CN103515641B - A kind of trivalent vanadium ion electrolyte and preparation method thereof and a kind of vanadium cell - Google Patents
A kind of trivalent vanadium ion electrolyte and preparation method thereof and a kind of vanadium cell Download PDFInfo
- Publication number
- CN103515641B CN103515641B CN201210200437.0A CN201210200437A CN103515641B CN 103515641 B CN103515641 B CN 103515641B CN 201210200437 A CN201210200437 A CN 201210200437A CN 103515641 B CN103515641 B CN 103515641B
- Authority
- CN
- China
- Prior art keywords
- sulfuric acid
- preparation
- vanadium
- 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.)
- Expired - Fee Related
Links
Classifications
-
- H—ELECTRICITY
- H01—ELECTRIC ELEMENTS
- H01M—PROCESSES OR MEANS, e.g. BATTERIES, FOR THE DIRECT CONVERSION OF CHEMICAL ENERGY INTO ELECTRICAL ENERGY
- H01M8/00—Fuel cells; Manufacture thereof
- H01M8/18—Regenerative fuel cells, e.g. redox flow batteries or secondary fuel cells
- H01M8/184—Regeneration by electrochemical means
- H01M8/188—Regeneration by electrochemical means by recharging of redox couples containing fluids; Redox flow type batteries
-
- 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 kind of preparation method of trivalent vanadium ion electrolyte, the trivalent vanadium ion electrolyte prepared by the method and a kind of vanadium cell.The preparation method of described trivalent vanadium ion electrolyte comprises the sulfuric acid solution containing vanadic sulfate as negative electrode, using sulfuric acid solution as anode, and the sulfuric acid of anode is equal with the mole containing the vanadic sulfate in the sulfuric acid solution of vanadic sulfate, and carry out constant-potential electrolysis, the mol ratio obtaining trivalent vanadium and full vanadium is greater than the trivalent vanadium ion electrolyte of 0.98.Adopt method provided by the invention stably can prepare the higher trivalent vanadium ion electrolyte of purity.
Description
Technical field
The present invention relates to a kind of preparation method of trivalent vanadium ion electrolyte, the trivalent vanadium ion electrolyte prepared by the method and a kind of vanadium cell.
Background technology
Vanadium oxide reduction flow battery, by mutually transforming the storage and the release that realize electric energy between the vanadium ion of different valence state, is unique battery system using same element composition in numerous chemical power source.The input of the electric energy of instability can be become continuous, safe and reliable output by it, can solve scale and utilize 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 field such as emergency power supply of communication system.Although enter practical stage to the research of vanadium cell, 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 of restriction development, wherein, the preparation of V electrolyte is the core of all-vanadium liquid flow energy storage system.
Theoretically, the electrolyte just very tetravalent vanadium ion solution of vanadium oxide reduction flow battery, 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.But positive pole and the many employings of electrolyte liquid the trivalent of material amount and the mixed solution of tetravalent vanadium ion such as to have, this is because the trivalent vanadium ion electrolyte of high-purity, high stability is difficult to obtain in current technology.
At present, all-vanadium ionic liquid flow battery mainly adopts vanadic sulfate as the active material of battery, its preparation method is the positive pole and the negative pole that the vanadic sulfate sulfuric acid solution of equivalent are poured into respectively vanadium cell, charge under the charge condition of vanadium cell, after being full of electricity, positive solution is all discharged, adopt in this way, in obtained trivalent vanadium ion electrolyte, the mol ratio of trivalent vanadium ion and full vanadium is about 0.80, the vanadic sulfate sulfuric acid solution changing equivalent continues charging, can use by chargeable battery after being full of electricity as other.The method needs replacing positive solution, carries out recharging, causes battery to be assembled and chemical industry program complexity, 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, thus affect production efficiency.
In addition, first sulfuric acid can also be mixed with the dilute sulfuric acid of 1:2, then first add vanadium trioxide, then add vanadic oxide, be obtained by reacting vanadic sulfate solution; Add Na again
2sO
4, the additive such as polyoxyethylene nonylphenol ether; And this vanadic sulfate solution is placed in cathode of electrolytic tank, being placed in same ion intensity electrolytic cell anode containing the sulfuric acid solution of sodium sulphate and carrying out electrolysis, obtain the vanadium cell V electrolyte that tetravalence vanadium and trivalent vanadium respectively account for 50% of total content of vanadium.Although the method was once considered to more rational method, but along with the development of vanadium cell, the people of the research of the especially long-term structure to vanadium cell, material and performance start to find, the quality of electrolyte directly can have influence on the performance of vanadium cell, even also can have influence on the stability of electrolyte itself, so extremely important to the further investigation (such as to the composition of electrolyte and the research of purity) of electrolyte.
In the prior art, stablize to make V electrolyte, improve the vanadium cell life-span, usually in vanadium cell, various additive is added, as CN1719655A discloses a kind of full vanadium ion fluid cell electrolyte, it is made up 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 dissolving in sulfuric acid system, improves the stability of electrolyte in charge and discharge process with this.Wherein, additive is selected from one or more in sodium sulphate, ethanol, glycerine, NPE, sodium pyrophosphate, prodan, urea and hydrogen peroxide.But additive adds objectionable impurities to electrolyte of vanadium redox battery system, along with improving constantly of requiring electrolyte, 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 needs to add additive and keep the defect of its stability, and provides a kind of and have trivalent vanadium ion electrolyte of higher degree and stability and preparation method thereof and a kind of vanadium cell.
The invention provides a kind of preparation method of trivalent vanadium ion electrolyte, wherein, the method comprises the sulfuric acid solution containing vanadic sulfate as negative electrode, using sulfuric acid solution as anode, and the sulfuric acid of anode is equal with the mole containing the vanadic sulfate in the sulfuric acid solution of vanadic sulfate, and carry out constant-potential electrolysis, the mol ratio obtaining trivalent vanadium and full vanadium is greater than the trivalent vanadium ion electrolyte of 0.98.
Present invention also offers the trivalent vanadium ion electrolyte obtained by said method.
