WO2016018165A1 - Simplified process for preparing electrolyte for vanadium redox batteries - Google Patents

Simplified process for preparing electrolyte for vanadium redox batteries Download PDF

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Publication number
WO2016018165A1
WO2016018165A1 PCT/PT2015/000039 PT2015000039W WO2016018165A1 WO 2016018165 A1 WO2016018165 A1 WO 2016018165A1 PT 2015000039 W PT2015000039 W PT 2015000039W WO 2016018165 A1 WO2016018165 A1 WO 2016018165A1
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Prior art keywords
process according
gases
mixture
vanadium
electrolyte
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PCT/PT2015/000039
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French (fr)
Inventor
Rui Pedro Da Costa Neto
João Luís TOSTE DE AZEVEDO
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Instituto Superior Técnico
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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
    • H01M8/00—Fuel cells; Manufacture thereof
    • H01M8/18—Regenerative fuel cells, e.g. redox flow batteries or secondary fuel cells
    • H01M8/184—Regeneration by electrochemical means
    • H01M8/188—Regeneration by electrochemical means by recharging of redox couples containing fluids; Redox flow type batteries
    • 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
    • H—ELECTRICITY
    • H01—ELECTRIC ELEMENTS
    • H01M—PROCESSES OR MEANS, e.g. BATTERIES, FOR THE DIRECT CONVERSION OF CHEMICAL ENERGY INTO ELECTRICAL ENERGY
    • H01M8/00—Fuel cells; Manufacture thereof
    • H01M8/20—Indirect fuel cells, e.g. fuel cells with redox couple being irreversible
    • 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
    • Y02E60/30—Hydrogen technology
    • Y02E60/50—Fuel cells

