CN104865226A - Rapid detection method and rapid detection apparatus of all-vanadium flow battery positive electrode side reaction - Google Patents
Rapid detection method and rapid detection apparatus of all-vanadium flow battery positive electrode side reaction Download PDFInfo
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Abstract
The present invention relates to a rapid detection method and a rapid detection apparatus of an all-vanadium flow battery positive electrode side reaction. The method comprises: acquiring the first discharging curve of an all-vanadium flow battery positive electrode electrolyte under preset parameters; acquiring the second discharging curve of the all-vanadium flow battery positive electrode electrolyte under preset parameters; according to the first discharging curve and the second discharging curve, determining the transmitted light intensity difference corresponding to the all-vanadium flow battery positive electrode side reaction; and determining the proportion of the all-vanadium flow battery positive electrode side reaction under the current parameter. With the method and the apparatus of the present invention, the proportion of the positive electrode side reaction of the vanadium battery under different parameters can be rapidly measured, the optimal vanadium battery parameter can be determined, and the basis is established for the determination of the parameters of the large-batch vanadium batteries in the industrial production.
Description
Technical field:
The invention belongs to field of measuring technique, particularly relate to a kind of method for quick and device of positive pole subsidiary reaction degree of the all-vanadium flow battery based on transmitted light intensity.
Background technology:
Vanadium redox battery (Vanadium Redox Flow battery; be called for short VRB or vanadium cell) invented (Journal of The Electrochemical Society in eighties of last century the eighties; 1986; 133:1057); because of advantages such as its easy scale, long service life, safety and environmental friendliness, become one of classic energy storage technology.
In vanadium cell, the operation material in both positive and negative polarity is all electrolytic solution (negative pole+2 ,+3 valency vanadium ion containing vanadium ion; Positive pole+4 ,+5 valency vanadium ion).Energy storage and the reacting environment of vanadium cell separate, and the electrolytic solution of both positive and negative polarity is stored in two fluid reservoirs respectively, flow in vanadium cell redox reaction occurs during use.In charging process ,+4 valency vanadium ions of positive pole change+5 valency vanadium ions into, and+3 valency vanadium ions in negative pole change+divalent vanadium ion into.Otherwise discharge process.
Vanadium cell in charging, except carrying out the chemical reaction of vanadium ion receiving and losing electrons, also inevitably there is other subsidiary reaction, in such as anode electrolyte, in the reaction of precipitated oxygen (or carbon dioxide) and electrolyte liquid, separate out the reaction of hydrogen.The difference of the subsidiary reaction degree of both positive and negative polarity can cause the unbalance of the ionic valence condition between both positive and negative polarity electrolytic solution, and then affects the charge/discharge capacity of vanadium cell.The subsidiary reaction of positive pole also can produce corrosion to the electrode of vanadium cell material with carbon elements such as (mainly) graphite cakes, reduces the serviceable life of vanadium cell, even causes electrolytic solution to reveal.Therefore, how effectively to reduce subsidiary reaction (particularly the subsidiary reaction of positive pole), be one of main direction of studying of vanadium battery field always.
Main (the Electrochimica Acta relevant to the overtension of monolithic vanadium cell of subsidiary reaction analysing oxygen (or separating out carbon dioxide) of positive pole, 2011,56:8783), the charging voltage therefore controlling monolithic vanadium cell effectively can suppress the subsidiary reaction of positive pole.But the actual vanadium cell used is that multi-disc serial battery forms, and due to the difference between each battery, is easy to the situation occurring that the charging voltage of indivedual sheet battery is too high, and then occurs the subsidiary reaction of positive pole.Therefore, the subsidiary reaction of positive pole is difficult to eliminate completely, can only reduce ratio shared by it by controlling various condition as far as possible.Except current potential above-mentioned, several factors is also had to determine the intensity of positive pole subsidiary reaction: in theory, concentration of electrolyte is lower, the density of charging current is lower, electrolyte flow rate is larger, then the degree of subsidiary reaction is lower.But, the actual vanadium cell used needs to increase concentration of electrolyte, increase current density to improve its energy density and power density, need to reduce electrolyte flow rate to the pressure of the energy loss and pipeline that reduce pump, these are all runed counter to the requirement reducing positive pole subsidiary reaction.Therefore, needs can detect the method for positive pole subsidiary reaction degree quickly and easily, judge the isoparametric optimum value of electrolyte flow rate, current density, under the prerequisite of restriction subsidiary reaction, obtain less electrolyte flow rate and larger current density, to improve the practicality of vanadium cell.