In addition, the present invention also provides a kind of vanadium cell, this vanadium cell comprises the battery unit of multiple series connection, each battery unit comprises positive electrode, negative pole assembly and the barrier film between this positive electrode and negative pole assembly, described positive electrode comprises the liquid flow frame and the collector be arranged on this liquid flow frame and anode plate that accommodate anode electrolyte, described negative pole assembly comprises the liquid flow frame and the collector be arranged on this liquid flow frame and negative plates that accommodate electrolyte liquid, wherein, described anode electrolyte is the sulfuric acid solution containing vanadic sulfate, described electrolyte liquid 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, thus realize the requirement of the highly purified trivalent vanadium battery electrolyte of preparation.Constant pressure source is exactly stabilized voltage power supply, when energy proof load (output current) changes, keeps voltage constant; Constant-current source is then when load variations, and the output voltage of energy corresponding adjustment oneself, makes output current remain unchanged; 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 ensures that the pressure drop on this sample resistance is constant, realizes constant current output, therefore, inventor infers, may because the current efficiency of constant-current electrolysis process be lower, the data error of simultaneously monitoring is comparatively large, thus adopts constant-current electrolysis cannot obtain the higher trivalent vanadium battery electrolyte of purity.A preferred embodiment of the invention, can shorten the time when carrying out electrolysis under the condition at decomposition voltage being 1.5V-50V, raise the efficiency, control electroaffinity, make current efficiency maintain the maximum of 100% this electric current, thus improves voltage efficiency.In addition, the speed that constant-potential electrolysis carries out and initial concentration have nothing to do, and also namely when identical external condition, are 0.1M and 10 by concentration
-6material electrolysis to the same degree of M with the same time, thus need can control electrolytic process more accurately.
What is more important, the present inventor stumbles on, using the sulfuric acid solution containing vanadic sulfate as negative electrode, sulfuric acid solution is carried out constant-potential electrolysis as anode under the sulfuric acid of the anode condition equal with the mole containing the vanadic sulfate in the sulfuric acid solution of vanadic sulfate, the trivalent vanadium ion electrolyte that purity is higher, performance is comparatively stable can be prepared.In the process of preparation 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 improve electrolytic efficiency; On the other hand, avoid the waste of vanadium, reduce the cost 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, the phenomenon analysing oxygen liberation of hydrogen is there is in constant-potential electrolysis process, even also have oxysulfide to produce, adopt groove deckle board steadily the carrying out not only bad for electrolysis of polymethyl methacrylate or polyvinyl chloride material, and new impurity can be introduced, the purity of the trivalent vanadium ion electrolyte obtained significantly is 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, the polyethylene groove deckle board that weight average molecular weight is greater than 3,000,000 not only can not introduce the impurity impacted electrolytic process, and electrolytic process stable for extended periods of time can be made, 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 the distance between battery lead plate is when being not less than 3cm, lower tank voltage can be kept in electrolytic process, be particularly conducive to the trivalent vanadium ion electrolyte preparing high-purity, high stability.
Further, when described trivalent vanadium ion electrolyte is used for vanadium cell, because the trivalent vanadium ion electrolyte adopting method of the present invention to obtain has higher purity, therefore, it is possible to significantly reduce the impact of impurity on trivalent vanadium ion electrolyte and vanadium battery material and barrier film.What is more important, the trivalent vanadium ion electrolyte that purity is higher can make trivalent vanadium ion realize supersaturation, not crystallization, 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 are described in detail in embodiment part subsequently.
Accompanying drawing explanation
Fig. 1 is the working state schematic representation of the electrolysis tank used in preparation 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 described in detail.Should be understood that, embodiment described herein, only for instruction and explanation of 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 the sulfuric acid solution containing vanadic sulfate as negative electrode, using sulfuric acid solution as anode, and the sulfuric acid of anode is equal with the mole containing the vanadic sulfate in the sulfuric acid solution of vanadic sulfate, and carry out constant-potential electrolysis, the mol ratio obtaining trivalent vanadium and full vanadium is greater than the trivalent vanadium ion electrolyte of 0.98.Wherein, described full vanadium refers to the summation of the vanadium ion of various valence state in trivalent vanadium ion electrolyte.
According to the present invention, in described trivalent vanadium ion electrolyte, the molar concentration MTV of full vanadium can carry out selecting and changing in wider scope, preferably, the molar concentration MTV of described full vanadium is between 1mol/L to 3mol/L, be more preferably 1-2mol/L, be not only more conducive to the carrying out of electrolysis like this, the excessive concentration of trivalent vanadium ion electrolyte can also be avoided, so that reach capacity state, produces the problem of easy crystallization.
The content of the present invention to the vanadic sulfate in the sulfuric acid solution of described vanadic sulfate and sulfuric acid is not particularly limited, but can carry out more reposefully to make electrolysis, and obtain the higher trivalent vanadium ion electrolyte of purity, under preferable case, the mol ratio of described vanadic sulfate and sulfuric acid is 1:1.5-3, is 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, such as, can be directly obtain purity in the vanadic sulfate crystal vitriolization solution of more than 98 % by weight, also can by vanadic oxide, vanadium trioxide and sulfuric acid solution be obtained by reacting, or also can by vanadic oxide, reducing agent and sulfuric acid solution are obtained by reacting.Wherein, described sulfuric acid solution all refers to sulphur aqueous acid.
Wherein, when adopting the sulfuric acid solution of the described vanadic sulfate of vanadic oxide, vanadium trioxide and 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 dissolved in sulfuric acid solution and obtain after reacting, wherein, the molal quantity of vanadic oxide and vanadium trioxide is preferably equal.The selectable range of the temperature of described reaction is wider, as long as can obtain the sulfuric acid solution of vanadic sulfate, but in order to be beneficial to the carrying out of reaction further, the temperature of described reaction is preferably 70-90 DEG C.The consumption of described sulfuric acid solution also can carry out selecting and changing in wider scope, and such as, the mol ratio of the sulfuric acid in described sulfuric acid solution and full vanadium material consumption can be 2.5-4:1.In addition, the sulfuric acid solution of described vanadic sulfate also can by the mixture roasting by vanadic oxide and vanadium trioxide, and the product of roasting obtained is dissolved in sulfuric acid solution obtains, wherein, sintering temperature can be 300-500 DEG C, and roasting time can be 1.5-2 hour, and the consumption of described sulfuric acid solution also can carry out selecting and changing in wider scope, such as, the mol ratio of the consumption of the sulfuric acid in described sulfuric acid solution and full vanadium material can be 2.5-4:1.
When adopting the sulfuric acid solution of the described vanadic sulfate of vanadic oxide, reducing agent (oxalic acid) and 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, adds oxalic acid and (other reducing agents also can be adopted to substitute, as SO under 40-80 DEG C 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 carry out selecting and changing in wider scope, and such as, 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 such as 98-100 % by weight, is preferably 99.5-100 % by weight.
