CN111509278A - Method for recovering capacity and efficiency of all-vanadium redox flow battery on line - Google Patents
Method for recovering capacity and efficiency of all-vanadium redox flow battery on line Download PDFInfo
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- H—ELECTRICITY
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- 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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Abstract
The invention relates to the field of all-vanadium redox flow batteries, in particular to a method for recovering the capacity and efficiency of an all-vanadium redox flow battery on line. After long-term circulation, the capacity and efficiency of the all-vanadium redox flow battery are obviously attenuated, the valence state, the concentration and the volume of the electrolyte of the positive and negative electrodes are balanced by mixing the electrolyte, then the valence state of the electrolyte in the battery is detected, and a proper amount of valence state reduction reagent is added into the electrolyte of the positive electrode by calculation, so that the valence state and the volume of the electrolyte of the positive and negative electrodes are matched, and the capacity of the electrolyte is completely recovered; the positive and negative terminals of the battery stack are further exchanged, and the positive and negative electrodes of the battery are exchanged under the condition that the battery stack is not disassembled, so that the number of oxygen-containing functional groups on the surfaces of the positive electrode and the negative electrode is balanced, and further the recovery of the battery efficiency is realized. The invention has simple process, easy operation, low cost and energy efficiency and capacity recovery rate close to 100%.
Description
Technical Field
The invention relates to the field of all-vanadium redox flow batteries, in particular to a method for recovering the capacity and efficiency of an all-vanadium redox flow battery on line.
Background
The use of a large amount of traditional fossil energy brings many problems such as climate warming and environmental pollution, and the vigorous development of renewable energy represented by wind energy and solar energy is an effective way to solve the problems. However, renewable energy has the characteristics of volatility, intermittence and the like, and often causes great impact on a power grid, so that the renewable energy becomes a bottleneck limiting the large-scale application of the renewable energy. The high-power, high-capacity and low-cost energy storage technology matched with the energy storage device is a key technology for promoting the adjustment of an energy structure and popularizing the development of renewable energy.
As a new generation of energy storage technology, the flow battery has good expandability, good safety, long service life and wide development prospect. The vanadium redox flow battery only adopts vanadium (the negative electrode is V)2+And V3+On the positive side, VO2+And VO2 +) As an energy storage medium, the problem of cross contamination among various metal ions does not exist, and the flow battery is the most widely researched flow battery and is the one closest to commercialization.
The most important problem existing in the current all-vanadium flow battery in long-term circulation is the problem of performance attenuation, and the performance attenuation mainly comprises two parts, namely, the attenuation of efficiency and capacity. The performance degradation not only greatly increases the maintenance frequency and cost of the later system, but also directly reduces the service life of the battery. Therefore, it is needed to develop a method capable of recovering efficiency and capacity, however, the existing all-vanadium flow battery capacity recovery method is complex, easy to introduce impurities or needs a noble metal catalyst, high in cost and limited in recovery rate, and there is almost no feasible recovery method for energy efficiency decay.
Disclosure of Invention
The invention aims to provide a method for effectively recovering the capacity and efficiency of an all-vanadium redox flow battery on line at low cost, the method is simple, the operation is easy, the price is low, and the recovery rate of coulomb efficiency and capacity can approach 100%.
In order to achieve the purpose, the invention provides the following technical scheme:
a method for recovering capacity and efficiency of an all-vanadium redox flow battery on line aims at electrolyte of the all-vanadium redox flow battery with unbalanced capacity after long-term circulation, the valence state, the concentration and the volume of the electrolyte of a positive electrode and a negative electrode are balanced by mixing the electrolyte, the valence state of the electrolyte in the battery is detected, and a valence state reduction reagent is added into the electrolyte of the positive electrode through calculation, so that the valence state and the volume of the electrolyte of the positive electrode and the negative electrode are matched, and the capacity of the electrolyte is completely recovered.
The method for recovering the capacity and the efficiency of the all-vanadium redox flow battery on line further comprises the step of exchanging the positive terminal and the negative terminal of the battery without disassembling the battery, so that the number of oxygen-containing functional groups on the surfaces of the positive electrode and the negative electrode is balanced, and the recovery of the battery efficiency is further realized.
