CN111551610A - Vanadium electrolyte concentration testing method, miniature vanadium battery and vanadium electrolyte concentration testing device - Google Patents
Vanadium electrolyte concentration testing method, miniature vanadium battery and vanadium electrolyte concentration testing device Download PDFInfo
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- 229910052720 vanadium Inorganic materials 0.000 title claims abstract description 227
- LEONUFNNVUYDNQ-UHFFFAOYSA-N vanadium atom Chemical compound [V] LEONUFNNVUYDNQ-UHFFFAOYSA-N 0.000 title claims abstract description 221
- 239000003792 electrolyte Substances 0.000 title claims abstract description 124
- 238000012360 testing method Methods 0.000 title claims abstract description 64
- 238000000034 method Methods 0.000 claims abstract description 51
- 229910001456 vanadium ion Inorganic materials 0.000 claims abstract description 29
- 238000007600 charging Methods 0.000 claims description 58
- 239000007772 electrode material Substances 0.000 claims description 34
- 230000008569 process Effects 0.000 claims description 19
- 239000003014 ion exchange membrane Substances 0.000 claims description 15
- 238000007599 discharging Methods 0.000 claims description 12
- 230000001590 oxidative effect Effects 0.000 claims description 8
- 238000004364 calculation method Methods 0.000 claims description 7
- UFHFLCQGNIYNRP-UHFFFAOYSA-N Hydrogen Chemical compound [H][H] UFHFLCQGNIYNRP-UHFFFAOYSA-N 0.000 claims description 4
- 230000008859 change Effects 0.000 claims description 4
- 229910052739 hydrogen Inorganic materials 0.000 claims description 4
- 239000001257 hydrogen Substances 0.000 claims description 4
- 238000007086 side reaction Methods 0.000 claims description 4
- 238000012937 correction Methods 0.000 claims description 3
- 230000005611 electricity Effects 0.000 claims description 3
- 238000004891 communication Methods 0.000 claims 1
- 239000003153 chemical reaction reagent Substances 0.000 abstract description 6
- 239000007788 liquid Substances 0.000 description 6
- 230000003647 oxidation Effects 0.000 description 6
- 238000007254 oxidation reaction Methods 0.000 description 6
- 238000010998 test method Methods 0.000 description 6
- 229910002804 graphite Inorganic materials 0.000 description 5
- 239000010439 graphite Substances 0.000 description 5
- OKTJSMMVPCPJKN-UHFFFAOYSA-N Carbon Chemical compound [C] OKTJSMMVPCPJKN-UHFFFAOYSA-N 0.000 description 4
- 238000012545 processing Methods 0.000 description 4
- 239000002699 waste material Substances 0.000 description 4
- RYGMFSIKBFXOCR-UHFFFAOYSA-N Copper Chemical compound [Cu] RYGMFSIKBFXOCR-UHFFFAOYSA-N 0.000 description 3
- 238000006243 chemical reaction Methods 0.000 description 3
- 229910052802 copper Inorganic materials 0.000 description 3
- 239000010949 copper Substances 0.000 description 3
- 238000001514 detection method Methods 0.000 description 3
- 230000007613 environmental effect Effects 0.000 description 3
- 238000007789 sealing Methods 0.000 description 3
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- 238000003487 electrochemical reaction Methods 0.000 description 2
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- 238000004519 manufacturing process Methods 0.000 description 2
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- 239000002245 particle Substances 0.000 description 2
- 238000002835 absorbance Methods 0.000 description 1
- 238000010521 absorption reaction Methods 0.000 description 1
- 239000004480 active ingredient Substances 0.000 description 1
- 235000013405 beer Nutrition 0.000 description 1
- 238000010277 constant-current charging Methods 0.000 description 1
- 230000007423 decrease Effects 0.000 description 1
- 238000005516 engineering process Methods 0.000 description 1
- 230000002349 favourable effect Effects 0.000 description 1
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- 239000003607 modifier Substances 0.000 description 1
- 230000000149 penetrating effect Effects 0.000 description 1
- 238000003918 potentiometric titration Methods 0.000 description 1
- 238000011084 recovery Methods 0.000 description 1
- 238000002798 spectrophotometry method Methods 0.000 description 1
- 238000004448 titration Methods 0.000 description 1
- 238000000870 ultraviolet spectroscopy Methods 0.000 description 1
- 238000004148 unit process Methods 0.000 description 1
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- G—PHYSICS
- G01—MEASURING; TESTING
- G01N—INVESTIGATING OR ANALYSING MATERIALS BY DETERMINING THEIR CHEMICAL OR PHYSICAL PROPERTIES
- G01N27/00—Investigating or analysing materials by the use of electric, electrochemical, or magnetic means
- G01N27/26—Investigating or analysing materials by the use of electric, electrochemical, or magnetic means by investigating electrochemical variables; by using electrolysis or electrophoresis
- G01N27/28—Electrolytic cell components
- G01N27/30—Electrodes, e.g. test electrodes; Half-cells
- G01N27/333—Ion-selective electrodes or membranes
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- G—PHYSICS
- G01—MEASURING; TESTING
- G01N—INVESTIGATING OR ANALYSING MATERIALS BY DETERMINING THEIR CHEMICAL OR PHYSICAL PROPERTIES
- G01N27/00—Investigating or analysing materials by the use of electric, electrochemical, or magnetic means
- G01N27/26—Investigating or analysing materials by the use of electric, electrochemical, or magnetic means by investigating electrochemical variables; by using electrolysis or electrophoresis
- G01N27/403—Cells and electrode assemblies
- G01N27/413—Concentration cells using liquid electrolytes measuring currents or voltages in voltaic cells
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- H—ELECTRICITY
- H01—ELECTRIC ELEMENTS
- H01M—PROCESSES OR MEANS, e.g. BATTERIES, FOR THE DIRECT CONVERSION OF CHEMICAL ENERGY INTO ELECTRICAL ENERGY
- H01M8/00—Fuel cells; Manufacture thereof
