prepared vanadium tetrachloride from Examples 3 or 4 was added to the iron slag solution and ethanol and water mixture.
  • Addition of the vanadium tetrachloride resulted in disassociation of vanadium pentoxide from the iron slag.
  • the combining of the magnetite ore with vanadium tetrachloride was followed by the addition of 25 mL of 1M sodium borohydride to the reaction vessel to produce vanadium (III) oxide according to the following reaction scheme:
  • a vanadium nanoparticle was formed from the vanadium (II) oxide in situ according to the following reaction scheme:
  • reaction mixture was allowed to incubate at ambient temperature and pressure for about 48 hours resulting in the formation of vanadium boride crystals.
  • the reaction mixture was stirred continuously during the incubation as well as during the process of adding the reactants.
  • Example 9 Change in color as an indicator of progression in the preparation of vanadium boride from boride from titaniferous magnetite ore or iron slag
  • Example 10 Preparation of vanadium boride microparticles and nanoparticles
  • the particle size of vanadium boride crystals formed in any one of Examples 5 to 8 is affected by the time and speed of stirring of the vanadium boride during and after its formation.
  • Micro- and nanoparticles of vanadium boride can be synthesized as a result of extended stirring times during and post synthesis.
  • Example 11 - Preparation of vanadium boride nanoparticles Vanadium boride is prepared by any one of Examples 5 to 8.
  • the vanadium boride nanoparticles are produced by ball milling under argon environment in a tungsten carbide vessel using tungsten carbide bearings with a diameter of 10 mm. The vessel is then sealed and placed in a Retsch PM 100 ball-milling machine. The vanadium boride is milled at 600 rpm for 4 hours continuously. After milling, the temperature of the vessel is allowed to return ambient temperature and the vanadium boride nanoparticles are collected under an argon atmosphere.
  • Vanadium boride produced by any of Examples 5 to 8 can be separated from residual magnetite ore and iron slag, titanium oxide, iron oxide, aluminum oxide or other metal oxides that precipitate at the bottom of the reaction vessel in the process of producing vanadium boride from the magnetite ore or iron slag, by decantation and washing as vanadium boride is insoluble in water and ethanol.
  • impurities such as sodium chloride and boric acid is dissolved in the ethanol water mixture. Such impurities can be separated by decantation and washing.
  • Vanadium boride from magnetite ore or iron slag from any one of Examples 5 to 8 can be used as an anode in a rechargeable battery.
  • the rechargeable battery is made up of two half-cells, an anode and an air cathode.
  • the vanadium boride is mixed with carbon and potassium hydroxide to form the anode, which contains about 50% to about 80% vanadium boride and about 20% to about 50% carbon to achieve an optimum electrical discharge via multiple electron oxidation of vanadium boride.
  • the electrolyte is an aqueous solution of potassium hydroxide (5M) as it is a suitable ionic conductor material.
  • a membrane acting as a separator is also provided to minimize any non-electrochemical interaction between the anode and the air cathode.
  • the vanadium boride undergoes an 11 electron per molecule oxidation which includes oxidation of the tetravalent transition metal ion, V (+4 ⁇ +5), and each of the two boron's 2xB (-2 ⁇ +3).
  • the discharge potential of the high capacity battery is expected to be approximately 1.34 volts (V), whereas theoretical discharge potential is approximately 1.55 volts (V).
  • the anode had an open circuit potential of approximately 1.34 volts.
  • Vanadium boride derived from titaniferous magnetite ore or iron slag produced by any one of Examples 5 and 7 may be dissolved in 2 M potassium hydroxide solution to produce an anode, and the anode is added to the first half cell of a batteries.
  • the battery may comprise two half-cells, which are in an electrochemical contact with each other through an electrolyte (potassium hydroxide). Potassium hydroxide can be used as an electrolyte in vanadium boride batteries because of its superior ionic conductivity.
  • the first half-cell may comprise the vanadium boride anode and the second half-cell comprises a carbon air cathode.
  • the anode, electrolyte, and carbon air cathodes and a separator, positioned to minimize any non-electrochemical interaction between the anode and the air cathode, may be sealed inside the battery cell.
  • An electrical discharge from the anode occurs via multiple electron oxidation of vanadium boride.
  • the battery may produce 1.34-volt open circuit discharge continuously.
  • Example 15 Preparation of a vanadium boride battery
  • Vanadium boride derived from iron slag as in Examples 6 or 8 may be dissolved in 2 M potassium hydroxide solution to produce an anode, and the anode is added to the first half cell of a batteries.
  • the battery may comprise two half-cells, which are in an electrochemical contact with each other through an electrolyte (potassium hydroxide). Potassium hydroxide may be used as an electrolyte in vanadium boride batteries because of its superior ionic conductivity.
  • the first half-cell may comprise the vanadium boride anode and the second half-cell may comprise a carbon air cathode.
  • the anode, electrolyte, and carbon air cathodes and a separator, positioned to minimize any non-electrochemical interaction between the anode and the air cathode, are sealed inside the battery cell.
  • An electrical discharge from the anode may occur via multiple electron oxidation of vanadium boride.
  • the battery may produce 1.34-volt open circuit discharge continuously.
  • Zinc Air button batteries with a 1 cm anode surface area can be used to produce a vanadium boride-air button cell.
  • 0.1 g of ground vanadium boride from magnetite ore produced by Examples 5 or 7 may be mixed with activated carbon at a ratio of 1 : 1 in a porcelain crucible and a 5M potassium hydroxide solution may be added to produce a slurry that is used to replace the zinc anode in a conventional 1 cm diameter zinc-air button cell.
  • the battery may discharge with a constant resistive load and exhibits higher potential.
  • a 5M potassium hydroxide solution is used as the electrolyte.
  • the loading of the anode material for each cell may be 10 mAh.
  • a zinc air button cell can be carefully opened, and the zinc anode and the carbon cathode material are removed.
  • the vanadium boride slurry may then be added in the place of the zinc anode.
  • a separator can then be placed over the vanadium boride anode.
  • An activated carbon slurry can be prepared using 5M potassium hydroxide to produce an activated carbon slurry.
  • the activated carbon slurry can replace the original carbon cathode in the lid of the of the button cell. The lid may then be placed on the separator above the anode making an airtight seal.
  • Zinc air button batteries with a 1 cm anode surface area can be used to produce a vanadium boride-air button cell.
  • 0.1 g of ground vanadium boride from iron slag produced by Examples 6 or 8 may be mixed with activated carbon at a ratio of 1 : 1 in a porcelain crucible and a 5M potassium hydroxide solution may be added to produce a slurry that is used to replace the zinc anode in a conventional 1 cm diameter zinc-air button cell.
