CN115882021B - Preparation method of 3.5-valent sulfuric acid hydrochloric acid system vanadium electrolyte - Google Patents
Preparation method of 3.5-valent sulfuric acid hydrochloric acid system vanadium electrolyte Download PDFInfo
- Publication number
- CN115882021B CN115882021B CN202310142956.4A CN202310142956A CN115882021B CN 115882021 B CN115882021 B CN 115882021B CN 202310142956 A CN202310142956 A CN 202310142956A CN 115882021 B CN115882021 B CN 115882021B
- Authority
- CN
- China
- Prior art keywords
- vanadium
- sulfuric acid
- valent
- electrolyte
- acid solution
- Prior art date
- Legal status (The legal status is an assumption and is not a legal conclusion. Google has not performed a legal analysis and makes no representation as to the accuracy of the status listed.)
- Active
Links
Images
Classifications
-
- 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
Landscapes
- Fuel Cell (AREA)
Abstract
The invention provides a preparation method of a 3.5-valent sulfuric acid hydrochloric acid system vanadium electrolyte, which comprises the following steps: respectively electrolyzing a sulfate acid solution of 4-valent vanadium ions and a sulfuric acid solution of (4+x) valent vanadium ions as negative and positive electrolyte, and respectively obtaining a 3.5-valent sulfuric acid hydrochloric acid system vanadium electrolyte and a sulfuric acid solution of (4+y) valent vanadium ions at the negative and positive electrodes; reducing the sulfuric acid solution of the (4+y) vanadium ions to obtain a sulfuric acid solution of the (4+x) vanadium ions; the sulfuric acid solution of (4+x) valence vanadium ion can be used as the positive electrode electrolyte of the all-vanadium redox flow battery and the sulfuric acid solution of 4 valence vanadium ion of the negative electrode for charging electrolysis, and the 3.5 valence sulfuric acid hydrochloric acid system vanadium electrolyte is obtained at the negative electrode. The preparation method of the 3.5-valent sulfuric acid hydrochloric acid system vanadium electrolyte provided by the invention has the advantages of quick electrolysis, quick reduction, safety, reliability, economy, high efficiency and recycling.
Description
Technical Field
The invention relates to the technical field of all-vanadium redox flow batteries, in particular to a preparation method of a 3.5-valent sulfuric acid hydrochloric acid system vanadium electrolyte.
Background
The vanadium redox flow battery is the first choice of a high-capacity long-time energy storage battery, and utilizes vanadium electrolyte to respectively circulate through a positive electrode and a negative electrode to perform electrochemical reaction so as to realize the mutual conversion of electric energy and chemical energy.
Patent application CN201310542929.2 discloses a preparation method of 3.5-valence vanadium electrolyte, which adopts an electrolysis device, takes half volume of 4-valence vanadium solution as positive electrolyte, takes one volume of 4-valence vanadium solution as negative electrolyte, controls electrolysis electricity under the action of current given by a power supply, reduces vanadium of the negative electrolyte from 4 to 3.5 and oxidizes vanadium of the positive electrolyte from 4 to 5. And after the electrolysis is finished, discharging the 3.5-valence vanadium solution of the cathode, adding 4-valence vanadium with the same volume, adding a reducing agent into the anode to reduce the 5-valence vanadium to 4-valence, and repeating the previous electrolysis.
However, this method has the following serious drawbacks: first, the method requires that the concentration of vanadium 4 in the volume of half of the vanadium 4 solution as the positive electrode electrolyte and the concentration of vanadium 4 in the volume of one part of the vanadium 4 solution as the negative electrode electrolyte of the electrolysis device must be completely equal to reduce the vanadium of the negative electrode electrolyte from 4 to 3.5 when the vanadium of the positive electrode electrolyte is oxidized from 4 to 5. Secondly, the electrolysis needs to oxidize all vanadium in the positive electrolyte from 4 to 5 (otherwise, the vanadium in the negative electrolyte is higher than 3.5), which takes a very long time to be possible to complete, and the method has no practicability, because as the electrolysis reaction proceeds, the concentration of the vanadium in the positive electrolyte from 4 is lower and approaches zero, the electrolysis reaction rate is slower and approaches zero, the electrolysis current is smaller and approaches zero, and theoretically, an infinitely long time is needed to oxidize all vanadium in the positive electrolyte from 4 to 5. In addition, it is also necessary to add a reducing agent to the positive electrode electrolyte to reduce the vanadium of valence 5 to valence 4 (otherwise, the vanadium valence of the next electrolytic negative electrode electrolyte is reduced to less than 3.5), if the reducing agent is added according to the stoichiometric ratio of completely reducing the vanadium of valence 5 to valence 4, it also takes very long time to reduce the vanadium of valence 5 to valence 4, and the practicability is lacking, because as the reduction reaction proceeds, the concentration of the vanadium of valence 5 in the positive electrode electrolyte and the concentration of the reducing agent are both lower and tend to zero, the reduction reaction rate is slower and lower and tends to zero, and it is theoretically necessary to take an infinitely long time to reduce the vanadium of the positive electrode electrolyte from valence 5 to valence 4.
If the incompletely reduced positive electrode electrolyte is directly used for the next electrolysis, the unreacted reducing agent (such as hydrazine hydrate, oxalic acid and the like) in the positive electrode electrolyte can have oxidation-reduction reaction with newly generated 5-valence vanadium, and a large amount of N is generated in the positive electrode electrolyte 2 、CO 2 When bubbles are generated, the positive electrolyte magnetic circulation pump is frequently disconnected, idles and even burns, and the smooth electrolytic reaction is seriously affected.
