CN102507472A - Electrolyte measurement method and electrolyte measurement device for vanadium redox flow battery - Google Patents
Electrolyte measurement method and electrolyte measurement device for vanadium redox flow battery Download PDFInfo
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Abstract
The invention relates to an electrolyte measurement method and an electrolyte measurement device for a vanadium redox flow battery. The electrolyte measurement method comprises the following steps of: measuring the absorption or transmission spectra of a plurality of groups of electrolyte samples with known configuration parameters under the irradiation of a set light waveband, recording the absorption or transmission spectra of the groups of electrolyte samples, and establishing a standard spectral database; in the light waveband, measuring the absorption or transmission spectrum of an electrolyte to be measured; finding out a spectrum closest to the measured spectrum from the standard spectral database; and determining configuration parameters corresponding to the closest spectrum to be measured parameters of the electrolyte to be measured. With the adoption of the electrolyte measurement method and the electrolyte measurement device for the vanadium redox flow battery, the concentrations of vanadium ions of various valences in the electrolyte of the vanadium battery can be effectively measured in an on-line manner, the measurement manner is simple, and the speed is fast.
Description
Technical field
The invention belongs to the Materials Measurement technical field, particularly relate to a kind of electrolytic solution detection method and pick-up unit of the all-vanadium flow battery based on optical absorption.
Background technology
Flow battery has that design power is big, long service life, free of contamination characteristics, is the important selection of large-scale accumulator system.Wherein, vanadium redox battery (Vanadium Redox Flow battery is called for short VRB or vanadium cell) be pay close attention to both at home and abroad at present maximum a kind of flow batteries (J. Electrochem. Soc. 1986,133:1057).
In the vanadium cell, the operation material in the both positive and negative polarity all is the electrolytic solution that contains vanadium ion.In the charging process, anodal+4 valency vanadium ions change into+5 valency vanadium ions, in the negative pole+3 valency vanadium ions change into+the divalent vanadium ion.Otherwise discharge process.Both positive and negative polarity electrolytic solution is separated by a kind of special proton permeability film in the vanadium cell.Desirable proton permeability film only lets proton pass through, and stops that vanadium ion passes through.Under the ideal situation, the vanadium ion concentration of the both positive and negative polarity electrolytic solution of all-vanadium flow battery remains unchanged, and the valence state change amount of both positive and negative polarity electrolytic solution is identical.
But in the actual conditions:
(1) since part+divalent vanadium ion oxidized with both positive and negative polarity electrolytic solution in the existence of subsidiary reaction, the valence state of vanadium cell both positive and negative polarity electrolytic solution changes also incomplete same, promptly the electrolytic solution valence state exists unbalance.
(2) amberplex that uses in the vanadium cell can not be stopped the infiltration of vanadium ion fully, and different osmotic can produce the volume change of both positive and negative polarity electrolytic solution.This all can cause the concentration of both positive and negative polarity electrolytic solution to change, and promptly concentration of electrolyte exists unbalance.
Owing to above reason, vanadium cell in actual use, the unbalance meeting of the concentration of electrolytic solution and valence state becomes along with discharging and recharging increased frequency seriously, reduces the charge/discharge capacity of vanadium cell, has a strong impact on the actual life of vanadium cell.In order to address this problem, need be able to detect the method for the vanadium ion concentration of various valence states in the electrolyte of vanadium redox battery immediately, grasp unbalance degree, thereby can when the vanadium cell state is undesirable, adjust system.
The valence state of existing electrolyte of vanadium redox battery and the detection method of concentration mainly contain open-circuit voltage method, potentiometric titration, chromatography and spectrophotometer method.The open-circuit voltage method can be measured the charging and discharging state of vanadium cell under the equilibrium state, and indirect calculation goes out concentration of electrolyte, but powerless to the vanadium cell under the imbalance state.Though potentiometric titration and chromatography can be measured each valence state vanadium ion concentration in the electrolytic solution, its step is complicated, and measuring speed is slower, and is not suitable for the real-time online of electrolyte of vanadium redox battery is detected.Spectrophotometer method is the fine selection of quick measure ion concentration; Successful Application (a kind of redox flow batteries that uses Fe and Cr ion in the siderochrome flow battery at present; Chinese invention patent 200880004746.2, U.S. Pat 7855005).But, vanadium ion excessive concentration in the electrolytic solution of vanadium cell (generally reaching 2mol/L), absorption coefficient is too big, and has interference between the vanadium ion of different valence state, and the absorption coefficient of single wavelength and different ions concentration are linear.So traditional spectrophotometer method based on single wavelength absorption coefficient; Limitation ground measure portion vanadium redox battery negative pole electrolyte concentration can only be arranged; And can't measure anodal electrolytic solution (Journal of Power Sources 2011,196:8822 – 8827, WO9003666).