The condition of the present invention to described constant-potential electrolysis is not particularly limited, as long as the mol ratio that can obtain trivalent vanadium and full vanadium is greater than the trivalent vanadium ion electrolyte of 0.98, preferably, it is 1.5V-50V that the condition of described constant-potential electrolysis comprises decomposition voltage, electrolysis temperature is 20-60 DEG C, and electrolysis time is 0.5-5 hour; More preferably, described decomposition voltage is 1.5V-10V, and electrolysis temperature is 20-40 DEG C, and electrolysis time is 0.5-3 hour.
According to the present invention, the oxygen in air can affect electrolytic process, and therefore, can carry out more reposefully to make electrolysis and improve the purity of the trivalent vanadium ion electrolyte obtained, under preferable case, described electrolysis is carried out in an 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 by the method that well known to a person skilled in the art and obtain, such as, can be judged roughly by test solution charge value and potential value and control electrolysis terminal, 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 unit, preferably carries out in a cell.The structure of described electrolysis tank can be identical with existing cell construction, such as, the battery lead plate that described electrolysis tank comprises groove deckle board, the anode pool surrounded by groove deckle board and cathode pool, conductive diaphragm between anode pool and cathode pool and lays respectively in anode pool and cathode pool, 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 the polyethylene of 3,500,000-500 ten thousand.
According to the present invention, described battery lead plate can be the existing various battery lead plate that can be used in preparation trivalent vanadium ion electrolyte, such as, 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 is mixed and the hot-forming sheet material obtained with conductive materials (as carbon black, graphite powder, graphite fibre etc.) by polymer (as PVC, nylon-6, nylon-11, low density polyethylene (LDPE), high density polyethylene (HDPE), low density polypropylene, high density poly propylene etc.).As mentioned above, when adopting platinum plate as battery lead plate, can improve the purity of trivalent vanadium ion electrolyte more significantly, therefore, described electrolytic zinc-coated steel sheet is preferably platinum plate.Distance between battery lead plate in anode pool and cathode pool can adjust according to actual conditions, as a rule, distance between battery lead plate is not less than 3cm, be preferably 3cm-20cm, lower tank voltage can be kept like this, be conducive to the trivalent vanadium ion electrolyte preparing high-purity, high stability.
According to the present invention, the conductive diaphragm of described electrolysis tank can be existing various conductive diaphragm, preferred employing be suitable for that in the sulfuric acid solution of vanadic sulfate electrolysis uses 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, be more preferably the perfluorinated sulfonic acid ion exchange membrane after activation processing, the current efficiency that maintenance that like this can be steady in a long-term is higher, is conducive to the trivalent vanadium ion electrolyte preparing high-purity, high stability.Method and the condition of described activation are known to the skilled person, and will repeat no more at this.
Present invention also offers according to the obtained trivalent vanadium ion electrolyte of said method.
Present invention also offers a kind of vanadium cell, this vanadium cell comprises the battery unit of multiple series connection, each battery unit comprises positive electrode, negative pole assembly and the barrier film between this positive electrode and negative pole assembly, described positive electrode comprises the liquid flow frame and the collector be arranged on this liquid flow frame and anode plate that accommodate anode electrolyte, described negative pole assembly comprises the liquid flow frame and the collector be arranged on this liquid flow frame and negative plates that accommodate electrolyte liquid, wherein, described anode electrolyte is the sulfuric acid solution containing vanadic sulfate, described electrolyte liquid is above-mentioned trivalent vanadium ion electrolyte.
Improvements of the present invention are to have employed the anode electrolyte of described trivalent vanadium ion electrolyte as vanadium cell, all can be same as the prior art for the annexation between the structure of vanadium cell and each structure, will repeat no more at this.
According to a specific embodiment of the present invention, trivalent vanadium ion electrolyte uses 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.Sulfuric acid solution containing vanadic sulfate is injected cathode pool 7, sulfuric acid solution with the vanadic sulfate equimolar amounts in vanadic sulfate sulfuric acid solution is injected anode pool 4, wherein in vanadic sulfate sulfuric acid solution, the concentration of vanadic sulfate is 1:1.5-3 with the mol ratio of sulfuric acid wherein, is preferably 1:1.5-2.Introduce electrolysis tank by nitrogen from gas access 10, under the stirring action of blender 3, the constant voltage source 1 being 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 be connected to the charge value of potentiometer 2 test solution of calomel electrode 6 and platinum electrode 9 by two ends and potential value judges roughly and controls electrolysis terminal, obtain trivalent vanadium ion electrolyte.Adopt the content of material in trivalent vanadium ion electrolyte described in ion chromatography, polarographic analysis, ICP mass spectrum and ICP spectrum analysis, and then obtain the concentration of trivalent vanadium ion.This trivalent vanadium electrolyte and vanadic sulfate sulfuric acid solution are injected vanadium battery negative electrode and positive pole respectively, can normally use after charging.
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 characteristic described in above-mentioned embodiment, in reconcilable situation, can be combined by any suitable mode.In order to avoid unnecessary repetition, the present invention illustrates no longer separately to various possible compound mode.
In addition, also can carry out combination in any between various different execution mode of the present invention, 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 the invention will be further described by embodiment.
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, theoretical capacity refers to the complete electrolysis of tetravalent vanadium ion in the sulfuric acid solution of described vanadic sulfate to be the electricity that the electronics of trivalent vanadium ion transfer calculates; Theoretical potential refers to by reverting in the process of divalent vanadium ion by pentavalent vanadium ion, and current potential presents classification hop change from 400mV to 150mV, wherein, the potential jump from tetravalent vanadium ion to trivalent vanadium ion is 200mV, and described theoretical potential is 200mV.Voltage efficiency is measured by discharge and recharge instrument (purchased from blue light Science and Technology Ltd. of Foshan City) and obtains.
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 pure, proportion is 1.84g/mL.
Preparation example 1
This preparation example is for illustration of trivalent vanadium ion electrolyte provided by the invention and preparation method thereof.
The making of electrolysis tank: adopt weight average molecular weight be 3,500,000 polyethylene manufacturing specification be 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 also fixing, then two of external connection constant voltage power positive cathode blocks of platinum plates are placed in anode pool and cathode pool respectively, wherein, the effective area of platinum plate is 100 × 100mm
2.
The preparation of the sulfuric acid solution containing vanadic sulfate: first add 550mL deionized water in reactor, then adds the 259mL concentrated sulfuric acid, when temperature rises at 80 DEG C, by 62 grams of V in the condition downhill reaction device stirred
2o
3with 74.5 grams of V
2o
5mixture progressively add in reactor and react, be settled to the sulfuric acid solution that 900mL obtains containing vanadic sulfate, as electrolyte raw material for standby with deionized water after reaction 0.5h.Test sulfuric acid concentration is 3.6mol/L, and the concentration of full vanadium is 1.79mol/L.
