CN102495269B - Electrolyte measurement sensor and electrolyte charge state measurement method for vanadium Redox battery - Google Patents
Electrolyte measurement sensor and electrolyte charge state measurement method for vanadium Redox battery Download PDFInfo
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- CN102495269B CN102495269B CN201110436681.2A CN201110436681A CN102495269B CN 102495269 B CN102495269 B CN 102495269B CN 201110436681 A CN201110436681 A CN 201110436681A CN 102495269 B CN102495269 B CN 102495269B
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Abstract
The invention discloses an electrolyte measurement sensor for a vanadium Redox battery. The electrolyte measurement sensor comprises a reference electrolyte chamber, a measured electrolyte chamber and an electrolyte partition membrane, wherein the reference electrolyte chamber is filled with reference electrolyte; the measured electrolyte chamber is used for storing measured electrolyte; the polarity of the measured electrolyte is opposite to that of the reference electrolyte; moreover, an insoluble electrode is arranged in each of the reference electrolyte chamber and the measured electrolyte chamber, so that voltage between the two insoluble electrodes can be conveniently measured. The invention also discloses an electrolyte measurement device for the vanadium Redox battery. By the electrolyte measurement sensor for the vanadium Redox battery, the voltage between the measured electrolyte and the reference electrolyte can be simply and conveniently measured. Moreover, the invention also discloses an electrolyte charge state measurement method. The charge state of the measured electrolyte is reflected by measuring a voltage ratio of the measured electrolyte to the reference electrolyte. The method is accurate and convenient.
Description
Technical field
The present invention relates to galvanic battery technical field, relate in particular to a kind of galvanic battery electrolytic solution survey sensor and electrolytic solution state of charge measuring method.
Background technology
Although lithium ion battery and Ni-MH battery have the energy density higher than lead accumulator, limit its application aspect compact battery and battery of electric vehicle because cost is higher.Based on this, scientific research personnel continually develops out other novel battery technology.Wherein, vanadium redox battery (being called for short vanadium cell, VBR, Vanadium Redox Battery) is because cost is low, efficiency is high and can stored energy show greatly good development prospect.Vanadium cell be largest in the world today, technology is most advanced, approach the efficient reversible fuel cell of industrialization most, has extremely good application prospect in fields such as wind-power electricity generation, photovoltaic generation, peak load regulation network, distribution power station, military electric power storage, traffic municipal administration, communication base station, ups powers.
The electrolytic solution of conventional vanadium cell is the acid solution containing vanadium, realizes storage or the release of electric energy by having different valent vanadium ion generation redox reactions.Please refer to Fig. 1, Fig. 1 is existing vanadium cell system architecture schematic diagram, and as shown in Figure 1, vanadium cell system comprises:
Battery 130, comprises positive electrode chamber, negative electrode chamber, and the separation membrane of isolating described positive electrode chamber and described negative electrode chamber;
Anodal fluid reservoir 111, store anode electrolyte, described anodal fluid reservoir 111 is connected with the positive electrode chamber of described battery 130 by the first pump 112, described the first pump 112 provides power, and described anode electrolyte is circulated between described anodal fluid reservoir 111 and the positive electrode chamber of described battery 130;
Negative pole fluid reservoir 121, store negative pole electrolytic solution, described negative pole fluid reservoir 121 is connected with the negative electrode chamber of described battery 130 by the second pump 122, and described the second pump 122 provides power, and described negative pole electrolytic solution circulates between described negative pole fluid reservoir 121 and the negative electrode chamber of described battery 130;
Wherein, the described acid solution containing vanadium is generally vanadic sulfate, and particularly, the vanadium ion in anode electrolyte is that the vanadium ion of pentavalent and tetravalence coexists, and the vanadium ion in negative pole electrolytic solution is that the vanadium ion of trivalent and divalence coexists.The redox reaction of both positive and negative polarity electrolytic solution is respectively:
Both positive and negative polarity electrolytic solution reacts in battery, for external loading provides electromotive force, and in the time that the positive electrode in load and positive electrode chamber and the indoor negative electrode of negative electrode are connected, battery discharge; When load is changed to an external power source, the relative and foreign electromotive force of the electrode of external power source and battery is during higher than battery, battery charging.The vanadium ion that vanadium ion under charged state in anode electrolyte is essentially in pentavalent negative pole electrolytic solution is all divalence substantially, in the time exporting (making it electric discharge), in anode electrolyte, generate the vanadium ion of tetravalence, and in negative pole electrolytic solution, generate the vanadium ion of trivalent.
