CN101257121A - Improved perfluorinated membranes and improved electrolytes for redox cells and batteries - Google Patents

Improved perfluorinated membranes and improved electrolytes for redox cells and batteries Download PDF

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CN101257121A
CN101257121A CNA2008100816601A CN200810081660A CN101257121A CN 101257121 A CN101257121 A CN 101257121A CN A2008100816601 A CNA2008100816601 A CN A2008100816601A CN 200810081660 A CN200810081660 A CN 200810081660A CN 101257121 A CN101257121 A CN 101257121A
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cell
solution
iii
vanadium
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CN101257121B (en
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尼古拉斯·迈克尔·卡扎科斯
迈克尔·卡扎科斯
乔治·克里斯托弗·卡扎科斯
玛丽亚·斯凯拉斯-卡扎科斯
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NewSouth Innovations Pty Ltd
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V-FUEL Pty Ltd
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    • Y—GENERAL TAGGING OF NEW TECHNOLOGICAL DEVELOPMENTS; GENERAL TAGGING OF CROSS-SECTIONAL TECHNOLOGIES SPANNING OVER SEVERAL SECTIONS OF THE IPC; TECHNICAL SUBJECTS COVERED BY FORMER USPC CROSS-REFERENCE ART COLLECTIONS [XRACs] AND DIGESTS
    • Y02—TECHNOLOGIES OR APPLICATIONS FOR MITIGATION OR ADAPTATION AGAINST CLIMATE CHANGE
    • Y02E—REDUCTION OF GREENHOUSE GAS [GHG] EMISSIONS, RELATED TO ENERGY GENERATION, TRANSMISSION OR DISTRIBUTION
    • Y02E60/00—Enabling technologies; Technologies with a potential or indirect contribution to GHG emissions mitigation
    • Y02E60/10—Energy storage using batteries
    • 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 relates to an electrode used for vanadium redox flow battery, a preparation of electrolyte and a rebalance method. The preparation comprises thermally sticking a carbon felt or agraphite felt to at least one side of a carbon-filled polyolefine substrate. A flat, low-resistance electrode having good mechanical property can be obtained by the preparation. The preparation includes dissolving at least one vanadium oxide powder to a supporting electrolyte and optional electrolysis steps. The preparation needs no toxic SO2 gas, by separating the power dissolving stage and the electrolysis stage, problems related to suspension powder electrolysis are eliminated. The rebalance method comprises partially reducing a half-cell electrolyte in the cathode chamber of an electrolytic cell.

Description

Be used for the preparation method of the electrode of vanadium flow battery group and electrolyte and balance method again
Technical field
The invention describes and be used for preparing improving one's methods of the electrode that uses in vanadium flow battery and battery pack and electrolyte.Vanadium flow battery group (being referred to as VFB herein) be included in adopt in the negative pole half-cell V (II)/V (III) electricity to and in anodal half-cell, adopt V (IV)/right whole vanadium oxide reduction battery and battery pack (being called V/VRB herein) of V (V) electricity.
In V/VRB, depend on charged state, each battery produces the cell voltage of 1.1V to 1.6V, but can use bipolar electrode that a plurality of batteries are electrically connected in series, thereby obtains battery pile or battery pack that voltage is concrete desirable value.Be used for the electrode that the redox cell group uses and must have following characteristic: low-cost, at the strong oxidizing condition of anodal half-cell have chemical stability, reaction has good catalytic action, has the favorable mechanical performance, has hypotonicity and have low resistivity at electrolyte to redox cell.People after tested many electrode materials that are used for VFB, but have only carbon-based material can satisfy all requirements of V/VRB.Carbon plate or graphite cake volume are very big and very heavy, and comparatively expensive, and vitreous carbon is exactly like this.The surface treated of filling carbon provides good substitute, this substitute is light except weight, have chemical stability and relatively cheap, also have the favorable mechanical performance.Yet these composite materials are lower at the electro-chemical activity of vanadium redox battery reaction, need activate by using such surface active layer, this surface active layer can catalysis charging-exoelectrical reaction, thereby excellent energy efficiency is provided in the cyclic process of V/VRB.Of the present invention theming as: be used for the modified model electrode of V/VRB and prepare the kind electrode method accordingly.
The commerce of V/VRB is used low-cost and efficiently the bipolar electrode preparation method except needs, also needs to prepare cheaply method of electrolyte.The present invention has also described such method, and this method comprises at first dissolving vanadium trioxide powder in dissolving tank, thereby makes the initial soln of V (III) ion in supporting electrolyte.Then vanadium pentoxide powder is added in V (III) solution in the dissolving tank, only about half of V (III) ionic reaction in vanadium pentoxide powder and the solution in dissolving tank, thus the mol ratio that makes V (III) ion and V (IV) ion is about V (III)/V (IV) mixture of 1: 1.This solution can be directly used in two half-cells of V/VRB, but also can make a part of solution experience electrolysis step, thereby V (IV) ion in V (III)/V (IV) mixture is reduced to V (III) ion.The V that will produce in electrolytic cell (III) solution returns dissolving tank then, in dissolving tank, add the vanadium pentoxide powder of additional amount and the supporting electrolyte of aequum, thereby the mol ratio of the V (III) that produces the additional amount that is used for V/VRB and V (IV) is 1: 1 a mixture (V3.5+).
A kind of version of said method comprises: the vanadium trioxide and the vanadium pentoxide powder of dissolving equimolar amounts in dissolving tank, thereby make V (IV) solution, then with the anode chamber (negative compartment) of this solution pumping, thereby make V (III) ion in supporting electrolyte and the ratio of V (IV) ion is about 50: 50 mixture by electrolytic cell.This V (3.5+) solution can be directly used in V/VRB, perhaps can a part of solution be turned back in the dissolving tank in the mode of continuous or semicontinuous circulation, the vanadium pentoxide powder and the supporting electrolyte that in dissolving tank, add additional amount, thereby make V (IV) solution, this V (IV) solution by pumping once more by the anode chamber of electrolytic cell, thereby make V (3.5+) solution of the additional amount that is used for V/VRB.
When the electrolyte of V/VRB owing to V (II) the ion oxidation by air in the negative pole half-cell electrolyte or when the negative pole liberation of hydrogen departs from balance in the process that V/VRB is charged, can use identical electrolytic cell that it is carried out balance again.
