CN103515641A - Trivalent vanadium ion electrolyte and preparation method thereof, and vanadium battery - Google Patents
Trivalent vanadium ion electrolyte and preparation method thereof, and vanadium battery Download PDFInfo
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- CN103515641A CN103515641A CN201210200437.0A CN201210200437A CN103515641A CN 103515641 A CN103515641 A CN 103515641A CN 201210200437 A CN201210200437 A CN 201210200437A CN 103515641 A CN103515641 A CN 103515641A
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- H—ELECTRICITY
- H01—ELECTRIC ELEMENTS
- H01M—PROCESSES OR MEANS, e.g. BATTERIES, FOR THE DIRECT CONVERSION OF CHEMICAL ENERGY INTO ELECTRICAL ENERGY
- H01M8/00—Fuel cells; Manufacture thereof
- H01M8/18—Regenerative fuel cells, e.g. redox flow batteries or secondary fuel cells
- H01M8/184—Regeneration by electrochemical means
- H01M8/188—Regeneration by electrochemical means by recharging of redox couples containing fluids; Redox flow type batteries
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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
- Y02E60/30—Hydrogen technology
- Y02E60/50—Fuel cells
Abstract
The invention provides a preparation method of a trivalent vanadium ion electrolyte, the trivalent vanadium ion electrolyte prepared with the method, and a vanadium battery. The trivalent vanadium ion electrolyte preparation method comprises the steps that: a sulfuric acid solution comprising vanadyl sulfate is adopted as a cathode, and a sulfuric acid solution is adopted as an anode, wherein the molar amount of the sulfuric acid of the anode equals that of the vanadyl sulfate in the sulfuric acid solution comprising vanadyl sulfate; constant-voltage electrolysis is carried out, such that the trivalent vanadium ion electrolyte with a molar ratio of trivalent vanadium to all vanadium higher than 0.98 is obtained. With the method provided by the invention, the trivalent vanadium ion electrolyte with relatively high purity can be stably obtained.
Description
Technical field
The present invention relates to a kind of preparation method of trivalent vanadium ion electrolyte, the trivalent vanadium ion electrolyte being prepared by the method and a kind of vanadium cell.
Background technology
Vanadium oxide reduction flow battery, by mutually transforming storage and the release that realizes electric energy between the vanadium ion of different valence state, is the battery system that in numerous chemical power sources, unique use element of the same race forms.It can become continuous, safe and reliable output by unsettled electric energy input, can solve scale and utilize the great energy storage technology problem in wind energy, solar power generation process.Vanadium oxide reduction flow battery also can be applicable to the peak load that disappears of existing network system, improves electric network security and reliability, and has wide application space in the fields such as emergency power supply of communication system.Although the research of vanadium cell has been entered to practical stage, but the optimization of the stability of high-concentration vanadium electrolyte, electrode material and electro-chemical activity thereof and system configuration becomes one of principal element of its commercial operations development of restriction, wherein, the preparation of V electrolyte is the core of all-vanadium liquid flow energy storage system.
Theoretically, the electrolyte of vanadium oxide reduction flow battery is tetravalent vanadium ion solution just very, and negative pole is trivalent vanadium ion solution.During charging, the tetravalent vanadium ion of positive pole becomes pentavalent vanadium ion, and the trivalent vanadium ion of negative pole becomes divalent vanadium ion.Yet adopt of anodal and negative pole electrolyte such as has at the trivalent of amount and the mixed solution of tetravalent vanadium ion more in current technology, this is that trivalent vanadium ion electrolyte because of high-purity, high stability is difficult to make.
At present, all-vanadium ionic liquid flow battery is mainly to adopt vanadic sulfate as the active material of battery, its preparation method is the vanadic sulfate sulfuric acid solution of equivalent to be poured into respectively to positive pole and the negative pole of vanadium cell, under the charge condition of vanadium cell, charge, after being full of electricity, positive solution is all discharged, adopt in this way, in the trivalent vanadium ion electrolyte making, trivalent vanadium ion is 0.80 left and right with the mol ratio of full vanadium, the vanadic sulfate sulfuric acid solution of changing equivalent continues charging, can use by chargeable battery as other after being full of electricity.The method need to be changed positive solution one time, carries out recharging, causes battery assembling and chemical industry program complicated, and makes the vanadium cell lost of life, owing to being limited to the charge condition of vanadium cell, also directly causing changing into the time long, thereby affects production efficiency.
In addition, can also first sulfuric acid be mixed with to the dilute sulfuric acid of 1:2, then first add vanadium trioxide, then add vanadic oxide, reaction obtains vanadic sulfate solution; Add again Na
2sO
4, the additive such as polyoxyethylene nonylphenol ether; And this vanadic sulfate solution is placed in to cathode of electrolytic tank, and the sulfuric acid solution that contains sodium sulphate of same ion intensity is placed in to electrolytic cell anode and carries out electrolysis, obtain 50% the vanadium cell V electrolyte that tetravalence vanadium and trivalent vanadium respectively account for total content of vanadium.Although the method was once considered to more rational method, but the development along with vanadium cell, especially for a long time the people of the research of the structure of vanadium cell, material and performance are started to find, the quality of electrolyte can directly have influence on the performance of vanadium cell, even also can have influence on the stability of electrolyte itself, so for example, to the further investigation of electrolyte (research to the composition of electrolyte and purity) extremely important.
In the prior art, in order to make V electrolyte stable, improve the vanadium cell life-span, conventionally in vanadium cell, add various additives, as CN1719655A discloses a kind of full vanadium ion fluid cell electrolyte, it is comprised of V salt sulfate, sulfuric acid, water, ethanol and additive, and described additive is one or more in sodium sulphate, sodium pyrophosphate, prodan, hydrogen peroxide.And for example, CN101635363A discloses a kind of full vanadium ion fluid cell electrolyte, comprises vanadic salts, sulfuric acid, additive and deionized water, also comprises the slaine that dissolves in sulfuric acid system, with this, improves the stability of electrolyte in charge and discharge process.Wherein, additive is selected from one or more in sodium sulphate, ethanol, glycerine, NPE, sodium pyrophosphate, prodan, urea and hydrogen peroxide.But additive has increased objectionable impurities to electrolyte of vanadium redox battery system, along with improving constantly that electrolyte is required, current electrolyte of vanadium redox battery quality can not meet the requirement for full vanadium ion fluid cell electrolyte.
Summary of the invention
The vanadium ion electrolyte purity that the object of the invention is to overcome prior art is not high, and need to add the defect that additive keeps its stability, and a kind of trivalent vanadium ion electrolyte with higher degree and stability and preparation method thereof and a kind of vanadium cell are provided.