If the reducing agent is excessively added, the vanadium in the positive electrode electrolyte can be completely reduced from 5 to 4 in a short time, but the residual reducing agent (such as hydrazine hydrate, oxalic acid and the like) in the positive electrode electrolyte can also have oxidation-reduction reaction with newly generated 5-valent vanadium in the next electrolysis process, so that a large amount of N is generated in the positive electrode electrolyte 2 、CO 2 When bubbles are generated, the magnetic circulation pump of the positive electrolyte is frequently disconnected, idled or even burned, the smooth electrolytic reaction is seriously affected, and the residual reducing agent in the positive electrolyte is more than once due to the accumulation effectMore, N is generated 2 、CO 2 The amount of the air bubbles is larger than that of the air bubbles at one time, and the situations of liquid breaking, idling, even pump burning and the like of the positive electrolyte magnetic circulation pump are frequent and serious at one time, so that the method is finally completely invalid.
Therefore, a preparation method of the 3.5-valent sulfuric acid hydrochloric acid system vanadium electrolyte, which is rapid in electrolysis, rapid in reduction, safe, reliable, economical and efficient, is needed at present.
Disclosure of Invention
The invention aims to solve the technical problem of providing a method for preparing a 3.5-valent sulfuric acid hydrochloric acid system vanadium electrolyte, which has the advantages of quick electrolysis, quick reduction, safety, reliability, economy, high efficiency and recycling.
In order to solve the technical problems, the invention provides a preparation method of a 3.5-valent sulfuric acid hydrochloric acid system vanadium electrolyte, which is characterized by comprising the following steps:
respectively charging and electrolyzing a sulfate acid solution of 4-valent vanadium ions and a sulfuric acid solution of 4-valent vanadium ions as a negative electrode electrolyte and a positive electrode electrolyte, obtaining a 3.5-valent sulfuric acid hydrochloric acid system vanadium electrolyte at the negative electrode, and obtaining a sulfuric acid solution of (4+z) valent vanadium ions at the positive electrode;
adding oxalic acid into the sulfuric acid solution of the (4+z) vanadium ions to react to obtain a sulfuric acid solution of the (4+x) vanadium ions, wherein 1> z > x >0;
respectively charging and electrolyzing a sulfate acid solution of 4-valent vanadium ions and a sulfuric acid solution of (4+x) valent vanadium ions as a negative electrode electrolyte and a positive electrode electrolyte, obtaining a 3.5-valent sulfuric acid hydrochloric acid system vanadium electrolyte at the negative electrode, and obtaining a sulfuric acid solution of (4+y) valent vanadium ions at the positive electrode;
adding oxalic acid into the sulfuric acid solution of the (4+y) vanadium ions to react to obtain the sulfuric acid solution of the (4+x) vanadium ions, wherein 1> y > x >0;
and (4+x) the sulfuric acid solution of the vanadium ions is used as positive electrode electrolyte and the sulfuric acid solution of the vanadium ions of 4 valence of the negative electrode for charging electrolysis, so that the 3.5 valence sulfuric acid hydrochloric acid system vanadium electrolyte is obtained at the negative electrode.
Further, x is more than or equal to 0.1, and y is more than or equal to 0.9.
Further, the sulfate acid solution of the 4-valent vanadium ion is prepared by adding hydrochloric acid into the sulfate acid solution of the 4-valent vanadium ion.
Further, the volume, the concentration of the 4-valent vanadium ions, the concentration of the S element and the concentration of the Cl element of the sulfuric acid solution of the 4-valent vanadium ions after hydrochloric acid is added are respectively equal to the volume, the total vanadium concentration, the concentration of the S element and the concentration of the Cl element of the 3.5-valent sulfuric acid hydrochloric acid system vanadium electrolyte obtained at the cathode.
Further, the sulfuric acid solution of the 4-valent vanadium ions is prepared by reducing vanadium pentoxide by sulfuric acid oxalic acid solution.
Further, the charging electrolysis is performed in an all-vanadium flow battery.
According to the preparation method of the 3.5-valent vanadium sulfate hydrochloric acid system vanadium electrolyte, the vanadium valence state of the positive electrode electrolyte is between 4 and 5, the sulfate acid solution of 4-valent vanadium ions and the sulfuric acid solution of (4+x) valent vanadium ions are respectively used as the negative electrode electrolyte and the positive electrode electrolyte of the all-vanadium flow battery to carry out charging electrolysis, the sulfate acid solution of 3.5-valent vanadium ions, namely the 3.5-valent sulfuric acid hydrochloric acid system vanadium electrolyte, is obtained at the negative electrode, the sulfuric acid solution of (4+y) valent vanadium ions is obtained at the positive electrode, oxalic acid is added into the obtained sulfuric acid solution of (4+y) valent vanadium ions according to the stoichiometric ratio for reduction, and the sulfuric acid solution of (4+x) valent vanadium ions is obtained again, wherein 1> y > x >0. And (3) repeating the steps circularly, and preparing the novel 3.5-valent sulfuric acid hydrochloric acid system vanadium electrolyte on the negative electrode.
In addition, the preparation method of the 3.5-valent sulfuric acid hydrochloric acid system vanadium electrolyte provided by the invention is simple and convenient, and the concentration of the 4-valent vanadium which is respectively used as the positive electrode electrolyte and the negative electrode electrolyte of the all-vanadium redox flow battery is not required to be equal, and the volume is not required to be doubled. In addition, when the full vanadium redox flow battery is charged and electrolyzed, only the vanadium of the positive electrode electrolyte is required to be oxidized from the valence of (4+x) to the valence of (4+y), wherein 1> y > x >0 is required to be oxidized, namely, only part of the vanadium of the valence of 4 is required to be oxidized to the valence of 5, and all the vanadium of the valence of 4 is not required to be oxidized to the valence of 5, so that the electrolytic reaction rate is high, and the electrolytic step time is greatly shortened. Meanwhile, oxalic acid is quantitatively added into the sulfuric acid solution of (4+y) vanadium ions obtained by the positive electrode after the charging electrolysis of the all-vanadium redox flow battery according to the stoichiometric ratio to reduce and obtain the sulfuric acid solution of (4+x) vanadium ions again, wherein 1> y > x >0 is the sulfuric acid solution of (4+y) vanadium ions, namely, only part of 5-valent vanadium is required to be reduced to 4-valent vanadium, and all 5-valent vanadium is not required to be reduced to 4-valent vanadium, so that the reduction reaction rate is high, and the reduction step time is greatly shortened.
