CN104865226B - A kind of method for quick and device of the side reaction of all-vanadium flow battery positive pole - Google Patents
A kind of method for quick and device of the side reaction of all-vanadium flow battery positive pole Download PDFInfo
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Abstract
The present invention relates to the method for quick and device of a kind of positive pole side reaction degree of all-vanadium flow battery based on transmitted light intensity, the method comprising the steps of：Obtain first discharge curve of the positive electrolyte for all-vanadiumredox flow battery under the parameter preset；Obtain second discharge curve of the positive electrolyte for all-vanadiumredox flow battery under the parameter preset；According to the first discharge curve and the second discharge curve, determine that the corresponding transmitted light intensity of the all-vanadium flow battery positive pole side reaction is poor；Determine the side reaction proportion of the all-vanadium flow battery positive pole under parameter current.The present invention can quickly measure positive pole side reaction ratio of the vanadium cell under different parameters, determine vanadium cell optimal parameter, be that the parametric measurement of high-volume vanadium cell in industrialized production is laid a good foundation.
Description
Technical field：
The invention belongs to field of measuring technique, the positive pole of more particularly to a kind of all-vanadium flow battery based on transmitted light intensity
The method for quick and device of side reaction degree.
Background technology：
Vanadium redox battery (Vanadium Redox Flow battery, abbreviation VRB or vanadium cell) is in upper
Individual century the eighties are developed (Journal of The Electrochemical Society, 1986,133:
1057), because of its easy scale, long service life, safe and environment-friendly etc. advantage, have become classic energy storage technology it
One.
In vanadium cell, the operation material in both positive and negative polarity is all electrolyte (negative pole+2 ,+trivalent vanadium ion containing vanadium ion；
The valency vanadium ion of positive pole+4 ,+5).The energy storage of vanadium cell and reacting environment are separated, and the electrolyte of both positive and negative polarity is stored respectively
Flowed into two fluid reservoirs, when using in vanadium cell and occur redox reaction.In charging process ,+4 valency vanadium ions of positive pole
Be changed into+5 valency vanadium ions, negative pole+trivalent vanadium ion is changed into+divalent vanadium ion.Otherwise discharge process.
Vanadium cell in charging, in addition to carrying out the chemical reaction of vanadium ion receiving and losing electrons, is also inevitably present
In other side reactions, such as anode electrolyte hydrogen is separated out in the reaction of precipitated oxygen (or carbon dioxide) and electrolyte liquid
Reaction.The difference of the side reaction degree of both positive and negative polarity can cause unbalance, the Jin Erying of the ionic valence condition between both positive and negative polarity electrolyte
Ring the charge/discharge capacity of vanadium cell.The side reaction of positive pole can also be produced to the electrode (the mainly carbon material such as graphite cake) of vanadium cell
Corrosion, reduces the service life of vanadium cell, or even causes electrolyte to reveal.Therefore, how effectively reduction side reaction (is particularly just
The side reaction of pole), it is always one of main direction of studying of vanadium battery field.
The side reaction of the analysis oxygen (or separating out carbon dioxide) of positive pole is mainly relevant with the overtension of monolithic vanadium cell
(Electrochimica Acta,2011,56:8783), thus control monolithic vanadium cell charging voltage can effectively suppress just
The side reaction of pole.But, actually used vanadium cell is that multi-disc battery is in series, due to the difference between each battery, very
Easily there is the too high situation of the charging voltage of indivedual piece batteries, and then the side reaction of positive pole occur.Therefore, the side reaction of positive pole
It is difficult to be completely eliminated, the ratio shared by it can only be reduced as far as possible by controlling various conditions.Except electricity above-mentioned
Beyond position, also several factors determine the intensity of positive pole side reaction：In theory, concentration of electrolyte is lower, the density of charging current more
Low, electrolyte flow rate is bigger, then the degree of side reaction is lower.But, actually used vanadium cell need increase concentration of electrolyte,
Increase current density to improve its energy density and power density, it is necessary to reduce electrolyte flow rate reduce pump energy loss and
The pressure of pipeline, these all with reduce positive pole side reaction requirement run counter to.It is therefore desirable to be able to conveniently and efficiently detect positive pole pair
The method of the extent of reaction, to judge the isoparametric optimum value of electrolyte flow rate, current density, on the premise of side reaction is limited,
Less electrolyte flow rate and larger current density are obtained, to improve the practicality of vanadium cell.
But, the method for quick detection vanadium cell positive pole side reaction is not capable of at present, and can only be in battery operation one
After a little charge and discharge cycles, by the air pressure change in both positive and negative polarity fluid reservoir respectively, electrolyte sample constant-current titration result or
On-line mass spectroscopy analysis (Electrochemistry Communications, 2013,28:58) side reaction of vanadium cell is estimated
Degree.These method and steps are cumbersome, time-consuming, are unfavorable for the parametric measurement of high-volume vanadium cell in industrialized production.And so
Long-time charge-discharge test after, positive pole side reaction may cause expendable damage to the electrode of vanadium cell.