Definitions

  • This invention belongs in the field of electric storage and consists of a simplified process for preparing electrolyte for vanadium redox batteries .
  • the process to be protected is not performed in an electrolytic medium but in a thermal reduction reactor.
  • the preparation time is shorter or equal to about half the time taken by the electrolytic process and requires, only at the end of the process, one weighing of the reactor after the set time has elapsed. Since the cost of preparing the electrolyte can be between 10% and 70% of the cost of the final vanadium redox battery, the development of a simpler process that is less costly in terms of energy could be a considerable asset in the field of vanadium redox batteries.
  • V 2 O 3 Vanadium tricxide
  • V 2 O 5 vanadium pentoxide
  • SO sulfur dioxide gas
  • the electrolyte in which the V 2 O 5 is reduced is prepared in hydrogen gas (H 2 ) medium., the V 2 O 3 is then dissolved in H 2 SO 4 in order to prepare the final electrolyte, more specifically for a vanadium redox battery.
  • H 2 hydrogen gas
  • the analytical techniques employed by the authors of the article could also be used at the end of the thermal reduction process of the invention to be protected, to characterise the V 2 O 3 crystals.
  • the V 2 O 5 used at the start of the process is already sufficiently pure and therefore only one weighing of theV 2 O 3 is performed at the end of the process. It is possible to know if all the V 2 O 5 was reduced to V 2 O 3 from the ratio of the masses of the reaction products.
  • the electrolyte is prepared in solution by the reduction or oxidation of vanadium through an electrochemical route (electrolysis) in liquid electrolyte; the SO 2 (in the form, of gas bubbles) is mixed with the electrolyte to reduce the vanadium with the higher oxidation state (5+) to the lower state (3+) .
  • the need for stabilizing agents to ensure that the vanadium species in the various oxidation states remain stable throughout the process of electrolyte preparation is also mentioned in this patent, reflecting all the additional complexity of this process.
  • the V 2 O 5 is converted by thermal reduction to V 2 O 3 and it is subsequently dissolved under well-controlled conditions in an acidic medium to yield the desired final electrolyte.
  • the electrolyte is prepared from V 2 O 5 reduction in acid electrolyte solution using inorganic acids with reducing agents, with a stated preference for H 2 SO 4 .
  • An. electrolytic reduction in an electrolytic cell is also part of this electrolyte preparation process.
  • this electrolyte preparation process is carried out in liquid medium, whereby V 2 O 5 (5+) is reduced to V 2 O 3 (3+) through the use of a liquid reducing agent.
  • the invention to be protected is clearly different from the previous proposals in that, it has a smaller number of process control parameters.
  • the electrolyte in a vanadium redox battery is one of the basic constituents of this electric energy storage system.
  • the various processes proposed to prepare the electrolyte are mostly in electrolytic medium and make use of electrolysis processes to perform the reduction and oxidation of the reagents. These processes are usually complex in that they control and monitor ail the concentrations of .species to oxidise and reduce in solution.
  • This invention relates to an electrolyte preparation process that can be used in ail vanadium redox batteries, as well as other redox batteries with other metals.
  • the process described in the invention to be protected is a thermal reduction process in gaseous medium with subsequent dissolution in electrolytic medium under well-controlled conditions.
  • the well-controlled dissolution conditions may be achieved by mechanical agitation, or magnetic agitation, or ultrasonic agitation, in concentrated H 2 SO 4 at a temperature between 30°C and 95°C for a period of more than 1 minute and less than 10 hours, at a pressure between atmospheric and 50 bar.
  • the dissolution process will be faster if the V 2 O 3 is crushed in a mortar or ball mill.
  • the main advantage of this invention is that it is a much simpler process than the processes described in the state of the art since it enables the final electrolyte to be obtained through only two sequential stages, which are the thermal reduction and dissolution in electrolytic medium.
  • the sequential stages are straightforward to reproduce and repeat.
  • the reactor used is not changed by oxidation. during the preparation of the electrolyte, whereas in the other processes the electrolysers can suffer oxidation arising from, the very- process of preparing the electrolyte.
  • the reduction reactor can be placed inside any furnace capable of imposing the above-mentioned temperature conditions.
  • the reactor can be made of carbon steel with high chromium content or stainless steel, 316 L or 304 L. It could also be a ceramic material such as zirconium or aluminium, or aluminium/glassy carbon, or zirconium/glassy carbon.
  • the electrolyte obtained from this process may be marketed to various vanadium redox battery manufacturers.
  • the process begins by introducing V 2 0 5 into a tubular- reactor in the presence of an inert atmosphere consisting of an inert gas, helium. (Ke) , argon ;Ar) or nitrogen (N 2 ) or of a combined mixture of these gases.
  • the reactor should be heated from the ambient temperature to between 300°C and 1000°C. The temperature may increase at a rate between 1°C/minute and 20°C/minute until the desired temperature is reached, within the range mentioned above. After reaching the desired temperature the reducing atmosphere to replace the inert atmosphere should be introduced.
  • the reducing atmosphere should consist of a reducing gas, from among hydrogen (H 2 ) , carbon monoxide (CO) , hydrogen sulphide (H 2 S) , methane (CH 4 ) or ammonia (NH 4 + ) or of a combined mixture of these gases diluted in N 2 or He or Ar .
  • the mixture of reducing gas or gases diluted in the inert gas or gases should have a volumetric percentage proportion of between 1% and 100%.
  • the flow rate of the reducing gas mixture should be proportional to the amount of V 2 O 5 within the tubular reactor. For example, for one gram V 2 O 5 to be completely reduced to V 2 O 3 will require a flow of a 3% mixture of H 2 (V/V; diluted in 12 L N 2 over a reduction period between 1 minute and 10 hours.
  • V-0 5 Once 100% of V-0 5 has been converted into V2O3, the latter is dissolved in a solution of H-SO 4 with a concentration of between 0.1 molar and 10 molar, previously degassed with H 2 or Ar or He. Dissolution is achieved by heating to a temperature between 30°C and 95°C and using a magnetic stirring bar and plate or ultrasonic bath or preferably a combination of the two previous pieces of mixing apparatus, with the preferred temperature being 90 °C.

Abstract

This invention relates to an electrolyte preparation process that involves two stages, one is the thermal reduction of vanadium pentoxide (V2O5) to vanadium trioxide (V2O3) in a tubular reactor, and the other is the dissolution of the resulting V2O3. It can be used in all types of vanadium redox batteries, also known as flow batteries. This process is simpler than the competing ones and requires, overall, less energy in the preparation of the electrolyte. The reduction step is thermal and uses reducing gases (hydrogen (H2), carbon monoxide (CO), hydrogen sulphide (H2S), methane (CH4) and ammonia (NH4 +) ) or a combined mixture of these gases. It is followed by the dissolution stage. This invention can be used in the industrial manufacture of electric energy storage systems, particularly in vanadium redox batteries (similar to the lead battery sector).

