CN113036198B - Preparation method and equipment of all-vanadium redox flow battery electrolyte - Google Patents
Preparation method and equipment of all-vanadium redox flow battery electrolyte Download PDFInfo
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Abstract
The invention relates to a preparation method and equipment of an all-vanadium redox flow battery electrolyte. The preparation method of the all-vanadium redox flow battery electrolyte provided by the invention is obtained by fully utilizing the decomposition of ammonium metavanadateV of2O5And ammonia gas, and the requirement on the purity of ammonium metavanadate is lower, so that the cost is saved, the operation is simple and convenient, and the valence state of the obtained all-vanadium redox flow battery electrolyte can be conveniently controlled.
Description
Technical Field
The invention belongs to the production field of flow batteries, and particularly relates to a preparation method and equipment of an all-vanadium flow battery electrolyte.
Background
The flow battery technology has natural advantages of large-scale energy storage: the size of the electric storage quantity is linearly proportional to the volume of the electrolyte, and the charging and discharging power is determined by the size and the quantity of the galvanic pile, so that the charging and discharging power from KW to MW grade difference can be designed according to the requirement, and the flow battery with different energy storage quantities can continuously discharge for 1 hour to several days. The reaction temperature of the battery is normal temperature and normal pressure, the flowing process of the electrolyte is a natural water-based circulating heat dissipation system, the safety performance is extremely high, and the accident influence is far lower than that of other large-scale energy storage schemes. There is no upper limit to the theoretical number of charge and discharge cycles due to its stable and reliable charge and discharge cycles.
The all-vanadium redox flow battery has the advantages of no pollution, long service life, high energy conversion efficiency and simple maintenance, and has a huge application prospect in the fields of solar energy and wind energy storage, power grid peak regulation, remote power supply systems, uninterruptible power supplies and the like. Compared with the traditional battery, the positive electrode and the negative electrode of the all-vanadium redox flow battery are subjected to vanadium ion reaction, so that cross infection and capacity loss are eliminated.
In the current all-vanadium flow battery, the electrolyte is prepared by using expensive vanadium oxide such as V2O5As a starting material, a reducing agent or a low-valence vanadium oxide is usually added to a diluted acidic solution to gradually reduce high-valence vanadium ions to an equilibrium state electrolyte.
Citation 1 discloses a preparation method of a vanadium battery electrolyte, which comprises the following steps: by mixing V2O5Mixing with deionized water to obtain slurry, adding supporting electrolyte to the slurry to obtain activated slurry,then adding a reducing agent into the activated slurry to obtain a crude electrolyte solution; and electrolyzing the crude electrolyte until the valence state is 3.5.
Citation 2 discloses a production process of a vanadium battery electrolyte, which includes the following steps: adding vanadium pentoxide into a sulfuric acid solution to obtain a suspension slurry; (2) introducing liquid SO into the suspension slurry2To obtain VOSO4And V2(SO4)3The mixed solution of (1); (3) adding VOSO4And V2(SO4)3The mixed solution is divided into two parts which are respectively added into an anode region and a cathode region of a diaphragm electrolytic cell, the anode electrolyte of the vanadium battery is obtained in the anode region, and the cathode electrolyte of the vanadium battery is obtained in the cathode region.
Citation 3 discloses a method for producing a 3.5-valent high-purity vanadium electrolyte, which comprises hydrolyzing high-purity vanadium oxychloride into vanadium pentoxide by fluidized bed gas-phase hydrolysis, accurately controlling and reducing the vanadium pentoxide into a low-valent vanadium oxide with the average valence of vanadium of 3.5 in a reduction-vulcanization bed, adding water and a sulfuric acid solution under an external microwave field, and dissolving at low temperature to obtain the 3.5-valent high-purity vanadium electrolyte.
In the cited documents 1 and 2, the crude electrolyte is prepared and then the electrolysis is performed to prepare the final electrolyte, and in the cited document 3, an external microwave field is required, and these preparation processes cannot be said to be simple. And moreover, vanadium oxychloride or vanadium pentoxide is used as a raw material, so that the cost is high.
In order to reduce the cost, in the cited document 4, a qualified vanadium solution produced by a vanadium plant is used as a raw material, and the vanadium electrolyte is prepared by five steps of impurity removal, vanadium precipitation, reduction, extraction and oil removal. The cited document 4 does reduce the raw material cost, but requires the use of a very large number of reagents, which leads not only to an increase in the overall cost, but also to an excessively complicated production process.