The preparation of sulfuric acid solution: add 200mL deionized water in reactor, progressively adds the 85.9mL concentrated sulfuric acid under the condition stirred, finally for subsequent use to 900mL with deionized water constant volume.
The preparation of trivalent vanadium ion electrolyte: the above-mentioned sulfuric acid solution containing vanadic sulfate getting 900mL injects the cathode pool 7 of electrolysis tank, and the above-mentioned sulfuric acid solution getting 900mL injects the anode pool 4 of electrolysis tank; Adopt constant voltage mode electrolysis, wherein, setting battery lead plate spacing is 3cm, and decomposition voltage is 3V, and electrolysis temperature is 20 DEG C.Carry out on-line monitoring by the electricity of potentiometer 2 pairs of electrolyte and current potential simultaneously, when detect electricity reach 1.1 times of theoretical capacity or detect current potential reach theoretical potential time, stop electrolysis, now electrolysis time is 1.5 hours.The electrolyte obtained is carried out ion chromatography, polarographic analysis, ICP mass spectrum and ICP spectrum analysis, the concentration that can obtain trivalent vanadium ion in described electrolyte is 1.78mol/L, and namely in electrolyte, mol ratio V (the III)/TV of trivalent vanadium and full vanadium is 99.6%.
Contrast preparation example 1
This contrast preparation example is for illustration of the trivalent vanadium ion electrolyte and preparation method thereof of reference.
Be prepared according to the sulfuric acid solution of method to described vanadic sulfate of preparation example 1, unlike, sulfuric acid solution in the anode pool of described electrolysis tank adopts the sulfuric acid solution containing vanadic sulfate to substitute, that is, the anode pool of electrolysis tank is identical with the electrolyte in cathode pool.The electrolyte obtained is carried out ion chromatography, polarographic analysis, ICP mass spectrum and ICP spectrum analysis, the concentration that can obtain trivalent vanadium ion in described electrolyte is 1.53mol/L, and namely in electrolyte, mol ratio V (the III)/TV of trivalent vanadium and full vanadium is 85.9%.
Contrast preparation example 2
This contrast preparation example is for illustration of the trivalent vanadium ion electrolyte and preparation method thereof of reference.
Be prepared according to the sulfuric acid solution of method to described vanadic sulfate of contrast preparation example 1, unlike, adopt current constant mode to carry out electrolysis, and control electric current is 3A.The electrolyte obtained is carried out ion chromatography, polarographic analysis, ICP mass spectrum and ICP spectrum analysis, the ratio that can obtain trivalent vanadium ion and tetravalent vanadium ion concentration in described electrolyte is about 1:1, and namely in electrolyte, mol ratio V (the III)/TV of trivalent vanadium and full vanadium is 50%.
Preparation example 2
This preparation example is for illustration of trivalent vanadium ion electrolyte provided by the invention and preparation method thereof.
The making of electrolysis tank: adopt weight average molecular weight be 4,000,000 polyethylene manufacturing specification be 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 also fixing, then two of external connection constant voltage power positive cathode blocks of platinum plates are placed in anode pool and cathode pool respectively, wherein, the effective area of platinum plate is 100 × 100mm
2.
The preparation of the sulfuric acid solution containing vanadic sulfate: first add 600mL deionized water in reactor, then adds the 288mL concentrated sulfuric acid, when temperature rises at 80 DEG C, by 75 grams of V in the condition downhill reaction device stirred
2o
3with 83.2 grams of V
2o
5mixture progressively add in reactor and react, be settled to the sulfuric acid solution that 900mL obtains containing vanadic sulfate, as electrolyte raw material for standby with deionized water after reaction 0.5h.Test sulfuric acid concentration is 4.0mol/L, and the concentration of full vanadium is 2.0mol/L.
The preparation of sulfuric acid solution: add 400mL deionized water in reactor, progressively adds the 95.9mL concentrated sulfuric acid under the condition stirred, finally for subsequent use to 900mL with deionized water constant volume.
The preparation of trivalent vanadium ion electrolyte: the above-mentioned sulfuric acid solution containing vanadic sulfate getting 900mL injects the cathode pool 7 of electrolysis tank, and the above-mentioned sulfuric acid solution getting 900mL injects the anode pool 4 of electrolysis tank; Adopt constant voltage mode electrolysis, wherein, setting battery lead plate spacing is 3cm, and decomposition voltage is 3.5V, and electrolysis temperature is 30 DEG C.Carry out on-line monitoring by the electricity of potentiometer 2 pairs of electrolyte and current potential simultaneously, when detect electricity reach 1.1 times of theoretical capacity or detect current potential reach theoretical potential time, stop electrolysis, now electrolysis time is 2.5 hours.The electrolyte obtained is carried out ion chromatography, polarographic analysis, ICP mass spectrum and ICP spectrum analysis, the concentration that can obtain trivalent vanadium ion in described electrolyte is 2.0mol/L, and namely in electrolyte, mol ratio V (the III)/TV of trivalent vanadium and full vanadium is 100%.
Preparation example 3
This preparation example is for illustration of trivalent vanadium ion electrolyte provided by the invention and preparation method thereof.
The making of electrolysis tank: adopt weight average molecular weight be 4,000,000 polyethylene manufacturing specification be 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 also fixing, then two of external connection constant voltage power positive cathode blocks of platinum plates are placed in anode pool and cathode pool respectively, wherein, the effective area of platinum plate is 100 × 100mm
2.
The preparation of the sulfuric acid solution containing vanadic sulfate: first add 600mL deionized water in reactor, then adds the 269mL concentrated sulfuric acid, when temperature rises at 80 DEG C, by 61.7 grams of V in the condition downhill reaction device stirred
2o
3with 74 grams of V
2o
5mixture progressively add in reactor and react, be settled to the sulfuric acid solution that 900mL obtains containing vanadic sulfate, as electrolyte raw material for standby with deionized water after reaction 0.5h.Test sulfuric acid concentration is 3.83mol/L, and the concentration of full vanadium is 1.78mol/L.
The preparation of sulfuric acid solution: add 200mL deionized water in reactor, progressively adds the 85.4mL concentrated sulfuric acid under the condition stirred, finally for subsequent use to 900mL with deionized water constant volume.
