CN201981262U - Circular electrolysis reacting device for preparing electrolyte of vanadium batter - Google Patents
Circular electrolysis reacting device for preparing electrolyte of vanadium batter Download PDFInfo
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- CN201981262U CN201981262U CN2010206432415U CN201020643241U CN201981262U CN 201981262 U CN201981262 U CN 201981262U CN 2010206432415 U CN2010206432415 U CN 2010206432415U CN 201020643241 U CN201020643241 U CN 201020643241U CN 201981262 U CN201981262 U CN 201981262U
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- Y—GENERAL TAGGING OF NEW TECHNOLOGICAL DEVELOPMENTS; GENERAL TAGGING OF CROSS-SECTIONAL TECHNOLOGIES SPANNING OVER SEVERAL SECTIONS OF THE IPC; TECHNICAL SUBJECTS COVERED BY FORMER USPC CROSS-REFERENCE ART COLLECTIONS [XRACs] AND DIGESTS
- Y02—TECHNOLOGIES OR APPLICATIONS FOR MITIGATION OR ADAPTATION AGAINST CLIMATE CHANGE
- Y02E—REDUCTION OF GREENHOUSE GAS [GHG] EMISSIONS, RELATED TO ENERGY GENERATION, TRANSMISSION OR DISTRIBUTION
- Y02E60/00—Enabling technologies; Technologies with a potential or indirect contribution to GHG emissions mitigation
- Y02E60/10—Energy storage using batteries
Abstract
The utility model provides a circular electrolysis reacting device for preparing electrolyte of a vanadium battery. The circular electrolysis reacting device comprises an electrolytic tank set, a feeding reaction kettle, a sedimentation pond, a liquid delivering pipeline and a pump. During the process of preparation, V205 and dilute sulphuric acid with the concentration of 0.5 molL-1-6molL-1 is added into the feeding reaction kettle, after stirring, a part of V5+ is dissolved; the solution is delivered into the sedimentation pond, clarified liquid at the upper layer of the sedimentation pond is delivered into a cathode chamber of the electrolytic tank set by the pump, the electrolytic tank set is connected with an external power supply, the V5+ is reduced in the cathode chamber of the electrolytic tank, V3+ solution is obtained from the outlet of the sedimentation pond, a part of the V3+ solution is returned to the feeding reaction kettle and react with V205 of a certain dosage to form turbid liquid consisting of V4+ solution and V2O5 solid, the turbid liquid is delivered into the sedimentation pond, the clarified liquid containing V4+ at the upper layer is delivered to the electrolytic tank set by the pump for electrolytic reaction. The circular electrolysis reacting device improves the working efficiency of preparing the electrolyte of the vanadium battery by electrolysis, shortens production period, reduces production cost, decreases pollution to environment and is beneficial for large scale production.
Description
Technical field
The utility model relates to the manufacturing field of flow battery, the particularly production unit of flow battery V electrolyte.
Background technology
Vanadium redox battery (abbreviation vanadium cell) be a kind of be the flow battery of active substance and electrolytic solution with vanadium ion solution.V electrolyte is the core of entire cell, and its production technology and production cost are restricting the development and the application of vanadium cell.General, electrolyte of vanadium redox battery is divided into anodal electrolytic solution and negative pole electrolytic solution, and wherein anodal electrolytic solution is by V
5+And V
4+Form, negative pole electrolytic solution is by V
3+And V
2+Constitute.Owing to exist with the Vanadium Pentoxide in FLAKES of+5 valencys or the form of ammonium vanadate usually at the occurring in nature vanadium, so the preparation method of V electrolyte normally reduces Vanadium Pentoxide in FLAKES or ammonium vanadate by chemistry or electrochemical method, obtains V
4+, V
3+And V
2+
Existing chemical preparation process generally needs high-temperature calcination and such as SO
2, H
2Or severe toxicity such as CO or inflammable gas participate in reaction, can increase energy consumption like this and cause environmental pollution, certainly will increase cost simultaneously, therefore, reducing cost, reduce energy consumption and suppressing environmental pollution just becomes improved emphasis of electrolyte of vanadium redox battery production technology and difficult point.