Discharging and recharging in operational process of vanadium cell, need to monitor in real time the state-of-charge of vanadium cell, so that the charging/discharging voltage electric current of monitoring battery, make it operate in all the time charging and discharging state efficiently, improve the transformation efficiency of electric energy, reduce energy loss, ensure that battery operates in safe charged scope all the time simultaneously, in order to avoid cause security incident or damage battery.
But up to now, can't carry out independent instrumentation to anodal liquid, negative pole liquid respectively, thereby affect the universal of redox flow batteries.
Summary of the invention
The object of the present invention is to provide galvanic battery electrolytic solution survey sensor and electrolytic solution state of charge measuring method, detect with the state-of-charge that facilitates counter-current cell, thereby improve the universal of galvanic battery.
For addressing the above problem, the present invention proposes a kind of galvanic battery electrolytic solution survey sensor, for measuring the charging and discharging state of electrolytic solution of galvanic battery, comprising:
Benchmark electrolyte liquor chamber, is full of the benchmark electrolytic solution of concentration known;
Tested electrolyte liquor chamber, for depositing tested electrolytic solution, the polarity of wherein said tested electrolytic solution is contrary with the polarity of described benchmark electrolytic solution; The bottom of described tested electrolyte liquor chamber is provided with an entrance, and its top is provided with an outlet, and described tested electrolytic solution enters described tested electrolyte liquor chamber from described entrance, flows out from described outlet;
Utmost point liquid separation membrane, is arranged between described benchmark electrolyte liquor chamber and tested electrolyte liquor chamber, and described benchmark electrolytic solution and described tested electrolytic solution are separated;
Wherein, the diffusion electrode that is provided with respectively insoluble electrode and is connected with described insoluble electrode in described benchmark electrolyte liquor chamber and described tested tank room.
Optionally, described galvanic battery is vanadium cell.
Optionally, the polarity of described benchmark electrolytic solution is anodal.
Optionally, described benchmark electrolytic solution is vanadic sulfate V solution, and wherein the concentration of vanadium ion is 1.2Mol/L.
Optionally, the polarity of described benchmark electrolytic solution is negative pole.
Optionally, described benchmark electrolytic solution is vanadic sulfate II solution, and wherein the concentration of vanadium ion is 0.9Mol/L.
Optionally, described diffusion electrode is carbon fibre electrode.
Meanwhile, for addressing the above problem, the present invention also proposes a kind of galvanic battery electrolytic solution measurement mechanism, comprising:
Above-mentioned galvanic battery electrolytic solution survey sensor;
Pump, provides power, and described tested electrolytic solution is injected to described tested electrolyte liquor chamber;
Display device, is connected with described galvanic battery electrolytic solution survey sensor, and the measurement result of described galvanic battery electrolytic solution survey sensor is carried out to digitizing demonstration; And
Guidance panel, provides control knob, and described galvanic battery electrolytic solution measurement mechanism is operated.
Optionally, described control knob comprises:
Correcting button, counter-current cell electrolytic solution measurement mechanism carries out zero correction;
Power switch; And
Switch pump, opens or closes described pump.
Optionally, the temperature compensation range of described galvanic battery electrolytic solution survey sensor is: 5～40 DEG C.