- H01M8/18—Regenerative fuel cells, e.g. redox flow batteries or secondary fuel cells
- H01M8/184—Regeneration by electrochemical means
- H01M8/188—Regeneration by electrochemical means by recharging of redox couples containing fluids; Redox flow type batteries
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- Y—GENERAL TAGGING OF NEW TECHNOLOGICAL DEVELOPMENTS; GENERAL TAGGING OF CROSS-SECTIONAL TECHNOLOGIES SPANNING OVER SEVERAL SECTIONS OF THE IPC; TECHNICAL SUBJECTS COVERED BY FORMER USPC CROSS-REFERENCE ART COLLECTIONS [XRACs] AND DIGESTS
- Y02—TECHNOLOGIES OR APPLICATIONS FOR MITIGATION OR ADAPTATION AGAINST CLIMATE CHANGE
- Y02E—REDUCTION OF GREENHOUSE GAS [GHG] EMISSIONS, RELATED TO ENERGY GENERATION, TRANSMISSION OR DISTRIBUTION
- Y02E60/00—Enabling technologies; Technologies with a potential or indirect contribution to GHG emissions mitigation
- Y02E60/30—Hydrogen technology
- Y02E60/50—Fuel cells
Abstract
The invention discloses a vanadium electrolyte concentration testing method, a vanadium electrolyte concentration testing device and a miniature vanadium battery, wherein the vanadium electrolyte concentration testing method comprises the following steps: step S1: injecting vanadium electrolyte to be detected with the same volume into the anode and the cathode of the miniature vanadium battery respectively; step S2: starting a charge-discharge tester to charge and discharge the miniature vanadium battery to obtain charge-discharge characteristic data of the miniature vanadium battery; step S3: and calculating the concentrations of tetravalent vanadium ions and trivalent vanadium ions according to the charge-discharge characteristic data. According to the vanadium electrolyte concentration testing method provided by the invention, the component concentration in the vanadium electrolyte is obtained by adopting a capacity voltage differential curve method according to the electrochemical characteristics of the vanadium electrolyte. The method is suitable for mixed electrolyte of trivalent vanadium and tetravalent vanadium, and can obtain the total vanadium concentration, the concentration of trivalent vanadium components and the concentration of tetravalent vanadium components. The method has the advantages of no need of assistance of other chemical reagents, simple operation and accurate test result.
Description
Technical Field
The invention belongs to the field of all-vanadium redox flow batteries, and particularly relates to a vanadium electrolyte concentration testing method, a vanadium electrolyte concentration testing device and a miniature vanadium battery.
Background
The total concentration of vanadium ions in the all-vanadium redox flow battery influences the capacity of the electrolyte capable of being stored and converted, and the ratio of the concentrations of the two vanadium ions influences the utilization rate of active ingredients. Therefore, the content and the proportion of the vanadium component in the electrolyte are very important indexes. After the vanadium electrolyte is processed by a production enterprise, the vanadium electrolyte is often directly sent to a project implementation place, and the concentration and the proportion index of vanadium in the electrolyte can not be conveniently subjected to on-site goods receiving inspection in the project implementation place, so that the electrolyte quality is not favorably monitored in time.
The traditional test for the concentration of the electrolyte components adopts a potentiometric titration method, for example, the industry standards NB/T42006-2013 and GB-T37204-2018 relate to the electrolyte test method for the all-vanadium redox flow battery, and the potentiometric titrator test method for the concentrations of the components with different valence states in the vanadium electrolyte is specified. In addition, the vanadium ion concentration can also be measured by an ultraviolet spectrophotometer method. Patent CN102621085A is a method for online detection of vanadium battery electrolyte concentration, disclosing a method for testing different valence state components in vanadium electrolyte by ultraviolet spectrophotometry.
The potentiometric titrator method can obtain an accurate titration result only by means of the potentiometric titrator, has higher requirements on the professional technology of operators, has complex operation steps, needs a large amount of chemical reagents, and needs professional recovery of waste liquid generated by testing.
The Lambert-beer law used in UV spectrophotometry is a limited law, which is only applicable to dilute solutions having a concentration of less than 0.01 mol/L. At high concentrations, the average distance between the light-absorbing particles decreases, and their molar absorption coefficients change due to charge distribution interactions between the particles, resulting in a deviation from beer's law. The concentration range of the electrolyte of the commercial vanadium redox flow battery is 1.5-1.7mol/L-1The electrolyte needs to be diluted to be tested becauseThe ultraviolet spectrophotometer responds more accurately to low concentration, when the concentration is too high, absorbance saturation occurs, and a test result completely deviates from a true value. When the electrolyte is diluted by more than one hundred times, the error of the test result is increased by one hundred times, and the concentration and proportion condition of the electrolyte cannot be truly reflected.
In view of the above, it is an urgent problem in the art to overcome the above-mentioned drawbacks of the prior art.
Disclosure of Invention
In order to overcome the technical problems in the prior art, the invention provides a vanadium electrolyte concentration testing method, a vanadium electrolyte concentration testing device and a miniature vanadium battery.