Further, cited document 5 discloses a method of producing NH4VO3A method for preparing electrolyte for vanadium battery by decomposition. In particular, it is reacting NH4VO3Thermally decomposing at 440-470 deg.C to produce V6O13Vanadium oxide as main component, then reducingAtmosphere V, e.g. hydrogen atmosphere6O13Reduction to V2O3And/or V2O4. Thus, in the cited document 5, NH4VO3Vanadium oxide and ammonia gas are generated after decomposition and then directly used for reducing the vanadium oxide, thereby obtaining V6O13. However, in actual production, there are very obvious problems, on one hand, ammonia gas directly performs a reduction reaction with vanadium oxide, the vanadium oxide becomes a catalyst for ammonia gas oxidation, that is, ammonia gas can be oxidized into nitrogen oxide, and nitrogen oxide itself is a substance seriously polluting the environment, therefore, in order to control pollution, reaction equipment is required to be connected with or a large number of decontamination devices are required to be added, such as an additional catalytic device, a heating device, a catalyst recovery or regeneration device, and the like, which additionally increases economic cost; on the other hand, if nitrogen oxides are combined with water produced by the reduction reaction of other kinds of ammonia in the system, nitric acid vapor may be produced, and corrosion of equipment may cause troubles in production.
Therefore, although various methods for preparing electrolytes for all-vanadium flow batteries have been attempted in the art, there is still room for further improvement in terms of overall low cost, use of fewer reagents, ease of preparation, reduction of environmental pollution, and the like.
Citations
Cited document 1: CN109742432A
Cited document 2: CN108777316A
Cited document 3: CN106257728A
Cited document 4: CN104319412A
Cited document 5: JP1996273692A
Disclosure of Invention
Problems to be solved by the invention
Aiming at the defects of complex process, strict requirement on raw material specification, generation of a large amount of pollutants, excessive use of equipment and reagents and higher cost in the preparation of vanadium redox flow battery electrolyte in the prior art, the invention mainly aims to provide an improved preparation method of vanadium redox flow battery electrolyte. The preparation method can be simply and conveniently carried out by using less reagents on the basis of reducing the cost during the electrolysis of the flow battery, does not generate a large amount of pollutants, and can reduce the environmental cost and the economic cost.
Means for solving the problems
The invention provides a method for preparing electrolyte of an all-vanadium redox flow battery, which only uses two or three reagents of ammonium metavanadate and sulfuric acid and/or hydrochloric acid, and fully utilizes V obtained by decomposing ammonium metavanadate2O5And ammonia gas, and the requirement on the purity of ammonium metavanadate is lower, so that the cost is saved, no pollutant is generated, the operation is simple and convenient, and the valence state of the obtained all-vanadium redox flow battery electrolyte can be conveniently controlled.
Specifically, the preparation method of the invention comprises the following steps:
[1] the invention firstly provides a preparation method of the electrolyte of the all-vanadium redox flow battery, which comprises the following steps:
a heat treatment step: which comprises reacting ammonium metavanadate NH4VO3Thermally decomposing to obtain a vanadium oxide solid, said vanadium oxide comprising at least part of V2O3；
Preparing an electrolyte: and mixing the vanadium oxide solid with sulfuric acid or hydrochloric acid or a sulfuric acid-hydrochloric acid mixed solution to obtain the all-vanadium redox flow battery electrolyte.
Preferably, the heat treatment step is carried out in one reaction apparatus, or in the same reaction site of one reaction apparatus.
[2] The production method according to [1], wherein the heat treatment step includes use of a closed pressure vessel.
[3]According to [1]]Or [2]]The preparation method, wherein the thermal decomposition comprises NH4VO3A step of decomposition to generate ammonia, a step of ammonia decomposition, V carried out simultaneously with or after said step of thermal decomposition2O5And (3) a reduction step.
[4]According to [3 ]]The preparation method, wherein in the step of ammonia gas decomposition, the product isGenerating nitrogen and hydrogen; at the V2O5In the step of reduction, the reduction reaction is carried out at least partially using hydrogen generated from the decomposition of the ammonia gas to convert V2O5At least partially reduced to V2O3。
[5]According to [1]]～[4]The production method of any one of the above, wherein V in the vanadium oxide solid is controlled by controlling decomposition temperature and/or pressure and/or time in the heat treatment step2O3And V2O5The ratio of (a) to (b).
[6]According to [1]]～[5]The preparation method, wherein V in the vanadium oxide solid2O3In an amount of 60 to 90wt%, V2O5The content of (B) is 10-40 wt%.