Background technology
The vanadium redox battery group that is referred to herein as V/VRB is described in Australian Patent 575247, AU 696452, AU 704534, United States Patent (USP) 6143443 and United States Patent (USP) 6562514 to some extent, and the bromination vanadium oxide reduction flow battery that is referred to herein as V/BrRB is simultaneously described in patent documentation PCT/AU02/01157, PCT/GB2003/001757 and PCT/AU2004/000310 to some extent.These two kinds of battery pack have all been used the vanadium electrolyte solution in two half-cells, but in the situation of V/VRB, in two half-cells, all use vanadic sulfate solution, and this battery adopts V (II)/V (III) electricity right in negative pole half-cell electrolyte, adopts V (IV)/V (V) electricity right in anodal half-cell electrolyte.Bromination vanadium redox battery group (V/BrRB) is all used the bromination vanadium solution in two half-cells, it adopts V (II)/V (III) electricity right in the negative pole half-cell, adopts Br in anodal half-cell -/ Br 3 -The electricity to or Br -/ ClBr 2 -Electricity is right.
Because most of metals will oxidation under the condition that positive pole stood, the therefore general carbon-based electrode that uses.Anodal and negative pole typically is graphite cake electrode, graphite foil electrode, glassy carbon electrode or is bonded to carbon felt electrode on the Markite substrate.United States Patent (USP) 5665212 has been described a kind of Markite substrate that is used for the redox flow batteries electrode, and it comprises the mixture of carbon black, polyolefin and rubber constituent, thereby also provides the favorable mechanical performance except high conductivity is provided.Although the polyolefin/rubber combined substrate of filling carbon will obtain not have the homogeneous surface of bubble and warpage but very difficult in carbon felt bonding process for graphite cake or glass carbon plate provide the optional substitute of a kind of low cost, low weight.The carbon felt is bonded to needed heating and cooling circulation causes forming bubble and defective on the electrode circumferential surface on each side of carbon composite base plate, this causes difficulty in the sealing that forms anti-leak between battery liquid flow frame (cell flow frame) and the electrode edge.
In the initial R﹠D process of V/VRB, by with vanadic sulfate VOSO 4Be dissolved in and prepare electrolyte in the sulfuric acid.The expensive people of making of vanadic sulfate make great efforts to use cheaply that the vanadic oxide raw material replace it, yet the low-solubility of vanadic oxide needs people to develop the vanadium solution that chemistry or electrodissolution method prepare the desired concn that is used for V/VRB electrolyte.Usually adopt two kinds of methods to prepare V/VRB electrolyte from vanadium pentoxide powder.First method comprises by reacting with chemical mode with sulfur dioxide dissolves vanadium pentoxide powder, thereby makes V (IV) solution in sulfuric acid.Second method comprises carries out the suspended powder electrolysis with the vanadium pentoxide powder in negative pole half pond of electrolytic cell, thereby makes V (III)/V (IV) mixture.The shortcoming of first method is that this method need use poisonous gas, and owing to be difficult to vanadium pentoxide powder is maintained suspended state, so the scale of suspended powder electrolysis is difficult to enlarge.The kinetics mechanism at a slow speed of suspended powder reducing process only means can use low current density, so the throughput rate of the V on the per unit area negative electrode (IV) is very low.In addition, when the suspended powder electrolysis is operated as continuous process, be difficult to stop undissolved powder, therefore need complicated filtration system to prevent the obstruction of discharge tube along with final solution is discharged from anode chamber.
An object of the present invention is to handle or improve one or more above-mentioned defectives, or a kind of useful alternative method is provided at least.
Only be used to and the invention provides the style of writing basis being included in any discussion that document in this specification, publication, process, equipment, material, goods, material etc. are done.Any this type of discussion should not be understood that to admit that it forms the theme on prior art basis, should not be understood that to admit that it is any part that extends to the common sense of the correlative technology field relevant with the technology of the present invention field at priority date of the present invention yet.
Summary of the invention
In the present invention, described and be used for preparing improving one's methods of the electrode that uses in the vanadium flow battery group and electrolyte.Before can standing, described improved electrode and electrode preparation method use the problem of the surface deterioration that polyolefin/rubber composite experienced of filling carbon.This method comprises the carbon felt is thermally bonded at least one side of the Markite substrate that contains carbon black filler and polyolefin (for example polyethylene or polypropylene).By regulating temperature, pressure and tack time, can obtain to be used for smooth, flawless termination electrode or the bipolar electrode of VFB.The conductivity of electrode of the present invention is the 0.1 ohm of cm that is applicable to V/VRB 2To 3 ohm of cm 2, and near the periphery of the felt after the bonding, do not have as using the air blister defect that polyolefin/rubber combined substrate produced of traditional filling carbon.
Described preparation method of electrolyte does not need to add toxicity SO 2Gas, and eliminated the problem relevant with the suspended powder electrolysis by powder dissolution and electrolysis stage being divided into two independent step.
In the use of VFB,, just might cause the charged state imbalance of anodal half-cell electrolyte and negative pole half-cell electrolyte because V (II) the ion oxidation by air in the negative pole half-cell perhaps produces hydrogen on negative pole in charging process.Above-mentioned two kinds of processes all can cause capacitance loss, described capacitance loss can not by simply again mixed electrolytic solution proofread and correct, therefore needs a kind of rebalance cell (rebalance cell) or balance method again, it reverts to about 1: 1 corrected value by the ratio with V (II) ion in the negative pole half-cell solution of V/VRB and V (V) ion in the anodal half-cell solution, restore balance, thus the recovery system capacity.By anode chamber with the half-cell electrolyte pumping of the charging of VFB or the part charging electrolytic cell by being used for electrolyte preparation process 2, can be V (IV) ion with V (V) the ion partial reduction in the anodal half-cell electrolyte or be V (II) ion, thereby the ratio of V (V) ion in the anodal half-cell electrolyte of V (II) ion in the negative pole half-cell electrolyte of the charging of V/VRB and charging can be reverted to required 1: 1 V (III) the ion partial reduction in the negative pole half-cell electrolyte.Can use identical method to come the bromination V electrolyte of V/BrRB is carried out balance again.
In entire description, term " redox cell " also can be described as redox cell group and whole vanadium oxide reduction battery or battery pack, and bromination vanadium redox battery or battery pack can be referred to as vanadium flow battery group or VFB.
The invention discloses and be used for preparing in vanadium flow battery and battery pack, particularly all use improving one's methods of the electrode that uses among the VFB of vanadic sulfate electrolyte and electrolyte at two half-cells.
