CN117374351A - All-vanadium redox flow battery electrolyte and preparation method thereof - Google Patents
All-vanadium redox flow battery electrolyte and preparation method thereof Download PDFInfo
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- CN117374351A CN117374351A CN202311666138.0A CN202311666138A CN117374351A CN 117374351 A CN117374351 A CN 117374351A CN 202311666138 A CN202311666138 A CN 202311666138A CN 117374351 A CN117374351 A CN 117374351A
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- 239000003792 electrolyte Substances 0.000 title claims abstract description 79
- 229910052720 vanadium Inorganic materials 0.000 title claims abstract description 34
- 238000002360 preparation method Methods 0.000 title claims abstract description 27
- 230000009467 reduction Effects 0.000 claims abstract description 76
- 239000000243 solution Substances 0.000 claims abstract description 48
- 238000000034 method Methods 0.000 claims abstract description 42
- 238000003756 stirring Methods 0.000 claims abstract description 42
- 239000003638 chemical reducing agent Substances 0.000 claims abstract description 40
- 238000006243 chemical reaction Methods 0.000 claims abstract description 31
- 239000011259 mixed solution Substances 0.000 claims abstract description 28
- 238000002156 mixing Methods 0.000 claims abstract description 28
- 229910001456 vanadium ion Inorganic materials 0.000 claims abstract description 26
- 239000002994 raw material Substances 0.000 claims abstract description 21
- 239000002253 acid Substances 0.000 claims abstract description 20
- UNTBPXHCXVWYOI-UHFFFAOYSA-O azanium;oxido(dioxo)vanadium Chemical compound [NH4+].[O-][V](=O)=O UNTBPXHCXVWYOI-UHFFFAOYSA-O 0.000 claims abstract description 18
- 238000006555 catalytic reaction Methods 0.000 claims abstract description 18
- QWPPOHNGKGFGJK-UHFFFAOYSA-N hypochlorous acid Chemical compound ClO QWPPOHNGKGFGJK-UHFFFAOYSA-N 0.000 claims abstract description 18
- 239000003054 catalyst Substances 0.000 claims abstract description 17
- 238000001514 detection method Methods 0.000 claims abstract description 10
- 238000005273 aeration Methods 0.000 claims abstract description 9
- QAOWNCQODCNURD-UHFFFAOYSA-N Sulfuric acid Chemical compound OS(O)(=O)=O QAOWNCQODCNURD-UHFFFAOYSA-N 0.000 claims description 52
- OKKJLVBELUTLKV-UHFFFAOYSA-N Methanol Chemical compound OC OKKJLVBELUTLKV-UHFFFAOYSA-N 0.000 claims description 36
- BDAGIHXWWSANSR-UHFFFAOYSA-N methanoic acid Natural products OC=O BDAGIHXWWSANSR-UHFFFAOYSA-N 0.000 claims description 18
- 230000003647 oxidation Effects 0.000 claims description 16
- 238000007254 oxidation reaction Methods 0.000 claims description 16
- OSWFIVFLDKOXQC-UHFFFAOYSA-N 4-(3-methoxyphenyl)aniline Chemical compound COC1=CC=CC(C=2C=CC(N)=CC=2)=C1 OSWFIVFLDKOXQC-UHFFFAOYSA-N 0.000 claims description 9
- 235000019253 formic acid Nutrition 0.000 claims description 9
- RYGMFSIKBFXOCR-UHFFFAOYSA-N Copper Chemical compound [Cu] RYGMFSIKBFXOCR-UHFFFAOYSA-N 0.000 claims description 8
- VEXZGXHMUGYJMC-UHFFFAOYSA-N Hydrochloric acid Chemical compound Cl VEXZGXHMUGYJMC-UHFFFAOYSA-N 0.000 claims description 8
- 229910052802 copper Inorganic materials 0.000 claims description 8
- 239000010949 copper Substances 0.000 claims description 8
- 229910021578 Iron(III) chloride Inorganic materials 0.000 claims description 5
- 229940032296 ferric chloride Drugs 0.000 claims description 5
- RBTARNINKXHZNM-UHFFFAOYSA-K iron trichloride Chemical compound Cl[Fe](Cl)Cl RBTARNINKXHZNM-UHFFFAOYSA-K 0.000 claims description 5
- 229940000207 selenious acid Drugs 0.000 claims description 4
- MCAHWIHFGHIESP-UHFFFAOYSA-N selenous acid Chemical compound O[Se](O)=O MCAHWIHFGHIESP-UHFFFAOYSA-N 0.000 claims description 4
- 125000004432 carbon atom Chemical group C* 0.000 claims description 3
- 125000004435 hydrogen atom Chemical group [H]* 0.000 claims description 3
- 229960002523 mercuric chloride Drugs 0.000 claims description 3
- LWJROJCJINYWOX-UHFFFAOYSA-L mercury dichloride Chemical compound Cl[Hg]Cl LWJROJCJINYWOX-UHFFFAOYSA-L 0.000 claims description 3
- 125000004430 oxygen atom Chemical group O* 0.000 claims description 3
- 230000008929 regeneration Effects 0.000 claims description 2
- 238000011069 regeneration method Methods 0.000 claims description 2
- NBIIXXVUZAFLBC-UHFFFAOYSA-N Phosphoric acid Chemical compound OP(O)(O)=O NBIIXXVUZAFLBC-UHFFFAOYSA-N 0.000 claims 2
- 229910000147 aluminium phosphate Inorganic materials 0.000 claims 1
- -1 ammonium ions Chemical class 0.000 abstract description 7
- 239000001257 hydrogen Substances 0.000 abstract description 3