In the method for recovering the capacity and the efficiency of the all-vanadium redox flow battery on line, in the long-term circulation process of the all-vanadium redox flow battery, when the capacity is attenuated to a certain specified value, an electrolyte balance valve between a positive liquid storage tank and a negative liquid storage tank is opened, the rapid balance of the volume and the concentration of positive and negative electrolytes is realized, and the electrolyte balance valve is closed.
The method for recovering the capacity and the efficiency of the all-vanadium redox flow battery on line comprises the steps of opening a gas balance valve between an anode liquid storage tank and a cathode liquid storage tank, adding a valence state reduction reagent into electrolyte on the anode side, heating and stirring the electrolyte on the anode side, closing heating and stirring equipment after reaction is finished, and cooling to room temperature to realize normal charging and discharging.
According to the method for recovering the capacity and the efficiency of the all-vanadium redox flow battery on line, in the long-term circulation process of the all-vanadium redox flow battery, when the capacity is attenuated to be below 60-70% of the initial capacity, liquid mixing treatment is carried out, and the valence state, the concentration and the volume of electrolyte rapidly reach an equilibrium state under the driving of magnetic stirring or a magnetic pump.
According to the method for recovering the capacity and the efficiency of the all-vanadium redox flow battery on line, a valence reduction reagent comprises one or more than two of the following components: oxalic acid, tartaric acid, hydrazine, and hydrogen sulfide.
The method for recovering the capacity and the efficiency of the all-vanadium redox flow battery on line is characterized in that the mass of a valence reduction reagent is added, and the method is calculated by the following method: completely charging vanadium ions in the positive electrolyte into vanadium (V) by using a small current, reversely deducing a deviation value x of a vanadium ion valence state in the mixed electrolyte and an initial electrolyte vanadium ion valence state +3.5 through a charging capacity Q, and further calculating the mass m of a valence state reduction reagent required to be added on the positive electrode side; or, leading out part of electrolyte through a pipeline, completely charging vanadium ions in the electrolyte into vanadium (V) by using a bypass battery, reversely pushing a deviation value x of a vanadium ion valence state in the electrolyte and an initial electrolyte vanadium ion valence state +3.5 through the charged capacity Q, and further calculating the mass m of a valence state reduction reagent required to be added on the positive electrode side; or, leading out part of electrolyte sample through a pipeline, measuring the valence state and concentration of vanadium ions by using potentiometric titration or spectral analysis, and further calculating the mass m of the valence-state reduction reagent required to be added on the positive electrode side.
According to the method for recovering the capacity and the efficiency of the all-vanadium redox flow battery on line, a formula for calculating the mass of a valence reduction reagent is as follows:
wherein m is the mass of the valence-state reducing agent, g, Q is the capacity of the battery charged to the saturation state, Ah, ηCEPercent coulombic efficiency at saturation, V is the volume of electrolyte on each side of the cell at initial state, L, CvThe concentration of vanadium ions in the electrolyte in the initial state of the battery is mol/L, M is the molar mass of the valence reduction reagent in g/mol, P is the purity of the valence reduction reagent in wt%, and n is the reagent and VO2 +The number of electron transfers during the reaction was 1 for one electron transfer and 2 for two electrons transfer.
The design idea of the invention is as follows: in the all-vanadium flow battery, due to the difference of transmembrane cross permeation rates of various vanadium ions at the positive electrode side and the negative electrode side, side reactions and the influence of air oxidation, the capacity is reduced continuously along with the increase of the number of cycles. Meanwhile, the anode-side electrode is in an oxidizing environment and the cathode-side electrode is in a reducing environment. This asymmetric environment causes the oxygen-containing functional groups on the carbon electrode surfaces on both sides to increase and decrease, which adversely affects the reaction rate of the vanadium couple, resulting in a decrease in energy efficiency with an increase in the number of cycles. The degradation of capacity and energy efficiency is usually solved by replacing the electrolyte and the electrode, and the maintenance cost of the vanadium battery is greatly increased. Aiming at the problem, the design idea of the invention is to rebalance the electrolyte capacity, the ion concentration and the valence state in the solution under the condition of not replacing the electrolyte and not disassembling the battery, and the number of functional groups on the surface of the carbon electrode at the positive and negative sides is transiently optimized by exchanging the positive and negative leads in one step, so that the all-vanadium redox flow battery is simple, convenient and easy to operate, has low cost, and can greatly prolong the service life of the all-vanadium redox flow battery by recovering the capacity and the energy efficiency.