We propose electrolyte of vanadium redox battery charged state (state of charge, SOC) online test method before this
(ZL201110327579.9；Journal of Applied Electrochemistry,2012,42:1025；Journal of
Spectroscopy, 2013,453980), contrasted by the standard spectrum in the transmitted spectrum and database that detect, it is real
The detection of existing electrolyte of vanadium redox battery charged state.We have found under study for action, due to the presence that different ions interact, vanadium electricity
The spectral detection of pond anode electrolyte sometimes has very high sensitivity, is that the positive pole of quick detection vanadium cell is secondary anti-
Answering degree to provide may.
The content of the invention
In view of existing method can not realize the quick detection of vanadium cell positive pole side reaction, the vanadium electricity proposed before this at us
On the basis of pond online test method (ZL201110327579.9), the present invention proposes a kind of vanadium cell based on transmitted light intensity
The method for quick of positive pole side reaction.
As one aspect of the present invention, there is provided a kind of detection means of all-vanadium flow battery positive pole side reaction, the detection
Device includes all-vanadium flow battery unit, optical detection unit and signal acquisition process unit, wherein,
Also include control unit,
Described control unit includes constant-current charge control unit, constant-current discharge control unit, self discharge control unit,
The constant-current charge control unit is used to control all-vanadium flow battery unit to carry out constant-current charge,
The constant-current discharge control unit is used to control all-vanadium flow battery unit to carry out constant-current discharge,
The self discharge control unit is used to control all-vanadium flow battery unit to carry out self discharge.
Further, the all-vanadium flow battery part includes：Be stored with anode electrolyte positive pole fluid reservoir, be stored with
The negative pole fluid reservoir of electrolyte liquid, cell reaction area, absorption cell,
Anode electrolyte flows out from positive pole fluid reservoir, first flows through absorption cell and flows into again in the cell reaction area, then
The cell reaction area is flowed out to return in positive pole fluid reservoir；
Electrolyte liquid flows out from negative pole fluid reservoir, flows into the cell reaction area, is then out the battery anti-
Area is answered to return in negative pole fluid reservoir.
It is preferred that, the absorption length of the absorption cell is 1mm.
It is preferred that, the optical detection unit includes light source, beam splitter, the first detector, the second detector,
The light that light source is sent is divided into two beams by beam splitter, wherein a branch of first detector that enters is to be used as light intensity
Monitoring data, another light beam passes through absorption cell, by the second detector measurement.
As another aspect of the present invention there is provided a kind of detection method of all-vanadium flow battery positive pole side reaction, wherein
Using any one above-mentioned detection means, and including step：
A) parameter preset in setting detection means；
B) the first discharge curve of the all-vanadium flow battery positive pole under the parameter preset is obtained；
C) the second discharge curve of the all-vanadium flow battery positive pole under the parameter preset is obtained；
D) according to the first discharge curve and the second discharge curve, determine that the all-vanadium flow battery positive pole side reaction is corresponding
Transmitted light intensity is poor；
E) side reaction of the all-vanadium flow battery positive pole under parameter current is determined；
F) judge whether to need to change parameter preset, if desired change parameter preset then return to step a), otherwise terminate.
It is preferred that, determine that the side reaction of positive pole under the different in flow rate and density of charging current accounts for the ratio of overall reaction.It is preferred that,
Step b) includes：
B1, by charging or changing the mode such as electrolyte, make the anode electrolyte original state of measured vanadium cell to fill
Pure+5 valency of electricity condition 100%, GND electrolyte is the excessive vanadium that can be oxidized and can be reduced of relative positive pole
Solion (such as+2, mixed electrolytic solution of+trivalent vanadium ion)；
B2, battery shelved into (without discharge and recharge), only allow battery plus-negative plate electrolyte flow through the recycle stream of battery
It is dynamic, the barrier film of both positive and negative polarity electrolyte is separated because vanadium ion is slowly penetrated, the charged state of anode electrolyte gradually subtracts
It is small, transmitted light intensity can from it is initial when maximum (the A points in Fig. 2) and persistently reduce, measure and record, obtain the first curve
(d in Fig. 2).
It is preferred that, step c) includes：
C1, by charging, anode electrolyte is changed into again pure+5 valency of charged state 100%, makes anode electrolyte
Transmitted light intensity returns to maximum (the A points in Fig. 2)；
C2, in the first preset time, keep both positive and negative polarity electrolyte circulation (c in Fig. 2)；
C3, electricity Q default to battery progress constant-current discharge (e in Fig. 2),
After C4, electric discharge, battery is shelved into the second preset time (f in Fig. 2),
C5, the constant-current charge (g in Fig. 2) for carrying out to battery default electricity Q again,
After C6, charging, battery is shelved into the 3rd preset time (h in Fig. 2).