Summary of the invention
For overcoming the existing defective of scheme in the online detection of the concentration of electrolyte of vanadium cell, the present invention proposes a kind of novel detection method and pick-up unit based on each valency vanadium ion concentration of optical absorption measurement.
A kind of electrolytic solution detection method of all-vanadium flow battery may further comprise the steps:
(1) under the continuous or discrete optical band irradiation of setting, measure the absorption or the transmitted spectrum of the electrolytic solution sample of many group known configurations parameters, each group of record absorbs or transmitted spectrum, sets up the standard spectrum database;
(2) in said optical band, measure the absorption or the transmitted spectrum of electrolytic solution to be measured;
(3) spectrum of measuring in the same step of measuring in the step (2) of spectrum (1) is compared analysis, from the standard spectrum database find out with step (2) the most close spectrum of spectrum of measurement;
(4) the most close spectrum configuration parameter corresponding is confirmed as the detected parameters of electrolytic solution to be measured in the step (2).
Preferably, said configuration parameter comprises vanadium ion total concentration and/or each valency vanadium ion ratio/concentration in the electrolytic solution, preferably also comprises the acidity of electrolytic solution.
Preferably, be to measure in step (1) and the step (2) to the electrolytic solution that on propagation path of light, has same length.
Preferably, said optical band is continuous, and comparative analysis described in the step (3) comprises that the curve shape according to absorption or transmitted spectrum judges whether close; Perhaps, said optical band disperses, comparative analysis described in the step (3) comprise measurement of comparison to the discrete spectrum data of spectrum judge whether close.
Preferably; Each group of calculating and writing down unit light intensity in the step (1) absorbs or transmitted spectrum; Step (2) is calculated the absorption or the transmitted spectrum of the unit light intensity of electrolytic solution to be measured, and whether the absorption or the transmitted spectrum of comparative analysis unit light intensity be close in the step (3).
Preferably, the absorption of electrolytic solution or the measurement of transmitted spectrum may further comprise the steps in step (1) and/or (2):
A. make the electrolytic solution of vanadium cell flow through absorption cell with light transmission path;
B. make light expose to said absorption cell along said light transmission path;
C. the light that sees through electrolyte layer enters into the spectrum resolution device and is resolved, and by the spectral information after the capturing apparatus picked-up parsing;
D. processing module is analyzed the spectral information that the capturing apparatus transmission comes, and calculates the absorption or the transmitted spectrum of electrolytic solution.
Preferably, also detect light intensity among the step b and be delivered to processing module, in the steps d, said processing module is according to said spectral information and intensity signal, the absorption of unit of account light intensity or transmitted spectrum.
A kind of electrolytic solution pick-up unit of all-vanadium flow battery comprises:
Light source module is used to provide have continuously or discrete multi-wavelength's optical band;
Absorption cell has passage and light transmission path that electrolysis liquid is come in and gone out, the light that light source module sends along the light transmission path from electrolyte stream through passing;
Detecting module is used to obtain the spectral information of the light that passes said absorption cell;
Processing module; Be used for calculating absorption or transmitted spectrum according to said spectral information; Many groups spectrum that the electrolytic solution sample based on known parameters in itself and the standard database is obtained compares; Find out and said absorption or the most close spectrum of transmitted spectrum, and the parameter of the most close said pairing electrolytic solution sample of spectrum is confirmed as the detected parameters of electrolytic solution to be measured.
Preferably, said electrolytic solution pick-up unit also comprises:
Memory module is used to store the known configurations parameter of different electrolytes sample and the absorption or the transmitted spectrum of these electrolytic solution samples, sets up standard database, and absorption in the said standard database or transmitted spectrum detect via said electrolytic solution pick-up unit and obtain.
