CN108172871A - A kind of electrolyte of vanadium redox battery charging state in-situ monitoring method and device with temperature-compensating - Google Patents

A kind of electrolyte of vanadium redox battery charging state in-situ monitoring method and device with temperature-compensating Download PDF

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Publication number
CN108172871A
CN108172871A CN201810005658.XA CN201810005658A CN108172871A CN 108172871 A CN108172871 A CN 108172871A CN 201810005658 A CN201810005658 A CN 201810005658A CN 108172871 A CN108172871 A CN 108172871A
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China
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soc
temperature
electrolyte
value
orp
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CN201810005658.XA
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Chinese (zh)
Inventor
刘俊
尹兴荣
吴雪文
吴雄伟
孙小生
徐辉
唐红梨
向小绢
张洁
彭礼
胡永清
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湖南省银峰新能源有限公司
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Priority to CN201810005658.XA priority Critical patent/CN108172871A/en
Publication of CN108172871A publication Critical patent/CN108172871A/en

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    • H—ELECTRICITY
    • H01—BASIC ELECTRIC ELEMENTS
    • H01M—PROCESSES OR MEANS, e.g. BATTERIES, FOR THE DIRECT CONVERSION OF CHEMICAL ENERGY INTO ELECTRICAL ENERGY
    • H01M8/00—Fuel cells; Manufacture thereof
    • H01M8/04—Auxiliary arrangements, e.g. for control of pressure or for circulation of fluids
    • H01M8/04298—Processes for controlling fuel cells or fuel cell systems
    • H01M8/04313—Processes for controlling fuel cells or fuel cell systems characterised by the detection or assessment of variables; characterised by the detection or assessment of failure or abnormal function
    • H01M8/04537—Electric variables
    • H—ELECTRICITY
    • H01—BASIC ELECTRIC ELEMENTS
    • H01M—PROCESSES OR MEANS, e.g. BATTERIES, FOR THE DIRECT CONVERSION OF CHEMICAL ENERGY INTO ELECTRICAL ENERGY
    • H01M8/00—Fuel cells; Manufacture thereof
    • H01M8/04—Auxiliary arrangements, e.g. for control of pressure or for circulation of fluids
    • H01M8/04298—Processes for controlling fuel cells or fuel cell systems
    • H01M8/04992—Processes for controlling fuel cells or fuel cell systems characterised by the implementation of mathematical or computational algorithms, e.g. feedback control loops, fuzzy logic, neural networks or artificial intelligence
    • Y—GENERAL TAGGING OF NEW TECHNOLOGICAL DEVELOPMENTS; GENERAL TAGGING OF CROSS-SECTIONAL TECHNOLOGIES SPANNING OVER SEVERAL SECTIONS OF THE IPC; TECHNICAL SUBJECTS COVERED BY FORMER USPC CROSS-REFERENCE ART COLLECTIONS [XRACs] AND DIGESTS
    • Y02—TECHNOLOGIES OR APPLICATIONS FOR MITIGATION OR ADAPTATION AGAINST CLIMATE CHANGE
    • Y02E—REDUCTION OF GREENHOUSE GAS [GHG] EMISSIONS, RELATED TO ENERGY GENERATION, TRANSMISSION OR DISTRIBUTION
    • Y02E60/00—Enabling technologies; Technologies with a potential or indirect contribution to GHG emissions mitigation
    • Y02E60/30—Hydrogen technology
    • Y02E60/50—Fuel cells

Abstract

The present invention provides a kind of electrolyte of vanadium redox battery charging state in-situ monitoring method and device with temperature-compensating, method is：At multiple temperatures, a series of ORP value of the positive and negative anodes electrolyte under SOC states is measured；Establish electrolyte ORP value and ln (SOC under temperature ta/(1‑SOCa)) or ln ((1 SOCc)/SOCc) relation curve Y=aX+b, fitting obtain linear equation of a, b value about temperature t, by temperature t1Lower surveyed ORP value substitutes into temperature t1Under formula Y=a1X+b1In can acquire X values；X is substituted into SOC X databases, the SOC value of electrolyte can be acquired.This method is to ORP and ln (SOCa/(1‑SOCa)) or ln ((1 SOCc)/SOCc) relational expression carries out real-time temperature adjustmemt, significantly reduce the test error of the SOC as caused by temperature change.