It is preferred that, step d) includes：
According to the second discharge curve (such as Fig. 2) obtained by the first discharge curve, step c) obtained by step b), it is determined that described
The corresponding transmitted light intensity of all-vanadium flow battery positive pole side reaction is poor；
Further, step C4 obtains curve (f) and obtains light intensity difference of the curve (d) under same time with step B2
(Q1) it is actual discharge electricity Q during constant-current dischargePutWith in this period due to infiltration reduce electricity sum, i.e.,
Q1=QPut+QElectric discharge infiltration；
Step C6 obtains curve (h) and step C4 and obtains curve (f) according to the extended line of curve d rules when identical
Between under light intensity difference (Q2) be actual charge capacity Q during constant-current chargeFillWith in this period due to infiltration reduce electricity
The difference of amount, i.e.,
Q2=QFill–QCharging infiltration；
Then step C6 obtain curve (h) and light intensity differences (Q3 in Fig. 2) of the curve d under same time be Q1 and Q2 it
Difference：
Q3=Q1-Q2=(QPut-QFill)+(QElectric discharge infiltration-QCharging infiltration)；
And the theoretical capacity for being charged and discharged process is equal, the reason for creating a difference is exactly a part of electric quantity consumption in charging
In side reaction, then the Part I Q of above formulaPut-QFillIt is exactly the side reaction required by us；
QIt is secondary=QPut-QFill=Q3-(QElectric discharge infiltration-QCharging infiltration)
To sum up, the light intensity difference produced by side reaction consumption electricity is：
QIt is secondary=Q3-Q0；Wherein Q0=QElectric discharge infiltration-QCharging infiltrationFor a constant.
It is preferred that, in step f), according to the transmitted light intensity of anode electrolyte difference and positive pole side reaction into qualitative relationships, can
The qualitative size for determining side reaction proportion.
It is preferred that, step f) includes：According to the transmitted light intensity of prior calibration or the anode electrolyte of theoretical calculation with
Transmitted light intensity difference, is converted into charged state by the relation of charged state, so that it is determined that under each parameter vanadium cell positive pole side reaction
Percentage.
It is preferred that, change the different parameter of step a), such as electrolyte flow rate, charging or discharging current density, concentration of electrolyte,
According to b)-e) the step of measurement vanadium cell side reaction produce light intensity difference QIt is secondary, it is possible to qualitatively measure the pair of vanadium cell
Response intensity.
It is preferred that,, can according to the transmitted light intensity of anode electrolyte difference with positive pole side reaction into positive correlation in step f)
The qualitative size for determining side reaction proportion.
It is preferred that, step f) includes：
Transmitted light intensity difference, is converted into charging shape by F1, the transmitted light intensity according to anode electrolyte and charged state relation
State is poor；
F2, the side reaction percentage for determining vanadium cell positive pole under parameter current；
It is preferred that, in step F1, according to prior calibration or the theoretical relation for determining transmitted light intensity and charged state.
It is preferred that：Step a) includes：Set electrolyte flow rate, the density of charging current, discharge current density, concentration of electrolyte
In at least one；
It is preferred that, successively using 40,80,120,160,200mA/cm2The constant-current discharge that is carried out to it of current density and
Constant-current charge；
It is preferred that, absorption pond length is 0.5-2mm, and preset wavelength is more than 400nm one or more wavelength；
It is preferred that, absorption pond length is 1mm, and preset wavelength wave band is visible light wave range 420-690nm；
It is preferred that, the density of charging current in step C3 and step C5 is equal or unequal.
Pass through quick detection apparatus and method provided by the present invention, compared with existing side reaction metering system, this hair
Bright advantage is as follows：
(1) measure quick, convenient：The vanadium electricity under a certain parameter can be rapidly and quantitatively measured within the time of a few minutes
The positive pole side reaction in pond accounts for the ratio of overall reaction；The ratio total time of vanadium cell positive pole side reaction under many kinds of parameters is measured also one
Within hour.
(2) nondestructive measurement：The electricity charged during measurement is minimum, it is to avoid corruption of the positive pole side reaction to electrode in measurement process
Erosion.
The present invention can quickly measure positive pole side reaction ratio of the vanadium cell under different parameters, determine that vanadium cell is most preferably joined
Number, is that the parametric measurement of high-volume vanadium cell in industrialized production is laid a good foundation.
Brief description of the drawings
Under Fig. 1 is visible light wave range, transmitted spectrum average value of the anode electrolyte of vanadium battery under different charged states.
