CN110857911A - Method for testing electrolyte balance degree of portable all-vanadium redox flow battery - Google Patents
Method for testing electrolyte balance degree of portable all-vanadium redox flow battery Download PDFInfo
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- G—PHYSICS
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- G01N—INVESTIGATING OR ANALYSING MATERIALS BY DETERMINING THEIR CHEMICAL OR PHYSICAL PROPERTIES
- G01N21/00—Investigating or analysing materials by the use of optical means, i.e. using sub-millimetre waves, infrared, visible or ultraviolet light
- G01N21/17—Systems in which incident light is modified in accordance with the properties of the material investigated
- G01N21/25—Colour; Spectral properties, i.e. comparison of effect of material on the light at two or more different wavelengths or wavelength bands
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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
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- G01N27/42—Measuring deposition or liberation of materials from an electrolyte; Coulometry, i.e. measuring coulomb-equivalent of material in an electrolyte
Abstract
The invention discloses a method for testing electrolyte balance degree of a portable all-vanadium redox flow battery. The method comprises the following steps: step 1: drawing an absorbance-concentration standard working curve; step 2: respectively and simultaneously sampling the positive electrolyte and the negative electrolyte, mixing the positive electrolyte and the negative electrolyte in equal volume, and obtaining a mixed solution A after the oxidation-reduction reaction is finished; and step 3: obtaining the concentration C of trivalent vanadium ions in the mixed solution A by adopting a portable ultraviolet-visible spectrophotometerV 3+(ii) a And 4, step 4: adding a reducing agent into the mixed solution A to obtain a mixed solution B, and obtaining the maximum concentration C of trivalent vanadium ions in the mixed solution B within the testing time by adopting a portable ultraviolet-visible spectrophotometermThe concentration of tetravalent vanadium ions in the mixed solution A is CVO 2+，CVO 2+＝Cm‑CV 3+(ii) a And 5: calculating the degree of unbalance K, K ═ C of the whole electrolyteVO 2+‑CV 3+)/(CVO 2++CV 3+). The method is convenient, simple and rapid to operate, convenient to carry, accurate in detection and suitable for field detection of the actual running place of the flow battery.
Description
Technical Field
The invention relates to a portable all-vanadium redox flow battery electrolyte balance testing method, in particular to a method for detecting by using a portable device so as to obtain electrolyte balance data, and belongs to the technical field of redox flow battery electrolyte detection.
Background
In order to realize sustainable development and improve energy environment, human beings begin to utilize new energy such as wind energy and solar energy on a large scale, however, due to instability of new energy power generation, the impact on a power grid is large during grid connection. Therefore, a large-scale energy storage system capable of smoothing power fluctuation and maintaining power balance is developed, wherein the all-vanadium redox flow battery has the advantages of high efficiency, long service life, large capacity, deep charging and discharging and the like, and is one of the main existing large-scale energy storage devices.
The vanadium redox flow battery adopts V (II)/V (III) and V (IV)/V (V) as redox couples to complete the interconversion of vanadium ions with different valence states and the storage and release of electric energy in the charging/discharging process. In order to ensure the maximum capacity of the all-vanadium redox flow battery, the positive and negative electrolytes need to maintain a balanced state, that is, the amounts of vanadium ions in the positive and negative electrolytes for oxidation reaction and reduction reaction are the same, for example, when the charge capacity (SOC) of the battery system is 0, VO in the positive electrolyte is present2+And V in the negative electrode electrolyte3+The amount needs to be consistent or close, VO in the positive electrolyte when the battery system charge (SOC) is 100%2 +And V in the negative electrode electrolyte2+The number needs to be uniform or close. Under an ideal condition, the charge states of positive and negative electrolytes of the all-vanadium redox flow battery are consistent, but due to transmembrane migration of vanadium ions and water molecules, hydrogen evolution reaction and oxidation reaction of the negative electrolyte and the like, the charge states of the positive and negative electrolytes are inconsistent in long-term operation. If the proportion of vanadium ions in the positive electrolyte and the negative electrolyte is out of balance, the electric capacity of the battery system is reduced, so that the stored energy of the battery is reduced, more importantly, the unbalanced electrolyte inevitably causes other side reactions, such as generation of harmful gases, corrosion of electrodes and the like, and finally the whole battery system is possibly scrapped. Therefore, the balance state of the positive electrolyte and the negative electrolyte of the all-vanadium redox flow battery can be monitored in real timeThe method provides a guiding function for the maintenance and management work of the electrolyte of the vanadium galvanic pile running for a long time, and ensures the safe and stable running of the galvanic pile.