- 229910052739 hydrogen Inorganic materials 0.000 abstract description 3
- VEXZGXHMUGYJMC-UHFFFAOYSA-M Chloride anion Chemical compound [Cl-] VEXZGXHMUGYJMC-UHFFFAOYSA-M 0.000 abstract description 2
- 239000000047 product Substances 0.000 description 74
- 238000006722 reduction reaction Methods 0.000 description 64
- 230000000052 comparative effect Effects 0.000 description 8
- 238000005868 electrolysis reaction Methods 0.000 description 8
- 239000000126 substance Substances 0.000 description 8
- 238000004519 manufacturing process Methods 0.000 description 6
- 239000012535 impurity Substances 0.000 description 5
- LEONUFNNVUYDNQ-UHFFFAOYSA-N vanadium atom Chemical compound [V] LEONUFNNVUYDNQ-UHFFFAOYSA-N 0.000 description 5
- CURLTUGMZLYLDI-UHFFFAOYSA-N Carbon dioxide Chemical compound O=C=O CURLTUGMZLYLDI-UHFFFAOYSA-N 0.000 description 4
- GNTDGMZSJNCJKK-UHFFFAOYSA-N divanadium pentaoxide Chemical compound O=[V](=O)O[V](=O)=O GNTDGMZSJNCJKK-UHFFFAOYSA-N 0.000 description 4
- 239000000463 material Substances 0.000 description 4
- 238000004146 energy storage Methods 0.000 description 3
- 230000008569 process Effects 0.000 description 3
- 238000006479 redox reaction Methods 0.000 description 3
- OKTJSMMVPCPJKN-UHFFFAOYSA-N Carbon Chemical compound [C] OKTJSMMVPCPJKN-UHFFFAOYSA-N 0.000 description 2
- UGFAIRIUMAVXCW-UHFFFAOYSA-N Carbon monoxide Chemical compound [O+]#[C-] UGFAIRIUMAVXCW-UHFFFAOYSA-N 0.000 description 2
- XHCLAFWTIXFWPH-UHFFFAOYSA-N [O-2].[O-2].[O-2].[O-2].[O-2].[V+5].[V+5] Chemical compound [O-2].[O-2].[O-2].[O-2].[O-2].[V+5].[V+5] XHCLAFWTIXFWPH-UHFFFAOYSA-N 0.000 description 2
- 230000004913 activation Effects 0.000 description 2
- 230000002411 adverse Effects 0.000 description 2
- 230000009286 beneficial effect Effects 0.000 description 2
- 239000006227 byproduct Substances 0.000 description 2
- 229910052799 carbon Inorganic materials 0.000 description 2
- 239000001569 carbon dioxide Substances 0.000 description 2
- 229910002092 carbon dioxide Inorganic materials 0.000 description 2
- 229910002091 carbon monoxide Inorganic materials 0.000 description 2
- 230000003197 catalytic effect Effects 0.000 description 2
- 238000010586 diagram Methods 0.000 description 2
- 230000000694 effects Effects 0.000 description 2
- 239000010411 electrocatalyst Substances 0.000 description 2
- 238000005265 energy consumption Methods 0.000 description 2
- 239000007789 gas Substances 0.000 description 2
- 230000006872 improvement Effects 0.000 description 2
- 230000014759 maintenance of location Effects 0.000 description 2
- 230000033116 oxidation-reduction process Effects 0.000 description 2
- 230000002035 prolonged effect Effects 0.000 description 2
- 238000011946 reduction process Methods 0.000 description 2
- 239000002341 toxic gas Substances 0.000 description 2
- 229910001935 vanadium oxide Inorganic materials 0.000 description 2
- 230000032683 aging Effects 0.000 description 1
- 230000002238 attenuated effect Effects 0.000 description 1
- 239000000460 chlorine Substances 0.000 description 1
- 229910052801 chlorine Inorganic materials 0.000 description 1
- RCTYPNKXASFOBE-UHFFFAOYSA-M chloromercury Chemical compound [Hg]Cl RCTYPNKXASFOBE-UHFFFAOYSA-M 0.000 description 1
- LMBWSYZSUOEYSN-UHFFFAOYSA-N diethyldithiocarbamic acid Chemical compound CCN(CC)C(S)=S LMBWSYZSUOEYSN-UHFFFAOYSA-N 0.000 description 1
- 238000004090 dissolution Methods 0.000 description 1
- 239000008151 electrolyte solution Substances 0.000 description 1
- 150000002500 ions Chemical class 0.000 description 1
- 238000012986 modification Methods 0.000 description 1
- 230000004048 modification Effects 0.000 description 1
- 230000036632 reaction speed Effects 0.000 description 1
- 239000007787 solid Substances 0.000 description 1
- LSGOVYNHVSXFFJ-UHFFFAOYSA-N vanadate(3-) Chemical compound [O-][V]([O-])([O-])=O LSGOVYNHVSXFFJ-UHFFFAOYSA-N 0.000 description 1
- 150000003682 vanadium compounds Chemical class 0.000 description 1
Classifications
-
- 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
-
- H—ELECTRICITY
- H01—ELECTRIC ELEMENTS
- H01M—PROCESSES OR MEANS, e.g. BATTERIES, FOR THE DIRECT CONVERSION OF CHEMICAL ENERGY INTO ELECTRICAL ENERGY
- H01M2300/00—Electrolytes
- H01M2300/0002—Aqueous electrolytes
- H01M2300/0005—Acid electrolytes
-
- H—ELECTRICITY
- H01—ELECTRIC ELEMENTS
- H01M—PROCESSES OR MEANS, e.g. BATTERIES, FOR THE DIRECT CONVERSION OF CHEMICAL ENERGY INTO ELECTRICAL ENERGY
- H01M2300/00—Electrolytes
- H01M2300/0088—Composites
- H01M2300/0091—Composites in the form of mixtures
Abstract