[7]According to [1]]～[6]The preparation method of any one of the above, wherein in the obtained all-vanadium redox flow battery electrolyte, V3+And V4+Molar ratio of (V)3+:V4+Is 1:4 to 4: 1.
[8] The process according to any one of [1] to [7], wherein the purity of the ammonium metavanadate is 90% or more.
[9] The method according to any one of [1] to [8], wherein the thermal decomposition temperature of ammonium metavanadate in the heat treatment step is 400 to 1200 ℃ and/or the pressure is 1 to 10 atmospheres.
[10] Further, the present invention also provides an apparatus for carrying out the production method according to any one of the above [1] to [9], wherein the apparatus includes:
a thermal decomposition device and a dissolution device,
and optionally a reduction reaction apparatus.
Wherein the thermal decomposition device and the reduction reaction device, if present, comprise a temperature control unit and/or a pressure control unit.
ADVANTAGEOUS EFFECTS OF INVENTION
Through the implementation of the technical scheme, the method for preparing the electrolyte has the following effects:
1) in the preparation method of the electrolyte, the purity of the raw material ammonium metavanadate has no special requirement, and the applicability in actual production is strong;
2) in the preparation method of the electrolyte, ammonia gas obtained by decomposing ammonium metavanadate and hydrogen gas obtained by decomposing ammonia gas are used as reducing agents to reduce V obtained by decomposing ammonium metavanadate2O5The use of reagents is reduced, so that the cost is saved, the preparation process is simple, a large amount of pollutants such as nitric oxide and the like cannot be generated, the environmental burden is reduced, and the economic cost for eliminating the pollutants such as nitric oxide and the like is further reduced;
3) in the method for preparing an electrolyte according to the present invention, V can be easily controlled by controlling the decomposition conditions of ammonium metavanadate and/or the conditions of reduction reaction2O3And V2O5Can further easily control V in the electrolyte of the obtained all-vanadium redox flow battery3+And V4+And the valence state of the electrolyte.
Drawings
FIG. 1 is a diagram showing NH4VO3A flow chart of preparing the electrolyte by carrying out thermal decomposition, ammonia decomposition and vanadium pentoxide reduction in the same reaction vessel.
FIG. 2 is a diagram showing NH4VO3A flow chart of the preparation of the electrolyte by carrying out thermal decomposition, ammonia decomposition and vanadium pentoxide reduction in different reaction vessels.
Detailed Description
The following describes embodiments of the present invention, but the present invention is not limited to these embodiments. The present invention is not limited to the configurations described below, and various modifications are possible within the scope of the claims, and embodiments and examples obtained by appropriately combining the technical means disclosed in the respective embodiments and examples are also included in the technical scope of the present invention. All documents described in this specification are incorporated herein by reference.
Unless defined otherwise, technical and scientific terms used herein have the same meaning as commonly understood by one of ordinary skill in the art to which this invention belongs.
In the present specification, a numerical range represented by "a value to B value" or "a value to B value" means a range including the end point value A, B.
In the present specification, the term "one atmosphere" means "one standard atmosphere" that is, "1 atm", and 1 standard atmosphere is equal to 101325 pa.
In the present specification, the meaning of "may" includes both the meaning of performing a certain process and the meaning of not performing a certain process. In this specification, "optional" or "optionally" means that the subsequently described event or circumstance may or may not occur, and that the description includes instances where the event occurs and instances where it does not.
Reference throughout this specification to "some particular/preferred embodiments," "other particular/preferred embodiments," "some particular/preferred aspects," "other particular/preferred aspects," or the like, means that a particular element (e.g., feature, structure, property, and/or characteristic) described in connection with the embodiment is included in at least one embodiment described herein, and may or may not be present in other embodiments. In addition, it is to be understood that the described elements may be combined in any suitable manner in the various embodiments.
The terms "comprises" and "comprising," and any variations thereof, in the description and claims of this invention and the above-described drawings are intended to cover non-exclusive inclusions. For example, a process, method, or system, article, or apparatus that comprises a list of steps or elements is not limited to only those steps or elements listed, but may alternatively include other steps or elements not listed, or inherent to such process, method, article, or apparatus.