In order to achieve the purpose of the invention, the first aspect of the invention discloses a method for testing the concentration of a vanadium electrolyte, which is used for obtaining the concentration of components in the vanadium electrolyte by adopting a capacity voltage differential curve method according to the electrochemical characteristics of the vanadium electrolyte. The method is suitable for mixed electrolyte of trivalent vanadium and tetravalent vanadium, and can obtain the total vanadium concentration, the concentration of trivalent vanadium components and the concentration of tetravalent vanadium components. The method has the advantages of no need of assistance of other chemical reagents, simple operation and accurate test result. The method comprises the following steps:
step S1: injecting vanadium electrolyte to be detected with the same volume into the anode and the cathode of the miniature vanadium battery respectively;
step S2: charging and discharging the miniature vanadium battery to obtain the charge and discharge characteristic data of the miniature vanadium battery;
step S3: the concentrations of tetravalent vanadium ions and trivalent vanadium ions were calculated from the charge-discharge characteristic data.
The method is particularly suitable for vanadium electrolyte with vanadium element of trivalent vanadium and/or tetravalent vanadium, has simple operation process, can test only by taking a small amount of vanadium electrolyte sample to be tested, does not need complex operation in the test process, has low professional requirement on operators and is convenient to implement. In addition, the test method does not need other auxiliary chemical reagent solutions, does not generate excessive test waste liquid, and is beneficial to environmental protection while controlling the cost.
Further, step S1 includes filling the electrode materials in the positive electrode cavity and the negative electrode cavity of the miniature vanadium battery with the same volume of vanadium electrolyte to be measured, which specifically includes the following steps:
step S11: opening a first opening positioned at the bottom of the outer side faces of the positive electrode cover and the negative electrode cover and a second opening positioned at the top of the outer side faces of the positive electrode cover and the negative electrode cover;
step S12: injecting vanadium electrolyte to be detected into the electrode material from the first opening;
step S13: and closing the second opening and the first opening in sequence after the electrode material is filled.
When the first opening is used as an inlet of the vanadium electrolyte to be detected, the second opening is used as an air vent. The vanadium electrolyte to be measured is injected from the bottom, the liquid level slowly rises, bubbles are not easy to generate, dead volume is caused, and the measurement result is finally influenced.
Further, in step S2, the miniature vanadium redox battery is charged and discharged, and when the charging and discharging tester charges the miniature vanadium redox battery, the charge cut-off voltage is set to be 1.5-1.8V. Within the voltage range, the detection result has higher accuracy.
Further, in step S2, the micro vanadium battery is charged and discharged by adopting a constant current, and the current density of the constant current is 40-100 mA/cm2. Within the current range, the detection result has higher accuracy.
Further, in step S2, the charge-discharge characteristic data includes an electric quantity Q1 consumed by oxidizing all trivalent vanadium in the vanadium electrolyte to be tested to tetravalent vanadium during the charging process of the micro vanadium battery.
Further, the charge and discharge tester is adopted to charge and discharge the miniature vanadium battery and obtain charge and discharge characteristic data.
Further, in step S2, the electric quantity Q1 is obtained by:
step S21: obtaining a relation curve of charging voltage U and charging capacity Q corresponding to each other in the charging process;
step S22: and (3) solving a first derivative dU/dQ of the charging voltage U relative to the charging capacity Q to obtain a relation curve of the charging capacity Q and the first derivative dU/dQ, wherein the charging capacity Q corresponding to the trend abrupt change point of the relation curve is the electric quantity Q1.
Further, according to the coulomb law, after the vanadium electrolyte to be detected is charged, trivalent vanadium in the vanadium electrolyte to be detected is completely oxidized to electric quantity consumed by quadrivalent vanadium
Q1＝n×F×m (1)
In the formula (1), n is the number of reaction charges, and one charge is transferred in the reaction of oxidizing trivalent vanadium into tetravalent vanadium, so that n is 1; f is Faraday constant, and 96485 C.mol can be taken-1(ii) a m is the amount of trivalent vanadium species participating in the electrochemical reaction in mol.
m＝M(V3)×V (2)
In formula (2), M (V3) is the molar concentration of trivalent vanadium ions, and V is the volume of vanadium electrolyte injected into any electrode cavity.
Combining the formula (1) and the formula (2), the molar concentration M (V3) of the trivalent vanadium ions is obtained by the following calculation formula:
further, after oxidation of trivalent vanadium to tetravalent vanadium, an electrochemical reaction occurs in which tetravalent vanadium is further oxidized to pentavalent. The charging electric quantity value comprises two parts, wherein one part is the electric quantity consumed by oxidizing original tetravalent vanadium in the vanadium electrolyte to be tested to pentavalent vanadium, and the other part is the electric quantity consumed by further oxidizing tetravalent vanadium generated by oxidizing trivalent vanadium to pentavalent vanadium. Since the oxidation of vanadium is a single-electron reaction, theoretically, the electric quantity consumed by the oxidation of trivalent vanadium to tetravalent vanadium is equal to the electric quantity consumed by the further oxidation of trivalent vanadium to pentavalent vanadium, so that the molar concentration M (V4) of original tetravalent vanadium ions in the vanadium electrolyte to be measured is calculated as follows:
in formula (4), Q2 is the amount of electricity consumed by oxidation of all tetravalent vanadium to pentavalent vanadium.
In the formula (5), QSα is a hydrogen evolution side reaction correction coefficient which is an empirical constant and represents the influence of the charging state value and the hydrogen evolution side reaction on the coulombic efficiency, the influence is basically consistent for the same vanadium electrolyte to be measured, and the value range of the influence is 0.9-0.96.
