CN104181158A - Method for measuring concentration of tetravalent and pentavalent vanadium ions in vanadium battery electrolyte - Google Patents
Method for measuring concentration of tetravalent and pentavalent vanadium ions in vanadium battery electrolyte Download PDFInfo
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Abstract
The invention discloses a method for measuring the concentration of tetravalent and pentavalent vanadium ions in vanadium battery electrolyte. The method comprises the steps of oxidizing tetravalent vanadium to pentavalent vanadium by potassium permanganate in positive electrode test solution under the condition that a sulfuric acid medium exists; under the condition that urea exists, decomposing the excessive potassium permanganate by sodium nitrite; performing titration by taking N-phenyl anthranilic acid as an indicator and adopting an ammonium ferrous sulfate standard solution, and measuring the concentration of the total vanadium ions in the electrolyte; in another positive electrode test solution, under the condition that the sulfuric acid medium exists, performing the titration by taking N-phenyl anthranilic acid as the indicator and adopting the ammonium ferrous sulfate standard solution, and measuring the concentration of the pentavalent vanadium ions in the positive electrode electrolyte; subtracting the concentration of the pentavalent vanadium ions from the concentration of the total vanadium ions to obtain the concentration of the tetravalent vanadium ions. The method not only is convenient to operate, but also is high in accuracy rate of measurement on the concentration of the tetravalent and pentavalent vanadium ions in the vanadium battery electrolyte; the measurement result of the method is good in stability, reproducibility and accuracy; the demand of daily measurement on the concentration of the tetravalent and pentavalent vanadium ions in the vanadium battery electrolyte can be completely met.
Description
Technical field
The invention belongs to chemical detection technique field, be specifically related to the assay method of tetravalence and pentavalent vanadium ion concentration in a kind of electrolyte of vanadium redox battery.
Background technology
Vanadium cell is the accumulator taking vanadium ion solution as both positive and negative polarity active substance, vanadium cell has the advantages that to be better than other redox cell, as fast without cross pollution, reaction velocity, can deep discharge, be easy to increase and decrease the power of battery and capacity etc., thereby have purposes widely, as peak load regulation network, emergency power pack, electrical source of power etc.Because the active substance of vanadium cell both positive and negative polarity is vanadium ion, the electrochemical reaction degree of vanadium ion is determining the efficiency for charge-discharge of battery, is therefore necessary to set up a kind of economic, easy, safe and effective valence state vanadium analytical approach.The analytical approach of valence state vanadium mainly contains emission spectrometry and potentiometric titration etc., in current electrolyte for vanadium cell, the analysis of valence state vanadium is taking potentiometric titration as main, but report be all use toxicity strong, to the larger potassium dichromate of harm as titrant, operate relatively loaded down with trivial details, and need to use large-scale instrument and equipment, cost is higher.This law has proposed a kind of safe, easy, titrimetry method of effectively measuring tetravalence and pentavalent vanadium ion concentration taking l ferrous ammonium sulfate solution as titrant; do not need to use expensive instrument and equipment; time saving and energy saving; and do not need to consume a large amount of chemical reagent; can reduce the pollution to environment; protection operating personnel's is healthy, but large because measuring difficulty, and is difficult to apply.Therefore, also do not have at present effective method to carry out Accurate Determining to tetravalence in electrolyte of vanadium redox battery and pentavalent vanadium ion concentration.
Summary of the invention
The object of the present invention is to provide the assay method of tetravalence and pentavalent vanadium ion concentration in a kind of electrolyte of vanadium redox battery.
The object of the present invention is achieved like this, comprises pre-treatment, determination step, specifically comprises:
A, pre-treatment:
1) get the anodal test solution of electrolyte of vanadium redox battery, by 10～12mL/mL
sampleadd water, drip liquor potassic permanganate to test solution and take on a red color and keep 3 ~ 5min constant, then by 0.2～0.3g/mL
sampleadd urea, drip sodium nitrite solution and disappear to red, and excessive 1 ~ 3 sample liquid a to be tested that obtains measuring tetravalence and pentavalent vanadium ion concentration resultant;
2) get the anodal test solution of electrolyte of vanadium redox battery, by 10～12mL/mL
sampleadd water to obtain measuring the sample liquid b to be tested of pentavalent vanadium ion concentration;
B, mensuration: respectively in sample liquid a to be tested and sample liquid b to be tested, by 5 ~ 7/10ml
sampleadd N-phenylanthranilic acid solution as indicator, be titrated to solution respectively transfer bright green to by aubergine with iron ammonium sulfate standard solution, record consumes the volume V of iron ammonium sulfate standard solution
aand V
b, be calculated as follows, can obtain tetravalence and pentavalent vanadium ion concentration:
In formula: C
1for iron ammonium sulfate concentration of standard solution, unit is mol/L;
V
afor the ferrous sulphate standard solution volume that sample liquid a to be tested consumes, unit is ml;
V
bfor the ferrous sulphate standard solution volume that sample liquid b to be tested consumes, unit is ml;
V is the volume of test liquid, and unit is ml.