The invention discloses an all-vanadium redox flow battery electrolyte and a preparation method thereof, comprising the following steps: dispersing and mixing ammonium metavanadate and hypochlorous acid solution uniformly, adding acid solution after aeration stirring reaction, and mixing uniformly to obtain raw material mixed solution; reacting the raw material mixed solution with a reducing agent to obtain a primary reduction product; mixing the primary reduction product with electrolyte containing 3-valent vanadium ions and 4-valent vanadium ions, and reacting to obtain a secondary reduction product; taking the secondary reduction product as a negative electrode, taking a mixed solution of a catalyst, a reducing agent and an acid solution as a negative electrode, and performing electrochemical catalytic reaction to obtain a tertiary reduction product; and (3) carrying out concentration and valence state allocation on the three-stage reduction product after concentration and valence state detection to obtain a 3.5-valence electrolyte finished product. The method utilizes hypochlorous acid to remove ammonium ions, and simultaneously chloride ions and hydrogen ions generated by the reaction can improve the solubility of vanadium ions and the battery efficiency.
Description
Technical Field
The invention relates to the technical field of electrolyte preparation, in particular to an all-vanadium redox flow battery electrolyte and a preparation method thereof.
Background
The electrolyte is an energy storage medium of the all-vanadium redox flow battery, is one of key materials of the all-vanadium redox flow battery, not only determines the energy storage capacity of an energy storage system of the all-vanadium redox flow battery, but also directly influences the performance and stability of the system.
At present, the preparation method of the electrolyte of the all-vanadium redox flow battery mainly comprises a chemical reduction method and an electrolytic reduction method. The chemical reduction method is to prepare electrolyte by utilizing the redox reaction of a reducing agent and high-valence vanadium oxide or vanadate, the operation is simple, but the reaction is slower, in addition, because the solid is difficult to dissolve, high sulfuric acid concentration is needed, the reducing agent and the vanadium oxide cannot be completely reacted, and the prepared electrolyte has more impurities and affects the electrochemical performance of the electrolyte; the electrolytic reduction method is that mixed solution of vanadium pentoxide and sulfuric acid is added into a cathode electrolytic tank, sulfuric acid solution is added into an anode electrolytic tank, then direct current is introduced into the anode electrolytic tank through a constant current device, and high-valence vanadium compounds in the cathode electrolytic tank undergo reduction reaction to generate low-valence vanadium ions to prepare electrolyte, so that the reaction speed is high, and the impurity ion content is low. However, during electrolysis, a higher voltage is required to maintain a higher electrolysis rate, and the high voltage accelerates the aging of the electrolytic material and the equipment. In addition, the production speed of the electrolyte is limited by the electrolytic reduction speed of the high-valence vanadium, which is not beneficial to further improving the production efficiency.
CN114438514a discloses a method for preparing an electrolyte of an all-vanadium redox flow battery by taking ammonium metavanadate as a raw material, wherein diethyl dithiocarbamic acid is taken as a reducing agent, and sulfuric acid solution is taken as an electrolytic positive electrode by combining an electrolytic method to prepare the electrolyte. CN115411326A is a vanadium electrolyte prepared from ammonium metavanadate as a raw material, and the preparation method is free from a section for preparing vanadium pentoxide by roasting, and is free from a chemical reducing agent, and the vanadium electrolyte is directly prepared by a two-stage electrolytic method. Although these methods have some improvements over the conventional chemical reduction method and electrolytic reduction method, they have problems of residual impurities, low life of electrolytic materials and equipment, low production efficiency of electrolytic solution, low utilization rate of resources, and the like.
In order to further improve the preparation method of the electrolyte of the all-vanadium redox flow battery, the invention provides the preparation method of the electrolyte of the all-vanadium redox flow battery from three dimensions of impurity removal, process improvement and resource utilization.