Fig. 2 be the present invention a certain parameter of quickly measurement under, the principle schematic of the ratio of vanadium cell positive pole side reaction.
Fig. 3 is the schematic diagram of detection means in first embodiment of the invention.
Fig. 4 is the overall action box of the method for quick of the vanadium cell positive pole side reaction in second embodiment of the invention
Figure.
Fig. 5 is the step b of the method for quick of the vanadium cell positive pole side reaction in second embodiment of the invention block diagram.
Fig. 6 is the step c of the method for quick of the vanadium cell positive pole side reaction in second embodiment of the invention block diagram.
Fig. 7 is the step e of the method for quick of the vanadium cell positive pole side reaction in second embodiment of the invention block diagram.
Fig. 8 is positive pole side reaction ratio under the different in flow rate and density of charging current measured in third embodiment of the invention
Initial data.
Fig. 9 is the charged state that experimental calibration goes out in third embodiment of the invention and the relation of transmitted light intensity.
Figure 10 is positive pole side reaction under the different in flow rate and density of charging current finally given in third embodiment of the invention
Account for the ratio of overall reaction.
In figure, the technical characteristic representated by each reference is：
1st, light source, 2, absorption cell, 3, optical detection unit, 4, signal processing unit, 5, control unit, 51, constant-current charge
Control unit, 52, constant-current discharge control unit, 53, self discharge parameter control unit, 6 reaction zones, 7, anode electrolyte liquid storage
Tank, 8, electrolyte liquid fluid reservoir
Embodiment
An embodiment of the invention is further described below in conjunction with accompanying drawing.
It is that anode electrolyte of vanadium battery (2mol/L vanadium ion concentrations, 4.5mol/L sulfate concentrations) fills in difference such as Fig. 1
(pure+4 valency correspondence 0%, for the transmitted spectrum average value under 100%), (absorption length is 1mm to pure+5 valency to electricity condition, it is seen that light wave
Section 420-690nm).
Charged state (state of charge) SOC=C5/(C4+C5), wherein C4、C5The respectively concentration of+4 ,+5 valencys.
It may be seen that in pure+4 valency of charged state 0% and 100% pure+5 valency, the transmitted light of electrolyte is relative
Relatively strong, with the appearance of another valence state, the transmitted light intensity of electrolyte reduces rapidly.We are 0% and 100% charged state
Region amplification (two small figures in such as Fig. 1), it can be seen that can be by transmitted light intensity extremely delicately in the two regions
Detecting the change of the charged state of electrolyte --- this is the basis of the present invention.
Fig. 2 is the principle schematic for quickly measuring the ratio of vanadium cell positive pole side reaction under a certain parameter of the present invention.
Wherein ordinate is that transmitted light intensity, abscissa are pendulous frequency or time.State A points are the anolyte of vanadium cell
The charged state of liquid is 100% pure+5 valency, and now transmitted light intensity is maximum.
Battery is now shelved into (without discharge and recharge) (during in the maximum A points of transmitted light intensity), battery plus-negative plate is only allowed
Electrolyte is carried out flowing through circulating for battery, and the barrier film of both positive and negative polarity electrolyte is separated because vanadium ion is slowly penetrated,
The charged state of anode electrolyte can be gradually reduced, transmitted light intensity can from it is initial when maximum A and persistently subtract along curve d
It is few.
By charging, the transmitted light intensity of anode electrolyte is returned to maximum A, keep circulating for both positive and negative polarity electrolyte
To one section of curve c, one section of curve e is obtained to the constant-current discharge that battery carries out regulation electricity Q, battery is shelved after electric discharge for a period of time
Obtain one section of curve f, then carry out regulation electricity Q constant-current charge obtaining one section of curve g, battery is shelved after charging and obtains one section of song
Line h.
Curve f and light intensity difference Q1s of the curve d under same time is the actual discharge electricity Q during constant-current dischargePutWith
Due to the electricity sum that infiltration reduces in this period, i.e.,
Q1=QPut+QElectric discharge infiltration；
Curve h and curve f is constant-current charge process according to light intensity difference Q2 of the extended line of curve d rules under same time
In actual charge capacity QFillWith in this period due to infiltration reduce electricity difference, i.e.,
Q2=QFill–QCharging infiltration；
Then curve h and light intensity difference Q3s of the curve d under same time is Q1 and Q2 difference：
Q3=Q1-Q2=(QPut-QFill)+(QElectric discharge infiltration-QCharging infiltration)；
Equal in view of the theoretical capacity of charging and discharging process, the reason for uniquely creating a difference is exactly one in charging
Divide electric quantity consumption in side reaction, then the Part I Q of above formulaPut-QFillIt is exactly the side reaction required by us.