The present invention adopts and measures tetravalence and pentavalent vanadium ion resultant concentration in electrolytic solution, then measures pentavalent vanadium ion concentration, deducts pentavalent vanadium ion concentration obtain tetravalent vanadium ion concentration by tetravalence and pentavalent vanadium ion resultant concentration.The present invention is not only easy to operate, and measure electrolyte of vanadium redox battery in tetravalence and pentavalent vanadium ion concentration accuracy rate high, its measurement result has good stability, reappearance and accuracy, can meet the needs of tetravalence and pentavalent vanadium ion concentration in daily mensuration electrolyte of vanadium redox battery.
Embodiment
Below in conjunction with embodiment, the present invention is further illustrated, but never in any form the present invention is limited, and any conversion or the replacement done based on training centre of the present invention, all belong to protection scope of the present invention.
In electrolyte of vanadium redox battery of the present invention, the assay method of tetravalence and pentavalent vanadium ion concentration, comprises pre-treatment, determination step, specifically comprises:
A, pre-treatment:
1) get the anodal test solution of electrolyte of vanadium redox battery, by 10～12mL/mL
sampleadd water, drip liquor potassic permanganate to test solution and take on a red color and keep 3 ~ 5min constant, then by 0.2～0.3g/mL
sampleadd urea, drip sodium nitrite solution and disappear to red, and excessive 1 ~ 3 sample liquid a to be tested that obtains measuring tetravalence and pentavalent vanadium ion concentration resultant;
2) get the anodal test solution of electrolyte of vanadium redox battery, by 10～12mL/mL
sampleadd water to obtain measuring the sample liquid b to be tested of pentavalent vanadium ion concentration;
B, mensuration: respectively in sample liquid a to be tested and sample liquid b to be tested, by 5 ~ 7/10ml
sampleadd N-phenylanthranilic acid solution as indicator, be titrated to solution respectively transfer bright green to by aubergine with iron ammonium sulfate standard solution, record consumes the volume V of iron ammonium sulfate standard solution
aand V
b, be calculated as follows, can obtain tetravalence and pentavalent vanadium ion concentration:
In formula: C
1for iron ammonium sulfate concentration of standard solution, unit is mol/L;
V
afor the ferrous sulphate standard solution volume that sample liquid a to be tested consumes, unit is ml;
V
bfor the ferrous sulphate standard solution volume that sample liquid b to be tested consumes, unit is ml;
V is the volume of test liquid, and unit is ml.
Liquor potassic permanganate concentration described in A step 1) is 20 ~ 30g/L.
Concentration 8 ~ the 12g/L of the sodium nitrite solution described in A step 1).
N-phenylanthranilic acid solution concentration described in B step is 2g/L.
Described N-phenylanthranilic acid solution is that the N-phenylanthranilic acid of 0.2g is dissolved in the 2g/L sodium carbonate liquor of 100 ~ 110 DEG C of 100ml and shakes up and obtain.
Assay method of the present invention, comprise with conventional titrimetry titration sample liquid to be tested, according to the volume of this sample liquid quota of expenditure solution to be tested, record tetravalence and pentavalent vanadium ion concentration in electrolyte of vanadium redox battery again, it is characterized in that the preparation of described sample liquid process the following step to be tested:
A, the amount of pressing 10～12mL/mL sample, in the anodal test solution of electrolyte of vanadium redox battery, add water, dripping liquor potassic permanganate to test solution is stable redness and keeps 3～5min constant, the concentration of described liquor potassic permanganate is 25g/L, by the amount of 0.2～0.3g/mL sample, in test solution, add urea, shake limit, limit drips sodium nitrite solution and disappears to red, and excessive 1～3, the concentration of described sodium nitrite solution is 10g/L, must measure the sample liquid to be tested of tetravalence and pentavalent vanadium ion concentration resultant.