The present invention also discloses the method for the vanadium electrolyte solution of balance V/VRB again, and the anodal half-cell solution that makes V/VRB by this method by electroreduction, makes V (V) and the ratio of V (IV) revert to corrected value in electrolytic cell.
According to a first aspect of the invention, a kind of preparation method with electrode low-resistivity and favorable mechanical performance, that be used for redox flow batteries heap is provided, and this method comprises the carbon felt is thermally bonded on the one or both sides of the composite polyolefine material sheet of filling carbon.By optimizing temperature, pressure and compression time, can obtain smooth, low-resistance, the negligible electrode of warpage.
The composite polyolefine material of filling carbon is made of 5% to 30% carbon filler in polyethylene or polypropylene-base usually.The thickness of its sheet material is generally 0.1mm to 3mm, and conductivity is 0.1 ohm of cm to 10 ohm of cm.The thickness of carbon felt is 0.1mm to 8mm, by in the chamber that is placed on compression tool and composite material sheet is in contact with it, and described carbon felt is bonded at least one side of described composite material sheet.Mould is placed in the press of heating, and temperature is risen to 160 ℃ to 240 ℃.With 0.1kg/cm 2To 10kg/cm 2Pressure put on mould and keep 1 minute to 30 minutes, thereby make the surface of carbon felt infiltration composite material sheet and contact with the conductive network structure of carbon filler.When compression finishes, mould is taken out from press, and earlier it is cooled near room temperature before making the bipolar electrode demoulding opening mould.
According to a second aspect of the invention, provide a kind of vanadium redox battery or battery pack, it comprises:
The anodal half-cell that contains anodal half-cell solution, described anodal half-cell solution comprise sulfuric acid supporting electrolyte and one or more and are selected from ion in vanadium (III) ion, vanadium (IV) ion and vanadium (V) ion;
The negative pole half-cell that contains negative pole half-cell solution, described negative pole half-cell solution comprise sulfuric acid supporting electrolyte and one or more and are selected from ion in vanadium (IV) ion, vanadium (III) ion and vanadium (II) ion;
The electrode of the method preparation by first embodiment, described electrode contacts with negative pole half-cell solution with anodal half-cell solution.
These two kinds of half-cell solution are separated by the perfluorinate cation-exchange membrane that casting forms usually.Use can be assembled into vanadium cell bipolarity vanadium redox battery pile component by the bipolar electrode of the method preparation of first embodiment.The carbon felt can be Sigri, Le CarbonneLorraine, FMI (being mixed with fiber material), Toray or Toyoba carbon or graphite felt, carbon fibre material (supatex fabric CFT-3000 type for example, derive from the Ahlstroem company that is positioned at Finland) or cellulose carbon braid (for example GF-20 derives from the Nikon Carbon Co., Ltd. that is positioned at Japan).The outer rim of bipolar electrode can be welded to by vibration weldering method, infrared bonding method, ultrasonic bonding, hot weld method or Laser Welding method and be used for electrolyte is assigned to the liquid flow frame of half-cell chamber separately.
The V/VRB of second aspect also comprises the positive solution liquid reservoir, be connected positive solution supply and return line, negative solution liquid reservoir between positive solution liquid reservoir and the anodal half-cell, be connected negative solution supply between negative solution liquid reservoir and the negative pole half-cell and return line and at least one is in pump at least one positive solution supply and the return line and at least one and is in pump at least one negative solution supply and the return line.
The vanadium redox battery group of second aspect can be integrated in the production capacity system or electricity generation system that has photovoltaic array, wind turbine, wave-powered generator, diesel engine generator or other energy generating apparatus.
According to the of the present invention the 3rd concrete aspect, the preparation method of the electrolyte of a kind of vanadium redox battery that is used for second embodiment or battery pack is provided, this method comprises:
The first step comprises the vanadium trioxide powder dissolution in supporting electrolyte, thereby preparation contains the vanadium solution of V (III) ion;
Second step, comprise that vanadium pentoxide powder or thin slice with scheduled volume add in the solution of described first step preparation, wherein vanadic oxide and V (HI) ion reacts, thereby the mol ratio that makes in supporting electrolyte is about 50: 50 V (III) ion and the mixture solution (being called V (3.5+)) of V (IV) ion.
According to the of the present invention the 4th concrete aspect, a kind of preparation method who is used for the electrolyte of vanadium redox battery or battery pack is provided, this method comprises the vanadium trioxide powder of equimolar amounts and vanadium tetraoxide powder dissolution in supporting electrolyte, thereby preparation contains V (III) ion that mol ratio is about 1: 1 and the vanadium solution of V (IV) ion.
According to the of the present invention the 5th concrete aspect, a kind of preparation method who is used for the electrolyte of vanadium redox battery or battery pack is provided, this method comprises:
The first step comprises the vanadium solution that contain V (III) ion, V (IV) ion or V (III) ion/V (IV) ion mixture of preparation in supporting electrolyte;
Second step, comprise the vanadium pentoxide powder of scheduled volume or thin slice are added in the solution of described first step preparation that the solution that wherein makes is V (III) ion that was about 50: 50 of the mol ratio in supporting electrolyte and the mixture (being called V (3.5+)) of V (IV) ion in dissolving tank;
The 3rd step wherein with negative pole half pond of a part of V (3.5+) solution pumping by electrolytic cell, thereby was reduced to V (III) with it, was oxygen with water electrolysis on anode simultaneously;
The 4th step, comprise will be in described the 3rd step V (III) solution that make be recycled to the initial position of this process, herein will other vanadic oxide and acid supporting electrolyte join in V (III) solution in the dissolving tank, thereby prepare V (3.5+);
With the mode repeating step 1 to 4 of semicontinuous or continuous circulation, thereby preparation is used for V (3.5+) solution of VFB.
According to a sixth aspect of the invention, a kind of preparation method who is used for the electrolyte of vanadium redox battery or battery pack is provided, this method comprises the vanadium trioxide by mixing equimolar amounts in dissolving tank and V (IV) solion pumping that vanadic oxide the prepares anode chamber by electrolytic cell, making its partial reduction is V (III), thereby makes that the ratio of V (III) and V (IV) approximates 1: 1 greatly in the solution.The anode reaction of electrolytic cell comprises water is oxidized to oxygen.Can this V of a part (III)/V molar mixtures such as (IV) be turned back in the dissolving tank in the mode of continuous or semicontinuous circulation, the vanadic oxide and the supporting electrolyte that in dissolving tank, add other stoichiometric amount, thereby preparation V (IV) solution, this V (IV) solution is turned back in the anode chamber of electrolytic cell once more, thus the V that is used for VFB (3.5+) solution of preparation additional amount.