  • the battery may discharge with a constant resistive load and exhibits higher potential.
  • a 5M potassium hydroxide solution can be used as the electrolyte.
  • the loading of the anode material for each cell may be 10 mAh.
  • a zinc air button cell can be opened, and the zinc anode and carbon cathode material are removed.
  • the vanadium boride slurry is then added in the place of the zinc anode.
  • a separator is then placed over the vanadium boride anode.
  • An activated carbon slurry can be prepared using 5M potassium hydroxide to produce an activated carbon slurry.
  • the activated carbon slurry then replaces the original carbon cathode in the lid of the button cell.
  • the lid is then placed on the separator above the anode making an airtight seal.
  • Example 18 Preparation of a vanadium boride-air watch battery [0083]
  • a 20.0 mm x 3.2 mm CR2032 watch battery with a lithium anode is used to prepare the battery. The cell is opened and the lithium anode is removed. The carbon cathode material is also removed.
  • To produce the anode 0.5 g of ground vanadium boride from magnetite ore produced by Example 5 or 7 is mixed with activated carbon powder at a 1 : 1 ratio in a porcelain crucible followed by adding a 5M potassium hydroxide solution to prepare a vanadium boride slurry. The vanadium boride slurry is then added in the place of the lithium anode.
  • a separator is then placed over the vanadium boride anode.
  • An activated carbon slurry is prepared using 5M potassium hydroxide to produce a carbon air cathode.
  • the carbon air cathode is installed on the battery and the battery is tightly closed.
  • Example 19 Preparation of a vanadium boride-air watch battery
  • a 20.0 mm x 3.2 mm CR2032 watch battery with a lithium anode can be used to prepare the battery. The cell is opened and the lithium anode is removed. The carbon cathode material is also removed.
  • To produce the anode 0.5 g of ground vanadium boride from iron slag as produced by Examples 6 or 8 is mixed with activated carbon powder at a 1 : 1 ratio in a porcelain crucible followed by adding a 5M potassium hydroxide solution to prepare a vanadium boride slurry. The vanadium boride slurry is then added in the place of the lithium anode.
  • a separator is then placed over the vanadium boride anode.
  • An activated carbon slurry is prepared using 5M potassium hydroxide to produce a carbon air cathode.
  • the carbon air cathode is installed on the battery and the battery is tightly closed.
  • Example 20 Preparation of a vanadium boride-air coin battery
  • a 5 cm coin battery with a lithium anode can be used to prepare the battery.
  • 2 g of ground vanadium boride from magnetite ore as produced by Examples 5 or 7 is mixed with activated carbon powder (25%) in a porcelain crucible followed by the addition of 5M potassium hydroxide solution to prepare a vanadium boride anode slurry.
  • the vanadium boride slurry is then added in the place of the lithium anode.
  • a separator is then placed over the vanadium boride anode.
  • An activated carbon slurry is prepared using 5M potassium hydroxide to produce a carbon air cathode.
  • the carbon air cathode is installed on the battery and the battery is tightly closed.
  • Example 21 Preparation of a vanadium boride-air coin battery
  • a 5cm coin battery with a lithium anode can be used to prepare the battery.
  • 2 g of ground vanadium boride from iron slag as produced by Examples 6 or 8 is mixed with activated carbon powder (25%) in a porcelain crucible followed by the addition of 5M potassium hydroxide solution to prepare a vanadium boride anode slurry.
  • the vanadium boride slurry is then added in the place of the lithium anode.
  • a separator is then placed over the vanadium boride anode.
  • An activated carbon slurry is prepared using 5M potassium hydroxide to produce a carbon air cathode.
  • the carbon air cathode is installed on the battery and the battery is tightly closed.
  • Example 22 Comparison of vanadium boride batteries produced from various sources
  • Vanadium boride can be obtained from either vanadium chloride, magnetite ore as in Examples 5 and 7, or iron slag as in Examples 6 and 8.
  • Vanadium boride batteries using vanadium boride from each source can be prepared as follows. Vanadium boride is dissolved in 2 M potassium hydroxide solution to produce a vanadium boride anode. The anode is then placed in the first half-cell a battery. The battery comprises two half-cells, which are in electrochemical contact with each other through an electrolyte (potassium hydroxide). Potassium hydroxide is used for its superior ionic conductivity. The first half- cell comprises the vanadium boride anode and the second half-cell comprises a carbon cathode.
  • the first half-cell, second half cell, and electrolyte are combined in a battery cell and a separator is placed between the first half-cell and the second half-cell. The battery cell is then sealed.
  • An electrical discharge from the anode occurs via multiple electron oxidation of the vanadium boride.
  • the battery may produce 1.34-volt open circuit discharge continuously.
  • Batteries using vanadium boride prepared from magnetite and iron slag may have a constant electrical discharge for a longer duration of time than batteries prepared with vanadium boride from vanadium chloride only.
  • the increased discharge duration of batteries, prepared using vanadium boride may be due to the iron oxide coating, which makes the vanadium boride prepared from either magnetite ore of iron slag prepared from magnetite or iron slag.
  • Regeneration of electrochemically irreversible alkaline vanadium boride from fuel cell discharge products can be done by treating with magnesium. Specifically, dried vanadate and borate products are combined with magnesium and ball milled for approximately 24 hours under an argon atmosphere at room temperature. Impurities including (e.g., magnesium oxide and residual reactants) are removed by leaching the milled powder with a 10% hydrochloric acid solution for approximately 1 hour. The solution is then decanted after leaching and the solid product is washed with deionized water and vacuum dried.
  • Impurities including e.g., magnesium oxide and residual reactants
  • Regeneration of electrochemically irreversible alkaline vanadium boride from fuel cell discharge products can be done by treating with heated hydrogen gas. Specifically, dried vanadate and borate products are combined with magnesium and ball milled for approximately 24 hour under an argon atmosphere at room temperature. Heated hydrogen gas is then passed over the vanadate and borate and reduces it back to a starting material for reinsertion into a refueled battery. The recharging process is performed at over 100°C to eliminate water formed from the hydrogen as steam.
  • compositions, methods and devices are described in terms of “comprising” various components or steps (interpreted as meaning “including, but not limited to”), the compositions, methods, and devices can also “consist essentially of or “consist of the various components and steps, and such terminology should be interpreted as defining essentially closed-member groups.
  • a range includes each individual member.
  • a group having 1 -3 substituents refers to groups having 1 , 2, or 3 substituents.
  • a group having 1 -5 substituents refers to groups having 1 , 2, 3, 4, or 5 substituents, and so forth.