< first embodiment >
In a first embodiment of the invention, a preparation method of an all-vanadium flow battery electrolyte is provided, which comprises a heat treatment step and an electrolyte preparation step. The heat treatment step comprises reacting ammonium metavanadate NH4VO3Thermally decomposing to obtain a vanadium oxide solid, said vanadium oxide comprising at least part of V2O3(ii) a In the electrolyte preparation step, the vanadium oxide solid is mixed with sulfuric acid or hydrochloric acid or a sulfuric acid-hydrochloric acid mixed solution, so that the all-vanadium redox flow battery electrolyte is obtained.
The raw materials and the respective steps are specifically described below.
Raw materials
The present invention uses ammonium metavanadate as the starting material. The purity of ammonium metavanadate is not particularly limited, and in some preferred embodiments of the present invention, ammonium metavanadate having a purity of 90% or more may be used. Of course, the use of high purity ammonium metavanadate is not excluded from the present invention. The purity of the ammonium metavanadate can be more than 95%, more than 98.5%, even more than 99.9%. In addition, the ammonium metavanadate meeting the use requirement of the invention can be obtained by self-preparation or can be directly obtained by a commercial product.
In some embodiments of the invention, the ammonium metavanadate may be subjected to any pretreatment procedure as desired, and in some embodiments, such pretreatment procedures include one or more of purification of ammonium metavanadate, washing with water, drying, pulverization, grinding, and the like.
Further, as described below, the raw material of the invention also comprises a solvent sulfuric acid or hydrochloric acid or a sulfuric acid-hydrochloric acid mixed solution for forming the electrolyte of the all-vanadium flow battery. In some embodiments of the invention, sulfuric acid may be used in a molar concentration of generally 1.0 to 8.0mol/L, preferably 2.0 to 6.0 mol/L; the molar concentration of hydrochloric acid that can be used may be usually 2.0 to 12.0mol/L, and preferably 2.0 to 7.0 mol/L. When the sulfuric acid-hydrochloric acid mixed solution is used, the mixing ratio therebetween is not particularly limited.
In addition, as described below, although some raw materials are not necessary for realizing the technical solution of the present invention, in some cases described below, the following raw materials may be used:
additional vanadium pentoxide and vanadium trioxide, the purity of which is not particularly critical, may be used as is commonly commercially available;
additional ammonia and hydrogen, generally available as commercially available products;
additional hydrochloric acid, can generally be obtained from commercially available products.
The foregoing "additional" refers to additional added material in addition to the material produced from the starting materials in the present methods, processes or apparatuses.
Step of Heat treatment
According to the method, the ammonium metavanadate serving as a raw material is decomposed by heating treatment, so that the solid vanadium oxide at least partially containing vanadium trioxide is prepared.
In some specific embodiments of the present invention, the step of heat treating comprises: ammonium metavanadate NH4VO3The method comprises the steps of thermal decomposition, ammonia decomposition and vanadium pentoxide reduction.
(ammonium metavanadate NH)4VO3Pyrolysis)
In the step of thermal decomposition of ammonium metavanadate, ammonium metavanadate NH4VO3Decomposing under the heating condition, wherein the decomposition products comprise ammonia gas, vanadium pentoxide and water, and the reaction formula is as follows:
2NH4VO3·→·2NH3·+·V2O5·+·H2O
different vanadium oxides, e.g. V, can be obtained due to the thermal decomposition of ammonium metavanadate under different conditions2O5、V3O7、V6O13、VO2、V2O3And VO and the like. In some particular embodiments of the invention to obtain V2O5The thermal decomposition conditions of ammonium metavanadate were set as follows: the temperature is 400-1200 ℃, preferably 500-1100 ℃, and more preferably 700-1100 ℃; the pressure may be in the range of 1 to 10 atmospheres, preferably 2 to 8 atmospheres. Temperatures below 400 c can result in significant formation of other vanadium oxides. By controlling the temperature and pressure, the solids produced by thermal decompositionMiddle V2O5The content of (a) is more than 95%, or more than 98%, or more than 99%.
For the reaction vessel which can be used for the thermal decomposition of ammonium metavanadate, a closed pressure vessel is preferably used to facilitate the collection or enrichment of the generated ammonia gas. In addition, in some specific embodiments of the present invention, the reaction vessel further comprises a moisture absorption device for separating and absorbing moisture generated by the thermal decomposition of ammonium metavanadate.
The atmosphere in the thermal decomposition of ammonium metavanadate is not particularly limited, and the thermal decomposition may be performed in an air atmosphere or an oxygen atmosphere. In some embodiments, especially when only the thermal decomposition of ammonium metavanadate is performed in a reaction vessel used for the thermal decomposition of ammonium metavanadate, as described below, the thermal decomposition reaction may be conducted under an atmosphere having a certain oxygen content to increase the vanadium pentoxide content in the thermal decomposition product.