Combining the formula (4) and the formula (5), the calculation formula for further obtaining the mole concentration M (V4) of the original tetravalent vanadium ions in the vanadium electrolyte to be tested is as follows:
further, the calculation formula of the total molar concentration M (VTotal) of vanadium ions in the electrolyte to be detected is as follows:
M(VTotal)＝M(V3)+M(V4) (7)
further, a method for calculating the comprehensive valence state N in the electrolyte to be detected comprises the following steps:
in order to achieve the purpose of the invention, a second aspect of the invention discloses a vanadium electrolyte concentration testing device, which is used for the vanadium electrolyte concentration testing method.
Further, the charge and discharge tester comprises a main control unit, at least one charge and discharge channel and an acquisition unit, wherein the main control unit is respectively connected with the charge and discharge channel and the acquisition unit, the charge and discharge channel is connected with the miniature vanadium battery and can charge and discharge the miniature vanadium battery, the acquisition unit can acquire charge and discharge current and charge and discharge voltage of the miniature vanadium battery in the charge and discharge process, and the main control unit can control the charge and discharge channel to execute a charge and discharge command and obtain charge and discharge characteristic data based on the charge and discharge current and the charge and discharge voltage.
Further, the charging and discharging device further comprises a display unit, the display unit is connected with the main control unit, and the display unit can display charging and discharging characteristic data. The charge/discharge characteristic data may be presented in the form of a specific numerical value or may be presented in the form of a graph.
The invention discloses a micro vanadium battery used for the vanadium electrolyte concentration testing device, the micro vanadium battery comprises a positive electrode cover, a negative electrode cover and an ion exchange membrane, the open side of the positive electrode cover is opposite to and fixedly connected with the open side of the negative electrode cover, the ion exchange membrane is fixedly arranged between the open side of the positive electrode cover and the open side of the negative electrode cover, the ion exchange membrane and the positive electrode cover and the negative electrode cover form a positive electrode cavity and a negative electrode cavity respectively, a conductive current collecting module and an electrode material are fixedly arranged in the positive electrode cavity and the negative electrode cavity, the conductive current collecting module, the electrode material and the ion exchange membrane are sequentially and tightly contacted, and connecting terminals are arranged on the outer side of the positive electrode cover and the outer side of the negative electrode cover and connected with the conductive current collecting module.
The miniature vanadium battery can be loaded with a small amount of vanadium electrolyte samples to be tested, and the concentration of the vanadium electrolyte to be tested can be obtained after the samples are tested. The miniature vanadium redox battery is essentially a vanadium redox battery with a simplified structure, has a much smaller volume than a common vanadium redox battery system, is simple in structure and low in production cost, can be designed into a portable and movable device, can be embedded into an all-vanadium redox flow battery system to work as a subsystem, and has high universality.
Further, the positive electrode cover and the negative electrode cover are cylindrical cover bodies which are mirror-symmetrical, the open side of the positive electrode cover and the open side of the negative electrode cover are both any bottom surface of the cylindrical cover bodies, and the electrode material is a cylinder. The bottom surface of the cylindrical cover body is equivalent to an end plate of a common vanadium battery, the bottom surface and the side surface of the cylindrical cover body can be integrally formed, and the structure of the cylindrical cover body is much simpler than that of the common vanadium battery. The electrode material porous structure is used for bearing the vanadium electrolyte to be measured, the electrode material is designed into a cylinder, when the vanadium electrolyte to be measured is injected into the electrode material, dead volume is not easy to generate, the vanadium electrolyte to be measured is favorable for fully filling the electrode material, and influence on a measuring result is avoided.
Further, the outer side of the positive electrode cover and the outer side of the negative electrode cover are both provided with a first opening and a second opening, the first opening and the second opening are communicated with the electrode material, the first opening and the second opening can be opened or closed, and when any one of the first opening and the second opening is used as the inlet and outlet of the vanadium electrolyte to be tested, the other opening is used as an air vent.
Further, the first openings are respectively arranged at the bottom of the outer side of the positive electrode cover and the bottom of the surface of the outer side of the negative electrode cover, and the second openings are respectively arranged at the top of the outer side of the positive electrode cover and the top of the surface of the outer side of the negative electrode cover.
When the first opening is used as an inlet of the vanadium electrolyte to be detected, the second opening is used as a vent, the vanadium electrolyte to be detected enters from the bottom of the electrode cover, the liquid level slowly moves upwards, and bubbles or dead volume are not easily formed in the electrode cavity; when the first opening is used for the outlet of the vanadium electrolyte to be detected, the second opening is used as an air vent, and the vanadium electrolyte to be detected automatically flows out due to the action of gravity; when the second opening is used for the outlet of the vanadium electrolyte to be tested, the first opening is used as a vent, the miniature vanadium battery is overturned up and down, and the vanadium electrolyte to be tested can be discharged under the action of gravity.
Further, an electrode frame is fixedly arranged in each of the positive electrode cavity and the negative electrode cavity and used for loading electrode materials, a first channel and a second channel are formed in the electrode frame, the first opening is communicated with the electrode materials through the first channel, and the second opening is communicated with the electrode materials through the second channel.
Further, the opening is screwed out or in by a nut to achieve opening or closing.