Preferably, said detecting module comprises spectrum resolution device and capturing apparatus, and the light that sees through electrolytic solution is incident upon said spectrum resolution device and is resolved the spectral information after said capturing apparatus picked-up is resolved.
Preferably; Said light source module comprises light source, collimation lens, beam splitter, imaging len and photodetector; Said collimation lens becomes directional light with the light that light source sends, and said beam splitter is divided into two-way light with directional light, and wherein one road light converges on the said photodetector through said imaging len; Said photodetector is used for monitoring the intensity signal of said light source and is sent to said processing module; Another road illumination is mapped on the absorbing window of said absorption cell, the intensity signal that spectral information that processing module provides according to said capturing apparatus and said photodetector provide, the absorption of unit of account light intensity or transmitted spectrum.
Employing the present invention detects the electrolyte of vanadium redox battery ion concentration, with existing data by MoM and MEI, has following distinct advantages:
1. the open-circuit voltage method can only be measured the electrolytic solution of equilibrium state; And the present invention can measure the concentration of the electrolytic solution under the nonequilibrium condition.
Potentiometric titration and chromatography complex steps, be not suitable for online detection; And metering system of the present invention is simple, and measuring speed is fast, is fit to the on-line measurement of electrolyte of vanadium redox battery.
3. owing to vanadium ion concentration in the electrolytic solution of vanadium cell is higher; Absorption coefficient is bigger; And exist between the vanadium ion of different valence state and disturb; The absorption coefficient of single wavelength and different ions concentration are linear, therefore, and based on the spectrophotometer method of the single wavelength absorption coefficient concentration of each ion in the energy measurement electrolyte of vanadium redox battery not; The present invention is through comparing analysis with tested electrolytic solution with the spectrum of standard model; According to confirming electrolyte parameter with the close degree of spectrum of standard model, do not receive the restriction of the nonlinear relationship of the homo-ion concentration of electrolytic solution absorption coefficient, can effectively measure concentration and other any electrolyte parameter relevant of each ion in the electrolyte of vanadium redox battery with absorption/transmitted spectrum.
Description of drawings
Fig. 1 is the functional block diagram of a kind of embodiment of all-vanadium redox flow battery electrolyte pick-up unit of the present invention;
Fig. 2 is the structural representation of a kind of preferred embodiment of all-vanadium redox flow battery electrolyte pick-up unit of the present invention;
Fig. 3 is the process flow diagram of a kind of embodiment of all-vanadium redox flow battery electrolyte detection method of the present invention;
Fig. 4 is in a kind of preferred embodiment of all-vanadium redox flow battery electrolyte detection method of the present invention, measures the electrolytic solution sample to set up the process flow diagram of standard spectrum database.
Fig. 5 is in a kind of preferred embodiment of all-vanadium redox flow battery electrolyte detection method of the present invention, and the electrolytic solution of measuring vanadium cell to be measured is to confirm the process flow diagram of its electrolyte parameter.
Fig. 6 a is that the total concentration that adopts method, device of the present invention to record is 1.9mol/L to Fig. 6 h, the instance transmission spectrum curve of the anodal electrolytic solution of vanadium cell of difference+4 valencys and+5 price ratios example.
Embodiment
Below combine accompanying drawing that the present invention is further specified through embodiment.
Consult Fig. 1, in one embodiment, the electrolytic solution pick-up unit of all-vanadium flow battery comprises light source module 1, absorption cell 2, detecting module 3 and processing module 4.Wherein, light source module is used to provide the optical band with the multi-wavelength who perhaps disperses continuously; Absorption cell has passage (not shown) and the light transmission path that electrolysis liquid 5 is come in and gone out; 5 warps pass the light that light source module sends along the light transmission path from electrolyte stream, for example can absorption window (not shown) be set in the passage both sides of absorption cell and pass for the light that light source sends; Detecting module is used to obtain the spectral information of the light that passes said absorption cell; Processing module is used for calculating absorption or transmitted spectrum according to said spectral information; Many groups spectrum in itself and the standard database is compared; These many group spectrum all are that the different electrolytes sample by the known electrolytes parameter obtains; Through relatively, can find out and said absorption or the most close spectrum of transmitted spectrum, the parameter of the pairing electrolytic solution sample of this most close spectrum is promptly confirmed as the detected parameters of electrolytic solution to be measured.The known electrolytes parameter can be but be not limited to vanadium ion total concentration, each valence state vanadium ion concentration/ratio etc.; Comprise: anodal+4 ,+5 valency vanadium ions; Negative pole+2 ,+3 valency vanadium ions, can also be other any electrolyte parameter relevant, for example acidity with absorption/transmitted spectrum.