But, can not detect the method for vanadium cell positive pole subsidiary reaction at present fast, and can only after some charge and discharge cycles of battery operation, by result or on-line mass spectroscopy analysis (the Electrochemistry Communications of in both positive and negative polarity fluid reservoir point of other air pressure change, electrolytic solution sampling potentiometric titration, 2013,28:58) estimate the subsidiary reaction degree of vanadium cell.Loaded down with trivial details, the consuming time length of these method steps, is unfavorable for the parametric measurement of vanadium cell in enormous quantities in suitability for industrialized production.And after so long-time charge-discharge test, positive pole subsidiary 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 (ZL201110327579.9 before this; Journal of Applied Electrochemistry, 2012,42:1025; Journalof Spectroscopy, 2013,453980), contrasted by the standard spectrum in the transmitted spectrum that detects and database, realize the detection of electrolyte of vanadium redox battery charged state.We find under study for action, and due to the interactional existence of different ions, the spectral detection of anode electrolyte of vanadium battery has very high sensitivity at some time, for the positive pole subsidiary reaction degree detecting vanadium cell fast provides possibility.
Summary of the invention
In view of existing method all can not realize the quick detection of vanadium cell positive pole subsidiary reaction, on the basis of the vanadium cell online test method (ZL201110327579.9) proposed before this at us, the present invention proposes a kind of method for quick of the vanadium cell positive pole subsidiary reaction based on transmitted light intensity.
As one aspect of the present invention, provide the pick-up unit of a kind of all-vanadium flow battery positive pole subsidiary reaction, this pick-up unit comprises all-vanadium flow battery unit, optical detection unit and signal acquisition process unit, wherein,
Also comprise control module,
Described control module comprises constant-current charge control module, constant-current discharge control module, self discharge control module,
Described constant-current charge control module carries out constant-current charge for controlling all-vanadium flow battery unit,
Described constant-current discharge control module carries out constant-current discharge for controlling all-vanadium flow battery unit,
Described self discharge control module carries out self discharge for controlling all-vanadium flow battery unit.
Further, described all-vanadium flow battery part comprises: the positive pole fluid reservoir storing anode electrolyte, the negative pole fluid reservoir storing electrolyte liquid, cell reaction district, absorption cell,
Anode electrolyte flows out from positive pole fluid reservoir, first flows through absorption cell and flows in described cell reaction district again, then flows out described cell reaction district and gets back in positive pole fluid reservoir;
Electrolyte liquid flows out from negative pole fluid reservoir, flows in described cell reaction district, then flows out described cell reaction district and gets back in negative pole fluid reservoir.
Preferably, the absorption length of described absorption cell is 1mm.
Preferably, described optical detection unit comprises light source, beam splitter, the first detector, the second detector,
The light that light source sends is divided into two bundles through beam splitter, and wherein a branch of first detector that enters is using the monitor data as light intensity, and another bundle light transmission absorption cell, by the second detector measurement.
As another aspect of the present invention, provide the detection method of a kind of all-vanadium flow battery positive pole subsidiary reaction, wherein use any one pick-up unit above-mentioned, and comprise step:
A) parameter preset in pick-up unit is set;
B) first discharge curve of described all-vanadium flow battery positive pole under described parameter preset is obtained;
C) second discharge curve of described all-vanadium flow battery positive pole under described parameter preset is obtained;
D) according to the first discharge curve and the second discharge curve, determine that transmitted light intensity corresponding to described all-vanadium flow battery positive pole subsidiary reaction is poor;
E) subsidiary reaction of described all-vanadium flow battery positive pole under determining parameter current;
F) judge whether to need to change parameter preset, if desired change parameter preset and then return step a), otherwise terminate.
Preferably, determine that the subsidiary reaction of positive pole accounts for the ratio of overall reaction under different in flow rate and the density of charging current.Preferably, step b) comprising:
B1, by charging or changing the modes such as electrolytic solution, make the anode electrolyte original state of measured vanadium cell be pure+5 valencys of charged state 100%, battery cathode electrolytic solution be relative positive pole excessive can the oxidized and vanadium ion solution that can be reduced (mixed electrolytic solutions as+2 ,+3 valency vanadium ions);
B2, battery to be shelved (not carrying out discharge and recharge), battery plus-negative plate electrolytic solution is only allowed to carry out flowing through circulating of battery, because vanadium ion penetrates the barrier film separating both positive and negative polarity electrolytic solution lentamente, the charged state of anode electrolyte reduces gradually, transmitted light intensity can continue from the maximal value (the A point Fig. 2) time initial to reduce, measure and record, obtain the first curve (d in Fig. 2).