Description

DESCRIPTION
Simplified process for preparing electrolyte for vanadixim redox batteries Field of the invention
Technical field to which the invention belongs
This invention belongs in the field of electric storage and consists of a simplified process for preparing electrolyte for vanadium redox batteries .
State of the art
The preparation of electrolyte for vanadium batteries using conventional processes involves considerable technical complexity. Hence the reason for the focus in the invention to be protected.
The most relevant documents in the state of the art are:
US6143443 - This patent describes the process of preparing the electrolyte for vanadium redox batteries, in which the reduction always takes place in an electrolytic medium, using a wide range of reducing agents along with stabilizing agents. The electrolyte preparation process in an electrolytic medium is lengthy, involves a complex electrolytic cell composed of many parts liable to deteriorate during the course of the process, and requires monitoring the concentration of several chemical, species throughout the process.
Compared with this patent, the process to be protected is not performed in an electrolytic medium but in a thermal reduction reactor. The preparation time is shorter or equal to about half the time taken by the electrolytic process and requires, only at the end of the process, one weighing of the reactor after the set time has elapsed. Since the cost of preparing the electrolyte can be between 10% and 70% of the cost of the final vanadium redox battery, the development of a simpler process that is less costly in terms of energy could be a considerable asset in the field of vanadium redox batteries.
* Zhang_2005 A-new-method-for-preparing-V2O3-nanopowder, Materials Letters 59 (20055 2729 - 2731 - In this article, the authors describe the preparation of electrolytes as follows: Vanadium tricxide (V2O3) nan-oparticles are prepared by dissolving vanadium pentoxide (V2O5)in aqueous solution of sulfuric acid (H3SO4) with its subsequent reduction in aqueous medium using sulfur dioxide gas (SO?) . The V2O3 nanoparticles are then characterized through X-ray diffraction, showing that they had the desired crystal structure and there were no impurities. They further used transmit tance electron microscopy to determine the morphology and average particle size and concluded the structure was polycrystailine . The XPS spectrum was used to analyse the oxidation state of the oxide (X- ray phctoeiectron spectroscopy) . The authors only mention the preparation of the oxide by reduction in aqueous medium and perform its subsequent characterisation. There is no reference to any application for the produced oxide .
In the invention to be protected, the electrolyte in which the V2O5 is reduced is prepared in hydrogen gas (H2) medium., the V2O3 is then dissolved in H2SO4 in order to prepare the final electrolyte, more specifically for a vanadium redox battery. The analytical techniques employed by the authors of the article could also be used at the end of the thermal reduction process of the invention to be protected, to characterise the V2O3 crystals. In the present invention, the V2O5 used at the start of the process is already sufficiently pure and therefore only one weighing of theV2O3 is performed at the end of the process. It is possible to know if all the V2O5 was reduced to V2O3 from the ratio of the masses of the reaction products.
US2003143456 - In this patent, the electrolyte is prepared in solution by the reduction or oxidation of vanadium through an electrochemical route (electrolysis) in liquid electrolyte; the SO2 (in the form, of gas bubbles) is mixed with the electrolyte to reduce the vanadium with the higher oxidation state (5+) to the lower state (3+) . The need for stabilizing agents to ensure that the vanadium species in the various oxidation states remain stable throughout the process of electrolyte preparation is also mentioned in this patent, reflecting all the additional complexity of this process.
In the invention to be protected, the V2O5 is converted by thermal reduction to V2O3 and it is subsequently dissolved under well-controlled conditions in an acidic medium to yield the desired final electrolyte.
US525Q15S - In this patent, the electrolyte is prepared from V2O5 reduction in acid electrolyte solution using inorganic acids with reducing agents, with a stated preference for H2SO4. An. electrolytic reduction in an electrolytic cell is also part of this electrolyte preparation process. As in the patents mentioned earlier, this electrolyte preparation process is carried out in liquid medium, whereby V2O5 (5+) is reduced to V2O3 (3+) through the use of a liquid reducing agent.
The invention to be protected is clearly different from the previous proposals in that, it has a smaller number of process control parameters.
US 6362514 - This patent describes the preparation of electrolytes for vanadium redox batteries stabilised with various additives that prevent the precipitation of vanadium salts. This patent also gives an extensive list of the reducing agents typically used in electrolytic solutions to reduce vanadium to lower oxidation states. The reductions are always performed in electrolytic medium. In the invention to be protected, thermal reduction is carried out in gaseous medium. Summary of the invention