In some preferred embodiments, the electrolytic solution pick-up unit also comprises memory module (not shown), can supply processing module to read and write data.Establish standard database in the memory module, it stores the known electrolytes configuration parameter of different electrolytes sample and the absorption or the transmitted spectrum of these electrolytic solution samples.The same with the absorption or the transmitted spectrum of electrolytic solution to be measured, absorption in the said standard database or transmitted spectrum can detect through said electrolytic solution pick-up unit equally and obtain.
Consult Fig. 1 and Fig. 2; In some preferred embodiments; Said light source module comprises light source 11 and collimation lens 12; Light source 11 can but be not limited to adopt incandescent lamp, halogen tungsten lamp, xenon lamp, LED (light emitting diode), laser, LD (laser diode), SLD (super laser diode) etc., said collimation lens 12 becomes directional light with the light that light source 11 sends.More preferably; Light source module also comprises beam splitter 13, imaging len 14 and photodetector 34, and said beam splitter 13 is divided into two-way light with directional light, and wherein one road light converges on the said photodetector through said imaging len; Said photodetector is monitored the intensity signal of said light source; And the result is sent to said processing module, and another road illumination is mapped on the absorbing window of said absorption cell, and its transmissive part is delivered to processing module through the detecting module collection; The intensity signal that spectral information that processing module provides according to detecting module and said photodetector provide calculates the absorption or the transmitted spectrum of unit light intensity.
In different embodiment, light source 11 can be to comprise one to have continuously or discrete multi-wavelength's light source, also can be the synthetic light source of single light source or a plurality of light source.And as stated, except that light source 11, light source module can also comprise a plurality of optical element parts such as conduction, convergence, collimation, optical filtering.
Consult Fig. 2, said detecting module preferably includes spectrum resolution device and capturing apparatus, can adopt grating spectrograph 32 and CCD camera 33 respectively.In this embodiment; The light that sees through electrolytic solution is injected from the entrance slit 31 of said grating spectrograph; Be imaged on after the beam split on the said CCD camera that is arranged at said grating spectrograph exit, the CCD camera is delivered to processing module with the image information of its collection and is handled the required spectroscopic data of generation.The spectrum resolution device can but be not limited to adopt grating spectrograph, prism spectrometer, Fourier transform spectrometer etc., capturing apparatus can but be not limited to adopt photodiode, line CCD, area array CCD etc.
Consult Fig. 2, described absorption cell 2 has gateway 21,22 and absorption window 23. Gateway 21,22 can let the electrolytic solution 5 of vanadium cell flow into from an end of absorption cell 2, and the other end flows out; Absorption window 23 can let light that light source the sends electrolyte layer through constant depth, shines detecting module 3.As previously mentioned; Detecting module 3 is measured the spectrum (transmission spectrum or absorption spectra) of transmitted light with certain spectral resolution; And this spectroscopic data is transferred in the processing module 4, and processing module 4 compares the spectroscopic data of the electrolytic solution that detects with the spectroscopic data in the database, draw immediate data; Thereby confirm the composition and the concentration of tested electrolytic solution, for example vanadium ion total concentration, each valence state ratio/concentration.