Compared with the prior art, the technical scheme provided by the invention has the following advantages:
1. the vanadium electrolyte concentration testing device and the testing method provided by the invention are simple to operate, the requirement on the professional skill of a tester in the testing process is low, the implementation is convenient, and the testing result is accurate; 2. the vanadium electrolyte concentration testing device and the testing method provided by the invention have the advantages that other auxiliary chemical reagent solutions and testing waste liquid are not needed in the testing process, the cost is controlled, and meanwhile, the environmental protection is facilitated; 3. the miniature vanadium redox battery and the vanadium electrolyte concentration testing device provided by the invention have simple structures, can realize miniaturization, can be independently designed into a portable mobile device, can also be embedded into an all-vanadium redox flow battery system to be used as a subsystem to work, and have flexible application scenes;
drawings
The accompanying drawings, which are incorporated in and constitute a part of this specification, illustrate embodiments of the apparatus and method consistent with the invention and, together with the detailed description, serve to explain the advantages and principles consistent with the invention. In the drawings:
FIG. 1 is an exploded view of the appearance structure of a miniature vanadium battery provided by an embodiment of the invention;
FIG. 2 is an exploded view of the internal structure of a miniature vanadium battery provided by the embodiment of the invention;
FIG. 3 is a schematic view of a vanadium electrolyte concentration testing apparatus according to an embodiment of the present invention;
FIG. 4 is a first-turn charging curve diagram of a vanadium electrolyte sample 1 to be tested in the embodiment of the invention;
FIG. 5 is a graph obtained by performing first-order derivative data processing on a first-turn charging curve of a vanadium electrolyte sample 1 to be measured in the embodiment of the invention;
FIG. 6 is a first-turn charging curve diagram of a vanadium electrolyte sample to be tested in an embodiment of the invention;
fig. 7 is a graph obtained by performing first derivative data processing on the first-turn charging curve of the vanadium electrolyte sample 2 to be measured in the embodiment of the invention.
Description of the reference numerals
1-a first opening, 2-a second opening, 3-a wiring terminal, 4-an ion exchange membrane, 5-an electrode frame, 6-an electrode material, 7-a conductive plastic plate, 8-graphite paper, 9-a copper plate, 10-a positive electrode cover and 11-a negative electrode cover.
Detailed Description
Specific embodiments of the present invention will be described in detail below with reference to the accompanying drawings. However, the present invention is not limited to the embodiments described below. In addition, the technical features involved in the embodiments of the present invention described below may be combined with each other as long as they do not conflict with each other, and the technical idea of the present invention may be implemented in combination with other known techniques or other techniques identical to those known techniques.
Examples
The embodiment of the invention provides a vanadium electrolyte concentration testing method, a vanadium electrolyte concentration testing device and a miniature vanadium battery.
As shown in fig. 1 and fig. 2, the miniature vanadium battery used in the vanadium electrolyte concentration testing device provided by this embodiment includes a positive electrode cover 10, a negative electrode cover 11, and an ion exchange membrane 4, the open sides of the positive electrode cover 10 and the negative electrode cover 11 are opposite and fixedly connected, the ion exchange membrane 4 is fixedly disposed between the open sides of the positive electrode cover 10 and the negative electrode cover 11, the ion exchange membrane 4 forms a positive electrode cavity and a negative electrode cavity with the positive electrode cover 10 and the negative electrode cover 11 respectively, the positive electrode cavity and the negative electrode cavity are both fixedly provided with a conductive current collecting module and an electrode material 6, the conductive current collecting module, the electrode material 6, and the ion exchange membrane 4 are in close contact in sequence, the outer sides of the positive electrode cover 10 and the negative electrode cover 11 are both provided with a connection.
The positive electrode cover 10 and the negative electrode cover 11 are cylindrical cover bodies which are mirror-symmetrical, the open sides of the positive electrode cover 10 and the negative electrode cover 11 are both any bottom surface of the cylindrical cover bodies, the corresponding electrode cavities are also cylinders, and the motor materials fixedly arranged in the electrode cavities are also cylinders. In other embodiments, the outside of the electrode housing may be of other shapes, for example a cuboid, while the electrode cavity and the electrode material 6 are still designed as cylinders.
The connecting terminal 3 is arranged on the axis of the bottom surface of the cylindrical cover body, penetrates through the electrode cover and is connected with the conductive current collecting module, and the part penetrating through the electrode cover is sealed with the electrode cover. In other embodiments, the terminal 3 can also be arranged on the side of the cylindrical housing.
The outer sides of the positive electrode cover 10 and the negative electrode cover 11 are respectively provided with a first opening 1 and a second opening 2, the first opening 1 and the second opening 2 are communicated with the electrode material 6, the first opening 1 and the second opening 2 can be opened or closed, and when any one opening of the first opening 1 and the second opening 2 is used as an inlet and an outlet of the vanadium electrolyte to be detected, the other opening is used as an air vent.
The first opening 1 is arranged at the bottom of the outer side of the positive electrode cover 10 and the negative electrode cover 11, and the second opening 2 is arranged at the top of the outer side of the positive electrode cover 10 and the negative electrode cover 11.
Further, an electrode frame 5 is fixedly arranged in each of the positive electrode cavity and the negative electrode cavity, the electrode frame 5 is used for loading electrode materials 6, a first channel and a second channel are formed in the electrode frame 5, the first opening 1 is communicated with the electrode materials 6 through the first channel, and the second opening 2 is communicated with the electrode materials 6 through the second channel.
The opening is screwed out or in by a nut to achieve opening or closing.
The inner sides of the first opening 1 and the second opening 2 and the inner sides of the first channel and the second channel are provided with threads matched with nuts.
When the first opening 1 and the second opening 2 are in a closed state, namely the nut is in a screwed state, the end surface of the nut is flush with the inner side surface of the electrode frame 5, and the end surface and the inner side surface of the electrode frame jointly form the side surface of a complete cylinder, so that the space of the cylinder can be just filled with the electrode material 6.