At present, electrolyte balance test methods of all-vanadium redox flow batteries are mainly divided into two types: (1) respectively measuring the relative potentials of positive and negative electrolytes, namely OCV values, by using a standard electrode; obtaining SOC values corresponding to the positive electrolyte and the negative electrolyte according to the SOC-OCV curves of the positive electrolyte and the negative electrolyte respectively; by comparing the SOC values of the two, equilibrium data of the whole electrolyte can be obtained [ cited documents 1-2](ii) a (2) Drawing a standard working curve of absorbance-vanadium ion concentration; respectively carrying out spectrum scanning on the diluted positive and negative electrolytes by utilizing an ultraviolet visible spectrophotometer to obtain V3+And VO2+The absorbance of the characteristic absorption peak is matched with a standard working curve to obtain V3+And VO2+The concentration of (c); according to V3+And VO2+The concentration calculation of (2) to obtain equilibrium data of the whole electrolyte solution [ cited document 3]. Both the two technologies can rapidly and accurately measure the balance data of the electrolyte, but both the technologies need to utilize perfect laboratory equipment to test in a laboratory environment.
However, for all-vanadium redox flow battery systems constructed for matching with electric energy storage of photovoltaic power generation and wind power generation, because actual operation sites of the all-vanadium redox flow battery systems are generally in remote areas, necessary experimental test equipment is probably lacked around the all-vanadium redox flow battery systems, and the two test methods are often not practical to operate.
It can be seen that, although some research has been conducted on monitoring the balance problem of the positive and negative electrolytes of the all-vanadium redox flow battery in the prior art, the research on the convenience of the detection method or the portability of the detection device is not sufficient.
Cited document 1: CN 104345278A
Cited document 2: CN 107422267A
Cited document 3: CN 102621085A
Disclosure of Invention
Problems to be solved by the invention
In the process, a certain time is actually consumed from sampling to detection, and the condition of the continuously-operated flow battery actually changes in the period. After the detection result is obtained, the conclusion that the flow battery is different from the actual condition of the flow battery at the moment is often obtained. Further, the evaluation or intervention of the operating condition of the flow battery according to the data of the laboratory test often misses the optimal time window, and may also result in that although the manpower and material resources are consumed, the improvement of the actual condition of the flow battery operation is still insufficient. Thus, the timeliness, accuracy and convenience of current tests are inadequate.
The invention provides a portable electrolyte balance testing method for an all-vanadium redox flow battery, and a detection device and medicines involved in the method are convenient to carry, so that the method is suitable for being carried out in the actual operation place of the redox flow battery, and the obtained result can timely and accurately feed back the real condition of the redox flow battery in operation.
Means for solving the problems
The invention solves the technical problems by adopting the following technical scheme:
the invention firstly provides a method for testing the balance of electrolyte of an all-vanadium redox flow battery, which comprises the following steps:
step 1: preparing a series of trivalent vanadium ion standard solutions with known concentrations (in a laboratory environment), and obtaining an absorbance-concentration standard working curve by adopting an ultraviolet-visible spectrophotometry, wherein the curve can be used as a standard curve in future detection and used for calculating the concentration of the trivalent vanadium ions and the total balance degree of the electrolyte;
step 2: respectively and simultaneously sampling the positive electrolyte and the negative electrolyte, mixing the positive electrolyte and the negative electrolyte in equal volume, and obtaining a mixed solution A after the oxidation-reduction reaction is finished;
and step 3: adopting a portable ultraviolet-visible spectrophotometer to carry out wavelength scanning on the mixed solution A, and matching with the standard working curve in the step 1 to obtain the concentration C of trivalent vanadium ions in the mixed solution AV 3+；
And 4, step 4: adding a reducing agent into the mixed solution A to obtain a mixed solution B, wherein the amount of the reducing agent is enough to reduce all tetravalent vanadium ions in the mixed solution B, and after the reducing agent is added, the reducing agent reduces all tetravalent vanadium ions in the mixed solution B into trivalent vanadium ions. The electrolyte obtained finally is V3+/V2+The solution was mixed.