Preferably, step c) comprising:
C1, by charging, again anode electrolyte is become pure+5 valencys of charged state 100%, makes the transmitted light intensity of anode electrolyte return to maximal value (the A point in Fig. 2);
C2, in the first Preset Time, keep the circulation (c in Fig. 2) of both positive and negative polarity electrolytic solution;
C3, battery is carried out to the constant-current discharge (e in Fig. 2) of default electricity Q,
After C4, electric discharge, battery is shelved the second Preset Time (f in Fig. 2),
C5, battery is carried out again to the constant-current charge (g in Fig. 2) of default electricity Q,
After C6, charging, battery is shelved the 3rd Preset Time (h in Fig. 2).
Preferably, steps d) comprising:
According to step b) institute obtains the first discharge curve, step c) institute's second discharge curve that obtains (as Fig. 2), determine that transmitted light intensity corresponding to described all-vanadium flow battery positive pole subsidiary reaction is poor;
Further, step C4 obtain curve (f) and step B2 to obtain the light intensity difference of curve (d) under same time (Q1) be actual discharge electricity Q in constant-current discharge process
putdue to the electricity sum that infiltration reduces during this period of time, namely
Q1=Q
put+ Q
electric discharge infiltration;
Step C6 obtain curve (h) and step C4 to obtain curve (f) according to the light intensity difference of extended line under same time (Q2) of curve d rule be actual charge capacity Q in constant-current charge process
filldue to the difference of the electricity of infiltration reduction during this period of time, namely
Q2=Q
fill– Q
charging infiltration;
Then step C6 obtain the difference that curve (h) and the light intensity difference of curve d under same time (Q3 in Fig. 2) are Q1 and Q2:
Q3=Q1-Q2=(Q
put-Q
fill)+(Q
electric discharge infiltration-Q
charging infiltration);
And the theoretical capacity of charging and discharging process is equal, the reason created a difference in charging exactly a part of electric quantity consumption in subsidiary reaction, then the Part I Q of above formula
put-Q
fillit is exactly the subsidiary reaction required by us;
Q
secondary=Q
put-Q
fill=q3-(Q
electric discharge infiltration-Q
charging infiltration)
To sum up, the light intensity difference that side-reaction consumes electricity produces is:
Q
secondary=Q3-Q0; Wherein Q0=Q
electric discharge infiltration-Q
charging infiltrationit is a constant.
Preferably, step f) in, according to the qualitative relationships that the transmitted light intensity difference of anode electrolyte becomes with positive pole subsidiary reaction, the size of subsidiary reaction proportion qualitatively can be determined.
Preferably, step f) comprising: according to the transmitted light intensity of anode electrolyte and the relation of charged state of prior calibration or theory calculate, transmitted light intensity difference is converted into charged state, thus the subsidiary reaction number percent of vanadium cell positive pole under determining each parameter.
Preferably, change a) the different parameter of step, as electrolyte flow rate, charging or discharging current density, concentration of electrolyte etc., according to b)-e) the light intensity difference Q that produces of the step subsidiary reaction of measuring vanadium cell
secondary, just can measure the subsidiary reaction intensity of vanadium cell qualitatively.
Preferably, step f) in, the transmitted light intensity difference according to anode electrolyte becomes positive correlation with positive pole subsidiary reaction, qualitatively can determine the size of subsidiary reaction proportion.
Preferably, step f) comprising:
F1, according to the transmitted light intensity of anode electrolyte and the relation of charged state, transmitted light intensity difference is converted into charged state difference;
F2, determine the subsidiary reaction number percent of vanadium cell positive pole under parameter current;
Preferably, in step F 1, determine the relation of transmitted light intensity and charged state according to prior calibration or theory.
Preferred: step a) comprising: to set at least one in electrolyte flow rate, the density of charging current, discharge current density, concentration of electrolyte;
Preferably, use 40 successively, 80,120,160,200mA/cm
2current density to its constant-current discharge carried out and constant-current charge;
Preferably, absorption cell length is 0.5-2mm, and preset wavelength is one or more wavelength of more than 400nm;
Preferably, absorption cell length is 1mm, and preset wavelength wave band is visible light wave range 420-690nm;
Preferably, the density of charging current in step C3 and step C5 is equal or unequal.
By quick checkout equipment provided by the present invention and method, compared with existing subsidiary reaction metering system, advantage of the present invention is as follows:
(1) measure quick, convenient: the positive pole subsidiary reaction can measuring vanadium cell under a certain parameter within the time of a few minutes fast, quantitatively accounts for the ratio of overall reaction; Under measurement many kinds of parameters, the ratio T.T. of vanadium cell positive pole subsidiary reaction is also within one hour.
(2) nondestructive measurement: the electricity charged during measurement is minimum, to avoid in measuring process positive pole subsidiary reaction to the corrosion of electrode.
The present invention can the positive pole subsidiary reaction ratio of Quick Measurement vanadium cell under different parameters, determines vanadium cell optimal parameter, for the parametric measurement of vanadium cell in enormous quantities in suitability for industrialized production is laid a good foundation.