QIt is secondary=QPut-QFill=Q3-(QElectric discharge infiltration-QCharging infiltration)
Because the vanadium ion under the function of current is different to the infiltration rate of barrier film, the vanadium ion of different valence state is to barrier film
Infiltration is also different, therefore the Part II Q of above formulaElectric discharge infiltration-QCharging infiltrationTypically it is not zero, substantially one constant can pass through reality
Test and draw or theory is extrapolated.
To sum up, the light intensity difference of the electricity generation of side reaction is：
QIt is secondary=Q3-Q0；Wherein Q0=QElectric discharge infiltration-QCharging infiltrationFor an approximate constant.
Change different vanadium cell parameters, such as electrolyte flow rate, charging or discharging current density, concentration of electrolyte, according to Fig. 2
The step of measurement vanadium cell side reaction produce light intensity difference QIt is secondary, it is possible to the side reaction for qualitatively measuring vanadium cell is strong
Degree.Further according to the relation of the transmitted light intensity and charged state of prior calibration or the anode electrolyte of theoretical calculation, transmission
Light intensity difference is converted into charged state, it becomes possible to the quantitative side reaction percentage for obtaining vanadium cell under each parameter.
First embodiment
Fig. 3 is the schematic diagram of first embodiment of the invention device.Including all-vanadium flow battery unit (VRB), optical detection
Unit and signal acquisition process unit, also include control unit.
All-vanadium flow battery unit includes：Be stored with the positive pole fluid reservoir 7 of anode electrolyte, the electrolyte that is stored with liquid
Negative pole fluid reservoir 8, cell reaction area 6, absorption cell 2, it is preferred that the 2mol/L vanadium ions that are stored with respectively in both positive and negative polarity fluid reservoir,
Each 50ml of positive and negative electrode electrolyte of 4.5mol/L sulfate ions.Magnetic stirring apparatus is stirred the electrolyte inside fluid reservoir
Mix, it is fully mixed.
Peristaltic pump is extracted anode electrolyte, electrolyte liquid out and flowed into the cell reaction area 6, wherein anode electrolyte
First flow through absorption cell 2 and flow into the cell reaction area 6 again.It is preferred that, the absorption length of absorption cell 2 is 1mm.It is preferred that, it is described
Cell reaction area 6 is baby battery, it is furthermore preferred that baby battery is monolithic battery, effective area is 25cm2, both positive and negative polarity centre is used
The films of Nafion 117 are separated.
Battery electrolyte is flowed out behind the cell reaction area 6, is returned in positive pole fluid reservoir 7, negative pole fluid reservoir 8.
Followed by optical detecting parts：The light that light source is sent is divided into two beams by beam splitter.It is wherein a branch of to enter first
Monitoring data after detector in input signal acquisition process unit as light intensity, another light beam is passed through after absorption cell by the
Two detector measurements, obtained spectroscopic data is passed in signal acquisition process unit and recorded.It is preferred that, light source can use white light
Source of parallel light.
Described control unit includes constant-current charge control unit, constant-current discharge control unit, self discharge control unit,
The constant-current charge control unit is filled for controlling all-vanadium flow battery unit to proceed by constant current in predetermined instant
Electricity；
The constant-current discharge control unit is put for controlling all-vanadium flow battery unit to proceed by constant current in predetermined instant
Electricity；
The self discharge control unit is used to control all-vanadium flow battery unit to proceed by self discharge in predetermined instant.
Second embodiment
Fig. 4 is the schematic flow sheet for the method that second embodiment of the invention is provided.
This method uses the detection means described in first embodiment, and including step：
Set the parameter preset in detection means；
Obtain first discharge curve of the all-vanadium flow battery positive pole under the parameter preset；
Obtain second discharge curve of the all-vanadium flow battery positive pole under the parameter preset；
According to the first discharge curve and the second discharge curve, determine that the all-vanadium flow battery positive pole side reaction is corresponding
Penetrate light intensity difference；
A) side reaction of the all-vanadium flow battery positive pole under parameter current is determined；
B) judge whether to need to change parameter preset, if desired change parameter preset then return to step a), otherwise terminate.
Wherein, as shown in figure 5, step b) includes：
B1, by charging or changing the mode such as electrolyte, make the anode electrolyte original state of measured vanadium cell to fill
Pure+5 valency of electricity condition 100%, GND electrolyte is the excessive vanadium that can be oxidized and can be reduced of relative positive pole
Solion (such as+2, mixed electrolytic solution of+trivalent vanadium ion)；
B2, battery shelved into (without discharge and recharge), only allow battery plus-negative plate electrolyte flow through the recycle stream of battery
It is dynamic, the barrier film of both positive and negative polarity electrolyte is separated because vanadium ion is slowly penetrated, the charged state of anode electrolyte gradually subtracts
It is small, transmitted light intensity can from it is initial when maximum (the A points in Fig. 2) and persistently reduce, measure and record this curve.