The preparation of trivalent vanadium ion electrolyte: the above-mentioned sulfuric acid solution containing vanadic sulfate getting 900mL injects the cathode pool 7 of electrolysis tank, and the above-mentioned sulfuric acid solution getting 900mL injects the anode pool 4 of electrolysis tank; Adopt constant voltage mode electrolysis, wherein, setting battery lead plate spacing is 10cm, and decomposition voltage is 5V, and electrolysis temperature is 40 DEG C.Carry out on-line monitoring by the electricity of potentiometer 2 pairs of electrolyte and current potential simultaneously, when detect electricity reach 1.1 times of theoretical capacity or detect current potential reach theoretical potential time, stop electrolysis, now electrolysis time is 1.5 hours.The electrolyte obtained is carried out ion chromatography, polarographic analysis, ICP mass spectrum and ICP spectrum analysis, the concentration that can obtain trivalent vanadium ion in described electrolyte is 1.76mol/L, and namely in electrolyte, mol ratio V (the III)/TV of trivalent vanadium and full vanadium is 98.9%.
Preparation example 4
This preparation example is for illustration of trivalent vanadium ion electrolyte provided by the invention and preparation method thereof.
The making of electrolysis tank: adopt weight average molecular weight be 4,000,000 polyethylene manufacturing specification be 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 also fixing, then by two of external connection constant voltage power positive cathode pieces of carbon stick battery lead plate (fixed carbon content 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 anode pool and cathode pool respectively, wherein, the effective area of carbon stick battery lead plate is 100 × 100mm
2.
The preparation of the sulfuric acid solution containing vanadic sulfate: first add 600mL deionized water in reactor, then adds the 298.6mL concentrated sulfuric acid, when temperature rises at 80 DEG C, by 84 grams of V in the condition downhill reaction device stirred
2o
3with 100 grams of V
2o
5mixture progressively add in reactor and react, be settled to the sulfuric acid solution that 900mL obtains containing vanadic sulfate, as electrolyte raw material for standby with deionized water after reaction 0.5h.Test sulfuric acid concentration is 3.7mol/L, and the concentration of full vanadium is 2.41mol/L.
The preparation of sulfuric acid solution: add 400mL deionized water in reactor, progressively adds the 115.6mL concentrated sulfuric acid under the condition stirred, finally for subsequent use to 900mL with deionized water constant volume.
The preparation of trivalent vanadium ion electrolyte: the above-mentioned sulfuric acid solution containing vanadic sulfate getting 900mL injects the cathode pool 7 of electrolysis tank, and the above-mentioned sulfuric acid solution getting 900mL injects the anode pool 4 of electrolysis tank; Adopt constant voltage mode electrolysis, wherein, setting battery lead plate spacing is 3cm, and decomposition voltage is 1.5V, and electrolysis temperature is 60 DEG C.Carry out on-line monitoring by the electricity of potentiometer 2 pairs of electrolyte and current potential simultaneously, when detect electricity reach 1.1 times of theoretical capacity or detect current potential reach theoretical potential time, stop electrolysis, now electrolysis time is 1.1 hours.The electrolyte obtained is carried out ion chromatography, polarographic analysis, ICP mass spectrum and ICP spectrum analysis, online Potential Titration Analysis is carried out to obtaining electrolyte, the concentration that can obtain trivalent vanadium ion in described electrolyte is 2.4mol/L, and namely in electrolyte, mol ratio V (the III)/TV of trivalent vanadium and full vanadium is 99.6%.
Preparation example 5
This preparation example is for illustration of trivalent vanadium ion electrolyte provided by the invention and preparation method thereof.
The making of electrolysis tank: adopt weight average molecular weight be 4,000,000 polyethylene manufacturing specification be 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 also fixing, then by two of external connection constant voltage power positive cathode blocks of compound conductive plastic plates (by number-average molecular weight be 100,000 polyethylene and carbon black by weight the sheet material formed through hot pressing for the mixture of 1:1) be placed in anode pool and cathode pool respectively, wherein, the effective area of compound conductive plastic plate is 100 × 100mm
2.
The preparation of the sulfuric acid solution containing vanadic sulfate: first add 600mL deionized water in reactor, then adds the 235mL concentrated sulfuric acid, when temperature rises at 80 DEG C, by 41.2 grams of V in the condition downhill reaction device stirred
2o
3with 49.4 grams of V
2o
5mixture progressively add in reactor and react, be settled to the sulfuric acid solution that 900mL obtains containing vanadic sulfate, as electrolyte raw material for standby with deionized water after reaction 0.5h.Test sulfuric acid concentration is 3.57mol/L, and the concentration of full vanadium is 1.2mol/L.
The preparation of sulfuric acid solution: add 200mL deionized water in reactor, progressively adds the 57.6mL concentrated sulfuric acid under the condition stirred, finally for subsequent use to 900mL with deionized water constant volume.
The preparation of trivalent vanadium ion electrolyte: the above-mentioned sulfuric acid solution containing vanadic sulfate getting 900mL injects the cathode pool 7 of electrolysis tank, and the above-mentioned sulfuric acid solution getting 900mL injects the anode pool 4 of electrolysis tank; Adopt constant voltage mode electrolysis, wherein, setting battery lead plate spacing is 20cm, and decomposition voltage is 10V, and electrolysis temperature is 40 DEG C.Carry out on-line monitoring by the electricity of potentiometer 2 pairs of electrolyte and current potential simultaneously, when detect electricity reach 1.1 times of theoretical capacity or detect current potential reach theoretical potential time, stop electrolysis, now electrolysis time is 0.5 hour.The electrolyte obtained is carried out ion chromatography, polarographic analysis, ICP mass spectrum and ICP spectrum analysis, the concentration that can obtain trivalent vanadium ion in described electrolyte is 1.19mol/L, and namely in electrolyte, mol ratio V (the III)/TV of trivalent vanadium and full vanadium is 99.2%.
Preparation example 6
This preparation example is for illustration of trivalent vanadium ion electrolyte provided by the invention and preparation method thereof.
Be prepared according to the sulfuric acid solution of method to described vanadic sulfate of preparation example 1, unlike, in the manufacturing process of electrolysis tank, weight average molecular weight be 3,500,000 polyethylene adopt weight average molecular weight be 3,500,000 polyvinyl chloride substitute.The electrolyte obtained is carried out ion chromatography, polarographic analysis, ICP mass spectrum and ICP spectrum analysis, the concentration that can obtain trivalent vanadium ion in described electrolyte is 1.73mol/L, and namely in electrolyte, mol ratio V (the III)/TV of trivalent vanadium and full vanadium is 98.2%.
Preparation example 7
This preparation example is for illustration of trivalent vanadium ion electrolyte provided by the invention and preparation method thereof.