(step of Ammonia decomposition)
In the present invention, the ammonia gas generated in the thermal decomposition step of ammonium metavanadate can be subjected to a further decomposition reaction to generate nitrogen gas and hydrogen gas, and the specific reaction formula is as follows:
2NH3·→·N2·+·3H2
the ammonia decomposition may be carried out under heating conditions, and the heating temperature is not particularly limited, for example, 650 to 1200 ℃, preferably 800 to 900 ℃, and the pressure is not particularly limited, and may be 1 to 10 atmospheres. Further, it is further preferred that the decomposition reaction of ammonia gas is carried out in the presence of a catalyst. The present invention is not particularly limited with respect to the kind of such a catalyst. In addition, such catalysts may be in the form of a mesh, a plate or a honeycomb.
In some embodiments of the present invention, the decomposition reaction of ammonia gas may be carried out in situ in the reaction vessel used for the thermal decomposition of ammonium metavanadate as described above. In this case, the thermal decomposition of ammonium metavanadate according to the present invention uses one reaction vessel together with the decomposition of ammonia gas, and the decomposition reaction of ammonia gas is carried out simultaneously with or after the thermal decomposition of ammonium metavanadate, or the decomposition reaction of ammonia gas is started immediately after the generation of ammonia gas (see fig. 1).
In other embodiments of the present invention, the ammonia decomposition reaction may be performed by collecting ammonia gas generated in the reaction vessel used for the thermal decomposition of ammonium metavanadate and introducing the ammonia gas into an additional ammonia gas decomposition device (see fig. 2). As above, such an ammonia decomposition device may decompose ammonia gas under heating and optionally in the presence of a catalyst. In some preferred embodiments, the produced nitrogen and hydrogen can be separated by use in combination with an ammonia decomposition unit, typically, a Pressure Swing Adsorption (PSA) unit, for example, and the hydrogen recovered. In addition, in some specific embodiments, if the ammonium metavanadate thermal decomposition is performed in the presence of a relatively high oxygen content (for example, more than 21% of the gas concentration), a separate ammonia decomposition device is generally used, and the generated hydrogen and the decomposed ammonium metavanadate solid may be subjected to the following vanadium pentoxide reduction reaction in another reaction device different from the ammonium metavanadate thermal decomposition reaction device or in another place of the same reaction device.
In addition, although it is not a necessary process for achieving the technical effects or the technical solution of the present invention, in consideration of any necessity, for example, an unexpected loss of ammonia gas which may exist or a stability in generation or supply of ammonia gas, in addition to ammonia gas generated by decomposition of ammonium metavanadate, additional ammonia gas may be supplied to the reaction system, and such ammonia gas may be supplied to the ammonium metavanadate thermal decomposition reaction device or the ammonia gas decomposition device.
(step of reduction of vanadium pentoxide)
In the present invention, the hydrogen gas generated by the above-mentioned ammonia decomposition is used to thermally decompose the vanadium pentoxide generated from the ammonium metavanadate and at least partially reduce it to vanadium trioxide.
In some embodiments of the invention, the thermal decomposition of ammonium metavanadate and the decomposition of ammonia gas are carried out at the same location, e.g. in the same reaction apparatus, and the reduction of the hydrogen gas to the solids produced by the thermal decomposition of ammonium metavanadate is also carried out at this location or in the reaction apparatus (see fig. 1). Preferably, the solid is mainly or entirely vanadium pentoxide.
In other embodiments of the invention, the thermal decomposition of ammonium metavanadate and the decomposition of ammonia gas occur at different locations (see FIG. 2). At this time, the hydrogen generated by the decomposition of ammonia gas can be subjected to the reduction reaction of vanadium pentoxide by the following scheme:
i) hydrogen is introduced into a thermal decomposition reaction device of ammonium metavanadate and other positions (second positions) different from the decomposition reaction position (first position) of the ammonium metavanadate, optionally, the second position can be physically separated from the first position in a physical separation mode, and the second position receives solid (vanadium pentoxide) generated by thermal decomposition of the ammonium metavanadate;
ii) hydrogen is introduced into a separate reduction reactor which receives solid (vanadium pentoxide) from the thermal decomposition of ammonium metavanadate;
iii) the hydrogen gas is at least partially returned to the ammonium metatitanate thermal decomposition device or the ammonium metavanadate thermal decomposition reaction site (first site).