Disclosure of Invention
The invention aims to provide an all-vanadium redox flow battery electrolyte and a preparation method thereof, which solve the problems of impurity residue, low service lives of electrolytic materials and equipment, low production efficiency of the electrolyte, poor performance of the electrolyte and low resource utilization rate in the preparation process of the electrolyte;
in order to achieve the above purpose, the present invention provides the following technical solutions:
the application discloses a preparation method of an electrolyte of an all-vanadium redox flow battery, which comprises the following steps:
s1, uniformly mixing: dispersing and mixing ammonium metavanadate and hypochlorous acid solution uniformly, adding acid solution after aeration stirring reaction, and mixing uniformly to obtain raw material mixed solution;
s2, primary reduction: stirring the raw material mixed solution obtained in the step S1 and a reducing agent at the speed of 800-1000 rpm at the temperature of 40-60 ℃ for reaction for 8-12 hours to obtain a primary reduction product;
s3, secondary reduction: mixing the primary reduction product obtained in the step S2 with electrolyte containing 3-valent vanadium ions and 4-valent vanadium ions, and stirring at a speed of 800-1000 rpm for reaction for 1-2 hours to obtain a secondary reduction product;
s4, three-stage reduction: taking the secondary reduction product obtained in the step S3 as a negative electrode, taking a mixed solution of a catalyst, a reducing agent and an acid solution as a negative electrode, and performing current density of 100-500 mA/cm 2 The voltage is 1.0-3.0V, the stirring speed is 800-1000 rpm, and the electrochemical catalytic reaction is carried out for 1-10 hours, so that a three-stage reduction product is obtained;
s5, preparing a finished product: and (3) carrying out concentration and valence state allocation on the three-stage reduction product after concentration and valence state detection to obtain a 3.5-valence electrolyte finished product.
Preferably, the concentration of the hypochlorous acid solution in the step S1 is 2-5 mol/L.
Preferably, the acid solution in the step S1 is one of sulfuric acid and hydrochloric acid, and the concentration is 7-9 mol/L;
preferably, in the step S1, the weight ratio of the ammonium metavanadate, the hypochlorous acid solution and the acid solution is 1: (5-10): (1-6).
Preferably, the reducing agent in the step S2 is one of formic acid and methanol, and the mass ratio of the reducing agent to ammonium metavanadate is 1:wherein x is the number of carbon atoms in the formula of the reducing agent, y is the number of hydrogen atoms in the formula of the reducing agent, and z is the number of oxygen atoms in the formula of the reducing agent.
Preferably, in the step S3, the primary reduction product is mixed with electrolyte containing 3-valent vanadium ions and 4-valent vanadium ions according to the mass ratio of 1 (0.1-1).
Preferably, the catalyst in the step S4 is one of chloroplatinic acid, selenious acid, ferric chloride and mercuric chloride.
Preferably, in the step S4, the catalyst, the reducing agent and the acid solution are mixed according to the mass ratio of 1 (5-20) (100-500).
Preferably, in step S4, the weight ratio of the positive electrode to the negative electrode is 1: (0.1 to 10).
Preferably, the method further comprises the steps of preparing the reducer by regeneration: taking the oxidation product obtained in the step S2 and the positive electrode oxidation product obtained in the step S4 as a negative electrode, taking 0.5-2 mol/L dilute sulfuric acid as a positive electrode, taking 1% of copper as a catalyst, and the current density is 200-300 mA/cm 2 And (3) carrying out electrochemical catalytic reaction for 1-10 h under the condition of the voltage of 1-1.5V and the stirring speed of 800-1000 rpm to obtain the reducing agent.
Preferably, the heat produced in step S3 and step S4 will be used for heat exchange in step S2.
The invention discloses an all-vanadium redox flow battery electrolyte, which is prepared by adopting the preparation method of the all-vanadium redox flow battery electrolyte.
The invention has the beneficial effects that:
1. according to the preparation method of the electrolyte, ammonium ions are removed by using hypochlorous acid, and meanwhile, the solubility of vanadium ions and the battery efficiency can be improved due to chloride ions and hydrogen ions generated by the reaction. In addition, the primary reduction controls the moderate excess of pentavalent vanadium, can fully react the reducing substances, avoids adverse effects of residual or incomplete reaction byproducts of the reducing substances on the performance of the electrolyte, and improves the cycle stability and the battery efficiency of the electrolyte;
2. in the three-stage reduction process, the anode catalyzes oxidation-reduction substances through the electrocatalyst, so that the reaction activation energy can be reduced, the electrochemical potential can be reduced, the oxidation-reduction reaction rate can be improved, the energy conversion rate can be improved, and the service life of equipment can be prolonged;
3. the invention collects the carbon dioxide, carbon monoxide and other chamber gases and toxic gas products after the reduction substances are oxidized, converts the products into reduction substances through the electrochemical catalytic process, and is reused in the electrolyte preparation process. And meanwhile, heat in different working procedures is recycled, so that energy consumption is reduced. Finally, the purposes of reducing carbon emission and being environment-friendly are realized;
4. the invention can operate relatively independently among the working procedures, and can greatly improve the production efficiency of the electrolyte.
The features and advantages of the present invention will be described in detail by way of example with reference to the accompanying drawings.
Drawings
FIG. 1 is a flow chart of a method for preparing an electrolyte of an all-vanadium redox flow battery of the invention;
FIG. 2 is a graph showing the state of the electrolytic reaction at step S4 in example 1 of the present invention;
FIG. 3 is a graph showing the state of the electrolytic reaction at step S2 in comparative example 2 of the present invention;
FIG. 4 is a surface state diagram of an electrode plate in an electrolytic device prepared by using the electrolyte according to the invention after different electrolytic methods.
Detailed Description
The present invention will be further described in detail with reference to the drawings and examples, in order to make the objects, technical solutions and advantages of the present invention more apparent. It should be understood that the detailed description and specific examples, while indicating the invention, are intended for purposes of illustration only and are not intended to limit the scope of the invention. In addition, in the following description, descriptions of well-known structures and techniques are omitted so as not to unnecessarily obscure the present invention.