Accompanying drawing explanation
Fig. 1 is under visible light wave range, the transmitted spectrum mean value of anode electrolyte of vanadium battery under different charged state.
Fig. 2 is under a certain parameter of Quick Measurement of the present invention, the principle schematic of the ratio of vanadium cell positive pole subsidiary reaction.
Fig. 3 is the schematic diagram of pick-up unit in first embodiment of the invention.
Fig. 4 is the overall step block diagram of the method for quick of vanadium cell positive pole subsidiary reaction in second embodiment of the invention.
Fig. 5 is the block diagram of the step b of the method for quick of vanadium cell positive pole subsidiary reaction in second embodiment of the invention.
Fig. 6 is the block diagram of the step c of the method for quick of vanadium cell positive pole subsidiary reaction in second embodiment of the invention.
Fig. 7 is the block diagram of the step e of the method for quick of vanadium cell positive pole subsidiary reaction in second embodiment of the invention.
Fig. 8 is the raw data of positive pole subsidiary reaction ratio under the different in flow rate and the density of charging current measured in third embodiment of the invention.
Fig. 9 is the relation of charged state that in third embodiment of the invention, experimental calibration goes out and transmitted light intensity.
Figure 10 is the ratio that under the different in flow rate and the density of charging current finally obtained in third embodiment of the invention, positive pole subsidiary reaction accounts for overall reaction.
In figure, the technical characteristic representated by each Reference numeral is:
1, light source, 2, absorption cell, 3, optical detection unit, 4, signal processing unit, 5, control module, 51, constant-current charge control module, 52, constant-current discharge control module, 53, self discharge parameter control unit, 6 reaction zones, 7, anode electrolyte fluid reservoir, 8, electrolyte liquid fluid reservoir
Embodiment
Below in conjunction with accompanying drawing, an embodiment of the invention are further described.
As Fig. 1, for anode electrolyte of vanadium battery (2mol/L vanadium ion concentration, 4.5mol/L sulfate concentration) is in different charged state (pure+4 valency correspondences 0%, pure+5 valencys are 100%) under transmitted spectrum mean value (absorption length is 1mm, visible light wave range 420-690nm).
Charged state (state of charge) SOC=C
5/ (C
4+ C
5), wherein C
4, C
5be respectively the concentration of+4 ,+5 valencys.
We can see charged state 0% pure+4 valencys and 100% pure+5 valency time, the transmitted light of electrolytic solution is relatively strong, and along with the appearance of another kind of valence state, the transmitted light intensity of electrolytic solution reduces rapidly.We amplify (as the little figure of two in Fig. 1) the region that charged state is 0% and 100%, can see the change that can be detected the charged state of electrolytic solution in these two regions by transmitted light intensity extremely delicately---and this is basis of the present invention.
Fig. 2 is the principle schematic of the ratio of vanadium cell positive pole subsidiary reaction under a certain parameter of Quick Measurement of the present invention.
Wherein ordinate is transmitted light intensity, horizontal ordinate is pendulous frequency or time.State A point to be the charged state of the anode electrolyte of vanadium cell be 100% pure+5 valencys, now transmitted light intensity is maximum.
Now battery is shelved (not carrying out discharge and recharge) by (when being in the maximum A point of transmitted light intensity), battery plus-negative plate electrolytic solution is only allowed to carry out flowing through circulating of battery, because vanadium ion penetrates the barrier film separating both positive and negative polarity electrolytic solution lentamente, the charged state of anode electrolyte can reduce gradually, and transmitted light intensity can continue to reduce from maximal value A time initial along curve d.
By charging, the transmitted light intensity of anode electrolyte is made to return to maximal value A, the circulation of both positive and negative polarity electrolytic solution is kept to obtain one section of curve c, constant-current discharge battery being carried out to regulation electricity Q obtains one section of curve e, shelving battery a period of time after electric discharge obtains one section of curve f, the constant-current charge carrying out regulation electricity Q again obtains one section of curve g, shelves battery and obtain one section of curve h after charging.
Curve f and the light intensity difference Q1 of curve d under same time is the actual discharge electricity Q in constant-current discharge process
putdue to the electricity sum that infiltration reduces during this period of time, namely
Q1=Q
put+ Q
electric discharge infiltration;
Curve h and curve f is the actual charge capacity Q in constant-current charge process according to the light intensity difference Q2 of extended line under same time of curve d rule
filldue to the difference of the electricity of infiltration reduction during this period of time, namely
Q2=Q
fill– Q
charging infiltration;
Then curve h and the light intensity difference Q3 of curve d under same time is the difference of Q1 and Q2:
Q3=Q1-Q2=(Q
put-Q
fill)+(Q
electric discharge infiltration-Q
charging infiltration);
Consider that the theoretical capacity of charging and discharging process is equal, the reason that uniquely can create a difference in charging exactly a part of electric quantity consumption in subsidiary reaction, then the Part I Q of above formula
put-Q
fillit is exactly the subsidiary reaction required by us.