In recent years, the investigator begins to adopt electrolysis process with V
5+Carry out electrochemical reduction and prepare the lower valency V electrolyte, this method does not need high temperature and toxic gas to participate in reaction, easy and simple to handle and environmental protection.The single electrolyzer of the general employing of existing electrolytic preparation method, be that pair of electrodes is equipped with in both sides in the electrolyzer, the intermediary barrier film is separated into the positive and negative electrode chamber to electrolyzer, the mixture of sulfuric acid and Vanadium Pentoxide in FLAKES or ammonium vanadate is placed anode chamber, cathode chamber is injected with anode chamber solution usually and is had the sodium sulfate of same ion intensity or the sulphuric acid soln of sal epsom, after external circuit is connected, the V in the anode chamber
5+Just be reduced into V
4+, V
3+Or V
2+
Though this single electrolyzer is simple in structure, be convenient to operation, but there are some defectives too: at first, for the augmenting response space with productivity gain, its positive and negative electrode distance is bigger usually, can cause electrochemical reaction polarization increase in the electrolytic process like this, and current efficiency reduces, thereby cause waste of energy, the reaction times increases; Secondly, single electrolyzer has only a reaction vessel, must wait for reacting completely after feeding in raw material obtaining product, the production cycle of this discontinuous production process is controlled by the reaction times, reaction times increases, and its production cycle also can increase, and can cause time waste like this; Once more, because V
5+Can be reduced into V
4+, V
3+Or V
2+, adopt single electrolyzer to prepare electrolytic solution, the vanadium ion valence state of product is difficult to control.
Summary of the invention
In order to overcome the above-mentioned deficiency of single electrolyzer, the utility model provides a kind of cyclic electrolysis reaction unit of being made up of a plurality of electrolyzers, utilize this device preparation electrolyte of vanadium redox battery, can improve electrolytic reaction efficient, shorten the production cycle, control vanadium ion valence state in the product electrolytic solution easily and effectively.
For achieving the above object, the technical solution of the utility model is: the cyclic electrolysis reaction unit that the utility model relates to is by the electrolyzer group, the charging reaction still, settling bowl, infusion pipeline and pump are formed, described electrolyzer group is made up of the symmetrical electrolyzer more than 2 or 2, the negative electrode liquid outlet of electrolyzer group links to each other with charging reaction still fluid inlet by infusion pipeline, charging reaction liquid from reactor mouth communicates with the settling bowl fluid inlet, settling bowl upper end liquid outlet communicates with electrolyzer group negative electrode fluid inlet by infusion pipeline and pump, and settling bowl lower end liquid outlet links to each other with charging reaction still fluid inlet through pump; The electrolytic solution preparation flow is: at first with V
2O
5With concentration be 0.5 molL
-1~ 6 molL
-1Sulphuric acid soln add the charging reaction still, make part of V through stirring
5+Dissolving forms suspension liquid, sends into settling bowl and makes undissolved V
2O
5Precipitation, V is contained on the settling bowl upper strata
5+Clarified liq by the cathode compartment that is pumped into the electrolyzer group, lower sediment is by pumped back charging reaction still, the electrolyzer group links to each other with external source, V
5+Cathode compartment in the electrolyzer group is reduced, and obtains V from the outlet of electrolyzer group
3+Solution, part of V
3+Solution return the charging reaction still again with the V of certain metering
2O
5Hybrid reaction forms by V
4+Solution and V
2O
5The suspension liquid that solid is formed, suspension liquid is sent into settling bowl and is made V
2O
5Precipitation, V is contained on the upper strata
4+Clarified liq carry out electrolytic reaction by being pumped into the electrolyzer group, the part of V that electrolyzer group outlet obtains
3+Solution is sent into charging reaction still and certain V that measures again
2O
5Hybrid reaction, thus a continuous round-robin electrolytic reaction flow process formed.
Electrolyzer group described in the utility model is in series by symmetrical electrolyzer more than 2 or 2, each electrolyzer is assembled with modular form, each module comprises electrolytic cell frame, battery lead plate, barrier film, wherein being in the outermost battery lead plate of electrolyzer is single electrode plate, be that the electrode single face carries out electrode reaction, being in electrolyzer group intermediary battery lead plate is bipolar plates, i.e. the two-sided electrode reaction of carrying out of electrode, and a plurality of electrolyzer modules are assembled into the electrolyzer group by the pressure filter mode.