Referring to fig. 1, an embodiment of the invention provides a method for preparing an electrolyte of an all-vanadium redox flow battery, which is characterized by comprising the following steps:
s1, uniformly mixing: dispersing and mixing ammonium metavanadate and hypochlorous acid solution uniformly, adding acid solution after aeration stirring reaction, and mixing uniformly to obtain raw material mixed solution; wherein, the weight ratio of the ammonium metavanadate to the hypochlorous acid solution to the acid solution is 1: (5-10): (1-6);
specifically, in the step S1, the concentration of the hypochlorous acid solution is 2-5 mol/L; the acid solution is one of sulfuric acid and hydrochloric acid, and the concentration is 7-9 mol/L
S2, primary reduction: stirring the raw material mixed solution obtained in the step S1 and a reducing agent at the speed of 800-1000 rpm at the temperature of 40-60 ℃ for reaction for 8-12 hours to obtain a primary reduction product;
specifically, the reducing agent is one of formic acid and methanol, and the mass ratio of the reducing agent to ammonium metavanadate is 1:wherein x is the number of carbon atoms in the formula of the reducing agent, y is the number of hydrogen atoms in the formula of the reducing agent, and z is the number of oxygen atoms in the formula of the reducing agent.
S3, secondary reduction: mixing the primary reduction product obtained in the step S2 with electrolyte containing 3-valent vanadium ions and 4-valent vanadium ions according to the mass ratio of 1 (0.1-1), and stirring at the speed of 800-1000 rpm for reaction for 1-2 hours to obtain a secondary reduction product;
s4, three-stage reduction: taking the secondary reduction product obtained in the step S3 as a negative electrode, taking a solution prepared by mixing a catalyst, a reducing agent and an acid solution according to the mass ratio of 1 (5-20) (100-500) as a positive electrode, wherein the weight ratio of the positive electrode to the negative electrode is 1 (0.1-10), and the current density is 100-500 mA/cm 2 The voltage is 1.0-3.0V, the stirring speed is 800-1000 rpm, and the electrochemical catalytic reaction is carried out for 1-10 hours, so that a three-stage reduction product is obtained; wherein the catalyst is one of chloroplatinic acid, selenious acid, ferric chloride and mercuric chloride.
S5, preparing a finished product: and (3) carrying out concentration and valence state allocation on the three-stage reduction product after concentration and valence state detection to obtain a 3.5-valence electrolyte finished product.
In addition, the preparation of the reducing agent is also included: taking the oxidation product obtained in the step S2 and the positive electrode oxidation product obtained in the step S4 as a negative electrode, taking 0.5-2 mol/L dilute sulfuric acid as a positive electrode, taking 1% of copper as a catalyst, wherein the weight ratio of the positive electrode to the negative electrode is 1 (1-5), the current density is 200-300 mA/cm < 2 >, the voltage is 1-1.5V, and the electrochemical catalytic reaction is carried out for 1-10 h under the condition of the stirring speed is 800-1000 rpm, so as to obtain the reducing agent.
Wherein the heat produced in step S3 and step S4 will be used for heat exchange in step S2.
Example 1
The electrolyte preparation is carried out according to the following steps:
s1, dispersing and mixing 1 part by mass of ammonium metavanadate and 5 parts by mass of hypochlorous acid solution with the concentration of 5mol/L uniformly, adding 1 part by mass of sulfuric acid solution with the concentration of 9mol/L uniformly after aeration stirring reaction, and obtaining a raw material mixed solution;
s2, stirring and reacting the raw material mixed solution prepared in the step S1 with 0.2 part by mass of formic acid at the speed of 800rpm at the temperature of 50 ℃ for 8 hours to obtain a primary reduction product;
s3, mixing 1 part by mass of the primary reduction product prepared by the S2 with 0.1 part by mass of electrolyte containing 3-valent vanadium ions and 4-valent vanadium ions, and stirring at a speed of 800rpm for reaction for 1 hour to obtain a secondary reduction product;
s4, taking 1 part by mass of the secondary reduction product prepared by the S3 as a negative electrode, taking 10 parts by mass of a mixed solution formed by mercury chloride, formic acid and sulfuric acid solution according to the mass ratio of 1:5:100 as a positive electrode, and carrying out current density of 400mA/cm 2 Electrochemical catalytic reaction is carried out for 10 hours under the voltage of 3.0V and the stirring speed of 800rpm, so as to obtain a three-stage reduction product;
s5, carrying out concentration and valence state allocation on the three-stage reduction product prepared in the S4 after concentration and valence state detection to obtain a 3.5-valence electrolyte finished product. In addition, 1 part by mass of the oxidation product obtained in the step S2 and the positive electrode oxidation product obtained in the step S4 are taken as a negative electrode, 1 part by mass of 2mol/L dilute sulfuric acid is taken as a positive electrode, 1% of copper is taken as a catalyst, and the current density is 200mA/cm 2 Electrochemical catalytic reaction is carried out for 6 hours under the condition of voltage of 1.5V and stirring speed of 800rpm, so as to obtain formic acid. Meanwhile, the heat produced in step S3 and step S4 will be used for heat exchange in step S2.