The invention has the advantages and beneficial effects that:
(1) the method has the greatest beneficial effect that the capacity and the energy efficiency of the all-vanadium redox flow battery after long-term circulation can be recovered on line by approaching 100%.
(2) The electrolyte deviates from the balanced valence state, and the numerical values of the electrolyte capacity and the battery energy efficiency attenuation are all derived from the operation parameters of the battery, so that the quality of the added valence-state reduction reagent can be accurately deduced reversely according to the parameters, and an additional instrument is not needed for carrying out auxiliary test.
(3) The whole valence reduction process is simple and easy to implement, is a pure chemical reaction, and does not need additional catalysts and battery equipment.
(4) The method has the advantages of low consumption of the valence reduction reagent and low cost.
(5) The method directly switches the positive and negative leads of the all-vanadium redox flow battery, namely, the positive and negative electrodes of the galvanic pile are exchanged under the condition of not disassembling the battery, so that the number of oxygen-containing functional groups on the surfaces of the positive electrode and the negative electrode is balanced, and further, the recovery of the battery efficiency is realized.
Drawings
Fig. 1 is a schematic structural diagram of an all-vanadium redox flow battery energy storage system. In the figure: 1. electrolyte balance valve, 2, first magnetic drive pump, 3, second magnetic drive pump, 4, anodal current voltage lead wire, 5, negative pole current voltage lead wire, 6, first gas balance valve, 7, second gas balance valve, 8, first electrolyte heating agitator, 9, second electrolyte heating agitator, 10, anodal liquid storage pot, 11, negative pole liquid storage pot, 12, anodal, 13, negative pole.
Fig. 2 shows the capacity fade and recovery after 100 cycles of the battery of example 1.
Fig. 3 is a comparison of charge and discharge curves before and after 100 cycles of the vanadium redox battery in example 1.
Fig. 4 shows the capacity fade and recovery (electrolyte and electrode matching) after 100 cycles of the vanadium redox battery of example 2.
Fig. 5 shows the charge-discharge curve pair (electrolyte and electrode matched) for the vanadium cell of example 2 after 100 cycles.
Detailed Description
As shown in fig. 1, the energy storage system of the all-vanadium redox flow battery mainly includes: electrolyte balance valve 1, first magnetic drive pump 2, second magnetic drive pump 3, anodal current voltage lead wire 4, negative pole current voltage lead wire 5, first gas balance valve 6, the gaseous balance valve 7 of second, first electrolyte heating agitator 8, second electrolyte heating agitator 9, anodal liquid storage pot 10, negative pole liquid storage pot 11, anodal 12, negative pole 13 etc. specific structure as follows:
the lower parts of the anode liquid storage tank 10 and the cathode liquid storage tank 11 are communicated through a pipeline, and an electrolyte balance valve 1 is arranged on the pipeline; the top of the positive liquid storage tank 10 is connected with a positive electrode 12 through two parallel pipelines (one of the pipelines is provided with a first magnetic pump 2), the top of the negative liquid storage tank 11 is connected with a negative electrode 13 through two parallel pipelines (one of the pipelines is provided with a second magnetic pump 3), an ion exchange membrane is arranged between the positive electrode 12 and the negative electrode 13, a positive electrode current and voltage lead 4 is led out from the positive electrode 12, and a negative electrode current and voltage lead 5 is led out from the negative electrode 13.