Taking the moment when the reducing agent begins to be added as a starting point, scanning the wavelength of the mixed solution B by using a portable ultraviolet-visible spectrophotometer at intervals of unit time, and matching with the standard working curve in the step 1 to obtain the maximum concentration C of trivalent vanadium ions in the mixed solution B in the testing timemThe concentration of tetravalent vanadium ions in the mixed solution A is CVO 2+，CVO 2+＝Cm-CV 3+；
And 5: calculating the degree of unbalance K, K ═ C of the whole electrolyteVO 2+-CV 3+)/(CVO 2++CV 3+)。
According to the method described above, in step 2, sampling is performed at any state of charge SOC, preferably at a state of charge SOC of 0.
According to the method, in the step 2, the mixed solution A is a mixed solution of trivalent vanadium ions and tetravalent vanadium ions.
According to the method, in the step 3, the operating wavelength of the portable ultraviolet-visible spectrophotometer is 350-500 nm.
The method according to the above, the method further comprising: diluting the mixed solution A between the step 2 and the step 3.
According to the above method, in the step 4, the reducing agent is a metal reducing agent, preferably metallic zinc.
According to the method described above, in step 4, the unit time is 30s to 90s, preferably 40s to 70 s.
Invention ofEffect
The method for testing the balance of the electrolyte of the all-vanadium redox flow battery has the following excellent effects:
(1) the test method provided by the invention is simple to operate, is rapid and convenient, can realize the test of the electrolyte balance data of the all-vanadium redox flow battery under the condition of lacking complete laboratory conditions, and has the advantages of field property, timeliness and accuracy.
(2) The used detection device and the medicine are convenient to carry, and the on-site detection can be conveniently carried out at any time under the non-laboratory condition.
(3) The detection method provided by the invention is beneficial to accurately detecting the running condition of the flow battery for a long time, and can shorten the processing time when the electrolyte of the flow battery is unbalanced, so that the countermeasures are more targeted.
Detailed Description
Hereinafter, a mode for carrying out the present invention will be described in detail.
The invention provides a method for testing electrolyte balance degree of a portable all-vanadium redox flow battery. The method comprises the following steps:
step 1: preparing a series of trivalent vanadium ion standard solutions with known concentrations, and obtaining an absorbance-concentration standard working curve by adopting an ultraviolet-visible spectrophotometry. The curve can be prepared in advance under the laboratory condition, can be used as a standard curve in future detection and is used for calculating the concentration of trivalent vanadium ions and the total balance degree of electrolyte;
step 2: respectively and simultaneously sampling the positive electrolyte and the negative electrolyte, mixing the positive electrolyte and the negative electrolyte in equal volume, and obtaining a mixed solution A after the oxidation-reduction reaction is finished; the sampling mode is not particularly limited, and the sampling mode can be directly taken out from the positive electrode or negative electrode liquid storage device of the flow battery as long as the requirement of safe operation is met.
And step 3: adopting a portable ultraviolet-visible spectrophotometer to carry out wavelength scanning on the mixed solution A, and matching with the standard working curve to obtain the concentration C of trivalent vanadium ions in the mixed solution AV 3+；
And 4, step 4: and adding a reducing agent into the mixed solution A to obtain a mixed solution B, wherein the amount of the reducing agent is enough to reduce all tetravalent vanadium ions in the mixed solution B. In general, in field operation, the reducing agent is added in excess under the condition of not influencing the test, so that the test result is more accurate. After the reducing agent is added to the mixed solution B, the reducing agent first reduces all tetravalent vanadium ions in the mixed solution B to trivalent vanadium ions, and further, the trivalent vanadium ions further start to be reduced to divalent vanadium ions in a small amount due to the presence of an excessive amount of the reducing agent, forming V3 +/V2+The solution was mixed.
The excess amount of the reducing agent is used here to ensure that V is obtained3+Concentration maximum, in the following time, once V3 +The concentration of (2) begins to decrease, meaning that V in the mixed solution2+Generation is started. At this point, the recording of V can be stopped3+With the previously recorded V3+The highest concentration value is used as V in the original mixed electrolyte3+/V4+And V measured when no reducing agent was initially added3+And (4) calculating the balance degree of the original electrolyte.