And for addressing the above problem, the present invention also proposes a kind of electrolytic solution state of charge measuring method, utilize above-mentioned galvanic battery electrolytic solution measurement mechanism to measure tested electrolytic solution state of charge, the method comprises the steps:
One sample bottle is provided, and in this sample bottle, injects test standard electrolytic liquid; Described test is the electrolytic solution after tested electrolytic solution charges completely with standard electrolytic liquid;
Described galvanic battery electrolytic solution survey sensor is placed in to described test standard electrolytic liquid;
Open described pump, described test is injected to described tested electrolyte liquor chamber with standard electrolytic liquid;
Measure and calculate the first output voltage E of described test standard electrolytic liquid
1;
Described test is extracted out from described tested electrolyte liquor chamber with standard electrolytic liquid, and utilize tested electrolytic solution to clean described galvanic battery electrolytic solution survey sensor;
Described galvanic battery electrolytic solution survey sensor is placed in to tested electrolytic solution;
Open described pump, tested electrolytic solution is injected to described tested electrolyte liquor chamber;
Measure and calculate the second output voltage E of described galvanic battery electrolytic solution survey sensor
2;
Calculate the energy of tested electrolytic solution than R, and shown wherein R=E by described display device
2/ E
1× 100%.
Compared with prior art, galvanic battery electrolytic solution survey sensor proposed by the invention comprises benchmark electrolyte liquor chamber, tested electrolyte liquor chamber and utmost point liquid separation membrane, in described benchmark electrolyte liquor chamber, be full of benchmark electrolytic solution, described tested electrolyte liquor chamber is used for depositing tested electrolytic solution, the polarity of described tested electrolytic solution is contrary with the polarity of described benchmark electrolytic solution, and in described benchmark electrolyte liquor chamber and described tested electrolyte liquor chamber, be provided with insoluble electrode, therefore can measure easily the voltage between described two insoluble electrodes;
Compared with prior art, galvanic battery electrolytic solution measurement mechanism provided by the invention comprises galvanic battery electrolytic solution survey sensor, therefore can measure the voltage between tested electrolytic solution and standard electrolytic liquid easily;
Compared with prior art, electrolytic solution state of charge measuring method provided by the invention, by measuring the voltage of tested electrolytic solution and the ratio of test standard electrolytic liquid voltage, reflects the state of charge of tested electrolytic solution, and the method is accurately convenient.
Brief description of the drawings
Fig. 1 is existing vanadium cell system architecture schematic diagram;
The structural representation of the galvanic battery electrolytic solution survey sensor that Fig. 2 provides for the embodiment of the present invention;
The structural representation of the galvanic battery electrolytic solution measurement mechanism that Fig. 3 provides for the embodiment of the present invention;
The process flow diagram of the electrolytic solution state of charge measuring method that Fig. 4 provides for the embodiment of the present invention.
Embodiment
Galvanic battery electrolytic solution survey sensor the present invention being proposed below in conjunction with the drawings and specific embodiments, galvanic battery electrolytic solution measurement mechanism and electrolytic solution state of charge measuring method are described in further detail.According to the following describes and claims, advantages and features of the invention will be clearer.It should be noted that, accompanying drawing adopts the form of simplifying very much and all uses non-ratio accurately, only for convenient, the object of the aid illustration embodiment of the present invention lucidly.
Core concept of the present invention is, a kind of galvanic battery electrolytic solution survey sensor is provided, comprise benchmark electrolyte liquor chamber, tested electrolyte liquor chamber and utmost point liquid separation membrane, in described benchmark electrolyte liquor chamber, be full of benchmark electrolytic solution, described tested electrolyte liquor chamber is used for depositing tested electrolytic solution, the polarity of described tested electrolytic solution is contrary with the polarity of described benchmark electrolytic solution, and in described benchmark electrolyte liquor chamber and described tested electrolyte liquor chamber, be provided with insoluble electrode, therefore can measure easily the voltage between described two insoluble electrodes; A kind of galvanic battery electrolytic solution measurement mechanism is also provided simultaneously, utilizes above-mentioned galvanic battery electrolytic solution survey sensor to measure the voltage between tested electrolytic solution and standard electrolytic liquid, simple and convenient; And, a kind of electrolytic solution state of charge measuring method is also provided, by measuring the voltage of tested electrolytic solution and the ratio of test standard electrolytic liquid voltage, reflect the state of charge of tested electrolytic solution, the method is accurately convenient.