Battery lead plate material described in the utility model can form with graphite cake, conductive plastics, titanium or titanium alloy preparation, wherein carry out the one side of anodic reaction and generally want the coated catalysts coating, comprise platinum, rhodium, iridium, palladium, or these metal disperses are in the oxide matrix of conduction; Electrolytic cell frame can be made with PVC, PP or PE; Barrier film can adopt PP felt, microporous glass fiber film, supramolecule microporous PE film or Nafion film.
The flow velocity of electrolytic solution described in the utility model in each electrolyzer is 0.5cms
-1~ 10cms
-1, the galvanic current that puts on the electrolyzer group is 10A ~ 1000A, the current density that puts on the electrolyzer group is 100Am
-2~ 2000Am
-2
Anolyte in the electrolyzer group described in the utility model is the aqueous solution that contains supporting electrolyte, and supporting electrolyte is at least a of sulfuric acid, sodium sulfate, vitriolate of tartar, sal epsom, and concentration is 0.5molL
-1~ 6molL
-1Anolyte remains static in electrolyzer group anolyte compartment, because electrolytic reaction anode consumption water, so regularly want to add water in the anode chamber.
In the charging reaction still described in the utility model agitator is installed, its rotating speed is 100 commentaries on classics min
-1~ 1000 change min
-1The V that adds
2O
5Be by grind also/or filter the powder that the granularity that obtains is no more than 50 μ m; V
2O
5Add-on should be abundant, to guarantee and the effusive V of electrolyzer group cathode outlet
3+Solution mixes the back and forms suspension liquid.
Be provided with three products exports in the electrolysis reaction device described in the utility model, comprise: the negative electrode liquid outlet of certain one-level electrolyzer in electrolyzer group liquid outlet, settling bowl upper end liquid outlet and the electrolyzer group can obtain pure V respectively
3+Electrolytic solution, pure V
4+Electrolytic solution and V
3+: V
4+The electrolytic solution of=1:1, its concentration are 0.5molL
-1~ 6molL
-1
After prepared above-mentioned electrolytic solution can and concentrate through dilution and regulate vanadium ion concentration, as the positive and negative electrode electrolytic solution of vanadium cell.
Advantage of the present utility model and positively effect show as: utilize the electrolyzer group, directly with V
2O
5As raw material, prepare the electrolyte of vanadium redox battery of specific composition continuously, the utility model has improved the working efficiency of electrolytic preparation electrolyte of vanadium redox battery, has reduced waste of energy, has shortened the production cycle; Can control vanadium ion valence state in the product electrolytic solution easily and effectively, thereby simplify electrolytic solution subsequent disposal operation, reduce production cost; Simultaneously, do not use objectionable impurities as reactant, thereby reduced environmental pollution; Be of value to large-scale production.
Description of drawings
The perspective view of the electrolyzer group that Fig. 1 is made up of two electrolyzer modules.
The two dimensional structure synoptic diagram of the electrolyzer group that Fig. 2 is made up of a plurality of electrolyzer modules.
Fig. 3 is the composition and the electrolytic solution preparation flow synoptic diagram of cyclic electrolysis reaction unit.
Identify in the accompanying drawing: the 1-metal end plate; The 2-insulcrete; The 3-negative plate; The 4-positive plate; 5-negative electrode frame; 6-supramolecule PE barrier film; The 7-anode frame; The 8-bipolar plates; The 9-connecting ear; The import of 10-electrolytic solution; The 11-electrolyte outlet; The 12-storage tank; The 13-agitator; The 14-impeller pump; The 15-subsider; 16-electrolyzer group; The 17-dc charging motor; The 18-valve.