A first gas balance valve 6 and a first electrolyte heating stirrer 8 are arranged in the anode liquid storage tank 10, the first gas balance valve 6 is positioned at the upper part, and the first electrolyte heating stirrer 8 is positioned at the lower part; a second gas balance valve 7 and a second electrolyte heating stirrer 9 are arranged in the negative liquid storage tank 11, the second gas balance valve 7 is positioned at the upper part, and the second electrolyte heating stirrer 9 is positioned at the lower part.
In the long-term circulation process of the all-vanadium redox flow battery, when the energy efficiency and the capacity of the battery are lower than certain standards, the first magnetic pump 2 and the second magnetic pump 3 are closed, and the electrolyte balance valve 1 between the anode liquid storage tank 10 and the cathode liquid storage tank 11 is opened. During this process, the volume and concentration of the electrolyte can be allowed to reach equilibrium, and then the electrolyte equilibrium valve 1 is closed.
Further, charging the battery to a saturated state to obtain the battery capacity Q (Ah);
the numerical value x of the mixed electrolyte valence deviating from the equilibrium state by 3.5 can be reversely deduced through the battery capacity Q, and the specific calculation formula is as follows:
wherein Q is the battery charged to saturation Capacity (Ah), ηCEFor the coulombic efficiency (%) at the time of charging to saturation, V is the volume of electrolyte (L) on each side at the initial state of the cell, CvThe concentration (mol/L) of vanadium ions in the electrolyte in the initial state of the battery.
Furthermore, the battery capacity Q required to be consumed by the positive electrode side can be calculated by the numerical value x of the valence state of the electrolyte deviating from the equilibrium state by 3.5consume。
Wherein Q isconsumeThe battery capacity (Ah) required to be consumed by the positive electrode side, x is a numerical value of deviation of the valence state of the mixed electrolyte from the equilibrium state by 3.5, V is the volume (L) of the electrolyte on each side in the initial state of the battery, CvThe concentration (mol/L) of vanadium ions in the electrolyte in the initial state of the battery.
Further, the battery capacity Q required to be consumed by the positive electrode sideconsume(Ah), the mass m (g) of the valence-reducing agent to be added on the positive electrode side can be estimated.
Wherein m is the mass (g) of the valence-state reducing agent, QconsumeBattery capacity (Ah) required to be consumed for the positive electrode side, M is the molar mass (g/mol) of the valence-reduction reagent, P is the reagent purity (wt%), and n is the reagent and VO2 +Number of electron transfers during reaction (e.g. single electron transfer)Shift to 1, two electron transfer to 2).
Combining the above formulas, we can get:
wherein m is the mass (g) of the valence-state reducing agent, Q is the capacity (Ah) of the battery charged to the saturated state, ηCEFor the coulombic efficiency (%) at the time of charging to saturation, V is the volume of electrolyte (L) on each side at the initial state of the cell, CvThe concentration (mol/L) of vanadium ions in the electrolyte in the initial state of the battery, M is the molar mass (g/mol) of the valence reduction reagent, P is the purity (wt%) of the reagent, and n is the mixture of the reagent and VO2 +The number of electron transfers during the reaction (e.g., single electron transfer to 1, two electron transfer to 2).
Further, a valence state reduction reagent with the required mass m is added into the positive liquid storage tank 10, and the first gas balance valve 6 in the positive liquid storage tank 10 is opened.
Further, the first electrolyte heating stirrer 8 was turned on, and the positive electrode side electrolyte temperature was heated to 45 ℃ and stirred.
And after the reaction is finished, closing the first electrolyte heating stirrer 8, cooling to room temperature, and opening the first magnetic pump 2 and the second magnetic pump 3, so that normal charging and discharging can be realized.
In the first scheme, the deviated valence state of the electrolyte is obtained and calculated by charging the battery to the saturated state capacity Q, and the required quality of the valence reduction reagent can be accurately deduced according to the value. Wherein, the valence reduction reagent is one or more than two of oxalic acid, tartaric acid, hydrazine and hydrogen sulfide.