The electrolyte in a vanadium redox battery is one of the basic constituents of this electric energy storage system. The various processes proposed to prepare the electrolyte are mostly in electrolytic medium and make use of electrolysis processes to perform the reduction and oxidation of the reagents. These processes are usually complex in that they control and monitor ail the concentrations of .species to oxidise and reduce in solution. This invention relates to an electrolyte preparation process that can be used in ail vanadium redox batteries, as well as other redox batteries with other metals. The process described in the invention to be protected is a thermal reduction process in gaseous medium with subsequent dissolution in electrolytic medium under well-controlled conditions. The well-controlled dissolution conditions may be achieved by mechanical agitation, or magnetic agitation, or ultrasonic agitation, in concentrated H2SO4 at a temperature between 30°C and 95°C for a period of more than 1 minute and less than 10 hours, at a pressure between atmospheric and 50 bar. The dissolution process will be faster if the V2O3 is crushed in a mortar or ball mill.
Detailed description of the invention
The main advantage of this invention is that it is a much simpler process than the processes described in the state of the art since it enables the final electrolyte to be obtained through only two sequential stages, which are the thermal reduction and dissolution in electrolytic medium. The sequential stages are straightforward to reproduce and repeat. It should be noted that the reactor used is not changed by oxidation. during the preparation of the electrolyte, whereas in the other processes the electrolysers can suffer oxidation arising from, the very- process of preparing the electrolyte. The reduction reactor can be placed inside any furnace capable of imposing the above-mentioned temperature conditions. The reactor can be made of carbon steel with high chromium content or stainless steel, 316 L or 304 L. It could also be a ceramic material such as zirconium or aluminium, or aluminium/glassy carbon, or zirconium/glassy carbon.
The electrolyte obtained from this process may be marketed to various vanadium redox battery manufacturers.
The process begins by introducing V205 into a tubular- reactor in the presence of an inert atmosphere consisting of an inert gas, helium. (Ke) , argon ;Ar) or nitrogen (N2) or of a combined mixture of these gases. The reactor should be heated from the ambient temperature to between 300°C and 1000°C. The temperature may increase at a rate between 1°C/minute and 20°C/minute until the desired temperature is reached, within the range mentioned above. After reaching the desired temperature the reducing atmosphere to replace the inert atmosphere should be introduced. The reducing atmosphere should consist of a reducing gas, from among hydrogen (H2) , carbon monoxide (CO) , hydrogen sulphide (H2S) , methane (CH4) or ammonia (NH4 +) or of a combined mixture of these gases diluted in N2 or He or Ar . The mixture of reducing gas or gases diluted in the inert gas or gases should have a volumetric percentage proportion of between 1% and 100%. The flow rate of the reducing gas mixture should be proportional to the amount of V2O5 within the tubular reactor. For example, for one gram V2O5 to be completely reduced to V2O3 will require a flow of a 3% mixture of H2 (V/V; diluted in 12 L N2 over a reduction period between 1 minute and 10 hours.
The reducing gas should be chosen in accordance with these stoichiometric calculations: 1 mole of vanadium will need 2 moles of H2 gas to yield 1 mole of V3O3 and 2 moles of water {36 g) . If the vanadium is in the pure state of complete, reduction, 1 mole of V2O3 should weigh 149.83 g (M(V2O3)=; 149.88 g/moi) . The mass of 1 mole of V2O5 would initially be 181-88 g (M (V2O5) =181.88 g/mol) . One can check whether the reaction occurred completely or not by weighing the V2G5 at. the start of the process and during the process so as to arrive at a mass ratio between the V2O5 at the start, and the V2O3 at the end of 1.2135. When this mass ratio is reached it means that all the V2O5 has been converted to V2O3.
Examples
The preparation of 1 litre of solution with 1 mole of v2Os involves weighing 181.88 g of V2O5. 2 moles of H2 represent 44.8 L of H2 considering the molar volume of an ideal gas at standard temperature and pressure (STP) . It will, however, be necessary to supply excess K2. Therefore, 1.5 times more H2 than needed will be supplied, which is around 67,2 L throughout the whole reduction process.
Around 6 hours (360 minutes) at a temperature of 500 *C are estimated to be needed to reduce the whole amount of V2O5 to V2O3. For this, pure R2 will have to be supplied to the V2G5 powder at a flow rate of 0.19 L/min. If it is decided to use a mixture of reducing gases such as 5% of H2 in N2, flow rates of 0.19 L/min for H2 and 3.8 L/min for N2 will be needed.
Once 100% of V-05 has been converted into V2O3, the latter is dissolved in a solution of H-SO4 with a concentration of between 0.1 molar and 10 molar, previously degassed with H2 or Ar or He. Dissolution is achieved by heating to a temperature between 30°C and 95°C and using a magnetic stirring bar and plate or ultrasonic bath or preferably a combination of the two previous pieces of mixing apparatus, with the preferred temperature being 90 °C.