V described in the 6th aspect (IV) solution also can prepare by chemistry leaching vanadium extraction from dead catalyst or waste residue or flying dust.
In aspect the 3rd to the 6th, the dissolving of vanadium oxide powder can be carried out under near the condition of room temperature, and dissolving tank can be made by teflon, polyethylene or polypropylene.
The character of vanadium trioxide and the two exothermic heat of reaction of vanadic oxide can make the temperature of the solution in the dissolving tank rise on the room temperature, and this has the effect of the rate of dissolution that improves the vanadium oxide powder.But dissolving tank can be made by polyethylene or polypropylene, so need reaction temperature be remained under 90 ℃ by slow adding vanadium pentoxide powder.
In aspect the 3rd to the 6th, supporting electrolyte is the H of 2M to 9M 2SO 4, vanadium ion concentration can be 0.1 mole to 5 moles.More typical is that vanadium ion concentration is 1M to 4M or 1M to 3M.H 2SO 4Concentration is generally 2M to 9M, 3M to 8M, 4M to 6M or 4M to 8M.By using HBr or HBr/HCl mixture to replace sulfuric acid, the described method in the 3rd to the 6th aspect can be used for preparing V (3.5+) electrolyte that is used for V/BrRB.
According to a seventh aspect of the invention, a kind of battery that is used for described vanadium redox battery of second aspect or battery pack balance method again is provided, this method comprises anodal half-cell electrolyte or the negative pole half-cell electrolyte pumping anode chamber by the 5th and the 6th described electrolytic cell in aspect, and be respectively V (IV) ion with the partial reduction of V (V) ion or be V (II) ion with the partial reduction of V (III) ion, make the ratio of V (IV) and V (V) of anodal half-cell of VFB approximate the V (III) of negative pole half-cell and the ratio of V (II).The anodal electrolyte or the negative pole electrolyte that finally regulate are distinguished in the electrolyte liquid reservoir of pumped back VFB.The anode reaction of electrolytic cell comprises water is oxidized to oxygen.
In aspect the 5th to the 7th, the vanadium electrolytic cell can be single electrolytic cell or fitted to be bipolarity or the stacking of a plurality of electrolytic cells of monopole element.In the situation of sulfuric acid supporting electrolyte, the positive pole and the negative pole of electrolytic cell can be lead electrode.Alternatively, positive pole can be dimensional stable anode (DSA), and negative pole can be carbon, graphite or titanium.In the situation of the sulfuric acid supporting electrolyte that is used for V/VRB, electrolytic cell can use the bipolar electrode that is selected from Ti/DSA bipolar electrode or the plumbous bipolar electrode.The Ti/DSA bipolar electrode prepares by following step: the coating TiO that uses electro-chemical activity 2, RuO 2, Ir 2O 3, PtO 2An or side of its mixture coating titanium sheet, thereby the oxygen evolution reaction of catalysis side of the positive electrode.Negative side can be exposed Ti.
Two and half ponds of the 5th to the 7th described electrolytic cell in aspect can be separated by cation-exchange membrane (for example Nation or another kind of perfluorinate film) or non-selective microporosity separator (for example Daramic or other microporous polyethylene or polypropylene separator).Anodal Ban Chi chamber and negative pole Ban Chi chamber can comprise plate washer or porous polymer felt, to keep the constant distance between film or dividing plate and the electrode surface.
Description of drawings
Fig. 1 shows a kind of use perfluorinate cation-exchange membrane (1) and separates anodal half-cell Vanadium oxide reduction flow battery with the negative pole half-cell. Each half-cell include porous carbon or The felt of graphite material or pad (2 and 3), it is thermally bonded to the composite polyolefine material of filling carbon On the substrate as negative pole (4) or anodal (5), so that electrically contact with the collector body at the back side separately. Negative pole electrolyte half-cell solution and anode electrolyte half-cell solution are stored in outside storage separately In the liquid device (6 and 7), pump 8 and 9 be used for electrolyte pumping by corresponding the charging-The half-cell of exoelectrical reaction.
Fig. 2 shows by the termination electrode of method preparation of the present invention and the signal of bipolar electrode Figure. Fig. 2 (a) shows the cross section of termination electrode, and this termination electrode is by with a carbon or stone The China ink felt is bonded on the side of Markite substrate, and a slice Copper Foil or copper mesh are bonded to it Make on the opposite side. Fig. 2 (b) shows the cross section of bipolar electrode, this bipolarity Electrode comprises carbon or the graphite felt on the both sides that are thermally bonded to the Markite substrate. Fig. 2 (c) That the bipolar electrode of carbon felt side and the top view of termination electrode are shown.
Fig. 3 shows the typical charging-discharge curve that obtains, this Static Electro in static battery It is 25 microns that V (3.5+) solution of the 1.5M in 5M sulfuric acid and thickness are contained in the pond The perfluorinate film. Anodal and negative pole comprises that thickness is the Sigri carbon felt of 5mm, and it passes through at 240 ℃ The pressure that applies down 125kg reached 5 minutes and was thermally bonded on the polyethylene substrate of filling carbon. The composite polyethylene material sheet of filling carbon contains 25% carbon black and 75% high density polyethylene (HDPE). Copper collector contacts with the dorsal part of described composite material sheet, thereby plays the effect of collector body.
Fig. 4 show the electrode that adopts by the inventive method preparation, consisted of by 9 batteries VRB heap and charging-discharge curve of obtaining.