Description

A kind of electrolyte of vanadium redox battery charging state in-situ monitoring method with temperature-compensating and Device

Technical field

The present invention relates to the technical fields of fluid cell electrolyte charging state in-situ monitoring, particularly, are related to one kind and carry The electrolyte of vanadium redox battery charging state in-situ monitoring method and device of temperature-compensating.

Background technology

The method of electrolyte of vanadium redox battery charging state on-line monitoring mainly has at present：1) reference pile method is returned in electrolyte Road increases by one piece of small-sized monocell, and the charging state of electrolyte (SOC) is determined by detecting the terminal voltage of small-sized monocell.By The migration of diaphragm is penetrated in vanadium ion in the process of running, causes positive and negative anodes SOC inconsistent, therefore obtained by surveying terminal voltage Electrolyte charging state is average SOC, it is impossible to reflect the true SOC states of positive and negative anodes electrolyte.2) boosting battery method, in pile One section be independently arranged one piece of battery, the only logical liquid of the battery, obstructed overcurrent.By detect the open-circuit voltage of the piece monocell come Determine the SOC of electrolyte, this method and above-mentioned reference pile there are it is similary the problem of.3) reference solution method passes through test The positive and negative anodes electrolyte of known SOC and by the potential difference between the electrolyte in pipeline, it is this to determine the SOC of electrolyte The accuracy of method depends on the stabilization of reference solution.

A kind of use reference electrode is mentioned in patent CN105355946A and detects positive and negative anodes electrolyte charging state respectively Method.This method by measuring the redox potential (ORP) of battery plus-negative plate electrolyte, and bringing into opening of being established in real time Road voltage and ln (SOCa/(1-SOCa)) or ln ((1-SOCc)/SOCc) relational expression obtain battery plus-negative plate electrolyte in real time SOC.The ORP value for having ignored positive and negative anodes electrolyte of this method and the standard electrode potential of reference electrode are influenced by temperature, because , in the case where temperature fluctuation is larger, the error of SOC tests that this method measures can be bigger for this.

Invention content

Present invention aims at provide a kind of electrolyte of vanadium redox battery charging state in-situ monitoring method with temperature-compensating with Device does not consider the technical issues of temperature influences, and SOC test errors are big to solve the prior art.

To achieve the above object, the present invention provides a kind of electrolyte of vanadium redox battery charging states with temperature-compensating to supervise in situ Survey method, including step：

A, at multiple temperatures, a series of open-circuit voltage values ORP of the positive and negative anodes electrolyte under SOC states is measured；

B, it establishes under different temperatures, ORP and ln (SOCa/(1-SOCa)) or ln ((1-SOCc)/SOCc) relational expression Y= aX+b；A, b is and the relevant constant term of temperature；

In anode, Y is anode ORPaValue, X are ln (SOC/a(1-SOCa)；

In cathode, Y is cathode ORPcValue, X are ln ((1-SOCc)/SOCc)；

C, make to obtain a, b value and the curve of temperature t, be fitted and obtain linear equation of a, b value about temperature；

D, the temperature t that will be real-time monitored1Formula a, b value is substituted into about in the linear equation of temperature, you can surveyed At a temperature of a1, b1ORP value and ln (SOC under value and real time temperaturea/(1-SOCa)) or ln ((1-SOCc)/SOCc) relationship Curve is abbreviated as Y=a1X+b1；By temperature t1Lower surveyed ORP value substitutes into formula Y=a1X+b1In can acquire X values；

E, this X iterative numerical is entered in SOC databases, you can acquire the SOC value of electrolyte；

SOC databases are a SOC and ln (SOCa/(1-SOCa)) or a SOC and ln ((1-SOCc)/SOCc) it Between one-to-one relationship.