Therefore, at every unit time, the wavelength of the mixed solution B is scanned by a portable ultraviolet-visible spectrophotometer, and the maximum concentration C of the trivalent vanadium ions in the mixed solution B in the testing time is obtained by matching with the standard working curvemThe concentration of tetravalent vanadium ions in the mixed solution A is CVO 2+，CVO 2+＝Cm-CV 3+；
And 5: calculating the degree of unbalance K, K ═ C of the whole electrolyteVO 2+-CV 3+)/(CVO 2++CV 3+). The composition of the positive electrode/negative electrode solution of the flow battery can be rapidly adjusted according to the obtained unbalance value.
The method for preparing the standard solution in step 1 is not particularly limited, and may be performed according to a method generally used in the art. Meanwhile, the number of samples of the standard solution should be appropriate, and it is understood that the number of samples of the standard is important for the accuracy of drawing the standard working curve, and thus, standard solutions of different concentrations can be obtained more frequently as conditions allow.
The concentration range of the standard working curve obtained in step 1 should also be appropriate, and in some cases, it is required that the concentration range is as wide as possible and the intervals between different concentrations are as small as possible so as to obtain the final absorption peak intensity-CV 3 +A curve with good continuity of ion concentration. In the present invention, such a concentration range should include at least the trivalent vanadium ion concentration C in the mixed solution A described belowV 3+And the maximum concentration C of trivalent vanadium ions in the mixed solution Bm。
Step 1 can be completed in a laboratory in advance, in order to ensure the detection accuracy, in some preferred embodiments of the present invention, a portable uv-vis spectrophotometer identical to that used in steps 3 and 4 is required for detection, and since the instruments used in the whole detection method are identical, the subsequent detection steps 3 and 4 are not affected by the detection environment or time.
The step 2 relates to a process of sampling from the flow battery. In the invention, the sampling is required to be respectively carried out from the positive and negative liquid storage tanks of the redox flow battery. The sampling method is not limited, and may be determined according to the actual equipment. With respect to the working state of the flow battery during sampling, the method provided by the invention can be used for sampling during the working period of the flow battery and also can be used for sampling during the non-working period, as long as the safe operation condition is met.
Specifically, in some embodiments of the present invention, sampling test can be selected at any state of charge SOC of the all-vanadium redox flow battery, and therefore, the electrolyte balance test method provided by the present invention can monitor the balance problem of the positive and negative electrolytes of the all-vanadium redox flow battery at any time. Preferably, the sampling is performed when the state of charge SOC is 0, and at this time, when the positive electrolyte contains only tetravalent vanadium ions and the negative electrolyte contains only trivalent vanadium ions, the accuracy of the test method can be further increased.
In the positive electrode liquid tank of the flow battery, vanadium ions are expressed as V5+/V4+In the negative electrode liquid tank of the flow battery, the vanadium ions are V2+/V3+The form of (A) is stored. In the step 2, after the positive electrolyte sample obtained from the positive electrode and the negative electrolyte sample obtained from the negative electrode are mixed in equal volume, the pentavalent vanadium ions contained in the positive electrolyte and the divalent vanadium ions contained in the negative electrolyte undergo redox reaction to generate corresponding tetravalent vanadium ions and trivalent vanadium ions. In the state where the electrolytes of the positive and negative electrodes are not balanced, substantially all of V is present in the mixed solution5+Or V2+Will also generate V4+And V3+Because of whether it is V5+Or V2+Excessive, will continue to react with V3+Or V4+Reaction, therefore, the mixed solution a finally obtained is usually a mixed solution of tetravalent vanadium ions and trivalent vanadium ions. As such, the operating state of the flow battery can be determined by the degree of imbalance K described below.
In the step 3, the working wavelength of the portable ultraviolet visible spectrophotometer is 350-500 nm. Since the maximum absorption wavelength of the trivalent vanadium ions is 400-410nm, strong absorption is generated in the working wavelength, while the maximum absorption wavelength of the tetravalent vanadium ions is 760-770nm, no absorption is generated in the working wavelength, therefore, the concentration C of the trivalent vanadium ions in the mixed solution A is measuredV 3+And the interference of the absorption peak of the tetravalent vanadium ion is avoided. The portable ultraviolet-visible spectrophotometer is small in size and convenient to carry, so that the testing method provided by the invention is suitable for being carried out under the non-laboratory condition lacking large-scale detection equipment, such as the place where the all-vanadium redox flow battery operates, the non-equilibrium degree of the electrolyte can be detected immediately, and the method is simple, convenient and quick.