Example 2
The electrolyte preparation is carried out according to the following steps:
s1, dispersing and mixing 1 part by mass of ammonium metavanadate and 10 parts by mass of hypochlorous acid solution with the concentration of 2mol/L uniformly, adding 6 parts by mass of hydrochloric acid solution with the concentration of 7mol/L uniformly after aeration stirring reaction, and obtaining a raw material mixed solution;
s2, stirring and reacting the raw material mixed solution prepared in the step S1 with 0.05 part by mass of methanol at the speed of 1000rpm at the temperature of 40 ℃ for 12 hours to obtain a primary reduction product;
s3, mixing 1 part by mass of the primary reduction product prepared in the step S2 with 1 part by mass of electrolyte containing 3-valent vanadium ions and 4-valent vanadium ions, and stirring at a speed of 1000rpm for 2 hours to obtain a secondary reduction product;
s4, taking 1 part by mass of the secondary reduction product prepared by the S3 as a negative electrode, taking 0.1 part by mass of a mixed solution formed by selenious acid, methanol and sulfuric acid solution according to a mass ratio of 1:20:500 as a positive electrode, and carrying out current density of 500mA/cm 2 Electrochemical catalytic reaction is carried out for 5 hours under the voltage of 2.0V and the stirring speed of 800rpm, so as to obtain a three-stage reduction product;
s5, carrying out concentration and valence state allocation on the three-stage reduction product prepared in the S4 after concentration and valence state detection to obtain a 3.5-valence electrolyte finished product. In addition, 1 part by mass of the oxidation product obtained in the step S2 and the positive electrode oxidation product obtained in the step S4 are taken as a negative electrode, 5 parts by mass of 2mol/L dilute sulfuric acid is taken as a positive electrode, 1% of copper is taken as a catalyst, and the current density is 300mA/cm 2 Under the condition of voltage of 1.0V and stirring speed of 1000rpm, the electrochemical catalytic reaction is carried out for 1h, and the methanol is obtained. Meanwhile, the heat produced in step S3 and step S4 will be used for heat exchange in step S2.
Example 3
The electrolyte preparation is carried out according to the following steps:
s1, dispersing and mixing 1 part by mass of ammonium metavanadate and 7 parts by mass of hypochlorous acid solution with the concentration of 3mol/L uniformly, adding 5 parts by mass of sulfuric acid solution with the concentration of 8mol/L uniformly after aeration and stirring reaction, and obtaining a raw material mixed solution;
s2, stirring and reacting the raw material mixed solution prepared in the step S1 with 0.2 part by mass of formic acid at the speed of 1000rpm at the temperature of 40 ℃ for 12 hours to obtain a primary reduction product;
s3, mixing 1 part by mass of the primary reduction product prepared in the step S2 with 1 part by mass of electrolyte containing 3-valent vanadium ions and 4-valent vanadium ions, and stirring at a speed of 1000rpm for 2 hours to obtain a secondary reduction product;
s4, taking 1 part by massThe secondary reduction product prepared in S3 is taken as a negative electrode, 0.1 part by mass of mixed solution formed by chloroplatinic acid, formic acid and sulfuric acid solution according to the mass ratio of 1:20:500 is taken as a positive electrode, and the current density is 100mA/cm 2 Electrochemical catalytic reaction is carried out for 5 hours under the voltage of 1.0V and the stirring speed of 800rpm, so as to obtain a three-stage reduction product;
s5, carrying out concentration and valence state allocation on the three-stage reduction product prepared in the S4 after concentration and valence state detection to obtain a 3.5-valence electrolyte finished product. In addition, 1 part by mass of the oxidation product obtained in the step S2 and the positive electrode oxidation product obtained in the step S4 are taken as a negative electrode, 5 parts by mass of 2mol/L dilute sulfuric acid is taken as a positive electrode, 1% of copper is taken as a catalyst, and the current density is 300mA/cm 2 Electrochemical catalytic reaction is carried out for 1h under the condition of voltage of 1.0V and stirring speed of 1000rpm, so as to obtain formic acid. Meanwhile, the heat produced in step S3 and step S4 will be used for heat exchange in step S2.
Example 4
The electrolyte preparation is carried out according to the following steps:
s1, dispersing and mixing 1 part by mass of ammonium metavanadate and 7 parts by mass of hypochlorous acid solution with the concentration of 3mol/L uniformly, adding 5 parts by mass of sulfuric acid solution with the concentration of 8mol/L uniformly after aeration and stirring reaction, and obtaining a raw material mixed solution;
s2, stirring and reacting the raw material mixed solution prepared in the step S1 with 0.05 part by mass of methanol at the speed of 900rpm at the temperature of 60 ℃ for 10 hours to obtain a primary reduction product;
and S3, mixing 1 part by mass of the primary reduction product prepared by the S2 with 0.7 part by mass of electrolyte containing 3-valent vanadium ions and 4-valent vanadium ions, and stirring at a speed of 850rpm for reaction for 1.5 hours to obtain a secondary reduction product.