More importantly, the 5-valent vanadium is always excessive relative to the oxalic acid reducing agent in the reducing step of the positive electrode electrolyte after the charging electrolysis of the all-vanadium redox flow battery, so that the reducing reaction rate is high, the reducing step time is short, and the oxalic acid reducing agent is not remained in the reduced positive electrode electrolyte, thereby fundamentally preventing the situations of liquid breaking, idling, even pump burning and the like of the magnetic circulating pump of the positive electrode electrolyte in the next charging electrolysis and ensuring the smooth proceeding of the subsequent electrolysis step.
Therefore, the preparation method of the 3.5-valent sulfuric acid hydrochloric acid system vanadium electrolyte overcomes the defect that the current method for preparing the 3.5-valent vanadium electrolyte adopts 4-valent vanadium for both positive and negative electrode electrolytes, and has the characteristics of rapid electrolysis, rapid reduction, safety, reliability, economy, high efficiency, recycling performance and the like.
Drawings
FIG. 1 is a flow chart of a preparation method of a 3.5-valent sulfuric acid hydrochloric acid system vanadium electrolyte provided by the embodiment of the invention.
Detailed Description
Referring to fig. 1, the preparation method of the 3.5-valent sulfuric acid hydrochloric acid system vanadium electrolyte provided by the embodiment of the invention comprises the following steps:
and 1) respectively charging and electrolyzing a sulfate acid solution of 4-valent vanadium ions and a sulfuric acid solution of 4-valent vanadium ions as a negative electrode electrolyte and a positive electrode electrolyte of the all-vanadium redox flow battery, obtaining a 3.5-valent sulfuric acid hydrochloric acid system vanadium electrolyte at the negative electrode, and obtaining a sulfuric acid solution of (4+z) valent vanadium ions at the positive electrode.
Wherein the sulfate acid solution of the 4-valence vanadium ions is prepared by adding hydrochloric acid into the sulfuric acid solution of the 4-valence vanadium ions.
The volume, the concentration of the 4-valent vanadium ions, the concentration of the S element and the concentration of the Cl element of the sulfuric acid solution of the 4-valent vanadium ions after hydrochloric acid is added are respectively equal to the volume, the total vanadium concentration, the concentration of the S element and the concentration of the Cl element of the 3.5-valent sulfuric acid hydrochloric acid system vanadium electrolyte obtained at the cathode.
Wherein, the sulfuric acid solution of the 4-valence vanadium ion is prepared by reducing vanadium pentoxide by sulfuric acid oxalic acid solution, and the reaction is completely reacted according to the following reaction equation:
0.5V 2 O 5 +2H 2 SO 4 +0.5H 2 C 2 O 4 ·2H 2 O =VO(HSO 4 ) 2 +CO 2 ↑+2.5H 2 O
and, the molar amount of vanadium pentoxide and the molar amount of sulfuric acid are determined respectively from the molar amount of total vanadium in the prepared 3.5-valent sulfuric acid hydrochloric acid system vanadium electrolyte (i.e., the sum of the molar amounts of 3-valent vanadium and 4-valent vanadium) and the molar amount of S element, and the required molar amount of oxalic acid is determined from the molar amount of vanadium pentoxide according to the reaction equation. And adding pure water to dilute the mixture to the volume and concentration of the sulfuric acid solution of the required 4-valent vanadium ions after the reaction is completed.
Step 2) adding oxalic acid into the sulfuric acid solution of the (4+z) vanadium ions to reduce to obtain the sulfuric acid solution of the (4+x) vanadium ions, wherein 1> z > x >0.
Wherein, in the process of adding oxalic acid into sulfuric acid solution of (4+z) vanadium ions to reduce to obtain sulfuric acid solution of (4+x) vanadium ions, the following reaction equation for reducing 5 vanadium to 4 vanadium by oxalic acid is used for reaction and the adding amount of oxalic acid is set:
VO 2 HSO 4 +H 2 SO 4 +0.5H 2 C 2 O 4 ·2H 2 O= VO(HSO 4 ) 2 +CO 2 ↑+2H 2 O
reduction of (z-x) x 1mol VO 2 HSO 4
(z-x) ×1mol VO (HSO) was produced 4 ) 2
0.5 (z-x). Times.1 mol of H are added 2 C 2 O 4 ·2H 2 O
And 3) respectively charging and electrolyzing a sulfate acid solution of 4-valent vanadium ions and a sulfuric acid solution of (4+x) valent vanadium ions as a negative electrode electrolyte and a positive electrode electrolyte of the all-vanadium flow battery, obtaining a 3.5-valent sulfuric acid hydrochloric acid system vanadium electrolyte at the negative electrode, and obtaining a sulfuric acid solution of (4+y) valent vanadium ions at the positive electrode.
Step 4) adding oxalic acid into the sulfuric acid solution of the (4+y) vanadium ions to reduce to obtain the sulfuric acid solution of the (4+x) vanadium ions, wherein 1> y > x >0.
In the process of adding oxalic acid into sulfuric acid solution of (4+y) vanadium ions to reduce to obtain sulfuric acid solution of (4+x) vanadium ions, the following reaction equation for reducing 5-valent vanadium to 4-valent vanadium with oxalic acid is used for reaction, and the adding amount of oxalic acid is set:
VO 2 HSO 4 +H 2 SO 4 +0.5H 2 C 2 O 4 ·2H 2 O= VO(HSO 4 ) 2 +CO 2 ↑+2H 2 O
reduction of (y-x) x 1mol VO 2 HSO 4
(y-x) x 1mol VO (HSO) was produced 4 ) 2
0.5 (y-x) x 1mol H is added 2 C 2 O 4 ·2H 2 O
And 5) the sulfuric acid solution of the (4+x) valence vanadium ions can be used as the positive electrode electrolyte of the all-vanadium redox flow battery and the sulfuric acid solution of the (4) valence vanadium ions of the negative electrode for charging electrolysis, and the 3.5 valence sulfuric acid hydrochloric acid system vanadium electrolyte is obtained at the negative electrode.