Specific embodiments
Adopt electrolysis reaction device described in the utility model, wherein the electrolyzer group is made up of 11 electrolyzer modules, the cathode-anode plate size all is 800mm * 550mm, the cathode-anode plate spacing is 20mm in the electrolyzer module, negative plate is pure graphite cake, and positive plate is the titanium alloy sheet that iridium coating layer is arranged, and thickness is that the supramolecule microporous PE film of 1.5mm is as diaphragm of electrolyzer, electrolytic cell frame is the PVC frame, and thickness is 9.3mm.Add 2molL in the electrolyzer cathode chamber
-1Sulphuric acid soln, the 2molL of adding capacity in the reaction coppers
-1Sulphuric acid soln is opened pump and is made liquid flow cross whole electrolysis reaction device, and guarantees the electrolyzer group, and enough liquid is arranged in charging reaction still and the settling bowl, and flow rate of liquid is controlled at 2cms in the electrolyzer group
-1
In the charging reaction still, add 1810g(10mol) d
50The V of=50 μ m
2O
5, agitator speed is 300 commentaries on classics min
-1, suspension liquid precipitates through settling bowl, and supernatant liquid is sent into electrolyzer group negative electrode fluid inlet.Apply the electric current of 660A on the electrolyzer group, this moment, the voltage of single electrolyzer module was between 3.4 ~ 3.6V, kept constant, and the current density of cathode-anode plate is 1500Am
-2
After electrolyzer group cathode outlet liquid becomes green, in the charging reaction still, add the d of capacity again
50The V of=50 μ m
2O
5Guarantee that liquid is suspension liquid in the charging reaction still.Behind the 10min, respectively access 10ml liquid from electrolyzer group liquid outlet, settling bowl upper end liquid outlet and the 6th grade of negative electrode liquid outlet of electrolyzer group respectively, and carry out the vanadium ion Determination of Different Valence States, result such as following table:
The valence state of vanadium ion is formed in the electrolytic solution product that the table different positions obtains
| The product extracting position | The vanadium ion valence state is formed in the product |
| Electrolyzer group liquid outlet | c(V 3+):c(V 2+)=98:2 |
| Settling bowl upper end liquid outlet | c(V 4+):c(V 5+)=97:3 |
| The 6th grade of negative electrode liquid outlet of electrolyzer group | c(V 3+):c(V 4+)=51:49 |
Claims (1)
1. cyclic electrolysis reaction unit that is used to prepare electrolyte of vanadium redox battery, it is characterized in that: the cyclic electrolysis reaction unit that is adopted is by the electrolyzer group, the charging reaction still, settling bowl, infusion pipeline and pump are formed, described electrolyzer group is made up of the symmetrical electrolyzer more than 2 or 2, the negative electrode liquid outlet of electrolyzer group links to each other with charging reaction still fluid inlet by infusion pipeline, charging reaction liquid from reactor mouth communicates with the settling bowl fluid inlet, settling bowl upper end liquid outlet communicates with electrolyzer group negative electrode fluid inlet by infusion pipeline and pump, and settling bowl lower end liquid outlet links to each other with charging reaction still fluid inlet through pump.
2. the cyclic electrolysis reaction unit that is used to prepare electrolyte of vanadium redox battery according to claim 1, it is characterized in that: the electrolyzer group is in series by symmetrical electrolyzer module more than 2 or 2, each module comprises electrolytic cell frame, battery lead plate, barrier film, wherein being in the outermost battery lead plate of electrolyzer is single electrode plate, being in electrolyzer group intermediary battery lead plate is bipolar plates, and a plurality of electrolyzer modules are assembled into the electrolyzer group by the pressure filter mode.
3. the cyclic electrolysis reaction unit that is used to prepare electrolyte of vanadium redox battery according to claim 1 and 2, it is characterized in that: the battery lead plate material can form with graphite cake, conductive plastics, titanium or titanium alloy preparation, wherein carries out the one side of anodic reaction and generally wants the coated catalysts coating; Electrolytic cell frame can be made with PVC, PP or PE; Barrier film can adopt PP felt, microporous glass fiber film, supramolecule microporous PE film or Nafion film.
4. the cyclic electrolysis reaction unit that is used to prepare electrolyte of vanadium redox battery according to claim 1 is characterized in that: the flow velocity of electrolytic solution in each electrolyzer is 0.5cms
-1~ 10cms
-1, the galvanic current that puts on the electrolyzer group is 10A ~ 1000A, the current density that puts on the electrolyzer group is 100Am
-2~ 2000Am
-2
5. the cyclic electrolysis reaction unit that is used to prepare electrolyte of vanadium redox battery according to claim 1 is characterized in that: the anolyte in the electrolyzer group is the aqueous solution that contains supporting electrolyte, and concentration is 0.5molL
-1~ 6molL
-1
6. the cyclic electrolysis reaction unit that is used to prepare electrolyte of vanadium redox battery according to claim 1 is characterized in that: in the charging reaction still agitator is installed, its rotating speed is 100 commentaries on classics min
-1~ 1000 change min
-1The V that adds
2O
5Be by grind also/or filter the powder that the granularity that obtains is no more than 50 μ m.