A first sealing gasket is arranged on the annular contact surface of the electrode frame 5 and the conductive current collecting module, and a second sealing gasket is arranged on the annular contact surface of the electrode frame 5 and the ion exchange membrane 4. The function of the sealing gasket is to prevent the electrolyte carried by the electrode material 6 from flowing into other areas.
The ion exchange membrane 4 is clamped and fixed by an electrode frame 5.
The conductive current collecting module comprises a copper plate 9, a conductive plastic plate 7 and graphite paper 8 which are in close contact in sequence, wherein the graphite paper 8 is in close contact with the electrode material 6. The purpose of the graphite paper 8 is to reduce the contact resistance between the conductive plastic plate 7 and the copper current collector. In other embodiments, the conductive current collecting module is a conductive graphite plate.
The two electrode covers are clamped and fixed through the hoop. The two electrode covers are fixedly connected in various ways, and in other embodiments, the two end points of the outer side of the electrode cover in the radial direction can be provided with snap connections.
As shown in fig. 3, the vanadium electrolyte concentration testing apparatus provided in this example is used in the vanadium electrolyte concentration testing method provided in this example, and includes a charge and discharge tester and the above-mentioned miniature vanadium battery, where the charge and discharge tester is connected to the miniature vanadium battery, and the charge and discharge tester is used to charge and discharge the miniature vanadium battery and obtain charge and discharge characteristic data of the miniature vanadium battery.
The charge and discharge tester comprises a main control unit, at least one charge and discharge channel and an acquisition unit, wherein each charge and discharge channel can be connected with a miniature vanadium battery so as to realize the simultaneous test of multiple samples. The main control unit is respectively connected with the charge and discharge channel and the acquisition unit, the charge and discharge channel is connected with the miniature vanadium battery and can charge and discharge the miniature vanadium battery, the acquisition unit can acquire charge and discharge current and charge and discharge voltage of the miniature vanadium battery in the charge and discharge process, and the main control unit can control the charge and discharge channel to execute a charge and discharge command and obtain charge and discharge characteristic data based on the charge and discharge current and the charge and discharge voltage.
The charging and discharging characteristic data display device further comprises a display unit, the display unit is connected with the main control unit, and the display unit can display the charging and discharging characteristic data. The charge/discharge characteristic data may be presented in the form of a specific numerical value or may be presented in the form of a graph.
The miniature vanadium battery and vanadium electrolyte concentration testing device is simple in structure, can realize miniaturization, can be independently designed into a portable mobile device, can also be embedded into an all-vanadium redox flow battery system to work as a subsystem, and is flexible in application scene.
The method for testing the concentration of the vanadium electrolyte provided by the embodiment is suitable for the vanadium electrolyte of which vanadium element is trivalent vanadium and/or tetravalent vanadium, and comprises the following steps:
step S1: injecting vanadium electrolyte to be detected with the same volume into the anode and the cathode of the miniature vanadium battery respectively;
step S2: starting a charge and discharge tester to carry out constant current charging on the miniature vanadium battery, setting the charge cut-off voltage to be 1.5-1.8V, preferably 1.7V, and setting the current density of constant current to be 40-100 mA/cm2Preferably 80mA/cm2Obtaining miniature vanadium batteryThe charge and discharge characteristic data comprises the electric quantity Q1 consumed by oxidizing all trivalent vanadium in the vanadium electrolyte to be tested to tetravalent vanadium in the process of charging the miniature vanadium battery by the charge and discharge tester;
step S3: the concentrations of tetravalent vanadium ions and trivalent vanadium ions were calculated from the charge-discharge characteristic data.
Specifically, step S1 includes the steps of:
step S11: opening a first opening 1 positioned at the bottom of the outer side surfaces of the positive electrode cover 10 and the negative electrode cover 11 and a second opening 2 positioned at the top of the outer side surfaces of the positive electrode cover 10 and the negative electrode cover 11;
step S12: injecting vanadium electrolyte to be detected into the electrode material 6 from the first opening 1 by using an injector;
step S13: and after the electrode material 6 is filled, closing the second opening 2 and the first opening 1 in sequence, and connecting the miniature vanadium battery into a charge and discharge channel.
In step S2, a charging current value and a charging cut-off voltage are set in the main control unit, a charging/discharging command and related parameters are sent to the charging/discharging channel by the main control unit to charge the accessed miniature vanadium battery, the acquisition unit acquires charging/discharging raw data of the miniature vanadium battery in real time, including charging current, charging voltage, charging time and the like, and transmits the charging raw data to the main control unit, and the main control unit processes the charging/discharging raw data based on a built-in program to obtain charging/discharging characteristic data electric quantity Q1.
Specifically, the electric quantity Q1 is obtained by:
step S21: obtaining a relation curve of charging voltage U and charging capacity Q corresponding to each other in the charging process;
step S22: and (3) solving a first derivative dU/dQ of the charging voltage U relative to the charging capacity Q to obtain a relation curve of the charging capacity Q and the first derivative dU/dQ, and displaying the relation curve by a display unit, wherein the charging capacity Q corresponding to the trend abrupt change point of the relation curve is the electric quantity Q1.
Based on the coulomb law, after the vanadium electrolyte to be detected is charged, the molar concentration M (V3) of trivalent vanadium ions is calculated according to the charge-discharge characteristic data, and the calculation formula is as follows:
wherein F is Faraday constant, and 96485 C.mol is taken-1(ii) a V is the volume of vanadium electrolyte injected into any electrode cavity.
The calculation formula of the mole concentration M (V4) of the original tetravalent vanadium ions in the vanadium electrolyte to be tested is as follows:
wherein Q2 is the amount of electricity consumed by oxidation of all tetravalent vanadium to pentavalent vanadium; q is the total electric quantity in the charging process and is obtained by calculating the charging current and the charging time; alpha is a hydrogen evolution side reaction correction coefficient.