Be prepared according to the sulfuric acid solution of method to described vanadic sulfate of preparation example 1, unlike, in electrolytic process, battery lead plate spacing is 2cm.The electrolyte obtained is carried out ion chromatography, polarographic analysis, ICP mass spectrum and ICP spectrum analysis, the concentration that can obtain trivalent vanadium ion in described electrolyte is 1.71mol/L, and namely in electrolyte, mol ratio V (the III)/TV of trivalent vanadium and full vanadium is 98.1%.
Embodiment 1
This embodiment is for illustration of 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, employing weight average molecular weight is polyvinyl chloride (purchased from Zibo Chuan Yu plastics Co., Ltd) the plate making liquid flow frame of 3,500,000, and make vanadium liquid stream monocell, wherein, the size of liquid flow frame is 100 × 100 × 5mm, and in positive electrode liquid flow frame, inject the trivalent vanadium ion electrolyte that 175mL obtains by preparation example 1 respectively, the sulfuric acid solution containing vanadic sulfate that 175mL is obtained by preparation example 1 is injected in negative pole assembly liquid flow frame, obtain vanadium cell F1.
Above-mentioned vanadium cell F1 is used discharge and recharge instrument (BS-9362 secondary cell testing apparatus, Qingtian Industry Co., Ltd., Guangzhou, lower with) carry out charge-discharge test under the following conditions: with the charging current for charging of 4A to cut-ff voltage for 1.65V, then be discharged to cut-ff voltage for 1.0V with the discharging current of 4A, voltage efficiency is 93%.
Comparative example 1
This comparative example is for illustration of reference vanadium cell and preparation method thereof.
According to the method for embodiment 1, vanadium cell is prepared, unlike, the sulfuric acid solution containing 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.
Use discharge and recharge instrument to carry out charge-discharge test under the following conditions above-mentioned vanadium cell DF1: with the charging current for charging of 4A to cut-ff voltage for 1.65V, be then discharged to cut-ff voltage for 1.0V with the discharging current of 4A, voltage efficiency is 75%.
Comparative example 2
This embodiment is for illustration of vanadium cell provided by the invention and preparation method thereof.
According to the method for embodiment 1, vanadium cell is prepared, unlike, the sulfuric acid solution containing 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.
Use discharge and recharge instrument to carry out charge-discharge test under the following conditions above-mentioned vanadium cell DF2: with the charging current for charging of 4A to cut-ff voltage for 1.65V, be then discharged to cut-ff voltage for 1.0V with the discharging current of 4A, voltage efficiency is 73%.
Embodiment 2
This embodiment is for illustration of vanadium cell provided by the invention and preparation method thereof.
According to the method for embodiment 1, vanadium cell is prepared, unlike, the sulfuric acid solution containing vanadic sulfate that the trivalent vanadium ion electrolyte that described trivalent vanadium ion electrolyte adopts preparation example 2 to obtain substitutes, the sulfuric acid solution of described sulfur acid vanadyl adopts preparation example 2 to obtain, obtains vanadium cell F2.
Use discharge and recharge instrument to carry out charge-discharge test under the following conditions above-mentioned vanadium cell F2: with the charging current for charging of 4A to cut-ff voltage for 1.65V, be then discharged to cut-ff voltage for 1.0V with the discharging current of 4A, voltage efficiency is 91%.
Embodiment 3
This embodiment is for illustration of vanadium cell provided by the invention and preparation method thereof.
According to the method for embodiment 1, vanadium cell is prepared, unlike, the sulfuric acid solution containing vanadic sulfate that the trivalent vanadium ion electrolyte that described trivalent vanadium ion electrolyte adopts preparation example 3 to obtain substitutes, the sulfuric acid solution of described sulfur acid vanadyl adopts preparation example 3 to obtain, obtains vanadium cell F3.
Use discharge and recharge instrument to carry out charge-discharge test under the following conditions above-mentioned vanadium cell F3: with the charging current for charging of 4A to cut-ff voltage for 1.65V, be then discharged to cut-ff voltage for 1.0V with the discharging current of 4A, voltage efficiency is 90%.
Embodiment 4
This embodiment is for illustration of vanadium cell provided by the invention and preparation method thereof.
According to the method for embodiment 1, vanadium cell is prepared, unlike, the sulfuric acid solution containing vanadic sulfate that the trivalent vanadium ion electrolyte that described trivalent vanadium ion electrolyte adopts preparation example 4 to obtain substitutes, the sulfuric acid solution of described sulfur acid vanadyl adopts preparation example 4 to obtain, obtains vanadium cell F4.
Use discharge and recharge instrument to carry out charge-discharge test under the following conditions above-mentioned vanadium cell F4: with the charging current for charging of 4A to cut-ff voltage for 1.65V, be then discharged to cut-ff voltage for 1.0V with the discharging current of 4A, voltage efficiency is 89%.
Embodiment 5
This embodiment is for illustration of vanadium cell provided by the invention and preparation method thereof.
According to the method for embodiment 1, vanadium cell is prepared, unlike, the sulfuric acid solution containing vanadic sulfate that the trivalent vanadium ion electrolyte that described trivalent vanadium ion electrolyte adopts preparation example 5 to obtain substitutes, the sulfuric acid solution of described sulfur acid vanadyl adopts preparation example 5 to obtain, obtains vanadium cell F5.
Use discharge and recharge instrument to carry out charge-discharge test under the following conditions above-mentioned vanadium cell F5: with the charging current for charging of 4A to cut-ff voltage for 1.65V, be then discharged to cut-ff voltage for 1.0V with the discharging current of 4A, voltage efficiency is 89%.
Embodiment 6
This embodiment is for illustration of vanadium cell provided by the invention and preparation method thereof.
According to the method for embodiment 1, vanadium cell is prepared, unlike, the sulfuric acid solution containing vanadic sulfate that the trivalent vanadium ion electrolyte that described trivalent vanadium ion electrolyte adopts preparation example 6 to obtain substitutes, the sulfuric acid solution of described sulfur acid vanadyl adopts preparation example 6 to obtain, obtains vanadium cell F6.
Use discharge and recharge instrument to carry out charge-discharge test under the following conditions above-mentioned vanadium cell F6: with the charging current for charging of 4A to cut-ff voltage for 1.65V, be then discharged to cut-ff voltage for 1.0V with the discharging current of 4A, voltage efficiency is 85%.
Embodiment 7
This embodiment is for illustration of vanadium cell provided by the invention and preparation method thereof.
According to the method for embodiment 1, vanadium cell is prepared, unlike, the sulfuric acid solution containing vanadic sulfate that the trivalent vanadium ion electrolyte that described trivalent vanadium ion electrolyte adopts preparation example 7 to obtain substitutes, the sulfuric acid solution of described sulfur acid vanadyl adopts preparation example 7 to obtain, obtains vanadium cell F7.