Wherein, as shown in fig. 6, step c) includes：
C1, by charging, anode electrolyte is changed into again pure+5 valency of charged state 100%, makes anode electrolyte
Transmitted light intensity returns to maximum (the A points in Fig. 2)；
C2, in the first preset time, keep both positive and negative polarity electrolyte circulation, carry out self discharge (c in Fig. 2)；
C3, electricity Q default to battery progress constant-current discharge (e in Fig. 2),
After C4, electric discharge, battery is shelved into the second preset time, self discharge (f in Fig. 2) is carried out,
C5, the constant-current charge (g in Fig. 2) for carrying out to battery default electricity Q again,
After C6, charging, battery is shelved into the 3rd preset time, self discharge (h in Fig. 2) is carried out.
Wherein, step d) includes：
According to the second discharge curve (such as Fig. 2) obtained by the first discharge curve, step c) obtained by step b), it is determined that described
The corresponding transmitted light intensity of all-vanadium flow battery positive pole side reaction is poor；
Further, step C4 obtains curve (f) and obtains light intensity difference of the curve (d) under same time with step B2
(Q1) it is actual discharge electricity Q during constant-current dischargePutWith in this period due to infiltration reduce electricity sum, i.e.,
Q1=QPut+QElectric discharge infiltration；
Step C6 obtains curve (h) and step C4 and obtains curve (f) according to the extended line of curve d rules when identical
Between under light intensity difference (Q2) be actual charge capacity Q during constant-current chargeFillWith in this period by
The difference of the electricity reduced in infiltration, i.e. Q2=QFill–QCharging infiltration；
It is Q1 and Q2 difference that then step C6, which obtains curve (h) with light intensity differences (Fig. 2-Q3) of the curve d under same time,：
Q3=Q1-Q2=(QPut-QFill)+(QElectric discharge infiltration-QCharging infiltration)；
And the theoretical capacity for being charged and discharged process is equal, the reason for creating a difference is exactly a part of electric quantity consumption in charging
In side reaction, then the Part I Q of above formulaPut-QFillIt is exactly the side reaction required by us；
In a word, the light intensity difference produced by side reaction consumption electricity is：QIt is secondary=Q3-Q0；Wherein Q0=QElectric discharge infiltration-QCharging infiltrationFor one
Individual constant.
Wherein, in step f), the size of overall reaction ratio shared by positive pole side reaction both can be qualitatively determined, can also be determined
The size of overall reaction ratio shared by the determination positive pole side reaction of amount.
It is preferred that, to qualitatively determine, according to the transmitted light intensity of anode electrolyte difference and positive pole side reaction into non-linear
Proportional relation (transmitted light intensity difference it is bigger, positive pole side reaction is bigger；Transmitted light intensity difference is smaller, and positive pole side reaction is smaller), it can determine
Property determines the size of side reaction proportion.
It is preferred that, to quantitative determination, as shown in fig. 7, then including in step f)：
Transmitted light intensity difference, is converted into charging shape by F1, the transmitted light intensity according to anode electrolyte and charged state relation
State is poor；
F2, the side reaction percentage for determining vanadium cell positive pole under parameter current；
It is preferred that, in step F1, according to prior calibration or the theoretical relation for determining transmitted light intensity and charged state.
Wherein, step a) includes：Set in electrolyte flow rate, the density of charging current, discharge current density, concentration of electrolyte
At least one；
It is preferred that, successively using 40,80,120,160,200mA/cm2Current density constant-current discharge and perseverance are carried out to it
Current charge；
It is preferred that, absorption pond length is 0.5-2mm, and preset wavelength is more than 400nm one or more wavelength；
It is preferred that, absorption pond length is 1mm, and preset wavelength wave band is visible light wave range 420-690nm；It is preferred that, step
The density of charging current in C3 and step C5 is equal or unequal.
3rd embodiment
Provide an example specifically implemented.
Fig. 8 is the initial data of positive pole side reaction ratio under the different in flow rate and density of charging current measured in the present invention.
Wherein (a)-(d) is respectively the data measured under flow velocity 20,40,60,80ml.In every group of data, anode electrolyte is filled first
To transmitted light intensity maximum (100% charged state), then successively using 40,80,120,160,200mA/cm2Current density
Constant-current discharge and constant-current charge that electricity is 0.03Ah are carried out to it.Wherein respectively there is one section to shelve so as to electricity after charging, electric discharge
Liquid stabilized intensity is solved, has one section of charging process electrolyte transmitted light intensity is returned to maximum between different current measurements.Measurement
After complete each group current density, battery, which is shelved, measures light intensity reduction curve (the first discharge curve, every group of Fig. 8 that its self discharge is caused
Data decline), and be placed on using this first discharge curve as baseline in every group of measurement data (dotted line in Fig. 8).Every group
The difference (having been marked in Fig. 8) of the transmitted light intensity of electrolyte and the first electric discharge baseline, is exactly that positive pole side reaction is caused after electric discharge, charging
Transmitted light intensity it is poor.The light intensity difference caused from the side reaction of Fig. 8 different in flow rate, different current densities marked, we can see
Go out, electrolyte flow rate is smaller, side reaction is bigger, current density is bigger, side reaction is bigger.