S4, taking 1 part by mass of the secondary reduction product prepared by the S3 as a negative electrode, taking 5 parts by mass of a mixed solution formed by ferric chloride, methanol and sulfuric acid solution according to a mass ratio of 1:10:300 as a positive electrode, and carrying out current density of 200mA/cm 2 Electrochemical catalytic reaction is carried out for 1h under the voltage of 2.5V and the stirring speed of 1000rpm, so as to obtain a three-stage reduction product;
s5, carrying out concentration and valence state allocation on the three-stage reduction product prepared in the S4 after concentration and valence state detection to obtain a 3.5-valence electrolyte finished product. In addition, 1 part by mass of step S2The oxidation product of (2) and the positive electrode oxidation product obtained in the step S4 are taken as a negative electrode, 5 parts by mass of 0.5mol/L dilute sulfuric acid is taken as a positive electrode, 1% of copper is taken as a catalyst, and the current density is 240mA/cm 2 And (3) carrying out electrochemical catalytic reaction for 10 hours under the condition of the voltage of 1.2V and the stirring speed of 900rpm to obtain methanol. Meanwhile, the heat produced in step S3 and step S4 will be used for heat exchange in step S2.
Comparative example 1
The electrolyte preparation is carried out according to the following steps:
s1, directly and uniformly mixing 1 part by mass of ammonium metavanadate with 5 parts by mass of sulfuric acid solution with the concentration of 8mol/L to obtain a raw material mixed solution;
s2, stirring and reacting the raw material mixed solution prepared in the step S1 with 0.05 part by mass of methanol at the speed of 900rpm at the temperature of 60 ℃ for 10 hours to obtain a primary reduction product;
and S3, mixing 1 part by mass of the primary reduction product prepared by the S2 with 0.7 part by mass of electrolyte containing 3-valent vanadium ions and 4-valent vanadium ions, and stirring at a speed of 850rpm for reaction for 1.5 hours to obtain a secondary reduction product.
S4, taking 1 part by mass of the secondary reduction product prepared by the S3 as a negative electrode, taking 5 parts by mass of a mixed solution formed by ferric chloride, methanol and sulfuric acid solution according to a mass ratio of 1:10:300 as a positive electrode, and carrying out current density of 400mA/cm 2 Electrochemical catalytic reaction is carried out for 1h under the voltage of 2.5V and the stirring speed of 1000rpm, so as to obtain a three-stage reduction product;
s5, carrying out concentration and valence state allocation on the three-stage reduction product prepared in the S4 after concentration and valence state detection to obtain a 3.5-valence electrolyte finished product. In addition, 1 part by mass of the oxidation product obtained in the step S2 and the positive electrode oxidation product obtained in the step S4 are taken as a negative electrode, 5 parts by mass of 0.5mol/L dilute sulfuric acid is taken as a positive electrode, 1% of copper is taken as a catalyst, and the current density is 240mA/cm 2 And (3) carrying out electrochemical catalytic reaction for 10 hours under the condition of the voltage of 1.2V and the stirring speed of 900rpm to obtain methanol. Meanwhile, the heat produced in step S3 and step S4 will be used for heat exchange in step S2;
comparative example 2
The electrolyte preparation is carried out according to the following steps:
s1, dispersing and mixing 1 part by mass of ammonium metavanadate and 5 parts by mass of hypochlorous acid solution with the concentration of 5mol/L uniformly, adding 1 part by mass of sulfuric acid solution with the concentration of 9mol/L uniformly after aeration stirring reaction, and obtaining a raw material mixed solution;
s2, taking 1 part by mass of the secondary reduction product prepared by the S1 as a negative electrode, taking 10 parts by mass of sulfuric acid solution as a positive electrode, and carrying out electrochemical catalytic reaction for 10 hours under the conditions of current density of 400mA/cm < 2 >, voltage of 3.0V and stirring speed of 800rpm to obtain a reduction product;
s3, carrying out concentration and valence state allocation on the reduction product prepared in the S2 after concentration and valence state detection to obtain a 3.5-valence electrolyte finished product.
The electrolytes prepared by the methods of examples 1 to 4 and comparative examples 1 to 2 were charged into the stacks for charge-discharge cycle test, and the coulombic efficiency, voltage efficiency, energy efficiency and capacity retention after 100 th cycle of the stacks were recorded as shown in table 1:
TABLE 1
The results of examples 1-4 and comparative examples 1-2 according to Table 1 show that the electrolyte prepared by the method of the present invention has higher coulombic efficiency, voltage efficiency, energy efficiency and capacity retention rate, mainly because ammonium ions are removed by hypochlorous acid, and the dissolution rate of vanadium ions and battery efficiency can be improved by chlorine ions and hydrogen ions generated by the reaction. In addition, the primary reduction controls the moderate excess of pentavalent vanadium, so that the reducing agent can fully react, adverse effects on the performance of the electrolyte caused by residual or incomplete reaction byproducts of the reducing agent are avoided, and the efficiency and the circulation stability of the electrolyte are further improved.
Fig. 2 is a graph showing the state of the electrolysis reaction of step S4 in example 1, and fig. 3 is a graph showing the state of the electrolysis reaction of step S2 in comparative example 2, it can be seen that the current of the electrolysis of example 1 is always maintained at the maximum value, and the current of the electrolysis of comparative example 2 is rapidly attenuated as the reaction proceeds. Fig. 4 is a surface state diagram of the electrode pad in the electrolyte preparation electrolysis apparatus after different electrolysis methods, and it is obvious that the surface state of the electrode pad in example 1 is almost the same as the initial state, while many bubbles appear on the surface of the electrode pad in comparative example 2, and the surface damage is serious. The above results are mainly due to the fact that in the three-stage reduction process, the anode catalyzes oxidation-reduction substances through the electrocatalyst, so that the reaction activation energy can be reduced, the electrochemical potential can be reduced, the oxidation-reduction reaction rate can be improved, the energy conversion rate can be improved, and the service life of equipment can be prolonged.