The calculation formula of the total molar concentration M (VTotal) of vanadium ions in the electrolyte to be detected is as follows:
M(VTotal)＝M(V3)+M(V4)
the method for calculating the comprehensive valence state N in the electrolyte to be measured comprises the following steps:
based on the method, the concentration of the vanadium electrolyte sample 1 to be tested is tested, and the first circle charging curve is obtained and is shown in fig. 4. The first derivative data processing is performed on the charging curve of fig. 4 to obtain the curve shown in fig. 5.
As can be seen from FIG. 4, QS2.3144 mAh; as can be seen from fig. 5, Q1 is 0.7842 mAh; v ═ 0.04L (sample 1 volume).
Molar concentration M (V3) of trivalent vanadium ions in the electrolyte sample 1 to be tested:
M(V3)＝(0.7842*3600)/(96475*0.04)＝0.73moL/L
molar concentration M of tetravalent vanadium ions in electrolyte sample 1 to be tested (V4):
M(V4)＝[(2.3144-0.7842*2)*3600]/(96475*0.04*0.9025)
＝0.74moL/L
total molar concentration m (vtotal) of vanadium ions in the electrolyte sample 1 to be tested:
M(VTotal)＝M(V3)+M(V4)＝0.73+0.74＝1.47moL/L
comprehensive valence state N in the electrolyte sample to be tested 1:
N＝[M(V3)*3+M(V4)*4]＝(0.73*3+0.74*4)/1.47＝3.50
the method GB-T37204-2018 is adopted for testing, the total vanadium concentration is 1.51moL/L, and the comprehensive valence is 3.51.
Based on the method, the concentration of the vanadium electrolyte sample 2 to be tested is tested, and the first circle charging curve is obtained and is shown in fig. 6. The first derivative data processing is performed on the charging curve of fig. 6 to obtain the curve shown in fig. 7.
As can be seen from FIG. 6, QS2.64 mAh; as can be seen from fig. 5, Q1 is 0.89 mAh; v ═ 0.04L (sample 2 volume).
Molar concentration M (V3) of trivalent vanadium ions in the electrolyte sample 2 to be tested:
M(V3)＝(0.89*3600)/(96475*0.04)＝0.83moL/L
molar concentration M of tetravalent vanadium ions in electrolyte sample 2 to be tested (V4):
M(V4)＝[(2.64-0.89*2)*3600]/(96475*0.04*0.94)＝0.85moL/L
total molar concentration m (vtotal) of vanadium ions in the electrolyte sample 2 to be measured:
M(VTotal)＝M(V3)+M(V4)＝0.83+0.85＝1.68moL/L
comprehensive valence state N in the electrolyte sample 2 to be tested:
N＝[M(V3)*3+M(V4)*4]＝(0.83*3+0.89*4)/1.68＝3.505
the method GB-T37204-2018 is adopted for testing, the total vanadium concentration is 1.71moL/L, and the comprehensive valence is 3.51.
The test method is simple to operate, the requirement of the test process on the professional skills of testers is low, the test method is convenient to implement, the test result is accurate, other auxiliary chemical reagent solutions and test waste liquid are not needed in the related test process, and the test method is beneficial to environmental protection while controlling the cost.
The terms "first" and "second" as used herein do not denote any order, quantity, or importance, but rather are used to distinguish one element from another, unless otherwise specified. Similarly, modifiers similar to "about", "approximately" or "approximately" that occur before a numerical term herein typically include the same number, and their specific meaning should be read in conjunction with the context. Similarly, unless a specific number of a claim recitation is intended to cover both the singular and the plural, and also that claim may include both the singular and the plural.
In the description of the specific embodiments above, the use of the directional terms "upper", "lower", "left", "right", "top", "bottom", "vertical", "transverse", and "lateral", etc., are for convenience of description only and should not be considered limiting.
While specific embodiments of the invention have been described above, it will be appreciated by those skilled in the art that these are by way of example only, and that the scope of the invention is defined by the appended claims. Various changes and modifications to these embodiments may be made by those skilled in the art without departing from the spirit and scope of the invention, and these changes and modifications are within the scope of the invention.
Claims (16)
1. The method for testing the concentration of the vanadium electrolyte is characterized by comprising the following steps of:
step S1: injecting vanadium electrolyte to be detected with the same volume into the anode and the cathode of the miniature vanadium battery respectively;
step S2: starting a charge-discharge tester to charge and discharge the miniature vanadium battery to obtain charge-discharge characteristic data of the miniature vanadium battery;
step S3: and calculating the concentrations of tetravalent vanadium ions and trivalent vanadium ions according to the charge-discharge characteristic data.
2. The method for testing the concentration of the vanadium redox electrolyte according to claim 1, wherein in the step S2, when the charge/discharge tester charges the micro vanadium redox battery, the charge cut-off voltage is set to be 1.5-1.8V.
3. The method for testing the concentration of the vanadium electrolyte according to claim 1, wherein in the step S2, the charge and discharge tester charges and discharges the miniature vanadium battery by using a constant current, and the current density of the constant current is 40-100 mA/cm2。
4. The method for testing the concentration of the vanadium electrolyte according to claim 1, wherein in the step S2, the charge-discharge characteristic data includes an electric quantity Q1 consumed by the charge-discharge tester to oxidize all trivalent vanadium in the vanadium electrolyte to be tested to tetravalent vanadium during the process of charging the micro vanadium battery.