B, the amount of pressing 10～12mL/mL sample add water in the anodal test solution of electrolyte of vanadium redox battery, must measure the sample liquid to be tested of pentavalent vanadium ion concentration.
Described potassium permanganate, urea, sodium nitrite are commercial analysis net product.
The liquor potassic permanganate of described steps A is: potassium permanganate commercially available 2.5 g is dissolved in 100 mL water, shakes up.
The sodium nitrite solution of described steps A is: sodium nitrite commercially available 1 g is dissolved in 100 mL water, shakes up.
In described steps A and step B gained sample liquid to be tested, the mensuration of tetravalence and pentavalent vanadium ion concentration is:
A, respectively in the sample liquid to be tested of steps A and step B, by the amount of 5～7/10mL sample, add concentration be the N-phenylanthranilic acid solution of 2g/L as indicator, obtain vs A and vs B.
B, according to titrimetry of the prior art, with conventional iron ammonium sulfate standard solution vs A and the vs B of titration step a respectively, until vs transfers bright green to by aubergine, the volume that records vs A and vs B consumption iron ammonium sulfate standard solution is V
aand V
b, be calculated as follows, can obtain tetravalence and pentavalent vanadium ion concentration:
In formula: C
1for the iron ammonium sulfate concentration of standard solution calculating, unit is mol/L;
V
afor the volume of iron ammonium sulfate standard solution that titration vs A consumes, unit is mL;
V
bfor the volume of iron ammonium sulfate standard solution that titration vs B consumes, unit is mL;
V is the volume of sample solution, and unit is mL.
In described step a, N-phenylanthranilic acid solution is: N-phenylanthranilic acid commercially available 0.2g is dissolved in the sodium carbonate liquor (2g/L) of 100mL low-grade fever, shakes up.
The present invention compared with prior art has following advantages and effect: adopt such scheme to make after sample liquid to be tested, it is available titrimetry of the prior art, directly measure tetravalence and pentavalent vanadium ion concentration in electrolyte of vanadium redox battery, not only easy to operate, and tetravalence and the pentavalent vanadium ion concentration accuracy rate measured are high, its measurement result has good stability, reappearance and accuracy.The inventive method is reliable, practical, quick, can meet the needs of tetravalence and pentavalent vanadium ion concentration in daily mensuration electrolyte of vanadium redox battery completely.
Embodiment 1
1, the preparation of potassium dichromate standard solution:
1A, commercially available base weight potassium chromate is dried to 2h at 150 DEG C, and be cooled to room temperature in exsiccator;
1B, the amount of pressing 25mL/g potassium dichromate, be added to the water commercially available potassium dichromate, until potassium dichromate dissolves completely, is diluted with water to C (1/6K
2cr
2o
7) be the concentration of 0.035 mol/L, obtain potassium dichromate standard solution.
2, the preparation of iron ammonium sulfate standard solution and demarcation:
2A, the amount of pressing 15mL/g iron ammonium sulfate, dissolve commercially available iron ammonium sulfate completely with sulfuric acid (5+95), then use sulfuric acid (5+95) to be diluted to C[(NH
4)
2fe (SO
4)
26H
2o] be about the concentration of 0.035 mol/L, obtain iron ammonium sulfate standard solution.
2B, pipette three parts of potassium dichromate standard solution prepared by 10.00 mL step 1B, press the amount of 0.5mL/mL standard solution, add respectively commercially available phosphoric acid, press the amount of 2mL/mL standard solution, add respectively sulfuric acid solution, sulfuric acid solution is following volume ratio: Liu Suan ︰ water=1 ︰ 1, press the amount of 7mL/mL standard solution, add respectively water, shake up, be cooled to room temperature, obtain three parts of solution, respectively in three parts of solution, by the amount of 5/10mL standard solution, add concentration be the N-phenylanthranilic acid solution of 2g/L as indicator, obtain three portions of vss.
