CN108627768A - A kind of all-vanadium redox flow battery system SOC online test methods - Google Patents
A kind of all-vanadium redox flow battery system SOC online test methods Download PDFInfo
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- G01R31/36—Arrangements for testing, measuring or monitoring the electrical condition of accumulators or electric batteries, e.g. capacity or state of charge [SoC]
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Abstract
The present invention relates to all-vanadium flow battery field, specially a kind of all-vanadium redox flow battery system SOC (State of charge) online test method.For the demand of all-vanadium redox flow battery system real-time online SOC detections, pressure difference and flow by the porous media both sides disposed in on-line measurement pipeline, electrolyte viscosity number is obtained using Darcy's law, and then the data model for passing through the SOC and temperature and viscosity that are fitted in advance, and real-time electrolyte temperature measured value, realize that all-vanadium redox flow battery system SOC, SOC testing results can pass through battery control system real-time display in line computation and prediction.The present invention sensor and gathered data indispensable in making full use of all-vanadium redox flow battery system to run, while not introducing complicated metrical instrument and equipment, it realizes to the on-line checking of SOC, greatly improves the stability of system, reduce the O＆M difficulty and cost of system.
Description
Technical field
The present invention relates to all-vanadium flow battery field, specially a kind of all-vanadium redox flow battery system SOC (State-of-
Charge) online test method.
Background technology
In all-vanadium redox flow battery system operational process, SOC detections are extremely important, and accurate SOC on-line checkings can be carried significantly
The stability of high system simultaneously reduces O＆M cost.Currently, battery is mainly used in the SOC detections in all-vanadium flow battery Demonstration Application
Voltage method and its derivative similar method and offline sampled measurements method, significantly limit the accuracy and reality of SOC detections
Shi Xing.Meanwhile other SOC detection methods reported are restricted by factors such as the complexity of instrument and equipment and high costs,
It is confined to the laboratory research stage more, scale demonstration and comercial operation all-vanadium redox flow battery system can not be applied to.For existing
There are the limitation and complexity of SOC detection methods, researcher to propose indispensable in being applied merely with current all-vanadium redox flow battery system
Variable data acquire information, under conditions of not introducing additional complicated acquisition instrument and measuring apparatus, realize that SOC is counted online
The method calculated and detected.
Drag characteristic changing rule when porous media is crossed using liquid flow, pressure that can be based on Darcy's law and on-line measurement
Power, temperature and volumetric flow units realize the on-line checking of SOC using the data model of offline simulation.Researcher is first with reality
Test with take positive and negative anodes electrolyte under the testing liquid of different SOC states, off-line measurement different temperatures positive and negative anodes electrolyte it is viscous
Then angle value utilizes nonlinear data fitting method, establishes the number of positive and negative anodes SOC and positive and negative anodes electrolyte temperature and viscosity respectively
According to model.Further, researcher is acquired in real time by the way that porous media is respectively set to all-vanadium flow battery positive and negative anodes liquid stream pipeline
Porous media pressure at both sides difference and the temperature and flow for flowing through porous media electrolyte, calculate the viscosity number of positive and negative anodes electrolyte；
Viscosity number, temperature value and data model are finally utilized, real-time positive and negative anodes SOC predicted values are obtained.
This method design is simple, at low cost, implements to be easy, and is suitably applied scale demonstration and business system.It limits to
Property is gradual unbalance with positive and negative anodes capacity, and off-line data model accuracy will continuously decrease, and SOC calculates error can be more next
It is bigger, therefore this method use need to be premised on the good consistency of positive and negative anodes capacity.
Invention content
The purpose of the present invention is to provide a kind of all-vanadium redox flow battery system SOC online test methods, additional not introducing
Data acquisition and detecting instrument under conditions of, using it is existing it is indispensable acquire variable data, realize to SOC in line computation and reality
When forecast.The all-vanadium flow battery SOC detecting systems designed using the method for the present invention, are remarkably improved all-vanadium redox flow battery system
The stability of operation, and reduce system and O＆M cost.
The technical scheme is that：
A kind of all-vanadium redox flow battery system SOC online test methods, the porous medium arranged in pipe-line system, by real-time
The pressure difference of porous media both sides and the volumetric flow units by porous media are measured, is calculated viscous by the electrolyte of porous media
Degree, and then using the SOC obtained offline and the data of electrolysis fluid viscosity and temperature fitting black-box model, and pass through porous media
Electrolyte temperature value, calculates SOC value in real time.
The material selection of the all-vanadium redox flow battery system SOC online test methods, porous media has inoxidizability
With corrosive graphite felt or carbon felt, porous media is placed in main liquid stream pipeline or in branch's liquid stream pipeline, shape
For random geometry.