Q
secondary=Q
put-Q
fill=q3-(Q
electric discharge infiltration-Q
charging 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 also different to the infiltration of barrier film, therefore the Part II Q of above formula
electric discharge infiltration-Q
charging infiltrationgenerally non-vanishing, be a constant substantially, can draw by experiment or theoretical calculate goes out.
To sum up, the light intensity difference that the electricity of subsidiary reaction produces is:
Q
secondary=Q3-Q0; Wherein Q0=Q
electric discharge infiltration-Q
charging infiltrationit is an approximate constant.
Change different vanadium cell parameters, as electrolyte flow rate, charging or discharging current density, concentration of electrolyte etc., according to Fig. 2 step measure vanadium cell subsidiary reaction produce light intensity difference Q
secondary, just can measure the subsidiary reaction intensity of vanadium cell qualitatively.Again according to the transmitted light intensity of anode electrolyte and the relation of charged state of prior calibration or theory calculate, transmitted light intensity difference is converted into charged state, the subsidiary reaction number percent obtaining vanadium cell under each parameter that just can be quantitative.
First embodiment
Fig. 3 is the schematic diagram of first embodiment of the invention device.Comprise all-vanadium flow battery unit (VRB), optical detection unit and signal acquisition process unit, also comprise control module.
All-vanadium flow battery unit comprises: the positive pole fluid reservoir 7 storing anode electrolyte, the negative pole fluid reservoir 8 storing electrolyte liquid, cell reaction district 6, absorption cell 2, preferably, each 50ml of positive and negative electrode electrolytic solution of 2mol/L vanadium ion, 4.5mol/L sulfate ion is stored in both positive and negative polarity fluid reservoir respectively.The electrolytic solution of magnetic stirring apparatus to fluid reservoir inside stirs, and makes it fully mix.
Peristaltic pump is extracted anode electrolyte, electrolyte liquid to flow in described cell reaction district 6 out, and wherein anode electrolyte first flows through absorption cell 2 and flows into described cell reaction district 6 again.Preferably, the absorption length of absorption cell 2 is 1mm.Preferably, described cell reaction district 6 is baby battery, preferred, and baby battery is monolithic battery, and useful area is 25cm
2, both positive and negative polarity centre Nafion 117 film is separated.
After battery electrolyte flows out described cell reaction district 6, get back in positive pole fluid reservoir 7, negative pole fluid reservoir 8.
Next be optical detecting parts: the light that light source sends is divided into two bundles through beam splitter.Wherein a branch of monitor data entered as light intensity in input signal acquisition process unit after the first detector, by the second detector measurement after another bundle light transmission absorption cell, the spectroscopic data obtained passes to record in signal acquisition process unit.Preferably, light source can adopt white light source of parallel light.
Described control module comprises constant-current charge control module, constant-current discharge control module, self discharge control module,
Described constant-current charge control module starts to carry out constant-current charge at predetermined instant for controlling all-vanadium flow battery unit;
Described constant-current discharge control module starts to carry out constant-current discharge at predetermined instant for controlling all-vanadium flow battery unit;
Described self discharge control module starts to carry out self discharge at predetermined instant for controlling all-vanadium flow battery unit.
Second embodiment
Fig. 4 is the schematic flow sheet of the method that second embodiment of the invention provides.
The method uses the pick-up unit described in the first embodiment, and comprises step:
Parameter preset in setting pick-up unit;
Obtain first discharge curve of described all-vanadium flow battery positive pole under described parameter preset;
Obtain second discharge curve of described all-vanadium flow battery positive pole under described parameter preset;
According to the first discharge curve and the second discharge curve, determine that transmitted light intensity corresponding to described all-vanadium flow battery positive pole subsidiary reaction is poor;
A) subsidiary reaction of described all-vanadium flow battery positive pole under determining parameter current;
B) judge whether to need to change parameter preset, if desired change parameter preset and then return step a), otherwise terminate.
Wherein, as shown in Figure 5, step b) comprising:
B1, by charging or changing the modes such as electrolytic solution, make the anode electrolyte original state of measured vanadium cell be pure+5 valencys of charged state 100%, battery cathode electrolytic solution be relative positive pole excessive can the oxidized and vanadium ion solution that can be reduced (mixed electrolytic solutions as+2 ,+3 valency vanadium ions);
B2, battery to be shelved (not carrying out discharge and recharge), battery plus-negative plate electrolytic solution is only allowed to carry out flowing through circulating of battery, because vanadium ion penetrates the barrier film separating both positive and negative polarity electrolytic solution lentamente, the charged state of anode electrolyte reduces gradually, transmitted light intensity can continue from the maximal value (the A point Fig. 2) time initial to reduce, and measures and records this curve.