Fig. 9 is the charged state that experimental calibration goes out and the relation of transmitted light intensity, anode electrolyte volume 50ml, and composition is
2mol/L vanadium ions, 4.5mol/L sulfate ions, absorption pond length are 1mm.
Figure 10 is the charged state of application drawing 9 and the relation of transmitted light intensity, the light intensity difference that the side reaction in Fig. 8 is caused
According to charged state is converted to, further according to the change of theoretical charged state, under the different in flow rate and density of charging current calculated just
Pole side reaction accounts for the ratio of overall reaction.This result is to selecting the parameters such as suitable current density and flow velocity most important, favorably
In the industrialization process for promoting vanadium cell.
Pass through quick detection apparatus and method provided by the present invention, compared with existing side reaction metering system, this hair
Bright advantage is as follows：
(1) measure quick, convenient：The vanadium electricity under a certain parameter can be rapidly and quantitatively measured within the time of a few minutes
The positive pole side reaction in pond accounts for the ratio of overall reaction；The ratio total time of vanadium cell positive pole side reaction under many kinds of parameters is measured also one
Within hour.
(2) nondestructive measurement：The electricity charged during measurement is minimum, it is to avoid corruption of the positive pole side reaction to electrode in measurement process
Erosion.
The present invention can quickly measure positive pole side reaction ratio of the vanadium cell under different parameters, determine that vanadium cell is most preferably joined
Number, is that the parametric measurement of high-volume vanadium cell in industrialized production is laid a good foundation.
The preferred embodiment of the embodiment of the present invention is the foregoing is only, embodiment is not intended to limit the invention, for this
For art personnel, the embodiment of the present invention can have various changes and change.All spiritual and originals in the embodiment of the present invention
Any modifications, equivalent substitutions and improvements made within reason etc., should be included within the protection domain of the embodiment of the present invention.
Claims (10)
1. a kind of detection means of all-vanadium flow battery positive pole side reaction, including all-vanadium flow battery unit, optical detection unit,
And signal acquisition process unit, it is characterised in that：
Also include control unit,
Described control unit includes constant-current charge control unit, constant-current discharge control unit, self discharge control unit,
The constant-current charge control unit is used to control all-vanadium flow battery unit to carry out constant-current charge,
The constant-current discharge control unit is used to control all-vanadium flow battery unit to carry out constant-current discharge,
The self discharge control unit is used to control all-vanadium flow battery unit to carry out self discharge；
Also, described control unit is used for the constant-current charge, constant-current discharge and self discharge for controlling all-vanadium flow battery, to obtain
First discharge curve and the second discharge curve.
2. detection means according to claim 1, it is characterised in that：
All-vanadium flow battery part includes：Be stored with the positive pole fluid reservoir of anode electrolyte, the negative pole of the electrolyte that is stored with liquid
Fluid reservoir, cell reaction area, absorption cell,
Anode electrolyte first flows through absorption cell and flowed into again in the cell reaction area, is then out the cell reaction area and returns to just
In the fluid reservoir of pole；
Electrolyte liquid is flowed into the cell reaction area, is then out the cell reaction area and is returned in negative pole fluid reservoir.
3. detection means according to claim 2, it is characterised in that：The optical detection unit include light source, beam splitter,
First detector, the second detector,
The light that light source is sent is divided into two beams by beam splitter, wherein a branch of first detector that enters is using the monitoring as light intensity
Data, another light beam passes through absorption cell, by the second detector measurement.
4. a kind of detection method of all-vanadium flow battery positive pole side reaction, it is characterised in that：Usage right requires any one in 1-3
Detection means described in, and including step：
A) parameter preset in the detection means is set；
B) the first discharge curve of the all-vanadium flow battery positive pole under the parameter preset is obtained；
C) the second discharge curve of the all-vanadium flow battery positive pole under the parameter preset is obtained；
D) according to the first discharge curve and the second discharge curve, the corresponding transmission of the all-vanadium flow battery positive pole side reaction is determined
Light intensity difference；
E) side reaction of the all-vanadium flow battery positive pole under parameter current is determined；
F) judge whether to need to change parameter preset, if desired change parameter preset then return to step a)；Otherwise, then terminate.