Further, in some embodiments of the invention, the method further comprises: diluting the mixed solution A between the step 2 and the step 3. When the sampling amount is small, the mixed solution A can be properly diluted with deionized water, and such a method can make sampling difficult to reduce and increase the convenience of detection. In some embodiments of the invention, the dilution may be performed using an acidic solution, such as a hydrochloric acid solution or a sulfuric acid solution compatible with the electrolyte, and the like.
In the step 4, in the process of reducing high-valence vanadium ions by the reducing agent, it can be observed that the absorbance of trivalent vanadium ions gradually increases and then gradually decreases, because after all tetravalent vanadium ions are reduced to trivalent vanadium ions, the trivalent vanadium ions are further reduced to divalent vanadium ions, and therefore, when the absorbance of the trivalent vanadium ions reaches the highest value, that is, when the concentration of the trivalent vanadium ions is the highest, all tetravalent vanadium ions contained in the mixed solution a are converted to trivalent vanadium ions. From the maximum concentration C of trivalent vanadium ions in the mixed solution BmAnd the concentration C of trivalent vanadium ions in the mixed solution AV 3+The concentration C of the tetravalent vanadium ions in the mixed solution A can be calculatedVO 2+，CVO 2+＝Cm-CV 3+。
The reducing agent used in step 4 is preferably a metal reducing agent from the viewpoint of convenience in use, provided that the maximum absorption wavelength range of the metal ions formed by the metal does not overlap with the maximum absorption wavelength range of the trivalent vanadium ions. In the present invention, the reducing agent is further preferably metallic zinc, and in some preferred embodiments, metallic zinc in a granular or powder form, which is oxidized into divalent zinc ions in an oxidation-reduction reaction with higher vanadium ions or hydrogen ions, and the maximum absorption wavelength of the divalent zinc ions is about 520nm, without interfering with the detection of the concentration of trivalent vanadium ions, may be used. The addition mode of the reducing agent is not limited, and the reducing agent can be added under a relatively rapid condition or added in portions.
In the step 4, the time when the reducing agent starts to be added into the mixed solution a is taken as a timing starting point, the absorbance test is performed in a unit time, the unit time is preferably 30s to 90s, preferably 40s to 70s, in some embodiments of the present invention, the unit time is preferably 1min, and it is observed that the maximum concentration of the trivalent vanadium ions in the mixed solution B is reached at 5 to 7 min.
When the concentration of tetravalent vanadium ions C in the mixed solution A is higherVO 2+And a concentration of trivalent vanadium ions CV 3+When the electrolyte is equal or close to the positive electrolyte and the negative electrolyte, the positive electrolyte and the negative electrolyte reach a balanced state, and the running condition of the battery is good; on the contrary, the positive and negative electrolytes are in a non-equilibrium state, and the larger the non-equilibrium degree K value of the electrolytes is, the larger the degree of deviation of the positive and negative electrolytes of the flow battery from the equilibrium state is, and certain measures need to be adopted to maintain and manage the electrolytes of the flow battery.
The electrolyte balance testing method is reasonable in design, convenient to operate, accurate in detection and small in error, can provide a guiding function for maintenance and management work of the electrolyte of the all-vanadium redox flow battery running for a long time, and ensures safe and stable running of a galvanic pile.
Examples
The present invention will be described in more detail with reference to examples, but the present invention is not limited to these examples.
Example 1:
according to the battery monitoring system, when the SOC of a certain flow battery system which normally runs is reduced to be below 10%, 10ml of the SOC is respectively taken out from the anode electrolyte storage tank and the cathode electrolyte storage tank by using a liquid taking tool. Accurately taking 0.5ml of positive and negative electrolytes by using a pipette, mixing together to form 1ml of V3+/V4+The electrolyte is mixed. Adding hydrochloric acid solution with the concentration of 4mol/L to dilute the mixed electrolyte by 4 times, and then forming the final V to be measured3+/V4+And (3) an electrolyte.