2C, three portions of vss of the iron ammonium sulfate standard solution titration step 2B for preparing with step 2A respectively, until vs transfers bright green to by aubergine, recording the average external volume that three portions of vss consume iron ammonium sulfate standard solution is V
1, the concentration by formula (1) calculating iron ammonium sulfate standard solution:
In formula: C
1for the iron ammonium sulfate concentration of standard solution that formula (1) calculates, unit is mol/L; V
1the average external volume of the iron ammonium sulfate standard solution consuming for three portions of vss of titration, unit is mL; V
2for the volume of potassium dichromate standard solution, unit is mL; C
2for potassium dichromate concentration of standard solution, unit is mol/L.
3, the preparation of sample liquid to be tested:
3A, the amount of pressing 10mL/mL sample, in the anodal test solution of 10mL electrolyte of vanadium redox battery, add 100mL water, liquor potassic permanganate to the test solution that dropping concentration is 25g/L is stable redness and keeps 3min constant, press the amount of 0.2g/mL sample, in test solution, add 2g urea, shake limit, limit drips concentration to be 10g/L sodium nitrite solution disappears to red, and excessive 1, must measure the sample liquid to be tested of tetravalence and pentavalent vanadium ion concentration resultant.
3B, the amount of pressing 10mL/mL sample add 100mL water in the anodal test solution of 10mL electrolyte of vanadium redox battery, must measure the sample liquid to be tested of pentavalent vanadium ion concentration.
3C, respectively in the sample liquid to be tested of step 3A and step 3B, by the amount of 5/10mL sample, add concentration be the N-phenylanthranilic acid solution of 2g/L as 5 of indicator, obtain vs A and vs B.
3D, according to titrimetry of the prior art, with iron ammonium sulfate standard solution vs A and the vs B of titration step 3C respectively of step 2C, until vs transfers bright green to by aubergine, the volume that records vs A and vs B consumption iron ammonium sulfate standard solution is V
aand V
b, be calculated as follows:
In formula: C
1for the iron ammonium sulfate concentration of standard solution that formula (1) calculates, unit is mol/L; V
afor the volume of iron ammonium sulfate standard solution that titration vs A consumes, unit is mL; V
bfor the volume of iron ammonium sulfate standard solution that titration vs B consumes, unit is mL; V is the volume of sample solution, and unit is mL, obtains tetravalence and pentavalent vanadium ion concentration is respectively 0.26mol/L and 2.38mol/L.
Embodiment 2
1, the preparation of potassium dichromate standard solution is with embodiment 1:
2, the preparation of iron ammonium sulfate standard solution and demarcating with embodiment 1:
3, the preparation of sample liquid to be tested:
3A, the amount of pressing 12mL/mL sample, in the anodal test solution of 10mL electrolyte of vanadium redox battery, add 120mL water, liquor potassic permanganate to the test solution that dropping concentration is 25g/L is stable redness and keeps 5min constant, press the amount of 0.3g/mL sample, in test solution, add 3g urea, shake limit, limit drips concentration to be 10g/L sodium nitrite solution disappears to red, and excessive 3, must measure the sample liquid to be tested of tetravalence and pentavalent vanadium ion concentration resultant.
3B, the amount of pressing 12mL/mL sample add 120mL water in the anodal test solution of 10mL electrolyte of vanadium redox battery, must measure the sample liquid to be tested of pentavalent vanadium ion concentration.
3C, respectively in the sample liquid to be tested of step 3A and step 3B, by the amount of 7/10mL sample, add concentration be the N-phenylanthranilic acid solution of 2g/L as 7 of indicator, obtain vs A and vs B.
3D, according to titrimetry of the prior art, with iron ammonium sulfate standard solution vs A and the vs B of titration step 3C respectively of step 2C, until vs transfers bright green to by aubergine, the volume that records vs A and vs B consumption iron ammonium sulfate standard solution is V
aand V
b, be calculated as follows:
In formula: C
1for the iron ammonium sulfate concentration of standard solution that formula (1) calculates, unit is mol/L; V
afor the volume of iron ammonium sulfate standard solution that titration vs A consumes, unit is mL; V
bfor the volume of iron ammonium sulfate standard solution that titration vs B consumes, unit is mL; V is the volume of sample solution, and unit is mL, obtains tetravalence and pentavalent vanadium ion concentration is respectively 0.26mol/L and 2.38mol/L.