Use discharge and recharge instrument to carry out charge-discharge test under the following conditions above-mentioned vanadium cell F7: with the charging current for charging of 4A to cut-ff voltage for 1.65V, be then discharged to cut-ff voltage for 1.0V with the discharging current of 4A, voltage efficiency is 84%.
As can be seen from the above results, the purity of the trivalent vanadium ion electrolyte adopting method provided by the invention to obtain is higher, can obtain the vanadium cell that voltage efficiency is higher.As can be seen from the contrast of preparation example 1 and preparation example 6-7, embodiment 1 and embodiment 6-7, adopt the preferred electrolysis tank of the present invention and polar plate spacing, can obtain the trivalent vanadium ion electrolyte that purity is higher, the voltage efficiency of the vanadium cell obtained is higher.
Claims (12)
1. the preparation method of a trivalent vanadium ion electrolyte, it is characterized in that, the method comprises the sulfuric acid solution containing vanadic sulfate as negative electrode, using sulfuric acid solution as anode, and the sulfuric acid of anode is equal with the mole containing the vanadic sulfate in the sulfuric acid solution of vanadic sulfate, and carry out constant-potential electrolysis, the mol ratio obtaining trivalent vanadium and full vanadium is greater than the trivalent vanadium ion electrolyte of 0.98, and described constant-potential electrolysis carries out in a cell; The battery lead plate that described electrolysis tank comprises groove deckle board, the anode pool surrounded by groove deckle board and cathode pool, conductive diaphragm between anode pool and cathode pool and lays respectively in anode pool and cathode pool, the material of described groove deckle board is the polyethylene that weight average molecular weight is greater than 3,000,000.
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.
3. preparation method according to claim 2, wherein, the molar concentration M of full vanadium in described trivalent vanadium ion electrolyte
tVfor 1-2mol/L.
4. the preparation method according to claim 1,2 or 3, wherein, described is 1:1.5-3 containing the mol ratio of vanadic sulfate and sulfuric acid in the sulfuric acid solution of vanadic sulfate.
5. 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 DEG C, and electrolysis time is 0.5-5 hour.
6. preparation method according to claim 5, wherein, described decomposition voltage is 1.5V-10V, and electrolysis temperature is 20-40 DEG C, and electrolysis time is 0.5-3 hour.
7. preparation method according to claim 1, wherein, the material of described groove deckle board to be weight average molecular weight be 3,500,000-500 ten thousand polyethylene.
8. preparation method according to claim 1, wherein, described battery lead plate be selected from platinum plate, modified graphite plate, titanium base platinum, yttrium oxide, graphite felt, carbon stick and compound conductive plastic plate one or more; Distance between described battery lead plate is not less than 3cm.
9. preparation method according to claim 8, wherein, described battery lead plate is platinum plate.
10. preparation method according to claim 8, wherein, the distance between described battery lead plate is 3-20cm.
11. preparation methods according to claim 1, wherein, described conductive diaphragm is fluorine-containing polyolefin amberplex.
12. preparation methods according to claim 11, wherein, described conducting film is perfluorinated sulfonic acid ion exchange membrane.
Priority Applications (2)
| Application Number | Priority Date | Filing Date | Title |
|---|---|---|---|
| CN201210200437.0A CN103515641B (en) | 2012-06-18 | 2012-06-18 | A kind of trivalent vanadium ion electrolyte and preparation method thereof and a kind of vanadium cell |
| JP2013127045A JP5680145B2 (en) | 2012-06-18 | 2013-06-17 | Trivalent vanadium ion electrolyte, production method thereof and vanadium battery |
Applications Claiming Priority (1)
| Application Number | Priority Date | Filing Date | Title |
|---|---|---|---|
| CN201210200437.0A CN103515641B (en) | 2012-06-18 | 2012-06-18 | A kind of trivalent vanadium ion electrolyte and preparation method thereof and a kind of vanadium cell |
Publications (2)
| Publication Number | Publication Date |
|---|---|
| CN103515641A CN103515641A (en) | 2014-01-15 |
| CN103515641B true CN103515641B (en) | 2016-04-13 |
Family
ID=49897990
Family Applications (1)
| Application Number | Title | Priority Date | Filing Date |
|---|---|---|---|
| CN201210200437.0A Expired - Fee Related CN103515641B (en) | 2012-06-18 | 2012-06-18 | A kind of trivalent vanadium ion electrolyte and preparation method thereof and a kind of vanadium cell |
Country Status (2)
| Country | Link |
|---|---|
| JP (1) | JP5680145B2 (en) |
| CN (1) | CN103515641B (en) |
Families Citing this family (11)
| Publication number | Priority date | Publication date | Assignee | Title |
|---|---|---|---|---|
| CN105388127B (en) * | 2015-10-30 | 2018-01-26 | 清华大学深圳研究生院 | A kind of online test method and system of each ion concentration of all-vanadium flow battery |
| CN110858655B (en) * | 2018-08-24 | 2021-08-10 | 江苏泛宇能源有限公司 | Purification method and purification device for electrolyte of flow battery |
| CN111106374B (en) * | 2019-11-28 | 2021-01-01 | 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 |
| CN112225250B (en) * | 2020-10-16 | 2022-05-24 | 成都先进金属材料产业技术研究院有限公司 | Method for self-reduction hydrothermal synthesis of vanadium dioxide nano powder |
| CN112941540B (en) * | 2021-01-28 | 2024-01-26 | 湖南钒谷新能源技术有限公司 | Vanadium electrolyte production system and production method |
| CN113087018B (en) * | 2021-03-29 | 2022-07-15 | 中国科学技术大学 | Preparation method of vanadium trioxide nano material rich in vanadium holes |
| TWI754595B (en) * | 2021-06-03 | 2022-02-01 | 虹京金屬股份有限公司 | Method for manufacturing vanadium electrolyte |
| CN114142076A (en) * | 2021-11-30 | 2022-03-04 | 成都先进金属材料产业技术研究院股份有限公司 | Method for improving electrochemical activity of vanadium battery electrolyte |