5. The method for testing the concentration of vanadium electrolyte according to claim 4, wherein in the step S2, the quantity of electricity Q1 is obtained by:
step S21: obtaining a relation curve of charging voltage U and charging capacity Q corresponding to each other in the charging process;
step S22: and solving a first derivative dU/dQ of the charging voltage U relative to the charging capacity Q to obtain a relation curve of the charging capacity Q and the first derivative dU/dQ, wherein the charging capacity Q corresponding to the trend abrupt change point of the relation curve is the electric quantity Q1.
6. The method for testing the concentration of the vanadium electrolyte according to claim 4, wherein the molar concentration of the trivalent vanadium ions is calculated by the formula:
wherein M (V3) is the molar concentration of trivalent vanadium ions; q1 is the electric quantity consumed by oxidizing all trivalent vanadium in the vanadium electrolyte to be tested to tetravalent vanadium in the charging process; v is the volume of the vanadium electrolyte injected into any electrode cavity; f is the Faraday constant.
7. The method for testing the concentration of a vanadium electrolyte according to claim 4,
the mole concentration calculation formula of the tetravalent vanadium ions is as follows:
wherein M (V4) is the molar concentration of tetravalent vanadium ions; qSThe total electric quantity in the charging process, Q1 the electric quantity consumed by oxidizing all trivalent vanadium in the vanadium electrolyte to be tested to quadrivalent vanadium in the charging process, V the volume of the vanadium electrolyte injected into any electrode cavity, F the Faraday constant, and α the correction coefficient of hydrogen evolution side reaction.
8. A vanadium electrolyte concentration testing device, characterized in that the vanadium electrolyte concentration testing device is used for the vanadium electrolyte concentration testing method according to any one of claims 1 to 6,
the vanadium electrolyte concentration testing device comprises a charge and discharge tester and a miniature vanadium battery connected with the charge and discharge tester, wherein the charge and discharge tester is used for charging and discharging the miniature vanadium battery and obtaining charge and discharge characteristic data of the miniature vanadium battery.
9. The vanadium electrolyte concentration testing device according to claim 8, wherein the charge and discharge tester comprises a main control unit, at least one charge and discharge channel and an acquisition unit, the main control unit is respectively connected with the charge and discharge channel and the acquisition unit, the charge and discharge channel is connected with the miniature vanadium battery and can charge and discharge the miniature vanadium battery, the acquisition unit is used for acquiring charge and discharge currents and charge and discharge voltages of the miniature vanadium battery in a charge and discharge process, and the main control unit is used for controlling the charge and discharge channel to execute charge and discharge commands and obtaining the charge and discharge characteristic data based on the charge and discharge currents and the charge and discharge voltages.
10. The vanadium electrolyte concentration testing device according to claim 8, further comprising a display unit, wherein the display unit is connected with the main control unit, and the display unit is used for displaying the charge and discharge characteristic data.
11. A miniature vanadium battery, which is used for the vanadium electrolyte concentration testing device according to any one of claims 8 to 10,
the miniature vanadium battery comprises a positive electrode cover, a negative electrode cover and an ion exchange membrane;
the open side of the positive electrode cover and the open side of the negative electrode cover are opposite and fixedly connected, the ion exchange membrane is fixedly arranged between the open side of the positive electrode cover and the open side of the negative electrode cover, and the ion exchange membrane and the positive electrode cover and the negative electrode cover form a positive electrode cavity and a negative electrode cavity respectively;
the conductive current collecting module and the electrode material are fixedly arranged in the positive electrode cavity and the negative electrode cavity, the conductive current collecting module, the electrode material and the ion exchange membrane are sequentially in close contact, and the connecting terminals are arranged on the outer sides of the positive electrode cover and the negative electrode cover and connected with the conductive current collecting module.
12. The vanadium micro-battery of claim 11, wherein the positive electrode cap and the negative electrode cap are mirror-symmetric cylindrical cap bodies, the open side of the positive electrode cap and the open side of the negative electrode cap are both any bottom surface of the cylindrical cap bodies, and the electrode material is a cylinder.
13. The miniature vanadium battery according to claim 11, wherein both the outside of the positive electrode can and the outside of the negative electrode can are provided with a first opening and a second opening, the first opening and the second opening are in communication with the electrode material, and the first opening and the second opening can be opened or closed;
and when any one of the first opening and the second opening is used as an inlet and an outlet of the vanadium electrolyte to be tested, the other opening is used as an air vent.
14. The vanadium micro battery according to claim 13, wherein the first openings are respectively disposed at a bottom of an outer side of the positive electrode can and a bottom of an outer side of the negative electrode can, and the second openings are respectively disposed at a top of an outer side of the positive electrode can and a top of an outer side of the negative electrode can.
15. The miniature vanadium battery according to claim 13, wherein an electrode frame is fixedly arranged in each of the positive electrode cavity and the negative electrode cavity, the electrode frame is used for loading electrode materials, the electrode frame is provided with a first channel and a second channel, the first opening is communicated with the electrode materials through the first channel, and the second opening is communicated with the electrode materials through the second channel.
16. The miniature vanadium battery according to claim 13, wherein the first opening and the second opening are unscrewed and screwed in by nuts to open and close, respectively.
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| CN113820610A (en) * | 2021-09-21 | 2021-12-21 | 湖南钒谷新能源技术有限公司 | Method and system for detecting health state of all-vanadium redox flow battery after mixing |
| CN115616050A (en) * | 2022-12-02 | 2023-01-17 | 杭州德海艾科能源科技有限公司 | Preparation method and application of vanadium battery electrolyte ion concentration sensor material |
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