Please refer to Fig. 2, the structural representation of the galvanic battery electrolytic solution survey sensor that Fig. 2 provides for the embodiment of the present invention, as shown in Figure 2, the galvanic battery electrolytic solution survey sensor 100 that the embodiment of the present invention provides comprises:
Benchmark electrolyte liquor chamber, is full of the benchmark electrolytic solution 140 of concentration known;
Tested electrolyte liquor chamber, for depositing tested electrolytic solution, the polarity of wherein said tested electrolytic solution is contrary with the polarity of described benchmark electrolytic solution 140; The bottom of described tested electrolyte liquor chamber is provided with an entrance 123, and its top is provided with an outlet 124, and described tested electrolytic solution enters described tested electrolyte liquor chamber from described entrance 123, flows out from described outlet 124;
Utmost point liquid separation membrane 130, is arranged between described benchmark electrolyte liquor chamber and tested electrolyte liquor chamber, and described benchmark electrolytic solution 140 is separated with described tested electrolytic solution;
Wherein, the diffusion electrode (112,122) that is provided with respectively insoluble electrode (111,121) and is connected with described insoluble electrode in described benchmark electrolyte liquor chamber and described tested tank room.
Described diffusion electrode (112,122) is for spreading different types of ion of electrolytic solution; Described insoluble electrode (111,121) is for conducting the ion of electrolytic solution by kind.Can obtain the output voltage of benchmark electrolytic solution 140 and the galvanic battery of described tested electrolytic solution composition by measuring voltage between described two insoluble electrodes (111,121).
Further, described galvanic battery is vanadium cell; Certainly, the present invention is not as limit, and galvanic battery electrolytic solution survey sensor provided by the invention also can be measured for the galvanic battery to other kind.
Further, the polarity of described benchmark electrolytic solution 140 is anode electrolyte; And be preferably vanadic sulfate V solution (vanadium ion that vanadium ion in this solution is positive pentavalent), wherein the concentration of vanadium ion is 1.2Mol/L.
Further, the polarity of described benchmark electrolytic solution is negative pole electrolytic solution; And be preferably vanadic sulfate II solution (vanadium ion that vanadium ion in this solution is positive divalence), wherein the concentration of vanadium ion is 0.9Mol/L.
Further, described diffusion electrode is carbon fibre electrode.
Please continue to refer to Fig. 3, the structural representation of the galvanic battery electrolytic solution measurement mechanism that Fig. 3 provides for the embodiment of the present invention, as shown in Figure 3, the galvanic battery electrolytic solution measurement mechanism 200 that the embodiment of the present invention provides, comprising:
Above-mentioned galvanic battery electrolytic solution survey sensor 100;
Pump, provides power, described tested electrolytic solution is injected to the tested electrolyte liquor chamber of described galvanic battery electrolytic solution survey sensor 100; Wherein, described pump is preferably built in described galvanic battery electrolytic solution survey sensor 100;
Display device 210, is connected with described galvanic battery electrolytic solution survey sensor 100, and the measurement result of described galvanic battery electrolytic solution survey sensor 100 is carried out to digitizing demonstration; Particularly, described display device 210 is connected with described galvanic battery electrolytic solution survey sensor 100 by link 230; And
Guidance panel, provides control knob, and described galvanic battery electrolytic solution measurement mechanism 200 is operated.