| KR20230081268A (en) * | 2021-11-30 | 2023-06-07 | 롯데케미칼 주식회사 | Manufacturing method for vanadium electrolyte |
| CN114335644A (en) * | 2021-12-23 | 2022-04-12 | 大连博融新材料有限公司 | Electrolyte crystal dissolving-aid additive, preparation method and application thereof |
| CN114497665A (en) * | 2022-01-17 | 2022-05-13 | 武汉科技大学 | Method for reducing capacity attenuation of vanadium battery |
Citations (4)
| Publication number | Priority date | Publication date | Assignee | Title |
|---|---|---|---|---|
| CN1353870A (en) * | 2000-03-31 | 2002-06-12 | 斯奎勒尔控股有限公司 | Radox flow battery and method of operating it |
| CN101692500A (en) * | 2009-10-23 | 2010-04-07 | 攀钢集团研究院有限公司 | Method for preparing all-vanadium ionic liquid flow battery electrolyte and prepared electrolyte |
| CN102005583A (en) * | 2009-09-01 | 2011-04-06 | 比亚迪股份有限公司 | Gelled electrolyte of vanadium battery and vanadium battery |
| CN102110837A (en) * | 2011-01-30 | 2011-06-29 | 国网电力科学研究院武汉南瑞有限责任公司 | Preparation method of electrolyte for vanadium redox battery (VRB) |
Family Cites Families (5)
| Publication number | Priority date | Publication date | Assignee | Title |
|---|---|---|---|---|
| JPH04149965A (en) * | 1990-10-15 | 1992-05-22 | Agency Of Ind Science & Technol | Manufacture of vanadium electrolyte |
| DE69432428D1 (en) * | 1993-11-17 | 2003-05-08 | Pinnacle Vrb Ltd | STABILIZED ELECTROLYTE SOLUTIONS, METHODS AND THEIR PRODUCTION AND REDOX CELLS AND BATTERIES THAT CONTAIN THESE SOLUTIONS |
| JPH07211346A (en) * | 1994-01-14 | 1995-08-11 | Sumitomo Electric Ind Ltd | Manufacture of electrolyte for vanadium redox flow type battery and manufacture of vanadium redox flow type battery |
| AUPR722101A0 (en) * | 2001-08-24 | 2001-09-13 | Skyllas-Kazacos, Maria | Vanadium chloride/polyhalide redox flow battery |
| JP2004071165A (en) * | 2002-08-01 | 2004-03-04 | Nippon Oil Corp | Production method for electrolyte for vanadium redox battery |
-
2012
- 2012-06-18 CN CN201210200437.0A patent/CN103515641B/en not_active Expired - Fee Related
-
2013
- 2013-06-17 JP JP2013127045A patent/JP5680145B2/en active Active
Patent Citations (4)
| Publication number | Priority date | Publication date | Assignee | Title |
|---|---|---|---|---|
| CN1353870A (en) * | 2000-03-31 | 2002-06-12 | 斯奎勒尔控股有限公司 | Radox flow battery and method of operating it |
| CN102005583A (en) * | 2009-09-01 | 2011-04-06 | 比亚迪股份有限公司 | Gelled electrolyte of vanadium battery and vanadium battery |
| CN101692500A (en) * | 2009-10-23 | 2010-04-07 | 攀钢集团研究院有限公司 | Method for preparing all-vanadium ionic liquid flow battery electrolyte and prepared electrolyte |
| CN102110837A (en) * | 2011-01-30 | 2011-06-29 | 国网电力科学研究院武汉南瑞有限责任公司 | Preparation method of electrolyte for vanadium redox battery (VRB) |
Also Published As
| Publication number | Publication date |
|---|---|
| JP2014003021A (en) | 2014-01-09 |
| CN103515641A (en) | 2014-01-15 |
| JP5680145B2 (en) | 2015-03-04 |
Similar Documents
| Publication | Publication Date | Title |
|---|---|---|
| CN103515641B (en) | A kind of trivalent vanadium ion electrolyte and preparation method thereof and a kind of vanadium cell | |
| US9413025B2 (en) | Hybrid flow battery and Mn/Mn electrolyte system | |
| CN102804472B (en) | Redox flow battery | |
| Dong et al. | A novel titanium/manganese redox flow battery | |
| KR101415538B1 (en) | MANUFACTURING DEVICE OF ELECTROLYTE SOLUTION FOR VANADIUM REDOX FlOW BATTERY USING ELECTROLYSIS AND MANUFACTURING METHOD OF THE SAME | |
| CN105742727B (en) | A kind of preparation method of secondary cell, purposes and its cathode | |
| Zhao et al. | Revealing sulfuric acid concentration impact on comprehensive performance of vanadium electrolytes and flow batteries | |
| US20200388857A1 (en) | Redox flow batteries employing diamond | |
| CN105406098B (en) | The method that vanadic sulfate is prepared using the electrolyte of vanadium redox battery that fails | |
| CN103384929A (en) | Alkali metal-air flow batteries | |
| EP2642572A2 (en) | Electrode for redox flow battery, fabrication method thereof, apparatus and method for fabricating electrolyte for redox flow battery, device and method for measuring selected ion concentration of electrolyte, and stand-alone battery system | |
| JP6349414B2 (en) | Method for producing positive electrode electrolyte for redox flow battery and redox flow battery | |
| JP2015069936A (en) | Vanadium solid salt battery | |
| Piwek et al. | Vanadium-oxygen cell for positive electrolyte discharge in dual-circuit vanadium redox flow battery | |
| WO2021004259A1 (en) | Symmetrical aqueous sodium-ion battery | |
| WO2014126179A1 (en) | Vanadium solid-salt battery and method for producing same | |
| JP2016517160A (en) | Flow battery health maintenance method | |
| CN104854732B (en) | It is characterized as the electrochemical energy storage system and method for big negative pole half-cell potential | |
| Hossain et al. | Evolution of vanadium redox flow battery in electrode | |
| CN104300169B (en) | A kind of Alkaline Zinc vanadium flow battery | |
| CN101692500A (en) | Method for preparing all-vanadium ionic liquid flow battery electrolyte and prepared electrolyte | |
| KR101514881B1 (en) | Method of manufacturing electrolyte for Vanadium secondary battery and apparatus thereof | |
| WO2016069402A1 (en) | Production of vanadium electrolyte for a vanadium flow cell | |
| CN107871881A (en) | A kind of electrolyte for vanadium cell and preparation method thereof | |
| CN106450400A (en) | All-vanadium redox flow battery |
Legal Events
| Date | Code | Title | Description |
|---|---|---|---|
| C06 | Publication | ||
| PB01 | Publication | ||
| C10 | Entry into substantive examination | ||
| SE01 | Entry into force of request for substantive examination | ||
| C14 | Grant of patent or utility model | ||
| GR01 | Patent grant | ||
| CF01 | Termination of patent right due to non-payment of annual fee | ||
| CF01 | Termination of patent right due to non-payment of annual fee |
Granted publication date: 20160413 Termination date: 20170618 |