Wherein, as shown in Figure 6, step c) comprising:
C1, by charging, again anode electrolyte is become pure+5 valencys of charged state 100%, makes the transmitted light intensity of anode electrolyte return to maximal value (the A point in Fig. 2);
C2, in the first Preset Time, keep the circulation of both positive and negative polarity electrolytic solution, carry out self discharge (c in Fig. 2);
C3, battery is carried out to the constant-current discharge (e in Fig. 2) of default electricity Q,
After C4, electric discharge, battery is shelved the second Preset Time, carries out self discharge (f in Fig. 2),
C5, battery is carried out again to the constant-current charge (g in Fig. 2) of default electricity Q,
After C6, charging, battery is shelved the 3rd Preset Time, carry out self discharge (h in Fig. 2).
Wherein, steps d) comprising:
According to step b) institute obtains the first discharge curve, step c) institute's second discharge curve that obtains (as Fig. 2), determine that transmitted light intensity corresponding to described all-vanadium flow battery positive pole subsidiary reaction is poor;
Further, step C4 obtain curve (f) and step B2 to obtain the light intensity difference of curve (d) under same time (Q1) be actual discharge electricity Q in constant-current discharge process
putdue to the electricity sum that infiltration reduces during this period of time, namely
Q1=Q
put+ Q
electric discharge infiltration;
Step C6 obtain curve (h) and step C4 to obtain curve (f) according to the light intensity difference of extended line under same time (Q2) of curve d rule be actual charge capacity Q in constant-current charge process
fillduring this period of time in by
In the difference of the electricity that infiltration reduces, i.e. Q2=Q
fill– Q
charging infiltration;
Then step C6 obtain the difference that curve (h) and the light intensity difference of curve d under same time (Fig. 2-Q3) are Q1 and Q2:
Q3=Q1-Q2=(Q
put-Q
fill)+(Q
electric discharge infiltration-Q
charging infiltration);
And the theoretical capacity of charging and discharging process is equal, the reason created a difference in charging exactly a part of electric quantity consumption in subsidiary reaction, then the Part I Q of above formula
put-Q
fillit is exactly the subsidiary reaction required by us;
In a word, the light intensity difference that side-reaction consumes electricity produces is: Q
secondary=Q3-Q0; Wherein Q0=Q
electric discharge infiltration-Q
charging infiltrationit is a constant.
Wherein, step f) in, both can determine the size of overall reaction ratio shared by positive pole subsidiary reaction qualitatively, the size of overall reaction ratio shared by determination positive pole subsidiary reaction that also can be quantitative.
Preferably, to determine qualitatively, (transmitted light intensity difference is larger, and positive pole subsidiary reaction is larger to become nonlinear proportional relation according to the transmitted light intensity difference of anode electrolyte with positive pole subsidiary reaction; Transmitted light intensity difference is less, and positive pole subsidiary reaction is less), qualitatively can determine the size of subsidiary reaction proportion.
Preferably, to quantitative determination, as shown in Figure 7, then in step f) comprising:
F1, according to the transmitted light intensity of anode electrolyte and the relation of charged state, transmitted light intensity difference is converted into charged state difference;
F2, determine the subsidiary reaction number percent of vanadium cell positive pole under parameter current;
Preferably, in step F 1, determine the relation of transmitted light intensity and charged state according to prior calibration or theory.
Wherein, step a) comprising: set at least one in electrolyte flow rate, the density of charging current, discharge current density, concentration of electrolyte;
Preferably, use 40 successively, 80,120,160,200mA/cm
2current density constant-current discharge and constant-current charge are carried out to it;
Preferably, absorption cell length is 0.5-2mm, and preset wavelength is one or more wavelength of more than 400nm;
Preferably, absorption cell length is 1mm, and preset wavelength wave band is visible light wave range 420-690nm; Preferably, the density of charging current in step C3 and step C5 is equal or unequal.
3rd embodiment
Provide the example of a concrete enforcement.