Fig. 5 shows and uses microporous polyethylene or polypropylene separator or perfluorinate cation exchange Film (501) is separated the electrolytic cell in anodal half pond and negative pole half pond. Each half pond includes plate washer Or the felt of porous or pad (502 and 503), thereby keep dividing plate and negative pole and positive pole (504 Hes 505) constant distance between the surface. The sulfuric acid supporting electrolyte is stored in outside liquid reservoir (507) In, pump (509) is used for the supporting electrolyte pumping by oxygen evolution reaction taking place just at anode The utmost point half pond. In order to compensate owing to any loss of analysing the water that oxygen causes at anode, from storage liquid Device (513) periodically adds entry. Pump (508) is passed through from the vanadium oxide dissolving tank in negative pole half pond (506) charging. The exit in negative pole half pond of electrolytic cell is for being recycled to dissolving tank (506) , the equimolar V (III) in the sulfuric acid supporting electrolyte/V (IV) mixture, wherein from appearance The vanadium pentoxide powder of device (510) and be dispensed into molten from the sulfuric acid of liquid reservoir (511) Separate in the groove (506), thereby come by the V in vanadium pentoxide powder and the solution (III) ionic reaction Preparation V (IV) solion. To be recycled to from V (IV) solution of dissolving tank the negative of electrolytic cell In the utmost point chamber, this solution is upper by partial reduction at negative pole (504) in anode chamber, rubs thereby make You are than being 50: 50 V (III) and the mixture of V (IV). V (3.5+) solution with a part of gained Be recycled in the dissolving tank (506), simultaneously residue discharged as product, and be stored in groove (512) in, to be ready for use on VFB.
Embodiment
The electrode that is used for the vanadium flow battery group is by carbon felt or the thermo-compression bonding of graphite felt are prepared to high density polyethylene (HDPE), low density polyethylene (LDPE) or the polypropylene substrate of the filling carbon one or both sides of (contain 5% to 30%, preferably contain 10% to 20% or 20% to 30% carbon black).Felt-composite material base board component is placed mould and between the pressing plate of press, be heated to 160 ℃ to 240 ℃, preferred 180 ℃ to 220 ℃.With 0.1kg/cm 2To 10kg/cm 2, preferred 0.1kg/cm 2To 5kg/cm 2, more preferably 0.5kg/cm 2To 5kg/cm 2Pressure be applied to reach 1 minute to 30 minutes on the heated mold, preferred 5 minutes to 15 minutes, thereby make the surface of carbon felt infiltration composite material sheet and contact with the conductive network structure of carbon filler.When compression finishes, mould is taken out from press, make before making the electrode demoulding mold cools down near room temperature earlier opening mould.
Electrode of the present invention is used for vanadium redox battery or battery pack, electrolyte for 3M to 6M, preferred 3.5M to 5.5M, more preferably the 0.5M to 2.5M in the sulfuric acid of 4M to 5M, be preferably the vanadium ion of 1.0M to 2.0M.The vanadium of the 0.5M to 2.5M in the sulfuric acid supporting electrolyte of 3M to 6M of initial feed ((III) ion of the V by about 50% and 50% V (IV) ion are formed) solution can at first be placed anodal half-cell and negative pole half-cell.The perfluorinate amberplex that two kinds of half-cell electrolyte of flow battery are formed by casting is separated, in order to avoid these two kinds of solution (are recharged at this battery being pumped through battery or battery pile, thereby in the negative pole half-cell, producing V (II) ion, in anodal half-cell, produce V (V) ion) time mixes in a large number.When discharge, V (II) is converted into V (III) in the negative pole half-cell, and V (V) is reduced to V (IV) in anodal half-cell simultaneously.
Prepare the electrolyte that uses among the VFB of the present invention by following step: in negative pole half pond of electrolytic cell V (IV) electrolysis of solutions being reduced to V (3.5+), is oxygen with water electrolysis on anode simultaneously.The described electrolyte of a part is turned back in the dissolving tank, in dissolving tank, add V 2O 5Powder and sulfuric acid are by from V 2O 5The reaction of V (III) ion in the V of powder (V) ion and V (3.5+) solution produces V (IV) ion in the solution of required vanadium concentration and acid concentration.The solubilizing reaction of vanadic oxide can at room temperature carry out, but for the accelerate dissolution dynamic process, the temperature of dissolving tank be room temperature to boiling temperature, 40 ℃ to 100 ℃, 40 ℃ to 80 ℃, more preferably 40 ℃ to 60 ℃ be required.
Two and half pond electrolyte of electrolytic cell are separated by microporous polyethylene, capillary polypropylene or perfluorinate cation-exchange membrane, in order to avoid these two kinds of solution mix when being pumped through electrolytic cell or electrolytic cell heap in a large number.
The negative material that is used for electrolytic cell can be carbon or graphite felt, pad or the cloth that is positioned at the porous on graphite, vitreous carbon or the Markite substrate.Negative pole also can be lead flake or lead sponge or titanium sheet or titanium sponge.Because anodal half-cell reaction comprises the water oxidation producing oxygen, so carbon or graphite anode are undesirable, and this is because carbon surface can be oxidized to carbon dioxide simultaneously, thereby oxidation Decomposition takes place.Positive electrode is preferably lead flake or lead sponge, but also can be made by titanium metal plate that scribbles oxide or expanded metal.Also a plurality of electrolytic cells can be merged into the battery pile with one pole or bipolar electrode, these bipolar electrodes comprise lead flake or the lead sponge all compatible with the negative pole half-cell reaction with anodal half-cell reaction.One side is coated with suitable TiO 2/ RuO 2/ Ir 2O 3/ PtO 2Or the titanium-base of other oxide coating also can be used as the bipolar electrode of electrolytic cell heap.
Electrolytic cell is 5mA/cm at negative electrode and/or anodic current density usually 2To 500mA/cm 2, be preferably 10mA/cm 2To 250mA/cm 2, even 50mA/cm more preferably 2To 150mA/cm 2Condition under work.Electrolytic cell voltage typically is 1.5 volts to 5 volts, it more typically is 1.5 volts to 3 volts, and adjust the flow velocity of negative pole half pond solution, V (III) that makes the exit comprise mol ratio to be about 50: 50 and the mixture (being called V (3.5+)) of V (IV), V (III) is preferably 0.8: 1.2 to 1.2: 0.8 with the mol ratio of V (IV), more preferably 0.9: 1.1 to 1.1: 0.9, even more preferably 0.95: 1.05 to 1.05: 0.95.