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Abstract

L'invention concerne des procédés de production de borures de métaux tels que, entre autres, du borure de vanadium à partir de minerais métalliques et de laitier de fonte. L'invention concerne également des procédés de production de borure de vanadium in situ à partir de minerai de magnétite titanifère ou de laitier de fonte et les utilisations de borure de vanadium.
PCT/IB2013/054119 2013-03-14 2013-05-20 Procédés de production de borure de vanadium et utilisations associées Ceased WO2014140700A1 (fr)

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US9525164B1 (en) 2016-04-29 2016-12-20 King Abdulaziz University Method of reducing vanadium pentoxide to vanadium(III) oxide
RU2638396C2 (ru) * 2016-05-16 2017-12-13 Федеральное Государственное Бюджетное Образовательное Учреждение Высшего Образования "Новосибирский Государственный Технический Университет" Способ получения диборида ванадия
CN110197907A (zh) * 2019-05-09 2019-09-03 河北钒电新能源科技有限公司 一种高能电池阴极芯片

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WO1997012071A1 (fr) * 1995-09-27 1997-04-03 Commonwealth Scientific And Industrial Research Organisation Recuperation de vanadium
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EP2423164A1 (fr) * 2010-08-25 2012-02-29 Max-Planck-Gesellschaft zur Förderung der Wissenschaften e.V. Synthèse générale de borures métalliques dans des sels liquides en fusion

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US9525164B1 (en) 2016-04-29 2016-12-20 King Abdulaziz University Method of reducing vanadium pentoxide to vanadium(III) oxide
RU2638396C2 (ru) * 2016-05-16 2017-12-13 Федеральное Государственное Бюджетное Образовательное Учреждение Высшего Образования "Новосибирский Государственный Технический Университет" Способ получения диборида ванадия
CN110197907A (zh) * 2019-05-09 2019-09-03 河北钒电新能源科技有限公司 一种高能电池阴极芯片

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