Fig. 8 is the raw data of positive pole subsidiary reaction ratio under the different in flow rate and the density of charging current measured in the present invention.Wherein (a)-(d) be respectively flow velocity 20,40,60, the data measured under 80ml.Often organize in data, first anode electrolyte be charged to transmitted light intensity maximal value (charged state of 100%), then use 40 successively, 80,120,160,200mA/cm
2current density constant-current discharge that electricity is 0.03Ah and constant-current charge are carried out to it.Wherein charge, discharge after respectively have one section to shelve so that electrolytic solution stabilized intensity, have one section of charging process to make electrolytic solution transmitted light intensity return to maximal value between different current measurement.After measuring each group of current density, light intensity minimizing curve (the first discharge curve measured its self discharge and cause shelved by battery, Fig. 8 often organizes data decline), and this first discharge curve is placed on as baseline often organizes (dotted line in Fig. 8) in measurement data.After often organizing electric discharge, charging, the transmitted light intensity and first of electrolytic solution discharges the difference (marking in Fig. 8) of baseline, is exactly that the transmitted light intensity that causes of positive pole subsidiary reaction is poor.The light intensity difference that the different in flow rate marked from Fig. 8, the subsidiary reaction of different current density cause, we can find out, electrolyte flow rate is less, subsidiary reaction is larger, and current density is larger, subsidiary reaction is larger.
Fig. 9 is the relation of the charged state that goes out of experimental calibration and transmitted light intensity, and anode electrolyte volume 50ml, composition is 2mol/L vanadium ion, 4.5mol/L sulfate ion, and absorption cell length is 1mm.
Figure 10 is the charged state of application drawing 9 and the relation of transmitted light intensity, the light intensity difference data that subsidiary reaction in Fig. 8 causes are converted to charged state, again according to the change of theoretical charged state, under the different in flow rate calculated and the density of charging current, positive pole subsidiary reaction accounts for the ratio of overall reaction.This result is most important to parameter such as selection suitable current density and flow velocity etc., is conducive to the industrialization process promoting vanadium cell.
By quick checkout equipment provided by the present invention and method, compared with existing subsidiary reaction metering system, advantage of the present invention is as follows:
(1) measure quick, convenient: the positive pole subsidiary reaction can measuring vanadium cell under a certain parameter within the time of a few minutes fast, quantitatively accounts for the ratio of overall reaction; Under measurement many kinds of parameters, the ratio T.T. of vanadium cell positive pole subsidiary reaction is also within one hour.
(2) nondestructive measurement: the electricity charged during measurement is minimum, to avoid in measuring process positive pole subsidiary reaction to the corrosion of electrode.
The present invention can the positive pole subsidiary reaction ratio of Quick Measurement vanadium cell under different parameters, determines vanadium cell optimal parameter, for the parametric measurement of vanadium cell in enormous quantities in suitability for industrialized production is laid a good foundation.
The foregoing is only the preferred embodiment of the embodiment of the present invention, be not limited to the embodiment of the present invention, to those skilled in the art, the embodiment of the present invention can have various change and change.Any amendment done within all spirit in the embodiment of the present invention and principle, equivalent replacement, improvement etc., within the protection domain that all should be included in the embodiment of the present invention.
Claims (10)
1. a pick-up unit for all-vanadium flow battery positive pole subsidiary reaction, comprises all-vanadium flow battery unit, optical detection unit and signal acquisition process unit, it is characterized in that:
Also comprise control module,
Described control module comprises constant-current charge control module, constant-current discharge control module, self discharge control module,
Described constant-current charge control module carries out constant-current charge for controlling all-vanadium flow battery unit,
Described constant-current discharge control module carries out constant-current discharge for controlling all-vanadium flow battery unit,
Described self discharge control module carries out self discharge for controlling all-vanadium flow battery unit.
2. pick-up unit according to claim 1, is characterized in that:
All-vanadium flow battery part comprises: the positive pole fluid reservoir storing anode electrolyte, the negative pole fluid reservoir storing electrolyte liquid, cell reaction district, absorption cell,
Anode electrolyte first flows through absorption cell and flows in described cell reaction district again, then flows out described cell reaction district and gets back in positive pole fluid reservoir;
Electrolyte liquid flows in described cell reaction district, then flows out described cell reaction district and gets back in negative pole fluid reservoir.
3. pick-up unit according to claim 2, is characterized in that: described optical detection unit comprises light source, beam splitter, the first detector, the second detector,
The light that light source sends is divided into two bundles through beam splitter, and wherein a branch of first detector that enters is using the monitor data as light intensity, and another bundle light transmission absorption cell, by the second detector measurement.
4. a detection method for all-vanadium flow battery positive pole subsidiary reaction, is characterized in that: use the pick-up unit described in any one in claim 1-3, and comprise step:
A) parameter preset in described pick-up unit is set;
B) first discharge curve of described all-vanadium flow battery positive pole under described parameter preset is obtained;
C) second discharge curve of described all-vanadium flow battery positive pole under described parameter preset is obtained;
D) according to the first discharge curve and the second discharge curve, determine that transmitted light intensity corresponding to described all-vanadium flow battery positive pole subsidiary reaction is poor;
E) subsidiary reaction of described all-vanadium flow battery positive pole under determining parameter current;
F) judge whether to need to change parameter preset, if desired change parameter preset and then return step a); Otherwise, then terminate.