The invention provides a kind of preparation method of trivalent vanadium ion electrolyte, wherein, the method comprises using the sulfuric acid solution that contains vanadic sulfate as negative electrode, using sulfuric acid solution as anode, and the sulfuric acid of anode equates with the mole of vanadic sulfate in the sulfuric acid solution that contains vanadic sulfate, and carry out constant-potential electrolysis, obtain the trivalent vanadium ion electrolyte that the mol ratio of trivalent vanadium and full vanadium is greater than 0.98.
The present invention also provides the trivalent vanadium ion being obtained by said method electrolyte.
In addition, the present invention also provides a kind of vanadium cell, this vanadium cell comprises the battery unit of a plurality of series connection, each battery unit comprises anodal assembly, negative pole assembly and the barrier film between this positive pole assembly and negative pole assembly, described anodal assembly comprises the liquid flow frame that accommodates anode electrolyte and is arranged on collector and the anode plate on this liquid flow frame, described negative pole assembly comprises the liquid flow frame that accommodates negative pole electrolyte and is arranged on collector and the negative plates on this liquid flow frame, wherein, described anode electrolyte is the sulfuric acid solution that contains vanadic sulfate, described negative pole electrolyte is above-mentioned trivalent vanadium ion electrolyte.
The present invention adopts the method for constant-potential electrolysis to prepare trivalent vanadium ion electrolyte, can reduce error, improve precision, thereby realize the requirement of the highly purified trivalent vanadium battery electrolyte of preparation.Constant pressure source is exactly stabilized voltage power supply, in the situation of energy proof load (output current) change, keeps voltage constant; Constant-current source is the in the situation that of load variations, and the output voltage of energy corresponding adjustment oneself, remains unchanged output current; In fact the Switching Power Supply of constant-current source is exactly on the basis of constant pressure source, inner on output circuit, add sample resistance, circuit guarantees that the pressure drop on this sample resistance is constant, realizes constant current output, therefore, inventor infers, may be because the current efficiency of constant-current electrolysis process be lower, the data error of monitoring is larger simultaneously, thereby adopts constant-current electrolysis cannot obtain the trivalent vanadium battery electrolyte that purity is higher.A preferred embodiment of the invention is carried out electrolysis and can be shortened the time, raise the efficiency, control electroaffinity under the condition that is 1.5V-50V at decomposition voltage, makes current efficiency maintain the maximum of 100% this electric current, thereby improves voltage efficiency.In addition, the speed that constant-potential electrolysis carries out and initial concentration are irrelevant, when identical external condition, by concentration, are also 0.1M and 10
-6the material electrolysis of M to same degree need be with the same time, thereby can control more accurately electrolytic process.
What is more important, the present inventor stumbles on, carrying out constant-potential electrolysis using the sulfuric acid solution that contains vanadic sulfate as negative electrode, using sulfuric acid solution as anode and under the condition that equates with the mole of vanadic sulfate in the sulfuric acid solution that contains vanadic sulfate of the sulfuric acid of anode, can prepare the trivalent vanadium ion electrolyte that purity is higher, performance is comparatively stable.In preparing the process of trivalent vanadium ion electrolyte, adopt sulfuric acid solution to substitute existing vanadic sulfate solution as anode, on the one hand, not only in system, do not introduce other any impurity, also improved electrolytic efficiency; On the other hand, avoid the waste of vanadium, reduced the cost of preparing electrolyte.In addition, the groove deckle board material of existing electrolysis tank is generally polymethyl methacrylate or polyvinyl chloride, but the present inventor also finds through further investigation, in constant-potential electrolysis process, there is the phenomenon of analysing oxygen liberation of hydrogen, even also having oxysulfide produces, the groove deckle board that adopts polymethyl methacrylate or polyvinyl chloride material steadily carries out not only bad for electrolysis, and can introduce new impurity, and the purity of the trivalent vanadium ion electrolyte that obtains is significantly declined.According to another kind of preferred implementation of the present invention, when described trivalent vanadium ion electrolyte carries out constant-potential electrolysis in electrolysis tank provided by the invention, weight average molecular weight is greater than 3,000,000 polyethylene groove deckle board not only can not introduce the impurity that electrolytic process is impacted, and can make electrolytic process stable for extended periods of time, obtain the trivalent vanadium ion electrolyte that purity is higher.According to another preferred implementation of the present invention, when the battery lead plate of described electrolysis tank is platinum plate, and when the distance between battery lead plate is not less than 3cm, in electrolytic process, can keep lower tank voltage, be particularly conducive to the trivalent vanadium ion electrolyte of preparing high-purity, high stability.
Further, when by described trivalent vanadium ion used for electrolyte during in vanadium cell, because the trivalent vanadium ion electrolyte that adopts method of the present invention to obtain has higher purity, therefore can significantly reduce the impact of impurity on trivalent vanadium ion electrolyte and vanadium cell material and barrier film.What is more important, the trivalent vanadium ion electrolyte that purity is higher can make trivalent vanadium ion realize supersaturation, crystallization not, therefore, even if do not add any additive, also can keep the stable of vanadium cell performance.
Other features and advantages of the present invention partly in detail are described the embodiment subsequently.
Accompanying drawing explanation
Fig. 1 is the working state schematic representation of preparing the electrolysis tank using in trivalent vanadium ion electrolyte process.
Description of reference numerals
1-constant voltage source; 2-potentiometer; 3-blender; 4-anode pool; 5-platinum electrode; 6-calomel electrode; 7-cathode pool; 8-groove deckle board; 9-platinum electrode; 10-gas access.
Embodiment
Below in conjunction with accompanying drawing, the specific embodiment of the present invention is elaborated.Should be understood that, embodiment described herein only, for description and interpretation the present invention, is not limited to the present invention.
According to the present invention, the preparation method of described trivalent vanadium ion electrolyte comprises using the sulfuric acid solution that contains vanadic sulfate as negative electrode, using sulfuric acid solution as anode, and the sulfuric acid of anode equates with the mole of vanadic sulfate in the sulfuric acid solution that contains vanadic sulfate, and carry out constant-potential electrolysis, obtain the trivalent vanadium ion electrolyte that the mol ratio of trivalent vanadium and full vanadium is greater than 0.98.Wherein, described full vanadium refers to the summation of the vanadium ion of various valence states in trivalent vanadium ion electrolyte.