Taking 0.5ml of V to be measured3+/V4+Electrolyte is put into the handA fluorometer Hanna HI96730 portable fluorometer (420nm) test chamber was tested to obtain V3+Absorption peak to peak value of 11.4. According to the absorption peak-V which has been obtained previously in the laboratory3+Concentration curve to obtain corresponding V in mixed electrolyte3+The concentration is 0.875mol/L, and the concentration is the original V3+/V4+V in electrolyte3+The concentration of (c). 0.1g of zinc particles are taken, fully stirred and mixed, and then put into a photometer test cavity, V3+The peak value of the absorption peak of 17.2 is obtained according to the curve, and the corresponding V in the mixed electrolyte at the moment is obtained3+The concentration was 1.3 mol/L. This process is repeated until V3+The absorption peak of (a) reaches a maximum value of 28.8. Obtaining the corresponding V in the mixed electrolyte at the moment according to the curve3+The concentration is 2.126mol/L, which is the V in the original mixed electrolyte3+And V4+The sum of the ion concentrations of (a). According to the balance degree calculation formula, the electrolyte balance degree of the system is + 17.7%. The value exceeds the ideal interval of the electrolyte balance degree by +/-5 percent, so the balance degree of the electrolyte of the system is readjusted according to the test result.
Verification of simple test results
Using the original electrolyte in example 1, 0.5ml of each of positive and negative electrolytes was mixed thoroughly to obtain 1ml of a mixed electrolyte by the same extraction method. And 4 times of dilution is carried out on the mixed electrolyte by adding 4mol/L hydrochloric acid solution. 0.8ml of the diluted electrolyte was put into a Shimadzu UV-1650 UV-Vis spectroscopy test chamber to obtain V3+Absorption peak of 0.24, V4+Absorption peak of 0.57. Obtaining V according to the existing standard curve of the laboratory3+Has a concentration of 0.868mol/L, V4+The concentration of (2) is 1.25 mol/L. V in the original electrolyte3+And V4+The sum of the ion concentrations of (a) and (b) was 2.118. According to the balance degree calculation formula, the electrolyte balance degree of the system is + 18.0%. By comparison, the test results of the examples, i.e., the difference between the electrolyte balance degree and the total ion energy degree, were 0.3% and 0.38%, which were very close to each other. This indicates that the accuracy of the portable electrolyte balance test method is fully satisfactory.
Industrial applicability
The test method is simple, convenient and quick, and convenient to operate, so that the method can be suitable for field detection of the actual running place of the flow battery.
Claims (7)
1. A method for testing electrolyte balance degree of a portable all-vanadium redox flow battery is characterized by comprising the following steps:
step 1: preparing a series of trivalent vanadium ion standard solutions with known concentrations, and obtaining an absorbance-concentration standard working curve by adopting an ultraviolet-visible spectrophotometry;
step 2: respectively and simultaneously sampling the positive electrolyte and the negative electrolyte, mixing the positive electrolyte and the negative electrolyte in equal volume, and obtaining a mixed solution A after the oxidation-reduction reaction is finished;
and step 3: adopting a portable ultraviolet-visible spectrophotometer to carry out wavelength scanning on the mixed solution A, and matching with the standard working curve to obtain the concentration C of trivalent vanadium ions in the mixed solution AV 3+；
And 4, step 4: adding a reducing agent into the mixed solution A to obtain a mixed solution B, wherein the amount of the reducing agent is enough to reduce all tetravalent vanadium ions in the mixed solution B,
taking the moment when the reducing agent begins to be added as a starting point, scanning the wavelength of the mixed solution B by adopting a portable ultraviolet-visible spectrophotometer at intervals, and matching with the standard working curve to obtain the maximum concentration C of the trivalent vanadium ions in the mixed solution B in the testing timemThe concentration of tetravalent vanadium ions in the mixed solution A is CVO 2+，CVO 2+＝Cm-CV 3+；
And 5: calculating the degree of unbalance K, K ═ C of the whole electrolyteVO 2+-CV 3+)/(CVO 2++CV 3+)。
2. The method according to claim 1, wherein in step 2, sampling is performed at any state of charge SOC, preferably at 0.
3. The method according to claim 1 or 2, wherein in the step 2, the mixed solution a is a mixed solution of trivalent vanadium ions and tetravalent vanadium ions.
4. The method as set forth in any one of claims 1 to 3, wherein in the step 3, the operating wavelength of the portable UV-visible spectrophotometer is 350-500 nm.
5. The method according to any one of claims 1-4, further comprising: diluting the mixed solution A between the step 2 and the step 3.
6. The method according to any one of claims 1 to 5, wherein in step 4, the reducing agent is a metal reducing agent, preferably zinc.
7. The method according to any one of claims 1 to 6, wherein in step 4, the unit time is from 30s to 90s, preferably from 40s to 70 s.
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