The temperature, pressure and time of the hydrogen reduction reaction of vanadium pentoxide are not particularly limited, and may be adjusted according to the target ratio of the final vanadium trioxide to the vanadium pentoxide.
(control of temperature, pressure and time)
In the invention, the contents of vanadium trioxide and vanadium pentoxide in the final solid product can be controlled by the temperature and pressure of the reaction system.
In some embodiments of the present invention, as described above, the thermal decomposition of ammonium metavanadate, the decomposition of ammonia gas, and the reduction of vanadium pentoxide are performed in the same reaction device or in the same position of the same reaction device, and the temperature can be adjusted within the range of 400-1200 ℃ and the pressure can be adjusted within the range of 1-10 atm, and in this case, the total reaction result is that V is generated as vanadium oxide2O5And V2O3In the mixing ofA compound (I) is provided. This is because, under such conditions, ammonia gas is directly decomposed into nitrogen gas and hydrogen gas, and hydrogen gas is decomposed with V generated by ammonium metavanadate2O5Reacting a part of V2O5Reduction to V2O3。
In this case, V can be adjusted by controlling the temperature, pressure and time2O5And V2O3And with the V obtained2O5And V2O3The mixture of (a) is directly subjected to an electrolyte preparation step.
In other specific embodiments of the present invention, if the thermal decomposition of ammonium metavanadate, the decomposition of ammonia gas and the reduction of vanadium pentoxide are carried out in different reaction devices or different positions of the same reaction device respectively:
the decomposition temperature of ammonium metavanadate can be controlled to be 300-600 ℃, the pressure is 1-5 atmospheric pressures, and only V is contained in vanadium oxide generated by decomposing ammonium metavanadate2O5And ammonia gas is not decomposed. At this time, the ammonia gas may be collected and introduced into the ammonia gas decomposition reaction apparatus. Decomposing at 650-1200 deg.c and 1-10 atm to generate hydrogen (ammonia decomposing step). Preferably, the temperature of the ammonia decomposition reaction can be 800-900 ℃ and the pressure can be 5-10 atmospheric pressures.
Further, the hydrogen gas thus produced is decomposed with V produced by ammonium metavanadate2O5Reacting thereby V2O5At least partially reduced (i.e. V)2O5A reduction step). In this case, V can be controlled by controlling the temperature, pressure and flow rate of hydrogen gas in the reduction reaction2O5The ratio of the reduction. When a part of V2O5When reduced, V is obtained2O5And V2O3The mixture of (4), which can be used in the electrolyte solution formulating step. In some embodiments, the temperature of the reduction reaction may be 500-1300 deg.C, the pressure may be 1-10 atm, the flow rate of the hydrogen gas may be 0.1-100L/min, and the time of the reduction reactionCan be 0.5 to 5 hours. Preferably, the temperature of the reduction reaction is 600-1300 ℃, the pressure is 1-5 atm, the flow of the hydrogen is 0.1-50L/min, and the time of the reduction reaction is 1-5 hours. When the temperature is 1000-1300 ℃ and the pressure is 1-10 atmospheric pressures, V generated by decomposing ammonium metavanadate in the reduction reaction2O5All reduced to V by hydrogen2O3. In this case, V may be set2O3And V obtained by thermal decomposition of ammonium metavanadate at the temperature of 300-600 ℃ and the pressure of 1-5 atmospheric pressures2O5Mixing according to any proportion as required to obtain V2O5And V2O3A mixture of (a).
In addition, it should be noted that, since the thermal decomposition behavior of ammonium metavanadate in, for example, a nitrogen atmosphere, an argon atmosphere and an air atmosphere is different, the thermal decomposition atmosphere cannot be arbitrarily replaced. In the present invention, it is preferable that the decomposition of ammonium metavanadate is carried out in an air atmosphere.
(electrolyte preparation step)
In the present invention, if the vanadium oxide obtained by decomposition of ammonium metavanadate is V2O5And V2O3The mixture can be directly mixed with sulfuric acid or hydrochloric acid or a sulfuric acid-hydrochloric acid mixed solution, and heating is carried out, so that the all-vanadium flow battery electrolyte can be obtained.
If the vanadium oxide obtained by decomposition of ammonium metavanadate is only V2O5And make V2O5Obtained by carrying out a reduction reaction is V2O5And V2O3The mixture of (4), the mixture may be subjected to an electrolyte preparation step.
If the vanadium oxide obtained by decomposition of ammonium metavanadate is only V2O3Then V can be passed2O3And V2O5The mixture obtained by mixing according to a certain proportion is used for the electrolyte preparation step.