According to the present invention, in described trivalent vanadium ion electrolyte, the molar concentration MTV of full vanadium can select and change in wider scope, preferably, the molar concentration MTV of described full vanadium at 1mol/L between 3mol/L, 1-2mol/L more preferably, is not only more conducive to the carrying out of electrolysis like this, can also avoid the excessive concentration of trivalent vanadium ion electrolyte, so that the state that reaches capacity, produces the problem of easy crystallization.
The present invention is not particularly limited the content of the vanadic sulfate in the sulfuric acid solution of described vanadic sulfate and sulfuric acid, but can carry out more reposefully in order to make electrolysis, and obtain the trivalent vanadium ion electrolyte that purity is higher, under preferable case, the mol ratio of described vanadic sulfate and sulfuric acid is 1:1.5-3, more preferably 1:1.5-2.The sulfuric acid solution of described vanadic sulfate can adopt method known in those skilled in the art to prepare, for example, can by purity, be directly to obtain in vanadic sulfate crystal vitriolization solution more than 98 % by weight, also can be by vanadic oxide, vanadium trioxide are reacted and obtained with sulfuric acid solution, or also can be by vanadic oxide, reducing agent are reacted and obtained with sulfuric acid solution.Wherein, described sulfuric acid solution all refers to sulphur aqueous acid.
Wherein, when adopting the sulfuric acid solution of vanadic oxide, vanadium trioxide and the described vanadic sulfate of sulfuric acid solution reaction preparation, reaction equation is as follows:
V
2O
5+V
2O
3+4H
2SO
4=4VOSO
4+4H
2O，
Reaction condition is: vanadic oxide and vanadium trioxide are dissolved in sulfuric acid solution and react after obtain, wherein, the molal quantity of vanadic oxide and vanadium trioxide preferably equates.The selectable range of the temperature of described reaction is wider, as long as can access the sulfuric acid solution of vanadic sulfate, but in order to be further beneficial to the carrying out of reaction, the temperature of described reaction is preferably 70-90 ℃.The consumption of described sulfuric acid solution also can be selected and change in wider scope, and for example, the sulfuric acid in described sulfuric acid solution can be 2.5-4:1 with the mol ratio of full vanadium material consumption.In addition, the sulfuric acid solution of described vanadic sulfate also can pass through the mixture roasting of vanadic oxide and vanadium trioxide, and the product of roasting obtaining is dissolved in sulfuric acid solution and is obtained, wherein, sintering temperature can be 300-500 ℃, and roasting time can be 1.5-2 hour, and the consumption of described sulfuric acid solution also can be selected and change in wider scope, for example, the sulfuric acid in described sulfuric acid solution can be 2.5-4:1 with the mol ratio of the consumption of full vanadium material.
When adopting the sulfuric acid solution of vanadic oxide, reducing agent (oxalic acid) and the described vanadic sulfate of sulfuric acid solution reaction preparation, reaction equation is as follows:
V
2O
5+H
2SO
4=(VO
2)
2SO
4+H
2O
(VO
2)
2SO
4+H
2C
2O
4+H
2SO
4=2VOSO
4+2CO
2↑+2H
2O
Reaction condition is: under the existence of sulfuric acid solution, take vanadic oxide as raw material, add oxalic acid (also can adopt other reducing agents to substitute, as SO under 40-80 ℃ of heating condition
2with elemental sulfur etc.) reduction, or in sulfuric acid solution Direct Electrolysis, filter and get final product.Wherein, vanadic oxide and reducing agent are preferably equimolar amounts and add, and the consumption of described sulfuric acid solution also can be selected and change in wider scope, and for example, the mol ratio of the sulfuric acid in described sulfuric acid solution and the consumption of vanadic oxide can be 5-8:1.The purity of described vanadic oxide can be for example 98-100 % by weight, is preferably 99.5-100 % by weight.
The present invention is not particularly limited the condition of described constant-potential electrolysis, as long as can access the trivalent vanadium ion electrolyte that the mol ratio of trivalent vanadium and full vanadium is greater than 0.98, preferably, the condition of described constant-potential electrolysis comprises that decomposition voltage is 1.5V-50V, electrolysis temperature is 20-60 ℃, and electrolysis time is 0.5-5 hour; More preferably, described decomposition voltage is 1.5V-10V, and electrolysis temperature is 20-40 ℃, and electrolysis time is 0.5-3 hour.
According to the present invention, airborne oxygen can affect electrolytic process, and therefore, in order to make electrolysis can carry out more reposefully, also improve the purity of the trivalent vanadium ion electrolyte obtaining, under preferable case, described electrolysis is carried out in inert atmosphere.Described inert atmosphere can be selected from one or more in nitrogen and periodic table of elements zero group gas, is preferably argon gas.
According to the present invention, described electrolysis terminal can be measured and be obtained by the method that well known to a person skilled in the art, for example, can and control electrolysis terminal by test solution charge value and the rough judgement of potential value, after electrolysis completes, carry out the concentration that ion chromatography, polarographic analysis, ICP mass spectrum and ICP spectrum analysis obtain trivalent vanadium ion in electrolyte.
According to the present invention, the preparation of trivalent vanadium ion electrolyte can be carried out in existing various electrolysis units, preferably in electrolysis tank, carries out.The structure of described electrolysis tank can be identical with existing cell construction, for example, described electrolysis tank comprise groove deckle board, the anode pool being surrounded by groove deckle board and cathode pool, the conductive diaphragm between anode pool and cathode pool and lay respectively at anode pool and cathode pool in battery lead plate, the material of described groove deckle board is the polyethylene that weight average molecular weight is greater than 3,000,000, and preferable weight-average molecular weight is 3,500,000-5,000,000 polyethylene.
According to the present invention, described battery lead plate can be the existing various battery lead plates of preparing trivalent vanadium ion electrolyte that can be used in, for example, battery lead plate can be selected from one or more in platinum plate, modified graphite plate, titanium base platinum, yttrium oxide, graphite felt, carbon stick or compound conductive plastic plate.Wherein, described compound conductive plastic plate refers to and polymer (as PVC, nylon-6, nylon-11, low density polyethylene (LDPE), high density polyethylene (HDPE), low density polypropylene, high density poly propylene etc.) is mixed with conductive materials (as carbon black, graphite powder, graphite fibre etc.) and the hot-forming sheet material obtaining.As mentioned above, while adopting platinum plate as battery lead plate, can improve more significantly the purity of trivalent vanadium ion electrolyte, therefore, described electrolytic zinc-coated steel sheet is preferably platinum plate.Distance between battery lead plate in anode pool and cathode pool can be adjusted according to actual conditions, as a rule, distance between battery lead plate is not less than 3cm, be preferably 3cm-20cm, can keep lower tank voltage like this, be conducive to prepare the trivalent vanadium ion electrolyte of high-purity, high stability.