In the course of work of the VFB that adopts electrode by the inventive method preparation and V electrolyte, thereby two kinds of half-cell solution periodically mix again obtain initial V (3.5+) solution in two grooves.This mixing makes because ion is striden any chemical imbalance that film transfer causes obtains proofreading and correct, so capacity that can recovery system.If the electrolyte imbalance is owing to liberation of hydrogen on the negative pole in the charging process or owing to the V in the negative pole half-cell (II) oxidation by air causes, so simply solution is mixed again and can not recover capacity, this is because the ratio of the V (IV) again in the mixed solution and V (III) is higher than the ratio of V (IV) and V (III) in V (3.5+) electrolyte of initial feed.In this case, electrolyte rebalancing must comprise the vanadium ion partial reduction in anodal electrolyte or the mixed electrolyte, thereby the oxidation state of whole vanadium is returned to V (3.5+).This can realize by following step: chemical reducing agent (for example methyl alcohol or ethanol) is added in V (V) solution of charging, anodal VFB electrolyte pumping that perhaps will charge fully or partly charging is by the anode chamber of electrolytic cell of the present invention, thereby with the partial reduction of V (V) ion is V (IV) ion, makes the ratio of V (V) and V (IV) of gained equal the ratio of V (II) and V (III) in the negative pole half-cell solution.
Embodiment
Embodiment 1
By two of following step preparations according to carbon felt of the present invention/Markite electrode: the Markite sheet that will consist of the high density polyethylene (HDPE) of 20% carbon black and 80% places mould, in this external this mould, on a side of this Markite, place a copper felt, on its relative side, place the Sigri felt of a 5cm * 5cm.With the mould closure, and place on the pressing plate of heating and be heated to 240 ℃.The weight of 125kg was placed the mould top 15 minutes.Then the pressing plate of mould from heating taken out, and be cooled to room temperature.Two termination electrodes that prepare like this are used for vanadium redox battery.At first the carbon felt is immersed the H that is in 5M 2SO 4In the V (III) of 0.9M and the solution of the V (IV) of 0.9M in, electrode is placed between 2 liquid flow frames, it is the perfluorinate film (being sandwiched between the two end plates) that 25 microns casting forms that a thickness is arranged therebetween.Be to circulate under the condition of 500mA at battery charge and discharging current.
Charging-the discharge curve that is obtained by static battery structure is shown among Fig. 3.The average efficiency of gained is: voltage efficiency=92.7%, enclosed pasture efficient=87.2%, energy efficiency=80.8%.
Embodiment 2
Prepare bipolar electrode of the present invention by following step: the Sigri carbon felt of 5cm * 5cm is placed on the either side of Markite sheet of the embodiment 1 in the mould, be heated to 230 ℃ then.The weight of 100kg was placed the mould top 15 minutes.Then with mold cools down to room temperature, by the conductivity that electrode is placed between two copper sheets and logical 1 ampere electric current is tested this electrode.After the voltage drop of deduction collector body, the voltage of the bipolar electrode that is write down is reduced to 50mV.Adopting Ohm's law and electrode area is 25cm 2Condition, the resistivity of determining bipolar electrode is 1.25 ohm of cm 2
Use identical temperature and pressure to carry out the experiment second time, difference is that tack time is increased to 20 minutes.The resistivity of the bipolar electrode that makes is about 1 ohm of cm 2
Embodiment 3
Prepare bipolar electrode by following step: 2 carbon felts that are of a size of 400mm * 400mm are placed thickness respectively is 1mm, be of a size of on the both sides of Markite (consisting of 20% carbon black and 80% high density polyethylene (HDPE)) sheet of 600mm * 600mm.By under 230 ℃, applying 2.5kgcm -2Pressure 15 minutes, the carbon felt is thermally bonded to respectively on the both sides of Markite sheet.After being cooled to room temperature,, test the conductivity of gained electrode by adding 10 amperes electric current on the both sides that 2 copper sheets placed bipolar electrode and to copper sheet.The conductivity that found that bipolar electrode is 0.8 ohm of cm 2To 1.2 ohm of cm 2
Embodiment 4
Use the bipolar electrode of preparation among the embodiment 3 to assemble the battery pile that constitutes by 9 batteries, closing the vanadium solution that uses 1.8M under the static schema of pump and charge-test of discharge battery heap estimates its electrical property.Making battery pile is that 20 amperes, average discharge current are to experience charge-discharge cycles under 23 amperes the condition in charging current.The results are shown among Fig. 4.After measured, voltage efficiency is 88%, and enclosed pasture efficient is about 94%, and the total energy efficiency of generation is 82%.
Embodiment 5
The vanadic sulfate electrolyte that is used for V/VRB by the preparation of following step: at first with 0.75 mole V 2O 3Powder adds and also contains in 1 liter of volumetric flask of the 5 mol sulfuric acid of having an appointment.Thereby make the vanadium trioxide powder dissolution form V (III) ion solution of 1.5 mol.Vanadium pentoxide powders of/4th moles (being equivalent to 0.5 mole V (V)) are slowly added in V (III) solution, after dissolving, obtain the final solution of the V (IV) (being called V (3.5+)) of V (III)+1.0M of about 1.0M.In the process of vanadium oxide dissolving step, can be that room temperature arrives boiling temperature with the temperature maintenance of solution in the dissolving tank.
Subsequently will be from V (3.5+) the solution pumping of dissolving tank anode chamber by electrolytic cell, wherein this electrolytic cell adopts lead electrode, perfluorinate film and adopt sulfuric acid in positive pole half pond.The electric current that uses 5 amperes is V (3.5+) electrolysis of solutions 5.5 hours, thereby it is reduced to V (III).To turn back in the dissolving tank from V (III) solution of the 2M of electrolytic cell subsequently, the vanadic oxide and the sulfuric acid of additional amount is added in this dissolving tank, thus the V (3.5+) of the 2M of preparation additional amount.Entry or sulfuric acid be can add with the dilution of gained solution, required total vanadium concentration and total sulfate concentration used thereby reach for V/VRB.Adjust the required composition of V/VRB electrolyte, to adapt to local weather conditions.
Embodiment 6
The vanadic sulfate electrolyte that is used for about 3M of V/VRB by the preparation of following step: at first with 0.75 mole V 2O 3Powder adds and also contains in 1 liter of volumetric flask of the 6 mol sulfuric acid of having an appointment.Thereby make the vanadium trioxide powder dissolution form V (III) ion solution of 1.5 mol.0.75 mole vanadic oxide is slowly added in V (III) solution, at the final solution of the V that obtains the about 3M in sulfuric acid after the dissolving (IV).This solution is added in the anode chamber of electrolyte, in anode chamber, pass through to use 10mAcm -2To 150mAcm -2Electric current and half V (IV) ion is reduced to V (III) ion, water decomposes in positive pole half pond and produces oxygen simultaneously.V (III)/V (IV) solution of a part of gained is transported in the product storage tank, use for V/VRB, simultaneously rest solution is recycled in the dissolving tank, adds other vanadium pentoxide powder at this, with solution in V (III) ionic reaction and dissolving form V (IV) ion.This solution being carried back in the electrolytic cell to be reduced to V (3.5+) once more before, add other sulfuric acid so that total V density is maintained 3M in the mode of continuous or semicontinuous circulation.