In the second scheme, the electrolyte can be charged to the full charge state (saturation state) through a bypass electrolytic cell without completing the process through the cell itself, the value of the capacity Q of the cell charged to the saturation state is obtained, and the required mass of the valence-reduction reagent added is calculated according to the formulas (1), (2) and (3).
In the third scheme, the valence state of the mixed electrolyte can be measured by a spectrometer or a potentiometric titration method, so that the valence state x of the mixed electrolyte deviating from the equilibrium state can be calculated without charging the battery to the full charge state (saturation state). The mass of the valence-reduction agent to be added to the positive electrode-side electrolyte is estimated from the equations (2) and (3).
Further, the positive voltage current lead 4 and the negative voltage current lead 5 are switched, and the purpose of switching the leads corresponds to exchanging the positive electrode and the negative electrode of the battery without disassembling the battery. According to the latest catalytic research on the anode and cathode of the all-vanadium redox flow battery by the oxygen-containing functional group, the research shows that (Stimming et al. J. Phys. chem. C2016,120, 29,15893-15901, Zenital. adv. Sustainable Syst.2018,2,1700148) VO is generated due to the redox reaction on the anode side2 +/VO2+Is an outer sphere model, the reaction rate of which is mainly determined by the conductivity of the electrode, and the redox reaction V of the negative electrode side3+/V2+The method is an inner sphere model, the adsorption and desorption of the inner sphere model depend on oxygen-containing functional groups on the surface of an electrode, and the reaction rate mainly depends on the number of the oxygen-containing functional groups on the surface. After the all-vanadium redox flow battery is cycled for a long time, the positive electrode is at a higher potential, and the oxygen evolution potential and carbon corrosion increase the accumulation of oxygen-containing functional groups (such as hydroxyl, carboxyl and aldehyde functional groups) on the surface of the carbon fiber, so that the surface conductivity is reduced, and VO is enabled2 +/VO2+The reaction rate decreases. On the negative electrode side, oxygen-containing functional groups (such as hydroxyl, carboxyl and aldehyde functional groups) on the surface of the carbon fiber are gradually reduced due to the factors of hydrogen evolution reaction and the like when the electrode is in a reducing environment with lower potential, so that V is reduced3+/V2+The reaction rate is greatly reduced and thus the energy efficiency of the cell gradually decreases as the number of cycles increases. After the positive and negative electrodes of the battery are exchanged, the original positive electrode with the increased oxygen-containing functional groups is changed into the negative electrode, and V is compared with V before the exchange3+/V2+The reaction rate of (a) can be greatly increased, and the original negative electrode with reduced oxygen-containing functional groups is changed into a positive electrode, VO2 +/VO2+The reaction rate is increased and thus the energy efficiency of the entire battery is recovered.
Through the steps, the capacity, the concentration and the valence of the positive electrode side and the negative electrode side of the electrolyte and the number of functional groups of the positive electrode side and the negative electrode side of the battery are effectively matched, so that the capacity and the energy efficiency of the battery can be recovered.
The present invention will be described in further detail below with reference to examples and the accompanying drawings.
Example 1
In the all-vanadium redox flow battery in the embodiment, the electrolytes on the positive and negative sides are respectively 20m L, and the current density is 100mA/cm2In operation, the energy efficiency and capacity was seen to decay from 90.8% and 474mAh to 88.3% and 343mAh, respectively, after 100 cycles.
1) After the 100 th circle of discharge is finished, opening an electrolyte balance valve between the anode liquid storage tank and the cathode liquid storage tank to enable the volume and the concentration of the electrolyte to be balanced, and closing the electrolyte balance valve.
2) The battery is charged to a saturated state, the capacity of the battery is 653mAh after the battery is charged to the saturated state, and the valence state of the mixed electrolyte is 3.79 and is deviated from the equilibrium valence state by 0.29 according to the numerical value and the formula (1).
3) Further, from the numerical value deviated from the equilibrium valence and the formula (2), it is known that the battery capacity requiring 312 ma consumption on the positive electrode side can match the valence of the electrolyte on the positive and negative electrode sides.
4) From this value and the formula (3), it was deduced that 0.75 g of the valence reducing agent was required to be added to the positive electrode side.