According to the present invention, the conductive diaphragm of described electrolysis tank can be existing various conductive diaphragm, preferably adopt suitable in the sulfuric acid solution of vanadic sulfate electrolysis use ion selectivity strong, vanadium ion is impermeable, H+ migration velocity is fast, surface resistance is little, fluorine-containing polyolefin amberplex after the activation processing that simultaneously corrosion-resistant, resistance to oxidation, life-span are long, the perfluorinated sulfonic acid ion exchange membrane after activation processing more preferably, the higher current efficiency of maintenance that like this can be steady in a long-term, is conducive to prepare the trivalent vanadium ion electrolyte of high-purity, high stability.Method and the condition of described activation are known to the skilled person, and at this, will repeat no more.
The present invention also provides the trivalent vanadium ion making according to said method electrolyte.
The present invention also provides a kind of vanadium cell, this vanadium cell comprises the battery unit of a plurality of series connection, each battery unit comprises anodal assembly, negative pole assembly and the barrier film between this positive pole assembly and negative pole assembly, described anodal assembly comprises the liquid flow frame that accommodates anode electrolyte and is arranged on collector and the anode plate on this liquid flow frame, described negative pole assembly comprises the liquid flow frame that accommodates negative pole electrolyte and is arranged on collector and the negative plates on this liquid flow frame, wherein, described anode electrolyte is the sulfuric acid solution that contains vanadic sulfate, described negative pole electrolyte is above-mentioned trivalent vanadium ion electrolyte.
Improvements of the present invention have been to adopt described trivalent vanadium ion electrolyte as the anode electrolyte of vanadium cell, all can be same as the prior art for structure and the annexation between each structure of vanadium cell, at this, will repeat no more.
According to a specific embodiment of the present invention, trivalent vanadium ion electrolyte is used electrolysis tank preparation, and electrolytic process as shown in Figure 1.The material of described groove deckle board 8 is the polyethylene that weight average molecular weight is greater than 3,000,000.The sulfuric acid solution that contains vanadic sulfate is injected to cathode pool 7, by with vanadic sulfate sulfuric acid solution in the sulfuric acid solution of vanadic sulfate equimolar amounts inject anode pool 4, wherein in vanadic sulfate sulfuric acid solution, the mol ratio of the concentration of vanadic sulfate and sulfuric acid is wherein 1:1.5-3, is preferably 1:1.5-2.By nitrogen, from the 10 introducing electrolysis tanks of gas access, under the stirring action of blender 3, the constant voltage source 1 that is all connected with platinum electrode 5 by two ends carries out constant-potential electrolysis, and setting decomposition voltage is 1.5V-50V, and battery lead plate minimum range is 3cm; And by two ends, be connected with respectively the charge value of potentiometer 2 test solutions and the rough judgement of potential value of calomel electrode 6 and platinum electrode 9 and control electrolysis terminal, obtain trivalent vanadium ion electrolyte.Adopt described in ion chromatography, polarographic analysis, ICP mass spectrum and ICP spectrum analysis the content of material in trivalent vanadium ion electrolyte, and then obtain the concentration of trivalent vanadium ion.This trivalent vanadium electrolyte and vanadic sulfate sulfuric acid solution are injected respectively to vanadium cell negative pole and positive pole, after charging, can normally use.
More than describe the preferred embodiment of the present invention in detail; but the present invention is not limited to the detail in above-mentioned execution mode, within the scope of technical conceive of the present invention; can carry out multiple simple variant to technical scheme of the present invention, these simple variant all belong to protection scope of the present invention.
It should be noted that in addition each the concrete technical characterictic described in above-mentioned embodiment, in reconcilable situation, can combine by any suitable mode.For fear of unnecessary repetition, the present invention is to the explanation no longer separately of various possible compound modes.
In addition, between various execution mode of the present invention, also can carry out combination in any, as long as it is without prejudice to thought of the present invention, it should be considered as content disclosed in this invention equally.
Below will by embodiment, the invention will be further described.
Following embodiment and comparative example all adopt electrolysis tank as shown in Figure 1 to carry out being prepared of trivalent vanadium ion electrolyte.
In following examples and comparative example, the electric weight that the electronics that it is trivalent vanadium ion transfer that theoretical electric weight refers to the complete electrolysis of tetravalent vanadium ion in the sulfuric acid solution of described vanadic sulfate calculates; Theoretical current potential refers to by pentavalent vanadium ion being reverted in the process of divalent vanadium ion, and current potential presents classification hop from 400mV to 150mV to be changed, and wherein, the potential jump from tetravalent vanadium ion to trivalent vanadium ion is 200mV, and described theoretical current potential is 200mV.Voltage efficiency obtains by discharging and recharging instrument (purchased from Foshan City blue light Science and Technology Ltd.) mensuration.
In embodiment and comparative example,
V
2o
5raw material: V
2o
5content be 99.5 % by weight, purchased from Nanjing Nan Yuan Chemical Co., Ltd.;
V
2o
3raw material: V
2o
3content be 99.5 % by weight, purchased from Hangzhou Xin Ye Chemical Co., Ltd.;
H
2sO
4: analyze purely, proportion is 1.84g/mL.
Preparation example 1
This preparation example is used for illustrating trivalent vanadium ion electrolyte provided by the invention and preparation method thereof.
The making of electrolysis tank: the polyethylene manufacturing specification that employing weight average molecular weight is 3,500,000 is anode pool and the cathode pool of 170 * 170 * 170mm, and perfluorinated sulfonic acid ion exchange membrane is placed between anode pool and cathode pool and is fixed, then two blocks of platinum plates of external connection constant voltage power positive cathode are placed in respectively to anode pool and cathode pool, wherein, the effective area of platinum plate is 100 * 100mm
2.
The preparation of the sulfuric acid solution that contains vanadic sulfate: first add 550mL deionized water in reactor, then add the 259mL concentrated sulfuric acid in the condition downhill reaction device stirring, when temperature rises at 80 ℃, by 62 grams of V
2o
3with 74.5 grams of V
2o
5mixture progressively add in reactor and react, reaction is settled to 900mL with deionized water after 0.5h and obtains the sulfuric acid solution that contains vanadic sulfate, as electrolyte raw material for standby.Test sulfuric acid concentration is 3.6mol/L, and the concentration of full vanadium is 1.79mol/L.
The preparation of sulfuric acid solution: in reactor, add 200mL deionized water, under the condition stirring, progressively add the 85.9mL concentrated sulfuric acid, finally standby to 900mL with deionized water constant volume.