Wherein x is more than or equal to 0.1, and y is more than or equal to 0.9.
The charging electrolysis is performed in an all-vanadium redox flow battery comprising a galvanic pile, a pipeline, a positive and negative electrode vanadium electrolyte container and the like, and the 3.5-valent sulfuric acid hydrochloric acid system vanadium electrolyte is prepared by charging corresponding vanadium electrolyte into the positive and negative electrode electrolyte container of the all-vanadium redox flow battery for charging electrolysis.
When the 3.5-valent sulfuric acid hydrochloric acid system vanadium electrolyte is prepared by charging electrolysis, charging current and electrolysis voltage are respectively adjusted according to the electrode area of the single batteries connected in series and the number of the single batteries connected in series in the used all-vanadium redox flow battery stack. The electrolysis time is determined by the charging current, the volume and the concentration of the cathode vanadium electrolyte. The constant voltage charge can be carried out by taking the charge voltage limit of the electric pile as the electrolysis voltage, so that the charge current is maximum, the electrolysis time is shortest, and the electrolysis efficiency can be improved. Of course, constant current charging can be performed first, and then constant voltage charging can be performed, so that the electrolysis time is longer.
After the sulfuric acid solution of the positive (4+x) vanadium ions is charged and electrolyzed, partial 4-valent vanadium ions lose electrons to become 5-valent vanadium ions, so that the average valence state of the vanadium ions is increased to the (4+y) valence, oxalic acid is quantitatively added to reduce the (4+y) vanadium to return to the (4+x) valence, the new charge electrolysis can be carried out by matching with the sulfate acid solution (serving as negative electrode solution) of the newly prepared 4-valent vanadium ions, 3.5-valent sulfuric acid hydrochloric acid system vanadium electrolyte is obtained at the negative electrode, the valence state of the vanadium ions in the positive electrode electrolyte is increased to the (4+y) valence again, the vanadium ions can be reduced back to the (4+x) valence again by quantitatively adding oxalic acid, and the new 3.5-valent sulfuric acid hydrochloric acid system vanadium electrolyte can be continuously prepared at the negative electrode in a circulating way.
At present, oxalic acid is added into the charged and electrolyzed positive electrode electrolyte by manual addition. The oxalic acid reduces part of 5-valent vanadium ions into 4-valent vanadium ions to release CO 2 The ionic reaction of the gas, although fast, still takes several hours to complete, and stirring accelerates the completion of the reaction.
After each charging electrolysis, the container for containing the anode (4+y) vanadium electrolyte is pulled out from the all-vanadium redox flow battery, oxalic acid is added into the container to reduce the electrolyzed anode electrolyte, and the container for the anode (4+x) vanadium electrolyte which is completely reduced in advance is replaced, so that a new round of charging electrolysis is started, and the production efficiency can be greatly improved.
If oxalic acid is added into the positive electrode electrolyte for reduction during charging electrolysis, CO continuously generated in the positive electrode electrolyte 2 Bubbles frequently cause the positive electrolyte magnetic circulation pump to break, idle and even burn, and the smooth progress of the electrolytic reaction is seriously affected.
The preparation method of the 3.5-valent sulfuric acid hydrochloric acid system vanadium electrolyte provided by the invention is specifically described by the following examples.
Example 1
2M 0.5(VCl 3 +VO(HSO 4 ) 2 +HCl+2H 2 SO 4 ) Preparation of 3.5-valent sulfuric acid hydrochloric acid system vanadium electrolyte (M generation)Table mol/L, the same applies below
Step 1: two 500L 3.2M VO (HSO) 4 ) 2 Preparation of 4-valent vanadium electrolyte
0.5V 2 O 5 +2H 2 SO 4 +0.5H 2 C 2 O 4 ·2H 2 O =VO(HSO 4 ) 2 +CO 2 ↑+2.5H 2 O
V 2 O 5 Is characterized by comprising the following components in parts by mass: 2×500×3.2×0.5×182=291.2 (kg)
H 2 SO 4 Is characterized by comprising the following components in parts by mass: 2×500×3.2×2×98.1=628 (kg)
H 2 C 2 O 4 ·2H 2 Mass of O: 2×500×3.2×0.5×126=201.6 (kg)
600L of pure water was added to the reaction vessel, and 628kg of H was slowly added with stirring 2 SO 4 And 201.6kg H 2 C 2 O 4 ·2H 2 O, stir evenly. 291.2kg of V was slowly added with stirring 2 O 5 The reaction is carried out until no bubbles are generated. Filtering and equally dividing the solution into two 1000L packaging barrels, respectively adding pure water to adjust to 500L to obtain two 500L 3.2M VO (HSO) 4 ) 2 And 4-valence vanadium electrolyte.
Step 2:800L2M VO (HSO) 4 ) 2 Preparation of +2HCl 4-valent vanadium electrolyte
One part of 500L 3.2MVO (HSO) prepared in step 1 4 ) 2 Adding 116.7kg HCl into 4-valent vanadium electrolyte, adding pure water to 800L to obtain 800L2M VO (HSO) 4 ) 2 +2hcl 4-valent vanadium electrolyte.
Mass of HCl: 800×2×2× 36.46 =116.7 (kg).
Step 3:500L2M VO (HSO) 4 ) 2 +H 2 SO 4 Preparation of 4-valent vanadium electrolyte
Another 500L of 3.2MVO (HSO) was obtained from step 1 4 ) 2 500L×2M/3.2M=312.5L was removed from the 4-valent vanadium electrolyte, and 98.1kg of H was added thereto 2 SO 4 Adding pure water to 500L to obtain 500L2M VO (HSO) 4 ) 2 +H 2 SO 4 And 4-valence vanadium electrolyte.