7. the cyclic electrolysis reaction unit that is used to prepare electrolyte of vanadium redox battery according to claim 1, it is characterized in that: be provided with three products exports in the electrolysis reaction device, comprise: the negative electrode liquid outlet of certain one-level electrolyzer in electrolyzer group liquid outlet, settling bowl upper end liquid outlet and the electrolyzer group can obtain pure V respectively
3+Electrolytic solution, pure V
4+Electrolytic solution and V
3+: V
4+The electrolytic solution of=1:1, its concentration are 0.5molL
-1~ 6molL
-1
Priority Applications (1)
| Application Number | Priority Date | Filing Date | Title |
|---|---|---|---|
| CN2010206432415U CN201981262U (en) | 2010-12-06 | 2010-12-06 | Circular electrolysis reacting device for preparing electrolyte of vanadium batter |
Applications Claiming Priority (1)
| Application Number | Priority Date | Filing Date | Title |
|---|---|---|---|
| CN2010206432415U CN201981262U (en) | 2010-12-06 | 2010-12-06 | Circular electrolysis reacting device for preparing electrolyte of vanadium batter |
Publications (1)
| Publication Number | Publication Date |
|---|---|
| CN201981262U true CN201981262U (en) | 2011-09-21 |
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ID=44608726
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| Application Number | Title | Priority Date | Filing Date |
|---|---|---|---|
| CN2010206432415U Expired - Fee Related CN201981262U (en) | 2010-12-06 | 2010-12-06 | Circular electrolysis reacting device for preparing electrolyte of vanadium batter |
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|---|---|
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Cited By (5)
| Publication number | Priority date | Publication date | Assignee | Title |
|---|---|---|---|---|
| CN102011135A (en) * | 2010-12-06 | 2011-04-13 | 上海林洋储能科技有限公司 | Cyclic electrolysis reaction device and method for preparing vanadium battery electrolyte |
| CN102978647A (en) * | 2012-12-05 | 2013-03-20 | 吉首市汇锋矿业有限责任公司 | Electrolytic system and electrolytic method for preparing vanadium cell fluid |
| CN109841875A (en) * | 2019-03-21 | 2019-06-04 | 国网新源张家口风光储示范电站有限公司 | A kind of all-vanadium flow battery energy-storage module electrolyte valence state balance control method |
| CN111430743A (en) * | 2020-03-31 | 2020-07-17 | 湖南钒谷新能源技术有限公司 | Vanadium cell electrolyte reduction device |
| CN111957325A (en) * | 2020-09-05 | 2020-11-20 | 河南心连心化学工业集团股份有限公司 | Regeneration device and regeneration process of furfuryl alcohol waste catalyst |
-
2010
- 2010-12-06 CN CN2010206432415U patent/CN201981262U/en not_active Expired - Fee Related
Cited By (6)
| Publication number | Priority date | Publication date | Assignee | Title |
|---|---|---|---|---|
| CN102011135A (en) * | 2010-12-06 | 2011-04-13 | 上海林洋储能科技有限公司 | Cyclic electrolysis reaction device and method for preparing vanadium battery electrolyte |
| CN102978647A (en) * | 2012-12-05 | 2013-03-20 | 吉首市汇锋矿业有限责任公司 | Electrolytic system and electrolytic method for preparing vanadium cell fluid |
| CN109841875A (en) * | 2019-03-21 | 2019-06-04 | 国网新源张家口风光储示范电站有限公司 | A kind of all-vanadium flow battery energy-storage module electrolyte valence state balance control method |
| CN111430743A (en) * | 2020-03-31 | 2020-07-17 | 湖南钒谷新能源技术有限公司 | Vanadium cell electrolyte reduction device |
| CN111430743B (en) * | 2020-03-31 | 2021-06-01 | 湖南钒谷新能源技术有限公司 | Vanadium cell electrolyte reduction device |
| CN111957325A (en) * | 2020-09-05 | 2020-11-20 | 河南心连心化学工业集团股份有限公司 | Regeneration device and regeneration process of furfuryl alcohol waste catalyst |
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Legal Events
| Date | Code | Title | Description |
|---|---|---|---|
| C14 | Grant of patent or utility model | ||
| GR01 | Patent grant | ||
| C17 | Cessation of patent right | ||
| CF01 | Termination of patent right due to non-payment of annual fee |
Granted publication date: 20110921 Termination date: 20131206 |