Embodiment 3
1, the preparation of potassium dichromate standard solution is with embodiment 1:
2, the preparation of iron ammonium sulfate standard solution and demarcating with embodiment 1:
3, the preparation of sample liquid to be tested:
3A, the amount of pressing 11mL/mL sample, in the anodal test solution of 10mL electrolyte of vanadium redox battery, add 110mL water, liquor potassic permanganate to the test solution that dropping concentration is 25g/L is stable redness and keeps 4min constant, press the amount of 0.25g/mL sample, in test solution, add 2.5g urea, shake limit, limit drips concentration to be 10g/L sodium nitrite solution disappears to red, and excessive 2, must measure the sample liquid to be tested of tetravalence and pentavalent vanadium ion concentration resultant.
3B, the amount of pressing 11mL/mL sample add 110mL water in the anodal test solution of 10mL electrolyte of vanadium redox battery, must measure the sample liquid to be tested of pentavalent vanadium ion concentration.
3C, respectively in the sample liquid to be tested of step 3A and step 3B, by the amount of 6/10mL sample, add concentration be the N-phenylanthranilic acid solution of 2g/L as 6 of indicator, obtain vs A and vs B.
3D, according to titrimetry of the prior art, with iron ammonium sulfate standard solution vs A and the vs B of titration step 3C respectively of step 2C, until vs transfers bright green to by aubergine, the volume that records vs A and vs B consumption iron ammonium sulfate standard solution is V
aand V
b, be calculated as follows:
In formula: C
1for the iron ammonium sulfate concentration of standard solution that formula (1) calculates, unit is mol/L; V
afor the volume of iron ammonium sulfate standard solution that titration vs A consumes, unit is mL; V
bfor the volume of iron ammonium sulfate standard solution that titration vs B consumes, unit is mL; V is the volume of sample solution, and unit is mL, obtains tetravalence and pentavalent vanadium ion concentration is respectively 0.26mol/L and 2.38mol/L.
Test example 1
---the precision of detection method of the present invention, accuracy, recovery experiment
(1) Precision Experiment
Experimental technique: select 5 different anode electrolyte samples, measure vanadium ion concentration respectively by detection method of the present invention, calculate relative standard deviation, experimental result is in table 1.
The Precision Experiment result of table 1 detection method of the present invention
| Sample | Measured value (mol/L) | Mean value (mol/L) | Relative standard deviation RSD |
| Anode electrolyte sample 1 | 2.143，2.206，2.168，2.210，2.182 | 2.18 | 1.26 |
| Anode electrolyte sample 2 | 1.982，1.956，1.973，1.912，1.944 | 1.95 | 1.43 |
| Anode electrolyte sample 3 | 1.872，1.878，1.850，1.877，1.863 | 1.87 | 0.71 |
| Anode electrolyte sample 4 | 2.536，2.528，2.504，2.531，2.546 | 2.53 | 0.74 |
| Anode electrolyte sample 5 | 2.352，2.361，2.343，2.387，2.368 | 2.36 | 0.82 |
(2) accuracy experiment
Experimental technique: select 2 different vanadium ion concentration standard solution, measure vanadium ion concentration by detection method of the present invention respectively, each sample replicate determination 5 times, experimental result is in table 2.
The accuracy experimental result of table 2 detection method of the present invention
| Standard model | Standard value (mol/L) | Measured value (mol/L) | Mean value | Relative standard deviation RSD |
| Standard solution 1 | 2.00 | 2.023，1.986，1.997，2.057，2.049 | 2.02 | 1.38 |
| Standard solution 2 | 2.50 | 2.536，2.529，2.546，2.509，2.510 | 2.53 | 0.71 |
(3) recovery experiment
Experimental technique: select an anode electrolyte sample, add respectively the vanadium ion concentration standard solution of different amounts, measure vanadium ion concentration determination by detection method of the present invention, each sample parallel analysis 5 times, average, calculating the recovery is 97%-108%, and experimental result is in table 3.
The recovery experimental result of table 3 detection method of the present invention
| Sample | Standard value (mol/L) | Addition (mol/L) | Record total amount (mol/L) | The recovery (%) |
| Anode electrolyte sample 2 | 1.95 | 0.10 | 2.054 | 104 |
| Anode electrolyte sample 2 | 1.95 | 0.50 | 2.437 | 97 |
| Anode electrolyte sample 2 | 1.95 | 1.00 | 2.974 | 102 |
| Anode electrolyte sample 2 | 1.95 | 1.50 | 3.509 | 104 |
From above-mentioned experimental result, the analysis result deviation of detection method of the present invention is little, and precision, accuracy all can meet and analyze requirement, and analysis speed is fast, simple to operate, easily grasp, and have higher application value.