The preparation of trivalent vanadium ion electrolyte: the above-mentioned sulfuric acid solution that contains vanadic sulfate of getting 900mL injects the cathode pool 7 of electrolysis tank, and the above-mentioned sulfuric acid solution of getting 900mL injects the anode pool 4 of electrolysis tank; Adopt the electrolysis of constant voltage mode, wherein, setting battery lead plate spacing is 3cm, and decomposition voltage is 3V, and electrolysis temperature is 20 ℃.Electric weight and current potential by 2 pairs of electrolyte of potentiometer carries out on-line monitoring simultaneously, when detecting electric weight, reaches 1.1 times of theoretical electric weight or detects current potential while reaching theoretical current potential, stops electrolysis, and now electrolysis time is 1.5 hours.The electrolyte obtaining is carried out to ion chromatography, polarographic analysis, ICP mass spectrum and ICP spectrum analysis, and the concentration that can obtain trivalent vanadium ion in described electrolyte is 1.78mol/L, and in electrolyte, trivalent vanadium is 99.6% with mol ratio V (the III)/TV of full vanadium.
Contrast preparation example 1
This contrast preparation example is for illustrating trivalent vanadium ion electrolyte of reference and preparation method thereof.
According to the method for preparation example 1, the sulfuric acid solution of described vanadic sulfate is prepared, different is, sulfuric acid solution in the anode pool of described electrolysis tank adopts the sulfuric acid solution that contains vanadic sulfate to substitute, that is, the anode pool of electrolysis tank is identical with the electrolyte in cathode pool.The electrolyte obtaining is carried out to ion chromatography, polarographic analysis, ICP mass spectrum and ICP spectrum analysis, and the concentration that can obtain trivalent vanadium ion in described electrolyte is 1.53mol/L, and in electrolyte, trivalent vanadium is 85.9% with mol ratio V (the III)/TV of full vanadium.
Contrast preparation example 2
This contrast preparation example is for illustrating trivalent vanadium ion electrolyte of reference and preparation method thereof.
Method according to contrast preparation example 1 is prepared the sulfuric acid solution of described vanadic sulfate, different, adopts current constant mode to carry out electrolysis, and control electric current is 3A.The electrolyte obtaining is carried out to ion chromatography, polarographic analysis, ICP mass spectrum and ICP spectrum analysis, can obtain the ratio of trivalent vanadium ion and tetravalent vanadium ion concentration in described electrolyte and be about 1:1, in electrolyte, trivalent vanadium is 50% with mol ratio V (the III)/TV of full vanadium.
Preparation example 2
This preparation example is used for illustrating trivalent vanadium ion electrolyte provided by the invention and preparation method thereof.
The making of electrolysis tank: the polyethylene manufacturing specification that employing weight average molecular weight is 4,000,000 is anode pool and the cathode pool of 170 * 170 * 170mm, and perfluorinated sulfonic acid ion exchange membrane is placed between anode pool and cathode pool and is fixed, then two blocks of platinum plates of external connection constant voltage power positive cathode are placed in respectively to anode pool and cathode pool, wherein, the effective area of platinum plate is 100 * 100mm
2.
The preparation of the sulfuric acid solution that contains vanadic sulfate: first add 600mL deionized water in reactor, then add the 288mL concentrated sulfuric acid in the condition downhill reaction device stirring, when temperature rises at 80 ℃, by 75 grams of V
2o
3with 83.2 grams of V
2o
5mixture progressively add in reactor and react, reaction is settled to 900mL with deionized water after 0.5h and obtains the sulfuric acid solution that contains vanadic sulfate, as electrolyte raw material for standby.Test sulfuric acid concentration is 4.0mol/L, and the concentration of full vanadium is 2.0mol/L.
The preparation of sulfuric acid solution: in reactor, add 400mL deionized water, under the condition stirring, progressively add the 95.9mL concentrated sulfuric acid, finally standby to 900mL with deionized water constant volume.
The preparation of trivalent vanadium ion electrolyte: the above-mentioned sulfuric acid solution that contains vanadic sulfate of getting 900mL injects the cathode pool 7 of electrolysis tank, and the above-mentioned sulfuric acid solution of getting 900mL injects the anode pool 4 of electrolysis tank; Adopt the electrolysis of constant voltage mode, wherein, setting battery lead plate spacing is 3cm, and decomposition voltage is 3.5V, and electrolysis temperature is 30 ℃.Electric weight and current potential by 2 pairs of electrolyte of potentiometer carries out on-line monitoring simultaneously, when detecting electric weight, reaches 1.1 times of theoretical electric weight or detects current potential while reaching theoretical current potential, stops electrolysis, and now electrolysis time is 2.5 hours.The electrolyte obtaining is carried out to ion chromatography, polarographic analysis, ICP mass spectrum and ICP spectrum analysis, and the concentration that can obtain trivalent vanadium ion in described electrolyte is 2.0mol/L, and in electrolyte, trivalent vanadium is 100% with mol ratio V (the III)/TV of full vanadium.
Preparation example 3
This preparation example is used for illustrating trivalent vanadium ion electrolyte provided by the invention and preparation method thereof.
The making of electrolysis tank: the polyethylene manufacturing specification that employing weight average molecular weight is 4,000,000 is anode pool and the cathode pool of 170 * 170 * 170mm, and perfluorinated sulfonic acid ion exchange membrane is placed between anode pool and cathode pool and is fixed, then two blocks of platinum plates of external connection constant voltage power positive cathode are placed in respectively to anode pool and cathode pool, wherein, the effective area of platinum plate is 100 * 100mm
2.
The preparation of the sulfuric acid solution that contains vanadic sulfate: first add 600mL deionized water in reactor, then add the 269mL concentrated sulfuric acid in the condition downhill reaction device stirring, when temperature rises at 80 ℃, by 61.7 grams of V
2o
3with 74 grams of V
2o
5mixture progressively add in reactor and react, reaction is settled to 900mL with deionized water after 0.5h and obtains the sulfuric acid solution that contains vanadic sulfate, as electrolyte raw material for standby.Test sulfuric acid concentration is 3.83mol/L, and the concentration of full vanadium is 1.78mol/L.
The preparation of sulfuric acid solution: in reactor, add 200mL deionized water, under the condition stirring, progressively add the 85.4mL concentrated sulfuric acid, finally standby to 900mL with deionized water constant volume.