H 2 SO 4 Is characterized by comprising the following components in parts by mass: 500×2×1×98.1=98.1 (kg)
Step 4: first 800L2M 0.5 (VCl) 3 +VO(HSO 4 ) 2 +HCl+2H 2 SO 4 ) Preparation of 3.5-valent sulfuric acid hydrochloric acid system vanadium electrolyte
The 800L2M VO (HSO) obtained in step 2 4 ) 2 Using +2HCl 4-valent vanadium electrolyte as 37 pieces of negative electrolyte of 5kW all-vanadium redox flow battery, and using 500L2M VO (HSO) prepared in the step 3 4 ) 2 +H 2 SO 4 4-valence vanadium electrolyte is used as positive electrolyte, and constant voltage 60V charge 579.5Ah:
SOC － = 37×579.5/(800×2×26.8) = 50%
SOC + = 37×579.5/(500×2×26.8) = 80%
and (3) a negative electrode: VO (HSO) 4 ) 2 +3HCl+H + +e = VCl 3 +2H 2 SO 4 +H 2 O
And (3) a positive electrode: VO (HSO) 4 ) 2 +H 2 O－H + －e = VO 2 HSO 4 +H 2 SO 4 。
The anode is the first 800L2M 0.5 (VCl) 3 +VO(HSO 4 ) 2 +HCl+2H 2 SO 4 ) Vanadium electrolyte of 3.5-valent sulfuric acid hydrochloric acid system, anode to obtain 500L2M 0.8VO 2 HSO 4 +0.2VO(HSO 4 ) 2 +1.8H 2 SO 4 4.8-valence vanadium electrolyte.
Step 5:500L 2M 0.1VO 2 HSO 4 +0.9VO(HSO 4 ) 2 +1.1H 2 SO 4 Preparation of 4.1-valent vanadium electrolyte
500L2M 0.8VO obtained in step 4 2 HSO 4 +0.2VO(HSO 4 ) 2 +1.8H 2 SO 4 44.1kg of H is added into the 4.8-valent vanadium electrolyte 2 C 2 O 4 ·2H 2 O, stirring for about 2h until no bubbles are generated, obtaining 500L2M 0.1VO 2 HSO 4 +0.9VO(HSO 4 ) 2 +1.1H 2 SO 4 4.1 valence vanadium electrolyte:
VO 2 HSO 4 +H 2 SO 4 +0.5H 2 C 2 O 4 ·2H 2 O= VO(HSO 4 ) 2 +CO 2 ↑+2H 2 O
H 2 C 2 O 4 ·2H 2 mass of O: 0.7×500×2×0.5×126=44.1 (kg)
Step 6:800L 2M 0.5 (VCl) 3 +VO(HSO 4 ) 2 +HCl+2H 2 SO 4 ) Preparation of 3.5-valent sulfuric acid hydrochloric acid system vanadium electrolyte
Repeating the steps 1 and 2, and collecting 800L2M VO (HSO 4 ) 2 Using +2HCl4 valence vanadium electrolyte as negative electrolyte of 37 pieces of 5kW all-vanadium redox flow battery, and enabling 500L of 2M 0.1VO 2 HSO 4 +0.9VO(HSO 4 ) 2 +1.1H 2 SO 4 4.1-valence vanadium electrolyte is used as positive electrolyte, and constant voltage 60V charge 579.5Ah:
SOC － = 37×579.5/(800×2×26.8) = 50%
SOC + = 10% + 37×579.5/(500×2×26.8) = 90%
and (3) a negative electrode: VO (HSO) 4 ) 2 +3HCl+H + +e = VCl 3 +2H 2 SO 4 +H 2 O
And (3) a positive electrode: VO (HSO) 4 ) 2 +H 2 O－H + －e = VO 2 HSO 4 +H 2 SO 4
The negative electrode was 2M 0.5 (VCl) 3 +VO(HSO 4 ) 2 +HCl+2H 2 SO 4 ) Vanadium electrolyte of 3.5-valent sulfuric acid hydrochloric acid system, anode to obtain 500L2M 0.9VO 2 HSO 4 +0.1VO(HSO 4 ) 2 +1.9H 2 SO 4 4.9 valence vanadium electrolyte.
Step 7:500L 2M 0.1VO 2 HSO 4 +0.9VO(HSO 4 ) 2 +1.1H 2 SO 4 Preparation of 4.1-valent vanadium electrolyte
At 500L2M 0.9VO 2 HSO 4 +0.1VO(HSO 4 ) 2 +1.9H 2 SO 4 50.4kg of H is added into the 4.9-valent vanadium electrolyte 2 C 2 O 4 ·2H 2 O, stirring for about 2h until no bubbles are generated, obtaining 500L2M 0.1VO 2 HSO 4 +0.9VO(HSO 4 ) 2 +1.1H 2 SO 4 4.1 valence vanadium electrolyte:
VO 2 HSO 4 +H 2 SO 4 +0.5H 2 C 2 O 4 ·2H 2 O= VO(HSO 4 ) 2 +CO 2 ↑+2H 2 O
H 2 C 2 O 4 ·2H 2 mass of O: 0.8×500×2×0.5×126=50.4 (kg)
Step 8: repeating the step 6 and the step 7
And the method is repeated circularly, and new 3.5-valent sulfuric acid hydrochloric acid system vanadium electrolyte can be continuously prepared on the negative electrode.
Example 2
2.5M 0.5(VCl 3 +VO(HSO 4 ) 2 +2H 2 SO 4 ) Preparation of 3.5-valent sulfuric acid hydrochloric acid system vanadium electrolyte
Step 1: two 500L 4M VO (HSO) 4 ) 2 Preparation of 4-valent vanadium electrolyte
0.5V 2 O 5 +2H 2 SO 4 +0.5H 2 C 2 O 4 ·2H 2 O =VO(HSO 4 ) 2 +CO 2 ↑+2.5H 2 O
V 2 O 5 Is characterized by comprising the following components in parts by mass: 2×500×4×0.5×182=364 (kg)
H 2 SO 4 Is characterized by comprising the following components in parts by mass: 2×500×4×2×98.1=785 (kg)
H 2 C 2 O 4 ·2H 2 Mass of O: 2×500×4×0.5×126=252 (kg).