Further, described control knob comprises:
Correcting button 221, counter-current cell electrolytic solution measurement mechanism 200 carries out zero correction; For example, under the fully charged state of electrolytic solution, make be designated as " 1 " of display device 210 by adjusting correcting button 221;
Power switch 222; And
Switch pump 223, opens or closes described pump.
Further, the temperature compensation range of described galvanic battery electrolytic solution survey sensor 100 is: 5～40 DEG C,, in this temperature range, the measured value of described galvanic battery electrolytic solution survey sensor 100 is considered to accurately, outside this temperature range, measurement result may be inaccurate.
Please further refer to Fig. 4, the process flow diagram of the electrolytic solution state of charge measuring method that Fig. 4 provides for the embodiment of the present invention, as shown in Figure 4, the electrolytic solution state of charge measuring method that the embodiment of the present invention provides comprises the steps:
S101, provide a sample bottle, and in this sample bottle, inject test standard electrolytic liquid; Described test is the electrolytic solution after tested electrolytic solution charges completely with standard electrolytic liquid;
S102, described galvanic battery electrolytic solution survey sensor is placed in to described test standard electrolytic liquid;
S103, open described pump, described test is injected to described tested electrolyte liquor chamber with standard electrolytic liquid;
S104, measurement are also calculated the first output voltage E of described test standard electrolytic liquid
1;
S105, described test is extracted out from described tested electrolyte liquor chamber with standard electrolytic liquid, and utilize tested electrolytic solution to clean described galvanic battery electrolytic solution survey sensor;
S106, described galvanic battery electrolytic solution survey sensor is placed in to tested electrolytic solution;
S107, open described pump, tested electrolytic solution is injected to described tested electrolyte liquor chamber;
S108, measurement are also calculated the second output voltage E of described galvanic battery electrolytic solution survey sensor
2;
S109, calculate tested electrolytic solution the energy than R, and shown wherein R=E by described display device
2/ E
1× 100%.
In sum, the invention provides a kind of galvanic battery electrolytic solution survey sensor, comprise benchmark electrolyte liquor chamber, tested electrolyte liquor chamber and utmost point liquid separation membrane, in described benchmark electrolyte liquor chamber, be full of benchmark electrolytic solution, described tested electrolyte liquor chamber is used for depositing tested electrolytic solution, the polarity of described tested electrolytic solution is contrary with the polarity of described benchmark electrolytic solution, and in described benchmark electrolyte liquor chamber and described tested electrolyte liquor chamber, be provided with insoluble electrode, therefore can measure easily the voltage between described two insoluble electrodes; A kind of galvanic battery electrolytic solution measurement mechanism is also provided simultaneously, has utilized above-mentioned galvanic battery electrolytic solution survey sensor to measure the voltage between tested electrolytic solution and standard electrolytic liquid, simple and convenient; And, a kind of electrolytic solution state of charge measuring method is also provided, by measuring the voltage of tested electrolytic solution and the ratio of test standard electrolytic liquid voltage, reflect the state of charge of tested electrolytic solution, the method is accurately convenient.
Obviously, those skilled in the art can carry out various changes and modification and not depart from the spirit and scope of the present invention invention.Like this, if these amendments of the present invention and within modification belongs to the scope of the claims in the present invention and equivalent technologies thereof, the present invention is also intended to comprise these changes and modification interior.