5. detection method according to claim 4, it is characterised in that：Step b) includes：
B1, by way of charging or changing electrolyte, it is charging shape to make the anode electrolyte original state of measured vanadium cell
Pure+5 valency of state 100%, GND electrolyte is the excessive vanadium ion that can be oxidized and can be reduced of relative positive pole
Solution；
B2, battery shelved, only allow battery plus-negative plate electrolyte to carry out flowing through circulating for battery, due to vanadium ion slowly
The barrier film for separating both positive and negative polarity electrolyte is penetrated, the charged state of anode electrolyte is gradually reduced, transmitted light intensity can be from initial
When maximum and lasting reduction, measure and record, obtain the first curve.
6. detection method according to claim 5, it is characterised in that：Step c) includes：
C1, by charging, anode electrolyte is changed into again pure+5 valency of charged state 100%, makes the transmission of anode electrolyte
Light intensity returns to maximum；
C2, in the first preset time, keep both positive and negative polarity electrolyte circulation；
C3, electricity Q default to battery progress constant-current discharge；
After C4, electric discharge, battery is shelved into the second preset time；
C5, the constant-current charge for carrying out to battery default electricity Q again；
After C6, charging, battery is shelved into the 3rd preset time.
7. detection method according to claim 6, it is characterised in that：Step d) includes：
According to the second discharge curve obtained by the first discharge curve, step c) obtained by step b), the all-vanadium flow electricity is determined
Positive pole side reaction corresponding transmitted light intensity in pond is poor；
Further, step C4 obtains curve (f) and obtains light intensity difference (Q1) of the curve (d) under same time with step B2
It is the actual discharge electricity Q during constant-current dischargePutWith in this period due to infiltration reduce electricity sum, i.e.,
Q1=QPut+QElectric discharge infiltration；
Step C6 obtains curve (h) and step C4 and obtains curve (f) according to the extended line of curve d rules under same time
Light intensity difference (Q2) be actual charge capacity Q during constant-current chargeFillWith in this period due to infiltration reduce electricity it
Difference, i.e.,
Q2=QFill–QCharging infiltration；
It is Q1 and Q2 difference that then step C6, which obtains curve (h) with light intensity difference Q3s of the curve d under same time,：
Q3=Q1-Q2=(QPut-QFill)+(QElectric discharge infiltration-QCharging infiltration)；
And the theoretical capacity for being charged and discharged process is equal, the reason for creating a difference be exactly charging in a part of electric quantity consumption in pair
In reaction, then the Part I Q of above formulaPut-QFillIt is exactly the side reaction required by us；
QIt is secondary=QPut-QFill=Q3- (QElectric discharge infiltration-QCharging infiltration)
To sum up, the light intensity difference produced by side reaction consumption electricity is：
QIt is secondary=Q3-Q0；Wherein Q0=QElectric discharge infiltration-QCharging infiltrationFor a constant.
8. detection method according to claim 7, it is characterised in that：In step f), according to the transmitted light of anode electrolyte
It is strong it is poor with positive pole side reaction into qualitative relationships, can the qualitative size for determining side reaction proportion.
9. detection method according to claim 7, it is characterised in that：Step f) includes：
Transmitted light intensity difference, is converted into charged state poor by F1, the transmitted light intensity according to anode electrolyte and charged state relation；
F2, determine that the side reaction of vanadium cell positive pole under parameter current accounts for the percentage of overall reaction；
It is preferred that, in step F1, according to prior calibration or the theoretical relation for determining transmitted light intensity and charged state.
10. according to any described detection methods of claim 4-9, it is characterised in that：Step a) includes：Set electrolyte stream
At least one in speed, the density of charging current, discharge current density, concentration of electrolyte；
It is preferred that, successively using 40,80,120,160,200mA/cm2Current density constant-current discharge is carried out to it and constant current is filled
Electricity；
It is preferred that, absorption pond length is 0.5-2mm, and preset wavelength is more than 400nm one or more wavelength；
It is preferred that, absorption pond length is 1mm, and preset wavelength wave band is visible light wave range 420-690nm；
It is preferred that, the density of charging current in step C3 and step C5 is equal or unequal.
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| 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 |
| CN109494388B (en) * | 2017-09-28 | 2021-11-09 | 大连融科储能技术发展有限公司 | Method and system for monitoring side reaction of all-vanadium redox flow battery in real time |
| CN109725264B (en) * | 2019-01-22 | 2021-01-01 | 清华大学深圳研究生院 | In-situ detection method and device for current density distribution of flow battery electrode |
| CN116046730A (en) * | 2023-04-03 | 2023-05-02 | 宁德时代新能源科技股份有限公司 | Electrolyte monitoring device, method, storage medium, and program product |
| CN119324238B (en) * | 2024-12-18 | 2025-03-28 | 常州星辰新能源有限公司 | Real-time monitoring method and system for gassing side reaction of flow battery |
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