Meanwhile, the invention collects the carbon dioxide, carbon monoxide and other chamber gases and toxic gas products after the reducing substances are oxidized, converts the products into reducing substances through an electrochemical catalytic process and is reused in the electrolyte preparation process. And the heat in different working procedures is recycled, so that the energy consumption is reduced. Finally, the purposes of reducing carbon emission and being environment-friendly are achieved. In addition, the working procedures of the invention are operated relatively independently, so that the production efficiency of the electrolyte can be greatly improved.
The foregoing description of the preferred embodiments of the invention is not intended to be limiting, but rather is intended to cover all modifications, equivalents, or alternatives falling within the spirit and principles of the invention.
Claims (10)
1. The preparation method of the electrolyte of the all-vanadium redox flow battery is characterized by comprising the following steps of:
s1, uniformly mixing: dispersing and mixing ammonium metavanadate and hypochlorous acid solution uniformly, adding acid solution after aeration stirring reaction, and mixing uniformly to obtain raw material mixed solution;
s2, primary reduction: stirring the raw material mixed solution obtained in the step S1 and a reducing agent at the speed of 800-1000 rpm at the temperature of 40-60 ℃ for reaction for 8-12 hours to obtain a primary reduction product;
s3, secondary reduction: mixing the primary reduction product obtained in the step S2 with electrolyte containing 3-valent vanadium ions and 4-valent vanadium ions, and stirring at a speed of 800-1000 rpm for reaction for 1-2 hours to obtain a secondary reduction product;
s4, three-stage reduction: taking the secondary reduction product obtained in the step S3 as a negative electrode, taking a mixed solution of a catalyst, a reducing agent and an acid solution as a positive electrode, and performing current density of 100-500 mA/cm 2 Voltage 1.Performing electrochemical catalytic reaction for 1-10 h at the stirring speed of 800-1000 rpm at 0-3.0V to obtain a three-stage reduction product;
s5, preparing a finished product: and (3) carrying out concentration and valence state allocation on the three-stage reduction product after concentration and valence state detection to obtain a 3.5-valence electrolyte finished product.
2. The method for preparing the electrolyte of the all-vanadium redox flow battery as set forth in claim 1, wherein the method comprises the following steps: in the step S1, the concentration of the hypochlorous acid solution is 2-5 mol/L.
3. The method for preparing the electrolyte of the all-vanadium redox flow battery as set forth in claim 1, wherein the method comprises the following steps: the acid solution in the step S1 is one or more of sulfuric acid, hydrochloric acid and phosphoric acid, and the concentration is 7-9 mol/L.
4. The method for preparing the electrolyte of the all-vanadium redox flow battery as set forth in claim 1, wherein the method comprises the following steps: in the step S1, the weight ratio of the ammonium metavanadate to the hypochlorous acid solution to the acid solution is 1: (5-10): (1-6).
5. The method for preparing the electrolyte of the all-vanadium redox flow battery as set forth in claim 1, wherein the method comprises the following steps: the reducing agent in the step S2 is one of formic acid and methanol, and the mass ratio of the reducing agent to ammonium metavanadate is 1:wherein x is the number of carbon atoms in the formula of the reducing agent, y is the number of hydrogen atoms in the formula of the reducing agent, and z is the number of oxygen atoms in the formula of the reducing agent.
6. The method for preparing the electrolyte of the all-vanadium redox flow battery as set forth in claim 1, wherein the method comprises the following steps: and (3) mixing the primary reduction product in the step (S3) with electrolyte containing 3-valent vanadium ions and 4-valent vanadium ions according to the mass ratio of 1 (0.1-1).
7. The method for preparing the electrolyte of the all-vanadium redox flow battery as set forth in claim 1, wherein the method comprises the following steps: the catalyst in the step S4 is one of chloroplatinic acid, selenious acid, ferric chloride and mercuric chloride; the catalyst, the reducing agent and the acid solution are mixed according to the mass ratio of 1 (5-20) to 100-500.
8. The method for preparing the electrolyte of the all-vanadium redox flow battery as set forth in claim 1, wherein the method comprises the following steps: the method also comprises the steps of regeneration preparation of the reducing agent: taking the oxidation product obtained in the step S2 and the positive electrode oxidation product obtained in the step S4 as a negative electrode, taking 0.5-2 mol/L dilute sulfuric acid as a positive electrode, taking copper as a catalyst, and taking the current density of 200-300 mA/cm 2 Electrochemical catalytic reaction is carried out for 1-10 h under the condition of the voltage of 1-1.5V and the stirring speed of 800-1000 rpm; the reducing agent is obtained.
9. The method for preparing the electrolyte of the all-vanadium redox flow battery as set forth in claim 1, wherein the method comprises the following steps: the heat produced in step S3 and step S4 will be used for heat exchange in step S2.
10. An all-vanadium redox flow battery electrolyte, which is characterized in that: the all-vanadium redox flow battery electrolyte is prepared by adopting the preparation method of the all-vanadium redox flow battery electrolyte as set forth in any one of claims 1-9.
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