5) After adding the valence-state reducing agent, heating the electrolyte to 45 ℃ and stirring, and performing charge and discharge tests on the treated electrolyte, wherein the energy efficiency and the capacity are respectively 89.1% and 448mAh, and the recovery rates of the energy efficiency and the capacity respectively reach 98% and 94.5%, which is shown in figure 2; as shown in fig. 3, although the charge-discharge curve after recovery and the charge-discharge curve at the initial state of the battery can almost completely recover the capacity, the obvious charge plateau moves up and the obvious discharge plateau moves down, which indicates that the electrode has decayed at this time, resulting in irreversible polarization increase along with the progress of the cycle.
Example 2
In example 2, unlike example 1, the lead terminals of the positive electrode and the negative electrode of the battery are switched in addition to the valence state matching of the electrolyte, and the purpose of switching the lead terminals is equivalent to exchanging the positive electrode and the negative electrode of the battery without disassembling the battery.
1) The energy efficiency and capacity of the same cells decreased to 86.1% and 347mAh after 100 cycles, respectively. Opening an electrolyte balance valve between the anode liquid storage tank and the cathode liquid storage tank to enable the volume and the concentration of the electrolyte to be balanced, then closing the electrolyte balance valve, charging the battery to saturation, enabling the capacity of the obtained battery to be 656mAh when the battery is charged to the saturation state, and deducing that the valence state of the mixed electrolyte is 3.786 and deviates from the equilibrium valence state by 0.286 according to the numerical value and the formula (1).
2) Further, from the numerical value deviated from the equilibrium valence and the formula (2), it is known that the capacity of 306 ma-hour consumed by the positive electrode side is required to match the valence of the electrolyte at the positive and negative electrode sides.
3) From this value and the formula (3), it was deduced that 0.735 g of the valence reducing agent was added to the positive electrode side.
4) After addition of the reducing agent in the valence state, the electrolyte is heated to 45 ℃ and stirred. Then, the positive and negative connecting terminals of the battery are exchanged, and the charge and discharge test is continuously carried out on the processed electrolyte, so that the energy efficiency and the capacity are respectively 90.8% and 473mAh, and the energy efficiency and the capacity recovery rate respectively reach 100% and 99.8%, which is shown in figure 4; as shown in fig. 5, the charge-discharge curve after recovery and the charge-discharge curve in the initial state of the battery are almost completely matched as seen from the charge-discharge curve of the battery, which indicates that the increase in polarization caused by the electrode decay seen in fig. 3 has been solved, and it is seen that the recovery method can achieve an extremely high recovery efficiency.
The embodiment result shows that the capacity and the efficiency of the all-vanadium redox flow battery are obviously attenuated after long-term circulation, the valence state, the concentration and the volume of the electrolyte of the positive and negative electrodes are balanced by mixing the electrolyte, then the valence state of the electrolyte in the battery is detected, and a proper amount of valence state reducing reagent is added into the electrolyte of the positive electrode through calculation, so that the valence state and the volume of the electrolyte of the positive electrode and the negative electrode are matched, and the capacity of the electrolyte is completely recovered; the positive and negative terminals of the battery stack are further exchanged, and the positive and negative electrodes of the battery are exchanged under the condition that the battery stack is not disassembled, so that the number of oxygen-containing functional groups on the surfaces of the positive electrode and the negative electrode is balanced, and further the recovery of the battery efficiency is realized.
Claims (8)
1. The method is characterized in that aiming at the electrolyte of the all-vanadium redox flow battery with unbalanced capacity after long-term circulation, the valence state, the concentration and the volume of the electrolyte in the battery are all balanced by carrying out liquid mixing treatment on the electrolyte of positive and negative electrodes, the valence state of the electrolyte in the battery is detected, and a valence state reduction reagent is added into the electrolyte of the positive electrode through calculation, so that the valence state and the volume of the electrolyte of the positive electrode and the negative electrode are matched, and the capacity of the electrolyte is completely recovered.