Embodiment 7
By V with 300 moles 2O 3Powder dissolution is in the H of 6M 2SO 4Prepare the V that volume is 200 liters 3M (III) solution in the supporting electrolyte.The temperature of dissolving tank is about 60 ℃, but can be set between the arbitrary temp between the room temperature to 80 ℃, and but, the higher temperature up to boiling also can be used for improving the rate of dissolution of vanadium oxide powder.Then with this solution pumping by having 1500cm 2The cathode chamber of electrolytic cell heap electrode area, that constitute by 5 electrolytic cells.The electrode that adopts is for being bonded to the carbon felt on the Markite substrate (consisting of about 20% carbon black and 80% high density ethylene), and film is Nation 112.Make the H of 6M 2SO 4Solution circulated applies 75 amperes electric current by negative pole half pond.For V (3.5+) solution for preparing 3M, calculate required theoretical electrolysis time by Faraday's law:
Molal quantity=It/nF
For the V (3.5+) for preparing 3M, the V of half molal quantity (III) ion must be oxidized to V (IV) ion, so molal quantity=300, I=75 ampere, n=1, F=96,500 coulombs/equivalent.In the above-mentioned equation of these numerical value substitutions, for single electrolytic cell, theoretical electrolysis time calculated value is 107.2 hours.For the electrolytic cell heap that is made of 5 electrolytic cells, current efficiency is 100% o'clock, and theoretical electrolysis time is 21.4 hours.Suppose at 50mAcm -2Condition under current efficiency be 90%, the then theoretical time becomes 23.8 hours.
Small amount of sample is being diluted 10 times of KMnO that also use 0.1M 4After the titration, the cathode chamber of the electrolytic cell heap that the V (3.5+) of 200 liters of 3M is cycled through be made of 5 electrolytic cells reaches 24 hours.Solution composition is 1.55 mol V (III)+1.44 mol V (IV) ions as calculated.
Embodiment 8
By under about 60 ℃ in dissolving tank with 0.75 mole every liter amount with V 2O 4Be dissolved in the H of 5M 2SO 4In prepare V (IV) solution of about 1.5M.With the anode chamber of this solution pumping by electrolytic cell, this electrolytic cell has plumbous positive pole and the carbon felt negative pole that is pressed against on the vitreous carbon substrate with copper collector then.The perfluorinate film that casting is formed is used as dividing plate, applies 60mAcm 2Electric current, thereby in anode chamber, V (IV) ion is reduced to V (III), on positive pole, discharge simultaneously oxygen.Suppose that current efficiency is 90%, calculate electrolysis time according to the method that a last embodiment describes.Then gained V (III) solution is added in the dissolving tank, with 0.25 mole every liter amount with V 2O 5Powder slowly adds in the dissolving tank, carries out vigorous stirring simultaneously, till all powder dissolving.0.5 0.5 mole V (III) reaction in the V (V) of mole and the solution, thereby make 1.0 moles V (IV) ion.Therefore gained solution is the H at 5M 2SO 4In V (III) ion of 1 mol and V (IV) ion of 1 mol.This solution can be directly used in two half-cells of V/VRB, perhaps can adjust composition at concrete local climate condition, so that V (II), V (III) or V (IV) ion precipitation at low temperatures reach minimum, or make the thermoprecipitation at high temperature of V (V) ion reach minimum.Yet V (3.5+) electrolyte for the 2M for preparing additional amount can turn back to all or part of final V (3.5+) solution in the dissolving tank, every liter of V that adds 0.5 mole in dissolving tank 2O 5Powder, with solution in V (III) ionic reaction, thereby make V (IV) solution of 3M.The temperature of dissolving tank can be set at room temperature to 80 ℃, and temperature is high more, and rate of dissolution is high more, but will regulate temperature upper limit to adapt to the desired temperature of the film that uses in the electrolytic cell.The H that adds other 5M 2SO 4So that the concentration of V (IV) is reduced to 2M, then with the anode chamber of solution pumping by electrolytic cell so that 50% V (IV) ion is reduced to V (III), thereby make V (3.5+) solution of the 2M that is used for V/VRB.
Embodiment 9
When finding that stored energy capacitance reduces to a half of initial capacity, the V/VRB of 1kW/5kWh used about 12 months.Anodal half-cell electrolyte and negative pole half-cell electrolyte mixed again can not increase battery capacity significantly, this explanation capacitance loss be owing to the V in the negative pole half-cell (II) ion oxidation by air or in charging process on the negative pole liberation of hydrogen cause.With battery discharge, reach the distinctive green of V (III) ion until the color of negative pole half-cell solution.Then the anodal half-cell electrolyte of V (the IV)/V (V) of partial discharge is added in the anode chamber of electrolytic cell of embodiment 8, till V (IV) solution that obtains sapphirine, it is returned in the anodal liquid reservoir of V/VRB.When the V/VRB after the balance is again recharged, find to have returned to initial stored energy capacitance.
Using V/VRB after 6 months again, the capacity of observing once more descends.In this case, carry out battery balance more in the following manner: battery is initially recharged until observe the distinctive yellow of V (V) ion in anodal half-cell solution till.Then with the anode chamber of negative pole half-cell electrolyte pumping, till the distinctive purple that reaches V (II) ion by electrolytic cell.When the electrolyte after the balance again in V/VRB discharges, find to have returned to initial capacity.
Available identical method is carried out balance again to the electrolyte of V/BrRB.

Claims (23)

1. preparation method who is used for the electrode of vanadium redox battery group, this method comprises carbon felt or graphite felt is bonded at least one side of the polyolefin substrate of filling carbon, wherein said substrate comprises carbon black and is selected from polyolefin in low density polyethylene (LDPE), high density polyethylene (HDPE) and the polypropylene, wherein described felt and described substrate are heated to 160 ℃ to 240 ℃ temperature, and apply 0.1kgcm -2To 10kgcm -2Pressure reach 1 minute to 30 minutes time, thereby described felt is bonded to described substrate.