At one more specifically among the embodiment; Light source adopts white point light source 11; Like 150W optical fiber output type white point light source; Its light that sends becomes directional light through an achromatic collimation lens 12 (like f=50mm), and the beam splitter 13 that is constituted by a semi-transparent semi-reflecting eyeglass afterwards is divided into two-way light.Wherein one road light through the achromatic imaging len 14 of another piece (like f=50mm) converge on the photodetector 34, the Strength Changes that is used for keeping watch on light source 11, and with result transmission in the computing machine that serves as processing module 4.Another road light vertical irradiation is to the absorbing window of absorption cell.The electrolytic solution 5 of vanadium cell flows into from the inlet 21 of absorption cell, flows out from exporting 22, in two diaphragms 23 of absorption cell, forms one deck (thick like 1mm) electrolyte layer.See through entrance slit 31 (like width 10 μ m) that the light of electrolyte layer enters into a grating spectrograph 32 (as having grating 300 lines) by beam split; Be imaged on then on the CCD camera 33 (like 1392 * 1040 pixels) that is positioned over the spectrometer outlet, be transferred to again in the computing machine 4.The program of operation is come through detector 34 transmission on the computing machine 4 intensity of light source information and the next spectral information of CCD camera 33 transmission; Calculate the transmission spectrum under the unit light intensity of electrolytic solution 5; Transmission spectrum with the standard model of having measured compares again, draws the vanadium ion kind and the related concentrations of electrolytic solution 5.
On the other hand, the present invention also provides a kind of electrolytic solution detection method of all-vanadium flow battery.Consult Fig. 3, the detection method of an embodiment may further comprise the steps:
(1) under the continuous or discrete optical band irradiation of setting, measure the absorption or the transmitted spectrum of the electrolytic solution sample of many group known configurations parameters, each group of record absorbs or transmitted spectrum, sets up the standard spectrum database;
(2) in said optical band, measure the absorption or the transmitted spectrum of electrolytic solution to be measured;
(3) spectrum of measuring in the same step of measuring in the step (2) of spectrum (1) is compared analysis, from the standard spectrum database find out with step (2) the most close spectrum of spectrum of measurement;
(4) the most close spectrum configuration parameter corresponding is confirmed as the detected parameters of electrolytic solution to be measured in the step (2).
Preferably; Be to measure in step (1) and the step (2) to the electrolytic solution that on propagation path of light, has same length; However; Also can measure, convert spectroscopic data to through data processing then with comparability to the electrolytic solution that on propagation path of light, has different length.
Said optical band can be continuous, and comparative analysis described in the step (3) comprises that the curve shape according to absorption or transmitted spectrum judges whether close; Perhaps, said optical band also can disperse, comparative analysis described in the step (3) comprise measurement of comparison to the discrete spectrum data of spectrum judge whether close.
Preferably; Each group of calculating and writing down unit light intensity in the step (1) absorbs or transmitted spectrum; Step (2) is calculated the absorption or the transmitted spectrum of the unit light intensity of electrolytic solution to be measured, and whether the curve shape of the absorption of comparative analysis unit light intensity or transmitted spectrum is close in the step (3).Preferably can also judge whether it is close electrolytic solution according to speed, the severe that curve shape changes, this moment different light intensity spectrum to make comparisons also be feasible.Because in vanadium ion change in concentration process, violent variation takes place for the intensity of its transmission spectrum and shape,, judge especially concisely and intuitively whether electrolytic solution spectrum is close so can utilize this characteristic to simplify spectrum processing mode relatively.
Consult Fig. 4, in a preferred embodiment, the flow process that step (1) is set up the standard spectrum database is following:
At first, according to certain total vanadium ion concentration, certain each valence state vanadium ion ratio and certain acidity configuration standard electrolytic solution;
Then, use pick-up unit shown in Figure 1 to measure the transmission spectrum of electrolytic solution, may further comprise the steps:
A. make the electrolytic solution of vanadium cell flow through absorption cell with light transmission path;
B. make light expose to said absorption cell along said light transmission path;
C. the light that sees through electrolyte layer enters into the spectrum resolution device and is resolved, and by the spectral information after the capturing apparatus picked-up parsing;
D. processing module is analyzed the spectral information that the capturing apparatus transmission comes, and calculates the absorption or the transmitted spectrum of electrolytic solution;
Next, calculate and write down the transmission spectrum of unit light intensity, and write down the concrete parameter (like total vanadium ion concentration, each valency ion ratio, acidity etc.) of this group electrolytic solution;
Change the parameter of standard electrolytic liquid, dispose another group standard electrolytic liquid again, and repeat above-mentioned steps, up to transmission spectrum and the parameter thereof of measuring and write down the standard electrolytic liquid of required whole parameter areas.