Preferably, step C is specially：

Make ORP and ln (SOCa/(1-SOCa)) or ln ((1-SOCc)/SOCc) pass of several a, b and temperature in relational expression It is curve, and carries out once linear fitting, obtains at=ct+d, bt=et+f, wherein c, d, e, f are constant.

It is single including monitoring with the device of the temperature-compensation method of above-mentioned electrolyte of vanadium redox battery charging state in-situ monitoring Member, data acquisition unit and data processing unit, the device are installed in vanadium cell system, are realized charged to positive and negative anodes electrolyte State is monitored in real time；

The monitoring unit includes the temperature sensor of resistance to strong acid, and temperature sensor is installed on pipeline, with electrolyte Contact；

The input terminal and output terminal of the data acquisition unit are connect respectively with monitoring unit, data processing unit；

The data processing unit is programmable logic controller (PLC) PLC.

Preferably, the monitoring unit further includes voltage check device, and voltage check device is by working electrode, reference electrode Composition；Wherein working electrode is any one in platinum electrode, graphite electrode, glass-carbon electrode, and reference electrode can be silver/chlorination Any one in silver-colored solid state reference electrode, silver/silver sulfate solid state reference electrode；Working electrode, reference electrode are mounted on pipe On road, with electrolyte contacts.

Preferably, the data acquisition unit can be any one in signal isolator, multimeter, electrochemical workstation Kind, the input impedance of the equipment is more than 10 megaohms.

The invention has the advantages that：

The present invention passes through to ORP and ln (SOCa/(1-SOCa)) or ln ((1-SOCc)/SOCc) relational expression progress is in real time Temperature adjustmemt significantly reduces the test error of the SOC as caused by temperature change so that the detection of electrolyte charging state is more It is precisely and convenient.Monitor the open-circuit voltage of positive and negative anodes electrolyte and electrolyte temperature in charge and discharge process in real time by monitoring device Degree, and the open-circuit voltage values surveyed and temperature are transmitted to data processing unit, it is carried out by the arithmetic logic edited in PLC It solves, you can obtain the real-time SOC states of electrolyte.

Other than objects, features and advantages described above, the present invention also has other objects, features and advantages. Below with reference to figure, the present invention is described in further detail.

Description of the drawings

The attached drawing for forming the part of the application is used to provide further understanding of the present invention, schematic reality of the invention Example and its explanation are applied for explaining the present invention, is not constituted improper limitations of the present invention.In the accompanying drawings：

Fig. 1 is the in-situ monitoring method flow chart of the vanadium cell positive and negative anodes electrolyte charging state of the preferred embodiment of the present invention；

Fig. 2 is the anode electrolyte electrolyte ORP at different temperatures of the preferred embodiment of the present inventionaWith ln (SOCa/ (1-SOCa)) graph of relation；

Fig. 3 is the battery cathode electrolyte electrolyte ORP at different temperatures of the preferred embodiment of the present inventioncWith ln ((1- SOCc)/SOCc) graph of relation and linear fit curve；

Fig. 4 is ORP in anode relational expressionaWith ln ((1-SOCa)/SOCa) relational expression in the relationship of constant term a and temperature Curve and once linear matched curve；

Fig. 5 is ORP in anode relational expressionaWith ln ((1-SOCa)/SOCa) relational expression in the relationship of constant term b and temperature Curve and once linear matched curve；

Fig. 6 is ORP in cathode relational expressioncWith ln ((1-SOCc)/SOCc) relational expression in the relationship of constant term a and temperature Curve and once linear matched curve；

Fig. 7 is ORP in cathode relational expressioncWith ln ((1-SOCc)/SOCc) relational expression in the relationship of constant term b and temperature Curve and once linear matched curve.