2. the described method of claim 1, the polyolefin substrate of wherein said filling carbon comprise 5% to 30% carbon black and 95% to 70% polyolefin.
3. the described method of claim 1, the polyolefin of wherein said filling carbon comprises 10% to 30% carbon black.
4. the described method of claim 1, the polyolefin of wherein said filling carbon comprises 10% to 20% carbon black.
5. the described method of claim 1, wherein said temperature is 180 ℃ to 220 ℃.
6. the described method of claim 1, wherein said pressure is 0.5kgcm -2To 5kgcm -2
7. the described method of claim 1, the wherein said time is 5 minutes to 15 minutes.
8. the described method of claim 1 to 7 wherein heats and pressurizeed 1 minute to 30 minutes.
9. the described method of claim 8 wherein heats and pressurizeed 5 minutes to 15 minutes.
10. a vanadium redox battery or battery pack with anodal half-cell and negative pole half-cell, described anodal half-cell and described negative pole half-cell have the electrode by the described method preparation of claim 1 to 9 separately, and described anodal half-cell comprises anodal half-cell solution, described negative pole half-cell comprises negative pole half-cell solution, wherein said anodal half-cell solution contains be selected from V (III) in sulfuric acid, vanadium ion among V (IV) and the V (V), described negative pole half-cell solution contain be selected from V (IV) in sulfuric acid, vanadium ion in V (III) and V (II) ion.
11. a preparation method who is used for the electrolyte of described vanadium redox battery of claim 10 or battery pack, this method comprises:
(a) at least a solid oxide vfanadium compound that will be selected from dissolving tank in vanadium trioxide and the vanadium tetraoxide is dissolved in the supporting electrolyte, thereby preparation is selected from the solution of the vanadium ion in V (III), V (IV) and V (III)/V (IV) mixture;
(b) the described solution oxide that can randomly in the cathode chamber of electrolytic cell, step (a) be prepared, thus the mol ratio of preparation in described supporting electrolyte is about 1: 1 V (III) ion and the mixture of V (IV) ion;
(c) the described solution reduction that can randomly in the anode chamber of electrolytic cell, step (a) be prepared, thus the mol ratio of preparation in described supporting electrolyte is about 1: 1 V (III) ion and the mixture of V (IV) ion;
(d) can randomly the solid-state vanadic oxide of stoichiometric amount and the supporting electrolyte of additional amount be joined in the solution that is prepared by step (a) to (c), thereby preparation contains the solution that is selected from the vanadium ion in V (IV) ion and V (III)/V (IV) ion mixture in described dissolving tank;
(e) can randomly in the anode chamber of electrolytic cell, at least a portion be reduced by V (IV) ion in the described solution of step (d) preparation, thereby the preparation mol ratio is about 1: 1 V (III) ion and the mixture of V (IV) ion;
(f) repeating step (d) and (e) randomly.
12. method according to claim 11 wherein mixes mol ratio and be about 3: 1 vanadium trioxide and vanadic oxide in dissolving tank, thereby the mol ratio of preparation in described supporting electrolyte is about V (III)/V (IV) mixture of 1: 1.
13. the described method of claim 11 wherein mix the vanadium trioxide and the vanadium tetraoxide of about equimolar amounts in dissolving tank, thereby the mol ratio of preparation in described supporting electrolyte is about V (III)/V (IV) mixture of 1: 1.
14. the described method of claim 11 to 13, wherein said supporting electrolyte are H 2SO 4, total sulfate concentration is 4M to 5M, the concentration of wherein said vanadium is 0.1M to 5M.
15., wherein be room temperature to 80 ℃ with the temperature maintenance of the solution in the described dissolving tank according to the described method of claim 11 to 14.
16. claim 12 and 13 described methods, wherein the temperature maintenance with the solution in the described dissolving tank is that room temperature is to boiling temperature.
17. claim 12 and 13 described methods, the V (III) in wherein said V (III)/V (IV) mixture is 0.8: 1.2 to 1.2: 0.8 with the mol ratio of V (IV).
18. method according to claim 11, wherein said two and half ponds are separated by dividing plate or the divided thin film that is selected from microporous polyethylene, capillary polypropylene, the perfluorinate cation-exchange membrane.
19. the described method of claim 11, wherein said negative pole is selected from lead, titanium and carbon, and described positive pole is selected from lead and dimensional stable anode.
20. claim 11 and 12 described methods, wherein said current density is 10mAcm -2To 250mAcm -2
21. the balance method again of described vanadium redox battery of claim 10 or battery pack, by this method with the partial reduction in the described anode chamber of the described electrolytic cell of claim 11 to 13 of a kind of half-cell electrolyte.
22. method according to claim 21, wherein the described anodal half-cell electrolyte pumping of described vanadium redox battery group is passed through described negative pole half pond of described electrolytic cell, thereby with the partial reduction of described V (V) ion is V (IV) ion, makes the mol ratio of V (V) ion in the described anodal half-cell electrolyte and V (IV) ion approximate V (II) ion in the described negative pole half-cell electrolyte and the mol ratio of V (III) ion.
23. method according to claim 21, wherein the described negative pole half-cell electrolyte pumping of described vanadium redox battery group is passed through described negative pole half pond of described electrolytic cell, thereby with the partial reduction of described V (III) ion is V (II) ion, makes the mol ratio of V (V) ion in the described anodal half-cell electrolyte and V (IV) ion approximate V (II) ion in the described negative pole half-cell electrolyte and the mol ratio of V (III) ion.
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CN111446478B (en) * 2020-04-03 2021-05-04 武汉科技大学 Method for preparing vanadium battery electrolyte by taking vanadium-rich liquid as raw material
CN111564643A (en) * 2020-05-09 2020-08-21 承德新新钒钛储能科技有限公司 End plate structure of flow battery
CN111564643B (en) * 2020-05-09 2022-02-22 承德新新钒钛储能科技有限公司 End plate structure of flow battery
WO2023288245A1 (en) * 2021-07-13 2023-01-19 Ess Tech, Inc. Rebalancing cell for redox flow battery system
CN116505049A (en) * 2023-06-27 2023-07-28 杭州德海艾科能源科技有限公司 Integrated battery cell for flow battery and manufacturing method thereof
CN116505049B (en) * 2023-06-27 2023-09-12 杭州德海艾科能源科技有限公司 Integrated battery cell for flow battery and manufacturing method thereof

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