The preparation of trivalent vanadium ion electrolyte: the above-mentioned sulfuric acid solution that contains vanadic sulfate of getting 900mL injects the cathode pool 7 of electrolysis tank, and the above-mentioned sulfuric acid solution of getting 900mL injects the anode pool 4 of electrolysis tank; Adopt the electrolysis of constant voltage mode, wherein, setting battery lead plate spacing is 10cm, and decomposition voltage is 5V, and electrolysis temperature is 40 ℃.Electric weight and current potential by 2 pairs of electrolyte of potentiometer carries out on-line monitoring simultaneously, when detecting electric weight, reaches 1.1 times of theoretical electric weight or detects current potential while reaching theoretical current potential, stops electrolysis, and now electrolysis time is 1.5 hours.The electrolyte obtaining is carried out to ion chromatography, polarographic analysis, ICP mass spectrum and ICP spectrum analysis, and the concentration that can obtain trivalent vanadium ion in described electrolyte is 1.76mol/L, and in electrolyte, trivalent vanadium is 98.9% with mol ratio V (the III)/TV of full vanadium.
Preparation example 4
This preparation example is used for illustrating trivalent vanadium ion electrolyte provided by the invention and preparation method thereof.
The making of electrolysis tank: the polyethylene manufacturing specification that employing weight average molecular weight is 4,000,000 is anode pool and the cathode pool of 170 * 170 * 170mm, and perfluorinated sulfonic acid ion exchange membrane is placed between anode pool and cathode pool and is fixed, then by two carbon stick battery lead plates of external connection constant voltage power positive cathode, (fixed carbon content is more than 98%, ash content<0.001, resistivity (m Ω cm)≤4, rupture strength (MPa)>=32, impregnation rate (%)>=8.5, the porosity (%) is 20-25, filling rate (%)>=85) be placed in respectively anode pool and cathode pool, wherein, the effective area of carbon stick battery lead plate is 100 * 100mm<sup TranNum="188">2</sup>.
The preparation of the sulfuric acid solution that contains vanadic sulfate: first add 600mL deionized water in reactor, then add the 298.6mL concentrated sulfuric acid in the condition downhill reaction device stirring, when temperature rises at 80 ℃, by 84 grams of V
2o
3with 100 grams of V
2o
5mixture progressively add in reactor and react, reaction is settled to 900mL with deionized water after 0.5h and obtains the sulfuric acid solution that contains vanadic sulfate, as electrolyte raw material for standby.Test sulfuric acid concentration is 3.7mol/L, and the concentration of full vanadium is 2.41mol/L.
The preparation of sulfuric acid solution: in reactor, add 400mL deionized water, under the condition stirring, progressively add the 115.6mL concentrated sulfuric acid, finally standby to 900mL with deionized water constant volume.
The preparation of trivalent vanadium ion electrolyte: the above-mentioned sulfuric acid solution that contains vanadic sulfate of getting 900mL injects the cathode pool 7 of electrolysis tank, and the above-mentioned sulfuric acid solution of getting 900mL injects the anode pool 4 of electrolysis tank; Adopt the electrolysis of constant voltage mode, wherein, setting battery lead plate spacing is 3cm, and decomposition voltage is 1.5V, and electrolysis temperature is 60 ℃.Electric weight and current potential by 2 pairs of electrolyte of potentiometer carries out on-line monitoring simultaneously, when detecting electric weight, reaches 1.1 times of theoretical electric weight or detects current potential while reaching theoretical current potential, stops electrolysis, and now electrolysis time is 1.1 hours.The electrolyte obtaining is carried out to ion chromatography, polarographic analysis, ICP mass spectrum and ICP spectrum analysis, to obtaining electrolyte, carry out online Potential Titration Analysis, the concentration that can obtain trivalent vanadium ion in described electrolyte is 2.4mol/L, and in electrolyte, trivalent vanadium is 99.6% with mol ratio V (the III)/TV of full vanadium.
Preparation example 5
This preparation example is used for illustrating trivalent vanadium ion electrolyte provided by the invention and preparation method thereof.
The making of electrolysis tank: the polyethylene manufacturing specification that employing weight average molecular weight is 4,000,000 is anode pool and the cathode pool of 170 * 170 * 170mm, and perfluorinated sulfonic acid ion exchange membrane is placed between anode pool and cathode pool and is fixed, then two blocks of compound conductive plastic plates of external connection constant voltage power positive cathode (polyethylene that is 100,000 by number-average molecular weight and carbon black are by weight the sheet material forming through hot pressing for the mixture of 1:1) are placed in respectively to anode pool and cathode pool, wherein, the effective area of compound conductive plastic plate is 100 * 100mm
2.
The preparation of the sulfuric acid solution that contains vanadic sulfate: first add 600mL deionized water in reactor, then add the 235mL concentrated sulfuric acid in the condition downhill reaction device stirring, when temperature rises at 80 ℃, by 41.2 grams of V
2o
3with 49.4 grams of V
2o
5mixture progressively add in reactor and react, reaction is settled to 900mL with deionized water after 0.5h and obtains the sulfuric acid solution that contains vanadic sulfate, as electrolyte raw material for standby.Test sulfuric acid concentration is 3.57mol/L, and the concentration of full vanadium is 1.2mol/L.
The preparation of sulfuric acid solution: in reactor, add 200mL deionized water, under the condition stirring, progressively add the 57.6mL concentrated sulfuric acid, finally standby to 900mL with deionized water constant volume.
The preparation of trivalent vanadium ion electrolyte: the above-mentioned sulfuric acid solution that contains vanadic sulfate of getting 900mL injects the cathode pool 7 of electrolysis tank, and the above-mentioned sulfuric acid solution of getting 900mL injects the anode pool 4 of electrolysis tank; Adopt the electrolysis of constant voltage mode, wherein, setting battery lead plate spacing is 20cm, and decomposition voltage is 10V, and electrolysis temperature is 40 ℃.Electric weight and current potential by 2 pairs of electrolyte of potentiometer carries out on-line monitoring simultaneously, when detecting electric weight, reaches 1.1 times of theoretical electric weight or detects current potential while reaching theoretical current potential, stops electrolysis, and now electrolysis time is 0.5 hour.The electrolyte obtaining is carried out to ion chromatography, polarographic analysis, ICP mass spectrum and ICP spectrum analysis, and the concentration that can obtain trivalent vanadium ion in described electrolyte is 1.19mol/L, and in electrolyte, trivalent vanadium is 99.2% with mol ratio V (the III)/TV of full vanadium.
Preparation example 6
This preparation example is used for illustrating trivalent vanadium ion electrolyte provided by the invention and preparation method thereof.