Specific embodiment

The embodiment of the present invention is described in detail below in conjunction with attached drawing, but the present invention can be limited according to claim Fixed and covering multitude of different ways is implemented.

Used by the temperature-compensation method of electrolyte of vanadium redox battery nuclear power state in situ detection designed referring to Fig. 1, the present invention Device includes monitoring unit, data acquisition unit and data processing unit, which is installed in vanadium cell system, realizes to just Electrolyte liquid charging state is monitored in real time.

The monitoring unit is made of voltage monitor, temperature sensor, and voltage check device is by working electrode, reference Electrode forms.Wherein working electrode be platinum electrode, graphite electrode, any one in glass-carbon electrode, for monitor anode or The electrode potential of vanadium ion electricity pair in electrolyte liquid；Reference electrode can be silver/silver chlorate solid state reference electrode, silver/sulfuric acid Any one in silver-colored solid state reference electrode has stable reference potential at a constant temperature；Working electrode and reference electricity There are potential difference values, i.e. ORP value between pole.Working electrode, reference electrode and temperature sensor are mounted on pipeline, with electrolysis Liquid contacts.

The data acquisition unit can be any one in signal isolator, multimeter, electrochemical workstation, defeated Enter impedance more than 10 megaohms.Data acquisition unit and data processing unit PLC are installed in Electric Appliance Cabinet.

Monitor the open-circuit voltage and electrolyte temperature of the positive and negative anodes electrolyte in charge and discharge process in real time by monitoring device, And the open-circuit voltage values surveyed and temperature are transmitted to data processing unit, it is asked by the arithmetic logic edited in PLC Solution, you can obtain the real-time SOC states of electrolyte.

The foundation of the arithmetic logic of the PLC is based on Nernst equation, and step is as follows：

The first step under the electrolyte of different temperatures, measures a series of ORP value under SOC states, see the table below 1 and table 2。

The lower ORP for surveying anode electrolyte under different SOC of 1 different temperatures of tableaValue and ln ((1-SOCa)/SOCa) value

The lower ORP for surveying electrolyte liquid under different SOC of 2 different temperatures of tablecValue and ln ((1-SOCc)/SOCc) value

Second step establishes the relation curve of ORP value and ln (SOC/ (1-SOC)) or ln ((1-SOC)/SOC) under temperature t, Relation curve by once linear as shown in figure 3, be fitted to obtain ORP value and ln (SOC/ (1-SOC)) or ln ((1-SOC)/SOC) Relational expression Y=aX+b, wherein anode Y be ORP value, X be ln (SOC/ (1-SOC)), cathode Y be ORP value, X be ln ((1- SOC)/SOC), a, b are and the relevant constant term of temperature.

3 anode ORP value of table and a, b value in relational expression

4 cathode ORP value of table and a, b value in relational expression

Pass through ORP and ln (SOCa/(1-SOCa)) or ln ((1-SOCc)/SOCc) constant term a, b and temperature in relational expression Relation curve, be fitted to obtain the linear equation of constant term and temperature by once linear, so as to obtain ORP and temperature t and ln (SOCa/(1-SOCa)) or ln ((1-SOCc)/SOCc) relational expression：

Anode：Y=(0.00002t+0.0338) X+ (0.0007t+0.921) 1)

Wherein Y surveys ORP by anodeaValue, X are ln (SOCa/(1-SOCa)), t is measured temperature.

Cathode：Y=(- 0.00006t+0.0384) X+ (- 0.0006t-0.403) 2)

Wherein Y surveys ORP by cathodecValue, X are ln ((1-SOCc)/SOCc), t is measured temperature.