5. detection method according to claim 4, is characterized in that: step b) comprising:
B1, by charging or changing the modes such as electrolytic solution, make the anode electrolyte original state of measured vanadium cell be pure+5 valencys of charged state 100%, battery cathode electrolytic solution be relative positive pole excessive can the oxidized and vanadium ion solution that can be reduced;
B2, battery to be shelved, battery plus-negative plate electrolytic solution is only allowed to carry out flowing through circulating of battery, because vanadium ion penetrates the barrier film separating both positive and negative polarity electrolytic solution lentamente, the charged state of anode electrolyte reduces gradually, transmitted light intensity can continue from maximal value time initial to reduce, measure and record, obtain the first curve.
6. the detection method according to claim 4 or 5, is characterized in that: step c) comprising:
C1, by charging, again anode electrolyte is become pure+5 valencys of charged state 100%, makes the transmitted light intensity of anode electrolyte return to maximal value;
C2, in the first Preset Time, keep the circulation of both positive and negative polarity electrolytic solution;
C3, battery is carried out to the constant-current discharge of default electricity Q;
After C4, electric discharge, battery is shelved the second Preset Time;
C5, battery is carried out again to the constant-current charge of default electricity Q;
After C6, charging, battery is shelved the 3rd Preset Time.
7. detection method according to claim 6, is characterized in that: steps d) comprising:
According to step b) institute obtains the first discharge curve, step c) second discharge curve that obtains, determine that transmitted light intensity corresponding to described all-vanadium flow battery positive pole subsidiary reaction is poor;
Further, step C4 obtain curve (f) and step B2 to obtain the light intensity difference of curve (d) under same time (Q1) be actual discharge electricity Q in constant-current discharge process
putdue to the electricity sum that infiltration reduces during this period of time, namely
Q1=Q
put+ Q
electric discharge infiltration;
Step C6 obtain curve (h) and step C4 to obtain curve (f) according to the light intensity difference of extended line under same time (Q2) of curve d rule be actual charge capacity Q in constant-current charge process
filldue to the difference of the electricity of infiltration reduction during this period of time, namely
Q2=Q
fill– Q
charging infiltration;
Then step C6 obtain the difference that curve (h) and the light intensity difference Q3 of curve d under same time are Q1 and Q2:
Q3=Q1-Q2=(Q
put-Q
fill)+(Q
electric discharge infiltration-Q
charging infiltration);
And the theoretical capacity of charging and discharging process is equal, the reason created a difference in charging exactly a part of electric quantity consumption in subsidiary reaction, then the Part I Q of above formula
put-Q
fillit is exactly the subsidiary reaction required by us;
Q
secondary=Q
put-Q
fill=q3-(Q
electric discharge infiltration-Q
charging infiltration)
To sum up, the light intensity difference that side-reaction consumes electricity produces is:
Q
secondary=Q3-Q0; Wherein Q0=Q
electric discharge infiltration-Q
charging infiltrationit is a constant.
8. detection method according to claim 7, is characterized in that: step f) in, according to the qualitative relationships that the transmitted light intensity difference of anode electrolyte becomes with positive pole subsidiary reaction, the size of subsidiary reaction proportion qualitatively can be determined.
9. detection method according to claim 7, is characterized in that: step f) comprising:
F1, according to the transmitted light intensity of anode electrolyte and the relation of charged state, transmitted light intensity difference is converted into charged state difference;
F2, determine that the subsidiary reaction of vanadium cell positive pole accounts for the number percent of overall reaction under parameter current;
Preferably, in step F 1, determine the relation of transmitted light intensity and charged state according to prior calibration or theory.
10., according to the arbitrary described detection method of claim 4-9, it is characterized in that: step a) comprising: set at least one in electrolyte flow rate, the density of charging current, discharge current density, concentration of electrolyte;
Preferably, use 40 successively, 80,120,160,200mA/cm
2current density constant-current discharge and constant-current charge are carried out to it;
Preferably, absorption cell length is 0.5-2mm, and preset wavelength is one or more wavelength of more than 400nm;
Preferably, absorption cell length is 1mm, and preset wavelength wave band is visible light wave range 420-690nm;
Preferably, the density of charging current in step C3 and step C5 is equal or unequal.
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| CN109725264A (en) * | 2019-01-22 | 2019-05-07 | 清华大学深圳研究生院 | A kind of in-situ detection method and device of the distribution of electrode of liquid flow cell current density |
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