Claims

1. Simplified process for preparing electrolyte for vanadium redox batteries characterised in that it comprises two stages: a first thermal reduction of vanadium pentoxide (V205) to vanadium trioxide (V20 3) with a mixture of reducing gases in a tubular reactor, in which the inert atmosphere is replaced by the reducing atmosphere during heating, and a second one of dissolution of the resulting V203 into sulfuric acid (H2S04) .
2. Process according to claim 1 characterised in that, the inert atmosphere inside the reactor consists of an inert gas, from among helium (He) , argon (Ar) or nitrogen (H2) , or of a combined, mixture of these gases.
3. Process according to claim 1. characterised in that, the reducing atmosphere consists of a reducing gas, from among hydrogen (H2) , carbon monoxide (CO) , hydrogen sulphide (H2S) , methane (CH4) or ammonia (NH4 +) , or of a combined mixture of these gases diluted in He or Ar or N2.
4. Process according to the previous claims characterised in that the mixture of reducing gas or gases is diluted in the mixture of inert gas or gases with a volumetric percentage proportion of between 1% and 100%.
5. Process according to claim 1 characterized in that the reactor temperature is between 300°C and 1000°C.
6. Process according to the previous claims, characterised in that the rate of increase of the reactor temperature is between 1°C/minute and 20°C/minute until the desired temperature, within the range mentioned in claim 5, is achieved.
7. Process according to the previous claims characterised in chat the flow rate of the reducing gas .mixture is proportional to the amount of V2O5 within the tubular reactor.
8. Process according to the previous claims characterised in that the end of the reaction is verified by weighing the V205 at the start of the process and the resulting V2O3 at the end of the process, until a mass ratio of 1.2135 is obtained.
9. Process according to claim 1 characterised by the dissolution of the resulting V2O5 in a solution of
H2SO4 with concentration between 0.1 molar and 10 molar, previously degassed with t½ or Ar or He.
10. Process according to claims 1 and 9, characterised in that the dissolution of the resulting V203 is effected through heating at a temperature between 30 °C and
95°C for a period greater than 1 minute and less than 10 hours at a pressure between atmospheric and 50 bar, with the help of mechanical agitation, or magnetic agitation or ultrasonic agitation or a combination thereof.
PCT/PT2015/000039 2014-07-31 2015-07-30 Simplified process for preparing electrolyte for vanadium redox batteries WO2016018165A1 (en)

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PT107816A PT107816A (en) 2014-07-31 2014-07-31 SIMPLIFIED PROCESS OF ELECTROLYTE PREPARATION FOR VANÁDIO REDOX PILE
PT107816 2014-07-31

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Cited By (2)

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Publication number Priority date Publication date Assignee Title
WO2019029615A1 (en) * 2017-08-09 2019-02-14 河钢股份有限公司承德分公司 Method for cleanly producing vanadium trioxide by vanadium-containing solution
WO2022103744A1 (en) * 2020-11-16 2022-05-19 Cougar Creek Technologies, Llc Fe-cr redox flow battery systems and methods of using the systems

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Publication number Priority date Publication date Assignee Title
WO2019029615A1 (en) * 2017-08-09 2019-02-14 河钢股份有限公司承德分公司 Method for cleanly producing vanadium trioxide by vanadium-containing solution
WO2022103744A1 (en) * 2020-11-16 2022-05-19 Cougar Creek Technologies, Llc Fe-cr redox flow battery systems and methods of using the systems
US11710844B2 (en) 2020-11-16 2023-07-25 Cougar Creek Technologies, Llc Fe-Cr redox flow battery systems and methods utilizing chromium complexes with nitrogen-containing ligands
US11735756B2 (en) 2020-11-16 2023-08-22 Cougar Creek Technologies, Llc Redox flow battery systems and methods utilizing a temporal energy profile
US11764385B2 (en) 2020-11-16 2023-09-19 Cougar Creek Technologies, Llc Redox flow battery systems and methods utilizing primary and secondary redox flow battery arrangements
US11955677B2 (en) 2020-11-16 2024-04-09 Cougar Creek Technologies, Llc Redox flow battery systems and methods utilizing primary and secondary redox flow battery arrangements

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