Formula 1 is brought into according to the real-time anode electrolyte ORPa and temperature t for measuring acquisition) in, survey negative electricity Solve liquid ORPc values and temperature t, substitute into formula 2) in solve, you can obtain anode electrolyte institute under temperature t and ORPa Corresponding ln (SOCa/ (1-SOCa)) and electrolyte liquid are in temperature t and ORPcLower corresponding ln ((1-SOCc)/SOCc), By in anode SOCa-ln(SOCa/(1-SOCa)) and cathode SOCc-ln((1-SOCc)/SOCc) logic fortune is carried out in database It calculates, you can obtain corresponding positive and negative anodes electrolyte SOC value.

Therefore, the present invention establishes ORP and temperature t, ln (SOCa/(1-SOCa)) or ln ((1-SOCc)/SOCc) relationship Formula, by measuring real time temperature t and the ORP value of anode electrolyte or electrolyte liquid, reduce in actual moving process because Error is monitored for SOC caused by temperature change.

Different phase of the application in vanadium cell operational process measures the open-circuit voltage and temperature of positive and negative anodes electrolyte Value, is solved by above-mentioned relational expression, obtains the real-time SOC value of positive and negative anodes electrolyte, and with passing through redox titration The SOC value for measuring electrolyte is compared, and the accuracy of SOC is surveyed in analysis by method of the present invention, as a result see under Table 5：

The comparison result of 5 real-time SOC value of table

Data can obtain from table, pass through a kind of electrolyte of vanadium redox battery charging state in-situ monitoring for being provided in the present invention The SOC value that temperature-compensation method and device are surveyed differs very little with by the SOC value that redox titration is surveyed, and SOC deviations are small In 3%.If in the case where not giving temperature-compensating, electrolyte is calculated using the equation established at 20.0 DEG C SOC；Such as sample 3#, when anode electrolyte temperature is at 35.0 DEG C, the SOC value as obtained by calculating is 86.0%, with oxidation also Original titration gained SOC (81.2%) difference is 4.8%, more than the SOC differences 0.8% of the gained after temperature correction；Sample 5#, When anode electrolyte temperature is 40.5 DEG C, the SOC value as obtained by calculating is 37.0%, poor with redox titration gained SOC It is 7.4% to be worth, and difference is much larger than the SOC differences 1.6% of the gained after temperature correction；And its difference can be with voltage measurement Shi Wendu and working curve are established the increase of the difference of temperature and are increased.In vanadium cell actual motion engineering, the temperature of electrolyte Degree is fluctuation with the variation of environment temperature, it is therefore desirable to establish a kind of electrolyte in-situ monitoring method of temperature-compensating, use In vanadium energy storage system, the operation conditions of battery is monitored.

The foregoing is only a preferred embodiment of the present invention, is not intended to restrict the invention, for the skill of this field For art personnel, the invention may be variously modified and varied.All within the spirits and principles of the present invention, that is made any repaiies Change, equivalent replacement, improvement etc., should all be included in the protection scope of the present invention.

Claims (5)