With reference to Fig. 5, in a preferred embodiment, measure the flow process of concentration of electrolyte and composition according to step (2)-(4) and can also explain as follows:
At first, make the electrolytic solution of vanadium cell flow through the absorption cell among Fig. 1; Gather the transmission spectrum information of electrolytic solution with the detecting module among Fig. 1; Calculate the transmission spectrum (as according to above-mentioned steps a-d) of the unit light intensity of the electrolytic solution of surveying;
Then, this unit light intensity transmission spectrum is compared (as utilizing disposal routes such as related algorithm) with the transmission spectrum of respectively organizing unit light intensity in the database, draw one group of spectroscopic data near test result;
At last, in database, search the parameters such as composition and ion concentration of the corresponding electrolytic solution of this group spectroscopic data, confirm as the parameter of the electrolyte of vanadium redox battery of surveying.
It is 1.9mol/L that Fig. 6 a shows the one group of total concentration that adopts the embodiment of the invention to record to Fig. 6 h, the instance transmission spectrum curve of the anodal electrolytic solution of vanadium cell of difference+4 valencys and+5 price ratios example.Wherein according in each electrolytic solution+4 price ratios examples called after 100%V4 is to 0%V4.From figure, can see: the absorption intensity of pure+4 valencys and pure+5 valencys is suitable, just spectral range different (shown in Fig. 6 a).But a small amount of along with in pure+4 valencys, mixing+5 valencys, the transmission light intensity reduces rapidly, and the transmission peaks about 450nm is reduced to 90% o'clock 0.05 (shown in Fig. 6 b) of 4 price ratios example from 0.6 of beginning, and then continue to reduce to+4 price ratios example 80% o'clock 5 * 10
-3(shown in Fig. 6 c), 70% 5 * 10
-4(shown in Fig. 6 d).Along with+5 price ratios example continues to increase, transmission peaks is mobile slightly to long wavelength's direction, and intensity continues to reduce (shown in Fig. 6 d).Reach minimum (about 3 * 10 to 40% o'clock transmission peaks intensity of+4 price ratios example
-5), centre wavelength moves to about 470nm (shown in Fig. 6 e).After this, along with+4 price ratios examples continue to drop to 30%, 20%, transmission peaks intensity begins to increase, the position begins to quicken to move to the long wavelength, and another peak (shown in Fig. 6 f) occurs in long wave strong point more.+ 4 price ratio examples continue to drop to 10%, and the projection spectral intensity rises to 0.01 rapidly, obviously bimodal (shown in Fig. 6 g) occur at visible light wave range.After this, the peak of transmission spectrum slows down, and intensity continues to raise, up to the shape that finally becomes pure pentavalent (shown in Fig. 6 h).
Can find out to Fig. 6 h from Fig. 6 a; Under high concentration; Exist between the vanadium ion of different valence state and disturb, cause the electrolytic solution transmissivity of its mixing to reduce greatly, can't use traditional single wavelength spectrophotometer to send out detection (like Journal of Power Sources 2011; 196:8822 – 8827, WO9003666).And in vanadium ion change in concentration process, violent variation takes place in the intensity of its transmission spectrum and shape, therefore through factors such as the shape of transmission spectrum, change in shape severe, speed are compared, can distinguish the electrolytic solution of different vanadium ion concentration.
Above content is to combine concrete preferred implementation to the further explain that the present invention did, and can not assert that practical implementation of the present invention is confined to these explanations.For the those of ordinary skill of technical field under the present invention, under the prerequisite that does not break away from the present invention's design, can also make some simple deduction or replace, all should be regarded as belonging to protection scope of the present invention.
Claims (11)
1. the electrolytic solution detection method of an all-vanadium flow battery is characterized in that, may further comprise the steps:
(1) under the continuous or discrete optical band irradiation of setting, measure the absorption or the transmitted spectrum of the electrolytic solution sample of many group known configurations parameters, each group of record absorbs or transmitted spectrum, sets up the standard spectrum database;
(2) in said optical band, measure the absorption or the transmitted spectrum of electrolytic solution to be measured;
(3) spectrum of measuring in the same step of measuring in the step (2) of spectrum (1) is compared analysis, from the standard spectrum database find out with step (2) the most close spectrum of spectrum of measurement;
(4) the most close spectrum configuration parameter corresponding is confirmed as the detected parameters of electrolytic solution to be measured in the step (2).