Claims (1)
1. an electrolytic solution state of charge measuring method, is characterized in that, comprises the steps:
First-class battery electrolyte measurement mechanism is provided, comprise first-class battery electrolyte survey sensor, pump, display device and guidance panel, described galvanic battery electrolytic solution survey sensor comprises: benchmark electrolyte liquor chamber, tested electrolyte liquor chamber and utmost point liquid separation membrane, wherein, in described benchmark electrolyte liquor chamber, be full of the benchmark electrolytic solution of concentration known, described tested electrolyte liquor chamber, be used for depositing tested electrolytic solution, the polarity of wherein said tested electrolytic solution is contrary with the polarity of described benchmark electrolytic solution, the bottom of described tested electrolyte liquor chamber is provided with an entrance, the top of described tested electrolyte liquor chamber is provided with an outlet, described tested electrolytic solution enters described tested electrolyte liquor chamber from described entrance, flow out from described outlet, described utmost point liquid separation membrane, be arranged between described benchmark electrolyte liquor chamber and tested electrolyte liquor chamber, described benchmark electrolytic solution and described tested electrolytic solution are separated, the diffusion electrode that is provided with respectively insoluble electrode and is connected with described insoluble electrode in described benchmark electrolyte liquor chamber and described tested electrolyte liquor chamber, described pump is used for providing power, described tested electrolytic solution is injected to described tested electrolyte liquor chamber, described display device is connected with described galvanic battery electrolytic solution survey sensor, the measurement result of described galvanic battery electrolytic solution survey sensor is carried out to digitizing demonstration, described guidance panel, control knob is provided, described galvanic battery electrolytic solution measurement mechanism is operated,
One sample bottle is provided, and in this sample bottle, injects test standard electrolytic liquid; Described test is the electrolytic solution after tested electrolytic solution charges completely with standard electrolytic liquid;
Described galvanic battery electrolytic solution survey sensor is placed in to described test standard electrolytic liquid;
Open described pump, described test is injected to described tested electrolyte liquor chamber with standard electrolytic liquid;
Measure and calculate the first output voltage E of described test standard electrolytic liquid
1;
Described test is extracted out from described tested electrolyte liquor chamber with standard electrolytic liquid, and utilize tested electrolytic solution to clean described galvanic battery electrolytic solution survey sensor;
Described galvanic battery electrolytic solution survey sensor is placed in to tested electrolytic solution;
Open described pump, tested electrolytic solution is injected to described tested electrolyte liquor chamber;
Measure and calculate the second output voltage E of described galvanic battery electrolytic solution survey sensor
2;
Calculate the energy of tested electrolytic solution than R, and shown wherein R=E by described display device
2/ E
1× 100%.
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| CN104730399A (en) * | 2015-04-10 | 2015-06-24 | 张立 | Energized electrode detection mechanism |
| CN105425164B (en) * | 2015-12-25 | 2018-05-04 | 华北电力科学研究院有限责任公司 | Charge state of all-vanadium redox flow battery on-line monitoring method and system |
| CN111983482B (en) * | 2019-05-24 | 2021-05-28 | 江苏泛宇能源有限公司 | Detection method of environment-friendly all-vanadium redox flow battery |
| CN112827361B (en) * | 2020-12-31 | 2021-09-21 | 平湖爱之馨环保科技有限公司 | Two-chamber three-electrode electrolysis electrodialysis device |
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| CN101614794A (en) * | 2009-07-14 | 2009-12-30 | 清华大学 | A kind of method for online detecting charge state of flow battery based on potential difference parameter |
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| JP4140691B2 (en) * | 2002-04-23 | 2008-08-27 | 住友電気工業株式会社 | Operating method of redox flow battery |
| CN101839964B (en) * | 2010-05-11 | 2012-07-04 | 三一电气有限责任公司 | Method and device for measuring charge state of all-vanadium redox flow battery in real time |
| CN202421282U (en) * | 2011-12-22 | 2012-09-05 | 上海裕豪机电有限公司 | Flow battery solution-measuring sensor and flow battery solution-measuring device |
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| CN101614794A (en) * | 2009-07-14 | 2009-12-30 | 清华大学 | A kind of method for online detecting charge state of flow battery based on potential difference parameter |
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| Title |
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| "全钒液流电池荷电状态检测方法研究";范永生 等;《华南师范大学学报(自然科学版)》;20091130;第112-114页 * |
| 范永生 等."全钒液流电池荷电状态检测方法研究".《华南师范大学学报(自然科学版)》.2009,第112-114页. |
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