500L of pure water was added to the reaction vessel, and 785kg of H was slowly added with stirring 2 SO 4 And 252kg H 2 C 2 O 4 ·2H 2 O, stir evenly. 364kg V was slowly added with stirring 2 O 5 The reaction is carried out until no bubbles are generated. Filtering and equally dividing the solution into two 1000L packaging barrels, respectively adding pure water to adjust to 500L to obtain two 500L 4M VO (HSO) 4 ) 2 And 4-valence vanadium electrolyte.
Step 2:800L2.5M VO (HSO) 4 ) 2 Preparation of +1.5HCl4 valent vanadium electrolyte
One 500L 4MVO (HSO) prepared in step 1 4 ) 2 Adding 109.4kg HCl and pure water into the 4-valent vanadium electrolyte to adjust to 800L to obtain 800L2.5M VO (HSO) 4 ) 2 +1.5HCl4 valence vanadium electrolyte.
Mass of HCl: 800×2.5×1.5× 36.46 =109.4 (kg)
Step 3:625L2M VO (HSO) 4 ) 2 +H 2 SO 4 Preparation of 4-valent vanadium electrolyte
Another 500L 4MVO (HSO) prepared from step 1 4 ) 2 625L×2M/4M=312.5L was removed from the 4-valent vanadium electrolyte, and 122.6kg of H was added 2 SO 4 Adding pure water to 625L to obtain 625L2M VO (HSO) 4 ) 2 +H 2 SO 4 And 4-valence vanadium electrolyte.
H 2 SO 4 Is characterized by comprising the following components in parts by mass: 625×2×1×98.1=122.6 (kg)
Step 4: first 800L2.5M 0.5 (VCl) 3 +VO(HSO 4 ) 2 +2H 2 SO 4 ) Preparation of 3.5-valent sulfuric acid hydrochloric acid system vanadium electrolyte
The 800L2.5M VO (HSO) obtained in step 2 was reacted with 4 ) 2 Using +1.5HCl4 valence vanadium electrolyte as a negative electrode electrolyte of 37 pieces of 5kW all-vanadium redox flow battery, and using 625L of 2M VO (HSO) prepared in the step 3 4 ) 2 +H 2 SO 4 4-valence vanadium electrolyte is used as positive electrolyte, and constant voltage 60V charge 724.4Ah:
SOC － = 37×724.4/(800×2.5×26.8) = 50%
SOC + = 37×724.4/(625×2×26.8) = 80%
and (3) a negative electrode: VO (HSO) 4 ) 2 +3HCl+H + +e = VCl 3 +2H 2 SO 4 +H 2 O
And (3) a positive electrode: VO (HSO) 4 ) 2 +H 2 O－H + －e = VO 2 HSO 4 +H 2 SO 4
The negative electrode is obtainedFirst 800L2.5M 0.5 (VCl) 3 +VO(HSO 4 ) 2 +2H 2 SO 4 ) Vanadium electrolyte of 3.5-valent sulfuric acid hydrochloric acid system, and anode is prepared to 625L2M 0.8VO 2 HSO 4 +0.2VO(HSO 4 ) 2 +1.8H 2 SO 4 4.8-valence vanadium electrolyte.
Step 5:625L2M 0.1VO 2 HSO 4 +0.9VO(HSO 4 ) 2 +1.1H 2 SO 4 Preparation of 4.1-valent vanadium electrolyte
625L2M 0.8VO obtained in step 4 2 HSO 4 +0.2VO(HSO 4 ) 2 +1.8H 2 SO 4 55.13kg H is added into the 4.8-valent vanadium electrolyte 2 C 2 O 4 ·2H 2 O, stir for about 2h until no bubbles are generated, obtaining 625L of 2M 0.1VO 2 HSO 4 +0.9VO(HSO 4 ) 2 +1.1H 2 SO 4 4.1 valence vanadium electrolyte:
VO 2 HSO 4 +H 2 SO 4 +0.5H 2 C 2 O 4 ·2H 2 O= VO(HSO 4 ) 2 +CO 2 ↑+2H 2 O
H 2 C 2 O 4 ·2H 2 mass of O: 0.7X15X125×2×0.5X1126= 55.13 (kg)
Step 6:800L 2.5M 0.5 (VCl) 3 +VO(HSO 4 ) 2 +2H 2 SO 4 ) Preparation of 3.5-valent sulfuric acid hydrochloric acid system vanadium electrolyte
Step 1 and step 2 were repeated, and the newly prepared 800L2.5M VO (HSO 4 ) 2 +1.5HCl4 vanadium electrolyte is used as the negative electrode electrolyte of 37 pieces of 5kW all-vanadium redox flow battery, and 625L2M 0.1VO is used 2 HSO 4 +0.9VO(HSO 4 ) 2 +1.1H 2 SO 4 4.1-valence vanadium electrolyte is used as positive electrolyte, and constant voltage 60V charge 724.4Ah:
SOC － = 37×724.4/(800×2.5×26.8) =50%
SOC + = 10% + 37×724.4/(625×2×26.8) = 90%
and (3) a negative electrode: VO (HSO) 4 ) 2 +3HCl+H + +e = VCl 3 +2H 2 SO 4 +H 2 O
And (3) a positive electrode: VO (HSO) 4 ) 2 +H 2 O－H + －e = VO 2 HSO 4 +H 2 SO 4
The negative electrode is 800L2.5M 0.5 (VCl) 3 +VO(HSO 4 ) 2 +2H 2 SO 4 ) Vanadium electrolyte of 3.5-valent sulfuric acid hydrochloric acid system, and 625L2M 0.9VO is obtained at the anode 2 HSO 4 +0.1VO(HSO 4 ) 2 +1.9H 2 SO 4 4.9 valence vanadium electrolyte.