2. electrolytic solution detection method as claimed in claim 1 is characterized in that, said configuration parameter comprises vanadium ion total concentration and/or each valency vanadium ion ratio/concentration in the electrolytic solution, preferably also comprises the acidity of electrolytic solution.
3. electrolytic solution detection method as claimed in claim 1 is characterized in that, in step (1) and the step (2) is to measure to the electrolytic solution that on propagation path of light, has same length.
4. like each described electrolytic solution detection method of claim 1-3, it is characterized in that said optical band is continuous, comparative analysis described in the step (3) comprises that the curve shape according to absorption or transmitted spectrum judges whether close; Perhaps, said optical band disperses, comparative analysis described in the step (3) comprise measurement of comparison to the discrete spectrum data of spectrum judge whether close.
5. electrolytic solution detection method as claimed in claim 3; It is characterized in that; Each group of calculating and writing down unit light intensity in the step (1) absorbs or transmitted spectrum; Step (2) is calculated the absorption or the transmitted spectrum of the unit light intensity of electrolytic solution to be measured, and whether the absorption or the transmitted spectrum of comparative analysis unit light intensity be close in the step (3).
6. electrolytic solution detection method as claimed in claim 3 is characterized in that, the absorption of electrolytic solution or the measurement of transmitted spectrum may further comprise the steps in step (1) and/or (2):
A. make the electrolytic solution of vanadium cell flow through absorption cell with light transmission path;
B. make light expose to said absorption cell along said light transmission path;
C. the light that sees through electrolyte layer enters into the spectrum resolution device and is resolved, and by the spectral information after the capturing apparatus picked-up parsing;
D. processing module is analyzed the spectral information that the capturing apparatus transmission comes, and calculates the absorption or the transmitted spectrum of electrolytic solution.
7. electrolytic solution detection method as claimed in claim 6 is characterized in that, also detects light intensity among the step b and is delivered to processing module, and in the steps d, said processing module is according to said spectral information and intensity signal, the absorption of unit of account light intensity or transmitted spectrum.
8. the electrolytic solution pick-up unit of an all-vanadium flow battery is characterized in that, comprising:
Light source module is used to provide have continuously or discrete multi-wavelength's optical band;
Absorption cell has passage and light transmission path that electrolysis liquid is come in and gone out, the light that light source module sends along the light transmission path from electrolyte stream through passing;
Detecting module is used to obtain the spectral information of the light that passes said absorption cell;
Processing module; Be used for calculating absorption or transmitted spectrum according to said spectral information; Many groups spectrum that the electrolytic solution sample based on known parameters in itself and the standard database is obtained compares; Find out and said absorption or the most close spectrum of transmitted spectrum, and the parameter of the most close said pairing electrolytic solution sample of spectrum is confirmed as the detected parameters of electrolytic solution to be measured.
9. electrolytic solution pick-up unit as claimed in claim 7 is characterized in that, also comprises:
Memory module is used to store the known configurations parameter of different electrolytes sample and the absorption or the transmitted spectrum of these electrolytic solution samples, sets up standard database, and absorption in the said standard database or transmitted spectrum detect via said electrolytic solution pick-up unit and obtain.
10. like claim 7 or 8 described electrolytic solution pick-up units; It is characterized in that; Said detecting module comprises spectrum resolution device and capturing apparatus, and the light that sees through electrolytic solution is incident upon said spectrum resolution device and is resolved the spectral information after said capturing apparatus picked-up is resolved.
11. like claim 7 or 8 described electrolytic solution pick-up units; It is characterized in that; Said light source module comprises light source, collimation lens, beam splitter, imaging len and photodetector; Said collimation lens becomes directional light with the light that light source sends, and said beam splitter is divided into two-way light with directional light, and wherein one road light converges on the said photodetector through said imaging len; Said photodetector is used for monitoring the intensity signal of said light source and is sent to said processing module; Another road illumination is mapped on the absorbing window of said absorption cell, the intensity signal that spectral information that processing module provides according to said capturing apparatus and said photodetector provide, the absorption of unit of account light intensity or transmitted spectrum.