Claims (5)
1. an assay method for tetravalence and pentavalent vanadium ion concentration in electrolyte of vanadium redox battery, is characterized in that comprising pre-treatment, determination step, specifically comprises:
A, pre-treatment:
1) get the anodal test solution of electrolyte of vanadium redox battery, by 10～12mL/mL
sampleadd water, drip liquor potassic permanganate to test solution and take on a red color and keep 3 ~ 5min constant, then by 0.2～0.3g/mL
sampleadd urea, drip sodium nitrite solution and disappear to red, and excessive 1 ~ 3 sample liquid a to be tested that obtains measuring tetravalence and pentavalent vanadium ion concentration resultant;
2) get the anodal test solution of electrolyte of vanadium redox battery, by 10～12mL/mL
sampleadd water to obtain measuring the sample liquid b to be tested of pentavalent vanadium ion concentration;
B, mensuration: respectively in sample liquid a to be tested and sample liquid b to be tested, by 5 ~ 7/10ml
sampleadd N-phenylanthranilic acid solution as indicator, be titrated to solution respectively transfer bright green to by aubergine with iron ammonium sulfate standard solution, record consumes the volume V of iron ammonium sulfate standard solution
aand V
b, be calculated as follows, can obtain tetravalence and pentavalent vanadium ion concentration:
In formula: C
1for iron ammonium sulfate concentration of standard solution, unit is mol/L;
V
afor the ferrous sulphate standard solution volume that sample liquid a to be tested consumes, unit is ml;
V
bfor the ferrous sulphate standard solution volume that sample liquid b to be tested consumes, unit is ml;
V is the volume of test liquid, and unit is ml.
2. the assay method of tetravalence and pentavalent vanadium ion concentration in electrolyte of vanadium redox battery according to claim 1, is characterized in that the liquor potassic permanganate concentration described in A step 1) is 20 ~ 30g/L.
3. the assay method of tetravalence and pentavalent vanadium ion concentration in electrolyte of vanadium redox battery according to claim 1, is characterized in that the concentration 8 ~ 12g/L of the sodium nitrite solution described in A step 1).
4. the assay method of tetravalence and pentavalent vanadium ion concentration in electrolyte of vanadium redox battery according to claim 1, is characterized in that the N-phenylanthranilic acid solution concentration described in B step is 2g/L.
5. according to the assay method of tetravalence in the electrolyte of vanadium redox battery described in claim 1 or 4 and pentavalent vanadium ion concentration, it is characterized in that described N-phenylanthranilic acid solution is that the N-phenylanthranilic acid of 0.2g is dissolved in the 2g/L sodium carbonate liquor of 100 ~ 110 DEG C of 100ml and shakes up and obtain.
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| CN105388127A (en) * | 2015-10-30 | 2016-03-09 | 清华大学深圳研究生院 | Online detecting method and system for concentration of all ions of all-vanadium redox flow battery |
| CN105388127B (en) * | 2015-10-30 | 2018-01-26 | 清华大学深圳研究生院 | A kind of online test method and system of each ion concentration of all-vanadium flow battery |
| CN106450401A (en) * | 2016-11-11 | 2017-02-22 | 攀钢集团攀枝花钢铁研究院有限公司 | Method for preparing vanadyl sulfate by utilizing waste vanadium electrolyte |
| CN106450401B (en) * | 2016-11-11 | 2019-08-30 | 攀钢集团攀枝花钢铁研究院有限公司 | A method of vanadic sulfate is prepared using discarded V electrolyte |
| CN109669142A (en) * | 2017-09-28 | 2019-04-23 | 大连融科储能技术发展有限公司 | A kind of method and system for the migration of real-time monitoring all-vanadium flow battery vanadium |
| CN116256463A (en) * | 2021-12-10 | 2023-06-13 | 中国科学院大连化学物理研究所 | Method for rapidly determining concentration of vanadium ions in electrolyte of vanadium battery |
| CN116256463B (en) * | 2021-12-10 | 2024-07-30 | 中国科学院大连化学物理研究所 | Method for rapidly determining concentration of vanadium ions in electrolyte of vanadium battery |
| CN118032690A (en) * | 2024-03-20 | 2024-05-14 | 液流储能科技有限公司 | Method for measuring concentration of ammonium ions in electrolyte |
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