2. The method for recovering the capacity and efficiency of the all-vanadium redox flow battery in the online manner of claim 1, further comprising exchanging the positive and negative terminals of the battery without disassembling the battery, so that the number of oxygen-containing functional groups on the surfaces of the positive electrode and the negative electrode is balanced, and further the recovery of the battery efficiency is realized.
3. The method for recovering the capacity and the efficiency of the all-vanadium redox flow battery on line according to claim 1, wherein during the long-term circulation of the all-vanadium redox flow battery, when the capacity is attenuated to a certain specified value, an electrolyte balance valve between a positive electrode liquid storage tank and a negative electrode liquid storage tank is opened, the volume and the concentration of positive and negative electrolytes are rapidly balanced, and the electrolyte balance valve is closed.
4. The method for recovering the capacity and efficiency of the all-vanadium redox flow battery on line according to claim 3, wherein a gas balance valve between the positive liquid storage tank and the negative liquid storage tank is opened, a valence-state reduction reagent is added into the electrolyte on the positive side, the electrolyte on the positive side is heated and stirred, after the reaction is finished, the heating and stirring equipment is closed, and normal charging and discharging are carried out after the temperature is cooled to room temperature.
5. The method for recovering the capacity and the efficiency of the all-vanadium redox flow battery on line according to claim 3, wherein in the long-term circulation process of the all-vanadium redox flow battery, when the capacity is attenuated to be below 60-70% of the initial capacity, liquid mixing treatment is performed, and the valence state, the concentration and the volume of the electrolyte rapidly reach an equilibrium state under the driving of magnetic stirring or a magnetic pump.
6. The method for recovering the capacity and the efficiency of the all-vanadium flow battery on line according to claim 1, wherein the valence-state reduction reagent comprises one or more than two of the following: oxalic acid, tartaric acid, hydrazine, and hydrogen sulfide.
7. The method for recovering the capacity and the efficiency of the all-vanadium redox flow battery on line according to claim 1, wherein the mass of the added valence-state reduction reagent is calculated by the following method: completely charging vanadium ions in the positive electrolyte into vanadium (V) by using a small current, reversely deducing a deviation value x of a vanadium ion valence state in the mixed electrolyte and an initial electrolyte vanadium ion valence state +3.5 through a charging capacity Q, and further calculating the mass m of a valence state reduction reagent required to be added on the positive electrode side; or, leading out part of electrolyte through a pipeline, completely charging vanadium ions in the electrolyte into vanadium (V) by using a bypass battery, reversely pushing a deviation value x of a vanadium ion valence state in the electrolyte and an initial electrolyte vanadium ion valence state +3.5 through the charged capacity Q, and further calculating the mass m of a valence state reduction reagent required to be added on the positive electrode side; or, leading out part of electrolyte sample through a pipeline, measuring the valence state and concentration of vanadium ions by using potentiometric titration or spectral analysis, and further calculating the mass m of the valence-state reduction reagent required to be added on the positive electrode side.
8. The method for recovering the capacity and the efficiency of the all-vanadium redox flow battery on line according to claim 7, wherein the formula for calculating the mass of the valence-state reduction reagent is as follows:
wherein m is the mass of the valence-state reducing agent, g, Q is the capacity of the battery charged to the saturation state, Ah, ηCEPercent coulombic efficiency at saturation, V is the volume of electrolyte on each side of the cell at initial state, L, CvThe concentration of vanadium ions in the electrolyte in the initial state of the battery is mol/L, M is the molar mass of the valence reduction reagent in g/mol, P is the purity of the valence reduction reagent in wt%, and n is the reagent and VO2 +The number of electron transfers during the reaction was 1 for one electron transfer and 2 for two electrons transfer.
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| CN112415077A (en) * | 2020-11-19 | 2021-02-26 | 湖南钒谷新能源技术有限公司 | All-vanadium redox flow battery electrolyte detection method and detection device |
| 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 |
| CN114094148A (en) * | 2022-01-19 | 2022-02-25 | 杭州德海艾科能源科技有限公司 | Online capacity recovery method for all-vanadium redox flow battery |
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