In any case, V in the mixture can be adjusted2O5And V2O3In proportion toObtaining the electrolyte of the all-vanadium redox flow battery with any valence state between 3-4 valence states.
In particular, V in the mixture2O3In an amount of 60 to 90wt%, V2O5The content of (B) is 10-40 wt%. Preferably, V2O3In an amount of 70 to 80 wt%, V2O5The content of (B) is 20-30 wt%.
In the electrolyte of the all-vanadium redox flow battery, V3+And V4+Ratio V of3+:V4+May be 1:4 to 4:1, preferably 1:3 to 3:1, more preferably 1:2 to 2:1, most preferably 1: 1. When V is3+And V4+When the ratio of (A) to (B) is 1:1, the electrolyte with the final valence of 3.5 is obtained.
As the sulfuric acid and hydrochloric acid solution, commercially available ones can be used as described above.
Other aspects
Other aspects of the technical solution of the present invention may be implemented, and although not essential, auxiliary means existing in the art may be adopted as long as the technical effects of the present invention are not affected.
In the electrolytic solution obtained by the method according to the present invention, various additives such as complexing agents, stabilizers and the like, which are conventional in the art, may be used without limitation.
< second embodiment >
A second embodiment of the invention provides an apparatus for carrying out the preparation method according to the invention.
Specifically, the apparatus of the present invention comprises: a thermal decomposition device, and a dissolution device, and optionally a reduction reaction device. Further, an ammonia gas decomposition device and a gas flow rate control device may be provided. Wherein the thermal decomposition device and, if present, the ammonia decomposition device and the reduction reaction device may include a temperature control unit and/or a pressure control unit.
In some preferred embodiments, the thermal decomposition device for ammonium metavanadate can use a sealed heating kettle. In some embodiments, the same apparatus may be used for the thermal decomposition apparatus and the reduction reaction apparatus for ammonium metavanadate.
In the embodiment of the present invention, the ammonia decomposition device is not particularly limited, and an ammonia decomposition device conventional in the art may be used. Further, the temperature control means, the pressure control means, the ammonia gas collecting device, and the gas flow rate control device are also not particularly limited, and any devices that are conventional in the art can be used.
In the present invention, the dissolving apparatus is also not particularly limited as long as it can resist corrosion by hot sulfuric acid and hydrochloric acid, and an apparatus for preparing a vanadium electrolyte, which is generally used in the art, may be used.
Examples
Specific examples of the present invention will be described below, and it should be noted that the following examples are only specific examples of the embodiments of the present invention and should not be construed as limiting the scope of the present invention.
Heating 500g ammonium metavanadate in a sealed heating kettle to 300 ℃, preserving heat for 3 hours, then heating to 550 ℃, preserving heat for 3 hours, and completely converting into V2O5And ammonia gas; leading out ammonia gas for decomposition, and decomposing the ammonia gas into nitrogen and hydrogen at 950 ℃; introducing nitrogen and hydrogen back to the sealed heating kettle at 650 deg.C2O5Reduction is carried out, and V can be controlled according to different time2O5Is reduced to V2O3See table below for specific percentages of (c). Obtained V2O5/V2O3The mixture is dissolved in heated sulfuric acid or hydrochloric acid or sulfuric acid-hydrochloric acid mixed solution to prepare the electrolyte under different equilibrium states.
| Reduction time | V2O5Is reduced to V2O3In percentage (b) |
| 1 hour | 30mol.％ |
| 2 hours | 55mol.％ |
| 3 hours | 75mol.％ |
| 4 hours | 90mol.％ |
| 5 hours | 100mol.％ |
It should be noted that, although the technical solutions of the present invention are described by specific examples, those skilled in the art can understand that the present disclosure should not be limited thereto.
Having described embodiments of the present disclosure, the foregoing description is intended to be exemplary, not exhaustive, and not limited to the disclosed embodiments. Many modifications and variations will be apparent to those of ordinary skill in the art without departing from the scope and spirit of the described embodiments. The terminology used herein is chosen in order to best explain the principles of the embodiments, the practical application, or improvements made to the technology in the marketplace, or to enable others of ordinary skill in the art to understand the embodiments disclosed herein.
Industrial applicability
The method provided by the invention can be used for simply and efficiently preparing the electrolyte for the all-vanadium redox flow battery in industry.