Step 7:625L2M 0.1VO 2 HSO 4 +0.9VO(HSO 4 ) 2 +1.1H 2 SO 4 Preparation of 4.1-valent vanadium electrolyte
At 625L2M 0.9VO 2 HSO 4 +0.1VO(HSO 4 ) 2 +1.9H 2 SO 4 63kg of H is added into the 4.9-valent vanadium electrolyte 2 C 2 O 4 ·2H 2 O, stir for about 2h until no bubbles are generated, obtaining 625L2M 0.1VO 2 HSO 4 +0.9VO(HSO 4 ) 2 +1.1H 2 SO 4 4.1 valence vanadium electrolyte:
VO 2 HSO 4 +H 2 SO 4 +0.5H 2 C 2 O 4 ·2H 2 O= VO(HSO 4 ) 2 +CO 2 ↑+2H 2 O
H 2 C 2 O 4 ·2H 2 mass of O: 0.8x625×2×0.5x126=63 (kg)
Step 8: repeating the step 6 and the step 7
And the method is repeated circularly, and new 3.5-valent sulfuric acid hydrochloric acid system vanadium electrolyte can be continuously prepared on the negative electrode.
The preparation method of the 3.5-valent vanadium electrolyte of the sulfuric acid hydrochloric acid system provided by the invention has the advantages that the vanadium valence state of the positive electrode electrolyte is between 4 and 5, the serious defect of the preparation method of the 3.5-valent vanadium electrolyte, in which the positive electrode electrolyte and the negative electrode electrolyte of a common electrolysis device are both 4-valent vanadium, is completely overcome, the electrolysis is rapid, the reduction is rapid, the method is simple and reliable, the cyclic implementation is realized, and the like, and the method can be effectively used for the high-efficiency low-cost preparation of the 3.5-valent vanadium electrolyte of the sulfuric acid hydrochloric acid system.
Finally, it should be noted that the above-mentioned embodiments are only for illustrating the technical solution of the present invention, and not for limiting the same, and although the present invention has been described in detail with reference to examples, it should be understood by those skilled in the art that modifications and equivalents may be made to the technical solution of the present invention without departing from the spirit and scope of the technical solution of the present invention, and all such modifications and equivalents are intended to be encompassed in the scope of the claims of the present invention.
Claims (6)
1. The preparation method of the 3.5-valent sulfuric acid hydrochloric acid system vanadium electrolyte is characterized by comprising the following steps of:
respectively charging and electrolyzing a sulfate acid solution of 4-valent vanadium ions and a sulfuric acid solution of 4-valent vanadium ions as a negative electrode electrolyte and a positive electrode electrolyte, obtaining a 3.5-valent sulfuric acid hydrochloric acid system vanadium electrolyte at the negative electrode, and obtaining a sulfuric acid solution of (4+z) valent vanadium ions at the positive electrode;
adding oxalic acid into the sulfuric acid solution of the (4+z) vanadium ions to react to obtain a sulfuric acid solution of the (4+x) vanadium ions, wherein 1> z > x >0;
respectively charging and electrolyzing a sulfate acid solution of 4-valent vanadium ions and a sulfuric acid solution of (4+x) valent vanadium ions as a negative electrode electrolyte and a positive electrode electrolyte, obtaining a 3.5-valent sulfuric acid hydrochloric acid system vanadium electrolyte at the negative electrode, and obtaining a sulfuric acid solution of (4+y) valent vanadium ions at the positive electrode;
adding oxalic acid into the sulfuric acid solution of the (4+y) vanadium ions to react to obtain the sulfuric acid solution of the (4+x) vanadium ions, wherein 1> y > x >0;
and (4+x) the sulfuric acid solution of the vanadium ions is used as positive electrode electrolyte and the sulfuric acid solution of the vanadium ions of 4 valence of the negative electrode for charging electrolysis, so that the 3.5 valence sulfuric acid hydrochloric acid system vanadium electrolyte is obtained at the negative electrode.
2. The method for preparing the 3.5-valent sulfuric acid hydrochloric acid system vanadium electrolyte according to claim 1, which is characterized in that: x is more than or equal to 0.1, and y is more than or equal to 0.9.
3. The method for preparing the 3.5-valent sulfuric acid hydrochloric acid system vanadium electrolyte according to claim 1, which is characterized in that: the sulfate acid solution of the 4-valence vanadium ions is prepared by adding hydrochloric acid into a sulfuric acid solution of the 4-valence vanadium ions.
4. The method for preparing the 3.5-valent sulfuric acid hydrochloric acid system vanadium electrolyte according to claim 3, which is characterized in that: the volume, the concentration of the 4-valent vanadium ions, the concentration of the S element and the concentration of the Cl element of the sulfuric acid solution with the 4-valent vanadium ions after hydrochloric acid is added are respectively equal to the volume, the total vanadium concentration, the concentration of the S element and the concentration of the Cl element of the 3.5-valent sulfuric acid hydrochloric acid system vanadium electrolyte obtained at the cathode.
5. The method for preparing the 3.5-valent sulfuric acid hydrochloric acid system vanadium electrolyte according to claim 1, which is characterized in that: the sulfuric acid solution of the 4-valence vanadium ions is prepared by reducing vanadium pentoxide by sulfuric acid oxalic acid solution.
6. The method for preparing the 3.5-valent sulfuric acid hydrochloric acid system vanadium electrolyte according to claim 1, which is characterized in that: the charging electrolysis is performed in an all-vanadium redox flow battery.