According to the method for preparation example 1, the sulfuric acid solution of described vanadic sulfate is prepared, different, in the manufacturing process of electrolysis tank, the polyethylene that weight average molecular weight is 3,500,000 adopts the polyvinyl chloride that weight average molecular weight is 3,500,000 to substitute.The electrolyte obtaining is carried out to ion chromatography, polarographic analysis, ICP mass spectrum and ICP spectrum analysis, and the concentration that can obtain trivalent vanadium ion in described electrolyte is 1.73mol/L, and in electrolyte, trivalent vanadium is 98.2% with mol ratio V (the III)/TV of full vanadium.
Preparation example 7
This preparation example is used for illustrating trivalent vanadium ion electrolyte provided by the invention and preparation method thereof.
According to the method for preparation example 1, the sulfuric acid solution of described vanadic sulfate is prepared, different, in electrolytic process, battery lead plate spacing is 2cm.The electrolyte obtaining is carried out to ion chromatography, polarographic analysis, ICP mass spectrum and ICP spectrum analysis, and the concentration that can obtain trivalent vanadium ion in described electrolyte is 1.71mol/L, and in electrolyte, trivalent vanadium is 98.1% with mol ratio V (the III)/TV of full vanadium.
Embodiment 1
This embodiment is used for illustrating vanadium cell provided by the invention and preparation method thereof.
(purchased from Liaoyang Jin Gu company, thickness is 5mm, and resistivity is 1.4 * 10 as battery electrode to adopt graphite felt
-3Ω cm), adopt graphite cake (thickness 3mm) as collector material, adopt homogeneous phase cation exchange film (purchased from Zhejiang Qianqiu Environmental Water Treatment Co., Ltd.) conductive diaphragm after activation processing, adopt polyvinyl chloride (purchased from Zibo Chuan Yu plastics Co., Ltd) plate that weight average molecular weight is 3,500,000 to make liquid flow frame, and make vanadium liquid and flow monocell, wherein, the size of liquid flow frame is 100 * 100 * 5mm, and in anodal assembly liquid flow frame, inject the trivalent vanadium ion electrolyte that 175mL is obtained by preparation example 1 respectively, in negative pole assembly liquid flow frame, inject the sulfuric acid solution that contains vanadic sulfate that 175mL is obtained by preparation example 1, obtain vanadium cell F1.
Above-mentioned vanadium cell F1 is used and discharges and recharges instrument (BS-9362 secondary cell testing apparatus, Qingtian Industry Co., Ltd., Guangzhou, lower with) carry out under the following conditions charge-discharge test: charging current for charging to the cut-ff voltage of 4A of take is 1.65V, then the discharging current of 4A of take is discharged to cut-ff voltage as 1.0V, and voltage efficiency is 93%.
Comparative example 1
This comparative example is used for illustrating reference vanadium cell and preparation method thereof.
Method according to embodiment 1 is prepared vanadium cell, different is, the sulfuric acid solution that contains vanadic sulfate that the trivalent vanadium ion electrolyte that described trivalent vanadium ion electrolyte adopts contrast preparation example 1 to obtain substitutes, the sulfuric acid solution of described sulfur acid vanadyl adopts contrast preparation example 1 to obtain, obtains vanadium cell DF1.
Above-mentioned vanadium cell DF1 is used and discharges and recharges instrument and carry out under the following conditions charge-discharge test: charging current for charging to the cut-ff voltage of 4A of take is 1.65V, the discharging current of 4A of then take is discharged to cut-ff voltage as 1.0V, and voltage efficiency is 75%.
Comparative example 2
This embodiment is used for illustrating vanadium cell provided by the invention and preparation method thereof.
Method according to embodiment 1 is prepared vanadium cell, different is, the sulfuric acid solution that contains vanadic sulfate that the trivalent vanadium ion electrolyte that described trivalent vanadium ion electrolyte adopts contrast preparation example 2 to obtain substitutes, the sulfuric acid solution of described sulfur acid vanadyl adopts contrast preparation example 2 to obtain, obtains vanadium cell DF2.
Above-mentioned vanadium cell DF2 is used and discharges and recharges instrument and carry out under the following conditions charge-discharge test: charging current for charging to the cut-ff voltage of 4A of take is 1.65V, the discharging current of 4A of then take is discharged to cut-ff voltage as 1.0V, and voltage efficiency is 73%.
Embodiment 2
This embodiment is used for illustrating vanadium cell provided by the invention and preparation method thereof.
Method according to embodiment 1 is prepared vanadium cell, different is, described trivalent vanadium ion electrolyte adopts the sulfuric acid solution that contains vanadic sulfate that the trivalent vanadium ion electrolyte that preparation example 2 obtains substitutes, the sulfuric acid solution of described sulfur acid vanadyl adopts preparation example 2 to obtain, and obtains vanadium cell F2.
Above-mentioned vanadium cell F2 is used and discharges and recharges instrument and carry out under the following conditions charge-discharge test: charging current for charging to the cut-ff voltage of 4A of take is 1.65V, the discharging current of 4A of then take is discharged to cut-ff voltage as 1.0V, and voltage efficiency is 91%.
Embodiment 3
This embodiment is used for illustrating vanadium cell provided by the invention and preparation method thereof.
Method according to embodiment 1 is prepared vanadium cell, different is, described trivalent vanadium ion electrolyte adopts the sulfuric acid solution that contains vanadic sulfate that the trivalent vanadium ion electrolyte that preparation example 3 obtains substitutes, the sulfuric acid solution of described sulfur acid vanadyl adopts preparation example 3 to obtain, and obtains vanadium cell F3.
Above-mentioned vanadium cell F3 is used and discharges and recharges instrument and carry out under the following conditions charge-discharge test: charging current for charging to the cut-ff voltage of 4A of take is 1.65V, the discharging current of 4A of then take is discharged to cut-ff voltage as 1.0V, and voltage efficiency is 90%.
Embodiment 4
This embodiment is used for illustrating vanadium cell provided by the invention and preparation method thereof.
Method according to embodiment 1 is prepared vanadium cell, different is, described trivalent vanadium ion electrolyte adopts the sulfuric acid solution that contains vanadic sulfate that the trivalent vanadium ion electrolyte that preparation example 4 obtains substitutes, the sulfuric acid solution of described sulfur acid vanadyl adopts preparation example 4 to obtain, and obtains vanadium cell F4.
Above-mentioned vanadium cell F4 is used and discharges and recharges instrument and carry out under the following conditions charge-discharge test: charging current for charging to the cut-ff voltage of 4A of take is 1.65V, the discharging current of 4A of then take is discharged to cut-ff voltage as 1.0V, and voltage efficiency is 89%.
Embodiment 5
This embodiment is used for illustrating vanadium cell provided by the invention and preparation method thereof.