1. a kind of electrolyte of vanadium redox battery charging state in-situ monitoring method with temperature-compensating, which is characterized in that including step：
A, at multiple temperatures, a series of open-circuit voltage values ORP of the positive and negative anodes electrolyte under SOC states is measured；
B, it establishes under different temperatures, ORP and ln (SOCa/(1-SOCa)) or ln ((1-SOCc)/SOCc) relational expression Y=aX+b； A, b is and the relevant constant term of temperature；
In anode, Y is anode ORPaValue, X are ln (SOC/a(1-SOCa)；
In cathode, Y is cathode ORPcValue, X are ln ((1-SOCc)/SOCc)；
C, make to obtain a, b value and the curve of temperature t, be fitted and obtain linear equation of a, b value about temperature；
D, the temperature t that will be real-time monitored1Formula a, b value is substituted into about in the linear equation of temperature, you can obtain under observed temperature A1, b1ORP value and ln (SOC under value and real time temperaturea/(1-SOCa)) or ln ((1-SOCc)/SOCc) relation curve, It is abbreviated as Y=a1X+b1；By temperature t1Lower surveyed ORP value substitutes into formula Y=a1X+b1In can acquire X values；
E, this X iterative numerical is entered in SOC databases, you can acquire the SOC value of electrolyte；
SOC databases are a SOC and ln (SOCa/(1-SOCa)) or a SOC and ln ((1-SOCc)/SOCc) between one One correspondence.
2. temperature-compensation method according to claim 1, which is characterized in that step C is specially：
Make ORP and ln (SOCa/(1-SOCa)) or ln ((1-SOCc)/SOCc) relationship of several a, b and temperature is bent in relational expression Line, and once linear fitting is carried out, obtain at=ct+d, bt=et+f, wherein c, d, e, f are constant.
3. the device of the temperature-compensation method with electrolyte of vanadium redox battery charging state in-situ monitoring described in claim 1, special Sign is, including monitoring unit, data acquisition unit and data processing unit, which is installed in vanadium cell system, realizes Positive and negative anodes electrolyte charging state is monitored in real time；
The monitoring unit includes the temperature sensor of resistance to strong acid, and temperature sensor is installed on pipeline, with electrolyte contacts；
The input terminal and output terminal of the data acquisition unit are connect respectively with monitoring unit, data processing unit；
The data processing unit is programmable logic controller (PLC) PLC.
4. device according to claim 3, which is characterized in that the monitoring unit further includes voltage check device, voltage Detection device is made of working electrode, reference electrode；Wherein working electrode is appointing in platinum electrode, graphite electrode, glass-carbon electrode Meaning is a kind of, and reference electrode can be any one in silver/silver chlorate solid state reference electrode, silver/silver sulfate solid state reference electrode； Working electrode, reference electrode are mounted on pipeline, with electrolyte contacts.
5. device according to claim 3, which is characterized in that the data acquisition unit can be signal isolator, ten thousand With any one in table, electrochemical workstation, the input impedance of the equipment is more than 10 megaohms.
CN201810005658.XA 2018-01-03 2018-01-03 A kind of electrolyte of vanadium redox battery charging state in-situ monitoring method and device with temperature-compensating CN108172871A (en)

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Citations (5)

* Cited by examiner, † Cited by third party
Publication number Priority date Publication date Assignee Title
CN101968532A (en) * 2009-07-28 2011-02-09 中国科学院金属研究所 In-situ monitoring method of state of charge of anode electrolyte of vanadium battery
CN104345278A (en) * 2013-08-05 2015-02-11 国家电网公司 SOC (State of Charge) detection method and system for vanadium redox battery
CN105425164A (en) * 2015-12-25 2016-03-23 华北电力科学研究院有限责任公司 All-vanadium redox flow battery state-of-charge online monitoring method and system
CN106054085A (en) * 2016-07-11 2016-10-26 四川普力科技有限公司 Method for estimating SOC of battery on the basis of temperature
CN106198453A (en) * 2016-08-25 2016-12-07 清华大学深圳研究生院 The online test method of the chief and vice reaction ratio of a kind of all-vanadium flow battery and device

Patent Citations (5)

* Cited by examiner, † Cited by third party
Publication number Priority date Publication date Assignee Title
CN101968532A (en) * 2009-07-28 2011-02-09 中国科学院金属研究所 In-situ monitoring method of state of charge of anode electrolyte of vanadium battery
CN104345278A (en) * 2013-08-05 2015-02-11 国家电网公司 SOC (State of Charge) detection method and system for vanadium redox battery
CN105425164A (en) * 2015-12-25 2016-03-23 华北电力科学研究院有限责任公司 All-vanadium redox flow battery state-of-charge online monitoring method and system
CN106054085A (en) * 2016-07-11 2016-10-26 四川普力科技有限公司 Method for estimating SOC of battery on the basis of temperature
CN106198453A (en) * 2016-08-25 2016-12-07 清华大学深圳研究生院 The online test method of the chief and vice reaction ratio of a kind of all-vanadium flow battery and device

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