Priority Applications (1)
| Application Number | Priority Date | Filing Date | Title |
|---|---|---|---|
| CN202310142956.4A CN115882021B (en) | 2023-02-21 | 2023-02-21 | Preparation method of 3.5-valent sulfuric acid hydrochloric acid system vanadium electrolyte |
Applications Claiming Priority (1)
| Application Number | Priority Date | Filing Date | Title |
|---|---|---|---|
| CN202310142956.4A CN115882021B (en) | 2023-02-21 | 2023-02-21 | Preparation method of 3.5-valent sulfuric acid hydrochloric acid system vanadium electrolyte |
Publications (2)
| Publication Number | Publication Date |
|---|---|
| CN115882021A CN115882021A (en) | 2023-03-31 |
| CN115882021B true CN115882021B (en) | 2023-06-23 |
Family
ID=85761403
Family Applications (1)
| Application Number | Title | Priority Date | Filing Date |
|---|---|---|---|
| CN202310142956.4A Active CN115882021B (en) | 2023-02-21 | 2023-02-21 | Preparation method of 3.5-valent sulfuric acid hydrochloric acid system vanadium electrolyte |
Country Status (1)
| Country | Link |
|---|---|
| CN (1) | CN115882021B (en) |
Families Citing this family (1)
| Publication number | Priority date | Publication date | Assignee | Title |
|---|---|---|---|---|
| CN116387583B (en) * | 2023-06-06 | 2023-09-19 | 北京普能世纪科技有限公司 | All-vanadium redox flow battery capacity recovery method |
Citations (1)
| Publication number | Priority date | Publication date | Assignee | Title |
|---|---|---|---|---|
| CN104037439A (en) * | 2013-03-05 | 2014-09-10 | 中国人民解放军63971部队 | Combined chemical-electrochemical method for preparing vanadium redox flow battery electrolyte |
Family Cites Families (6)
| Publication number | Priority date | Publication date | Assignee | Title |
|---|---|---|---|---|
| JPH1167257A (en) * | 1997-08-19 | 1999-03-09 | Kashimakita Kyodo Hatsuden Kk | Process for vanadium electrolyte |
| JP2004071165A (en) * | 2002-08-01 | 2004-03-04 | Nippon Oil Corp | Production method for electrolyte for vanadium redox battery |
| CN101619465B (en) * | 2008-07-02 | 2010-12-22 | 中国科学院大连化学物理研究所 | Method for preparing vanadium battery solution or adjusting capacity and special device thereof |
| CN102468499B (en) * | 2010-11-04 | 2016-01-06 | 新奥科技发展有限公司 | The renovation process of waste liquor of all-vanadium flow battery |
| WO2013054921A1 (en) * | 2011-10-14 | 2013-04-18 | 株式会社ギャラキシー | Vanadium electrolyte, production method therefor, and production device therefor |
| CN107069066B (en) * | 2017-03-13 | 2020-09-08 | 河南弘康光能科技有限公司 | All-vanadium redox flow battery electrolyte and preparation method thereof |
-
2023
- 2023-02-21 CN CN202310142956.4A patent/CN115882021B/en active Active
Patent Citations (1)
| Publication number | Priority date | Publication date | Assignee | Title |
|---|---|---|---|---|
| CN104037439A (en) * | 2013-03-05 | 2014-09-10 | 中国人民解放军63971部队 | Combined chemical-electrochemical method for preparing vanadium redox flow battery electrolyte |
Also Published As
| Publication number | Publication date |
|---|---|
| CN115882021A (en) | 2023-03-31 |
Similar Documents
| Publication | Publication Date | Title |
|---|---|---|
| CN101562256B (en) | Preparation method of electrolyte used for all vanadium redox flow batteries | |
| CN115882021B (en) | Preparation method of 3.5-valent sulfuric acid hydrochloric acid system vanadium electrolyte | |
| CN112390292A (en) | Bulk phase doped manganous-manganic oxide and preparation method and application thereof | |
| CN104064817B (en) | A kind of electrolyte additive for lead-acid accumulator and preparation method thereof | |
| CN106463752A (en) | Method for manufacturing positive electrode electrolyte for redox flow battery and redox flow battery | |
| CN117374351B (en) | All-vanadium redox flow battery electrolyte and preparation method thereof | |
| WO2024056104A1 (en) | Vanadium-chromium electrolyte, preparation method therefor, and flow battery comprising same | |
| CN116231023B (en) | Preparation method of 3.5-valent hydrochloric acid system and 3.5-valent sulfuric acid system vanadium electrolyte | |
| CN107845778B (en) | Method for modifying lead storage battery positive plate by polyaniline | |
| JPH07211346A (en) | Manufacture of electrolyte for vanadium redox flow type battery and manufacture of vanadium redox flow type battery | |
| JP2000072441A (en) | Production of vanadium sulfate solution | |
| CN1195333C (en) | Preparation method of charged beta-phase nickel oxyhydroxide | |
| CN110416585B (en) | Preparation method and preparation device of flow battery electrolyte | |
| CN111484076A (en) | Method for recovering high-purity vanadium from failure vanadium electrolyte | |
| US20240030462A1 (en) | Method for producing electrolyte for vanadium redox flow battery | |
| JPH07101615B2 (en) | Redox type secondary battery | |
| CN102306820A (en) | Electrolyte for vanadium battery and preparation method of electrolyte | |
| CN110156079B (en) | Preparation method of linear copper vanadate negative electrode material, product and application | |
| CN112993361B (en) | Preparation method of vanadium electrolyte | |
| CN115832345B (en) | Method for preparing vanadium battery electrolyte by using galvanic pile electrolysis | |
| CN107464952A (en) | The lithium oxygen battery of electrolyte and its preparation based on N Methylphenothiazine additives | |
| WO2020035037A1 (en) | Method for preparing liquid flow battery electrolyte | |
| JP3065630B2 (en) | Anode active material for lithium secondary battery, method for producing the same, and lithium secondary battery | |
| CN115744888A (en) | Preparation process of graphene negative electrode material of high-capacity battery | |
| JP2024001560A (en) | Manufacturing method and manufacturing apparatus of electrolyte for vanadium redox flow battery |
Legal Events
| Date | Code | Title | Description |
|---|---|---|---|
| PB01 | Publication | ||
| PB01 | Publication | ||
| SE01 | Entry into force of request for substantive examination | ||
| SE01 | Entry into force of request for substantive examination | ||
| GR01 | Patent grant | ||
| GR01 | Patent grant |