Claims (7)
1. A preparation method of an all-vanadium redox flow battery electrolyte comprises the following steps:
a heat treatment step: which comprises reacting ammonium metavanadate NH4VO3Thermal decomposition and simultaneous or subsequent V2O5Reducing to obtain a vanadium oxide solid, said vanadium oxide comprising at least V2O3(ii) a And
preparing an electrolyte: mixing the vanadium oxide solid with sulfuric acid or hydrochloric acid or a sulfuric acid-hydrochloric acid mixed solution to obtain the all-vanadium redox flow battery electrolyte,
wherein the step of thermally decomposing comprises NH4VO3Decomposing to produce ammonia and V2O5And a step of decomposing ammonia gas,
in the step of ammonia decomposition, nitrogen and hydrogen are generated,
at the V2O5In the step of reduction, the reduction reaction is carried out at least partially using hydrogen generated from the decomposition of the ammonia gas to convert V2O5At least partially reduced to V2O3，
Wherein said NH4VO3Decomposing to produce ammonia and V2O5The heating temperature in the step (2) is 550-700 ℃, the heating temperature in the step (2) of decomposing the ammonia gas is 800-1200 ℃,
in the electrolyte of the all-vanadium flow battery, V3+And V4+Molar ratio of (V)3+:V4+Is 1:4 to 4: 1.
2. The method of claim 1, wherein the heat treatment step includes the use of a closed pressure vessel.
3. The production method according to claim 1 or 2, wherein V in the vanadium oxide solid is controlled by controlling decomposition temperature and/or pressure and/or time in the heat treatment step2O3And V2O5The ratio of (a) to (b).
4. The method according to claim 1 or 2, wherein V is in the vanadium oxide solid2O3In an amount of 60 to 90wt%, V2O5The content of (B) is 10-40 wt%.
5. The method according to claim 1 or 2, wherein the purity of the ammonium metavanadate is 90% or more.
6. The method according to claim 1 or 2, wherein the pressure in the heat treatment step is 1 to 10 atmospheres.
7. An apparatus for carrying out the production method according to any one of claims 1 to 6, characterized in that the apparatus comprises:
a thermal decomposition device and a dissolving device,
and optionally a reduction reaction device is included,
wherein the thermal decomposition device and the reduction reaction device, if present, comprise a temperature control unit and/or a pressure control unit.
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| PCT/CN2022/089599 WO2022247572A1 (en) | 2021-05-26 | 2022-04-27 | Method and device for preparing all-vanadium redox flow battery electrolyte |
| ZA2023/11646A ZA202311646B (en) | 2021-05-26 | 2023-12-19 | Method and device for preparing all-vanadium redox flow battery electrolyte |
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| CN103401010A (en) * | 2013-08-13 | 2013-11-20 | 湖南省银峰新能源有限公司 | Method for preparing electrolytes of all-vanadium flow battery |
| CN105197995A (en) * | 2015-09-11 | 2015-12-30 | 攀钢集团攀枝花钢铁研究院有限公司 | Method for preparing vanadium trioxide |
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| US4562057A (en) * | 1984-03-29 | 1985-12-31 | Union Carbide Corporation | Preparation of low-carbon vanadium nitride |
| JP3610473B2 (en) * | 1998-08-25 | 2005-01-12 | 太陽鉱工株式会社 | Method for producing redox flow battery electrolyte |
| JP2002100390A (en) * | 2000-09-21 | 2002-04-05 | Taiyo Koko Co Ltd | Vanadium containing raw material for redox flow cell |
| CN101635363B (en) * | 2008-07-27 | 2012-05-30 | 比亚迪股份有限公司 | Vanadium ion redox flow battery electrolyte, preparation method thereof and battery thereof |
| CN102468509B (en) * | 2010-11-16 | 2015-05-20 | 中国海洋石油总公司 | Method for preparing electrolyte for vanadium battery |
| CN103904343B (en) * | 2014-04-02 | 2017-03-15 | 四川大学 | The preparation method of all-vanadium redox flow battery electrolytic solution |
| CN104164569A (en) * | 2014-06-24 | 2014-11-26 | 中国科学院过程工程研究所 | Method for preparing vanadium pentoxide by leaching vanadium slag with ammonium salt |
| CN113036198B (en) * | 2021-05-26 | 2021-08-24 | 江苏泛宇能源有限公司 | Preparation method and equipment of all-vanadium redox flow battery electrolyte |
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| CN105197995A (en) * | 2015-09-11 | 2015-12-30 | 攀钢集团攀枝花钢铁研究院有限公司 | Method for preparing vanadium trioxide |
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