Method according to embodiment 1 is prepared vanadium cell, different is, described trivalent vanadium ion electrolyte adopts the sulfuric acid solution that contains vanadic sulfate that the trivalent vanadium ion electrolyte that preparation example 5 obtains substitutes, the sulfuric acid solution of described sulfur acid vanadyl adopts preparation example 5 to obtain, and obtains vanadium cell F5.
Above-mentioned vanadium cell F5 is used and discharges and recharges instrument and carry out under the following conditions charge-discharge test: charging current for charging to the cut-ff voltage of 4A of take is 1.65V, the discharging current of 4A of then take is discharged to cut-ff voltage as 1.0V, and voltage efficiency is 89%.
Embodiment 6
This embodiment is used for illustrating vanadium cell provided by the invention and preparation method thereof.
Method according to embodiment 1 is prepared vanadium cell, different is, described trivalent vanadium ion electrolyte adopts the sulfuric acid solution that contains vanadic sulfate that the trivalent vanadium ion electrolyte that preparation example 6 obtains substitutes, the sulfuric acid solution of described sulfur acid vanadyl adopts preparation example 6 to obtain, and obtains vanadium cell F6.
Above-mentioned vanadium cell F6 is used and discharges and recharges instrument and carry out under the following conditions charge-discharge test: charging current for charging to the cut-ff voltage of 4A of take is 1.65V, the discharging current of 4A of then take is discharged to cut-ff voltage as 1.0V, and voltage efficiency is 85%.
Embodiment 7
This embodiment is used for illustrating vanadium cell provided by the invention and preparation method thereof.
Method according to embodiment 1 is prepared vanadium cell, different is, described trivalent vanadium ion electrolyte adopts the sulfuric acid solution that contains vanadic sulfate that the trivalent vanadium ion electrolyte that preparation example 7 obtains substitutes, the sulfuric acid solution of described sulfur acid vanadyl adopts preparation example 7 to obtain, and obtains vanadium cell F7.
Above-mentioned vanadium cell F7 is used and discharges and recharges instrument and carry out under the following conditions charge-discharge test: charging current for charging to the cut-ff voltage of 4A of take is 1.65V, the discharging current of 4A of then take is discharged to cut-ff voltage as 1.0V, and voltage efficiency is 84%.
As can be seen from the above results, adopt the purity of the trivalent vanadium ion electrolyte that method provided by the invention obtains higher, can access the vanadium cell that voltage efficiency is higher.From preparation example 1, can find out with the contrast of embodiment 6-7 with preparation example 6-7, embodiment 1, adopt the preferred electrolysis tank of the present invention and polar plate spacing, can access the trivalent vanadium ion electrolyte that purity is higher, the voltage efficiency of the vanadium cell obtaining is higher.
Claims (10)
1. the preparation method of a trivalent vanadium ion electrolyte, it is characterized in that, the method comprises using the sulfuric acid solution that contains vanadic sulfate as negative electrode, using sulfuric acid solution as anode, and the sulfuric acid of anode equates with the mole of vanadic sulfate in the sulfuric acid solution that contains vanadic sulfate, and carry out constant-potential electrolysis, obtain the trivalent vanadium ion electrolyte that the mol ratio of trivalent vanadium and full vanadium is greater than 0.98.
2. preparation method according to claim 1, wherein, the molar concentration M of full vanadium in described trivalent vanadium ion electrolyte
tVfor 1-3mol/L, be preferably 1-2mol/L.
3. preparation method according to claim 1 and 2, wherein, described in contain vanadic sulfate sulfuric acid solution in the mol ratio of vanadic sulfate and sulfuric acid be 1:1.5-3.
4. preparation method according to claim 1, wherein, the condition of constant-potential electrolysis comprises: decomposition voltage is 1.5V-50V, and electrolysis temperature is 20-60 ℃, and electrolysis time is 0.5-5 hour.
5. preparation method according to claim 4, wherein, described decomposition voltage is 1.5V-10V, and electrolysis temperature is 20-40 ℃, and electrolysis time is 0.5-3 hour.
6. preparation method according to claim 1, wherein, described constant-potential electrolysis carries out in electrolysis tank; Described electrolysis tank comprise groove deckle board, the anode pool being surrounded by groove deckle board and cathode pool, the conductive diaphragm between anode pool and cathode pool and lay respectively at anode pool and cathode pool in battery lead plate, the material of described groove deckle board is the polyethylene that weight average molecular weight is greater than 3,000,000, and preferable weight-average molecular weight is 3,500,000-5,000,000 polyethylene.
7. preparation method according to claim 6, wherein, described battery lead plate is selected from one or more in platinum plate, modified graphite plate, titanium base platinum, yttrium oxide, graphite felt, carbon stick and compound conductive plastic plate, is preferably platinum plate; Distance between described battery lead plate is not less than 3cm, is preferably 3-20cm.
8. preparation method according to claim 6, wherein, described conductive diaphragm is fluorine-containing polyolefin amberplex, is preferably perfluorinated sulfonic acid ion exchange membrane.
9. the trivalent vanadium ion electrolyte that the method described in any one prepares in claim 1-8.
10. a vanadium cell, this vanadium cell comprises the battery unit of a plurality of series connection, each battery unit comprises anodal assembly, negative pole assembly and the barrier film between this positive pole assembly and negative pole assembly, described anodal assembly comprises the liquid flow frame that accommodates anode electrolyte and is arranged on collector and the anode plate on this liquid flow frame, described negative pole assembly comprises the liquid flow frame that accommodates negative pole electrolyte and is arranged on collector and the negative plates on this liquid flow frame, it is characterized in that, described anode electrolyte is the sulfuric acid solution that contains vanadic sulfate, described negative pole electrolyte is trivalent vanadium ion electrolyte claimed in claim 9.
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| CN111106374A (en) * | 2019-11-28 | 2020-05-05 | 浙江浙能技术研究院有限公司 | Preparation device and method of high-purity equimolar-concentration trivalent/quadrivalent vanadium electrolyte |
| CN112225250A (en) * | 2020-10-16 | 2021-01-15 | 成都先进金属材料产业技术研究院有限公司 | Method for self-reducing hydrothermal synthesis of vanadium dioxide nano powder |
| CN112941540A (en) * | 2021-01-28 | 2021-06-11 | 湖南钒谷新能源技术有限公司 | Vanadium electrolyte production system and production method |
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| JP5680145B2 (en) | 2015-03-04 |
| JP2014003021A (en) | 2014-01-09 |
| CN103515641B (en) | 2016-04-13 |
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