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| CN104900898A (en) * | 2015-04-24 | 2015-09-09 | 南京工业大学 | Vanadium battery capacity attenuation reducing method |
| CN106198453A (en) * | 2016-08-25 | 2016-12-07 | 清华大学深圳研究生院 | The online test method of the chief and vice reaction ratio of a kind of all-vanadium flow battery and device |
| CN109211885A (en) * | 2017-06-29 | 2019-01-15 | 宁夏软件工程院有限公司 | A kind of electrolytic process manganese ion concentration measuring device and measurement method |
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| CN104900898A (en) * | 2015-04-24 | 2015-09-09 | 南京工业大学 | Vanadium battery capacity attenuation reducing method |
| CN104865226B (en) * | 2015-06-24 | 2017-07-14 | 清华大学深圳研究生院 | A kind of method for quick and device of the side reaction of all-vanadium flow battery positive pole |
| CN104865226A (en) * | 2015-06-24 | 2015-08-26 | 清华大学深圳研究生院 | Rapid detection method and rapid detection apparatus of all-vanadium flow battery positive electrode side reaction |
| CN106198453A (en) * | 2016-08-25 | 2016-12-07 | 清华大学深圳研究生院 | The online test method of the chief and vice reaction ratio of a kind of all-vanadium flow battery and device |
| CN106198453B (en) * | 2016-08-25 | 2019-03-26 | 清华大学深圳研究生院 | A kind of online test method and device of the chief and vice reaction ratio of all-vanadium flow battery |
| CN109211885B (en) * | 2017-06-29 | 2021-03-12 | 宁夏软件工程院有限公司 | Manganese ion concentration measuring equipment and method in electrolytic process |
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| CN110857911B (en) * | 2018-08-24 | 2021-11-26 | 江苏泛宇能源有限公司 | Method for testing electrolyte balance degree of portable all-vanadium redox flow battery |
| CN110857911A (en) * | 2018-08-24 | 2020-03-03 | 江苏泛宇能源有限公司 | Method for testing electrolyte balance degree of portable all-vanadium redox flow battery |
| WO2020038390A1 (en) * | 2018-08-24 | 2020-02-27 | 江苏泛宇能源有限公司 | Portable method for testing degree of balance of all-vanadium redox flow battery electrolyte |
| WO2020105687A1 (en) * | 2018-11-22 | 2020-05-28 | 株式会社堀場製作所 | Electrolytic solution analysis method, and electrolytic solution analyzing device |
| JPWO2020105687A1 (en) * | 2018-11-22 | 2021-10-14 | 株式会社堀場製作所 | Electrolyte analysis method and electrolyte analyzer |
| JP7227984B2 (en) | 2018-11-22 | 2023-02-22 | 株式会社堀場製作所 | Electrolyte analysis method and electrolyte analysis device |
| CN113640225A (en) * | 2021-08-23 | 2021-11-12 | 广西埃索凯新材料科技有限公司 | Sulfuric acid concentration monitoring system applied to manganese sulfate production |
| CN113640225B (en) * | 2021-08-23 | 2024-04-19 | 广西埃索凯新材料科技有限公司 | Sulfuric acid concentration monitoring system applied to manganese sulfate production |
| CN115655383A (en) * | 2022-12-27 | 2023-01-31 | 杭州德海艾科能源科技有限公司 | Method and system for detecting valence state imbalance state of electrolyte of all-vanadium redox flow battery |
| CN115655383B (en) * | 2022-12-27 | 2023-04-07 | 杭州德海艾科能源科技有限公司 | Method and system for detecting valence state imbalance state of electrolyte of all-vanadium redox flow battery |
| CN117721513A (en) * | 2024-02-18 | 2024-03-19 | 深圳市海里表面技术处理有限公司 | Self-adaptive silver plating method and system based on spectral analysis |
| CN117721513B (en) * | 2024-02-18 | 2024-04-16 | 深圳市海里表面技术处理有限公司 | Self-adaptive silver plating method and system based on spectral analysis |
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| CN102507472B (en) | 2014-04-30 |
| HK1167456A1 (en) | 2012-11-30 |
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