The all-vanadium redox flow battery system SOC online test methods, pressure sensor are mounted on porous media both sides, stream
Amount and temperature sensor are mounted on the arbitrary side of porous media, and sensor is connected with all-vanadium flow battery control system, and energy
Enough ensure to acquire pressure, flow and temperature data in real time.
The all-vanadium redox flow battery system SOC online test methods, temperature poor using the porous media pressure at both sides of acquisition
Degree and the infiltration coefficient of flow value and porous media, length and interfacial area value calculate the electrolysis by porous media in real time
Fluid viscosity value.
The all-vanadium redox flow battery system SOC online test methods calculate electrolysis fluid viscosity using following Darcy's law
Value：
Or
In formula, Δ P is pressure difference, and L is the length that electrolyte flows through porous media, and S is that electrolyte flows through porous media
Cross-sectional area, κ are porous media infiltration coefficient, and Q is the volume flow for flowing through porous media, and μ is electrolysis fluid viscosity.
The all-vanadium redox flow battery system SOC online test methods, off-line measurement concentration of electrolyte, temperature before battery operation
Degree and viscosity, and the data model of SOC and electrolyte temperature and viscosity are established, form is as follows：
SOC=f (T, μ)
In formula, T is electrolyte temperature, and μ is electrolysis fluid viscosity.
The all-vanadium redox flow battery system SOC online test methods, establish the data of SOC and electrolyte temperature and viscosity
Model uses nonlinear data fitting method.
The detection of the all-vanadium redox flow battery system SOC online test methods, positive SOC and cathode SOC need to be right respectively
Positive and cathode implements porous media and data acquisition, and off-line measurement and fitting data model and calculating SOC respectively.
The present invention design philosophy be：
All-vanadium redox flow battery system SOC detection methods of the present invention, first porous Jie by being disposed in on-line measurement pipeline
The pressure difference and flow of matter both sides obtain electrolyte viscosity number using Darcy's law；Then, the SOC and temperature by being fitted in advance
The data model of degree and viscosity, and electrolyte temperature measured value in real time, are realized to all-vanadium redox flow battery system SOC in line computation
And prediction, SOC testing results can pass through battery control system real-time display.The present invention makes full use of all-vanadium redox flow battery system to transport
Indispensable sensor and gathered data in row are realized while not introducing complicated metrical instrument and equipment to the online of SOC
Detection, greatly improves the stability of system, reduces the O＆M difficulty and cost of system.
The advantages of the present invention are：
1, the present invention proposes following idea for the more complex problem of existing SOC detection methods：It is not introduced in design any
Additional data acquisition device and detecting instrument, the effigurate porous media of installation tool in liquid stream pipeline pass through to obtain and flow
Pressure difference, electrolyte temperature and the volume flow of porous media are crossed, calculates electrolyte viscosity number, and then utilize offline fitting in advance
SOC and electrolyte temperature and viscosity data model, in the real-time SOC value of line computation.The present invention have process it is simple, at
This advantage low, that O＆M is easy.
2, all-vanadium redox flow battery system SOC online test methods of the present invention, can be respectively to all-vanadium flow battery
The SOC states of anode and electrolyte liquid implement on-line checking, and positive and negative anodes SOC detections are mutual indepedent, not by the disturbance of another pole
It influences, testing result is accurate, strong robustness.
Description of the drawings
Fig. 1 is the implementation steps flow chart of all-vanadium redox flow battery system SOC online test methods of the present invention.
Fig. 2 is the schematic diagram of all-vanadium redox flow battery system SOC online test methods of the present invention application.In figure, 1 anode
Fluid reservoir；2 cathode fluid reservoirs；3 piles；4 porous medias one；5 porous medias two；6 pumps one；7 pumps two；FM, flowmeter；TT, temperature
Spend sensor；PT, pressure sensor.
Specific implementation mode
In specific implementation process, as shown in Figure 1, all-vanadium redox flow battery system SOC online test methods of the present invention, offline
Experiment and fitting SOC and electrolyte temperature and viscosity data model, online acquisition porous media both sides pressure difference and electrolyte temperature
And flow, real-time SOC value is calculated using Darcy's law, details are as follows for specific steps：
(1) offline simulation SOC and electrolyte temperature and viscosity data model.First, by actual motion all-vanadium flow battery
System concentration of electrolyte prepares positive and negative anodes and tests original solution, is placed in charging in monocell and is obtaining a series of corresponding SOC just
Electrolyte liquid sample；Then, the electrolyte sample that the positive and negative anodes of acquisition are corresponded to different SOC is respectively placed in insulating box, is adjusted
Whole calorstat temperature, measure respectively single SOC electrolyte sample 5 DEG C, 10 DEG C, 15 DEG C, 20 DEG C, 25 DEG C, 30 DEG C, 35 DEG C, 40
Viscosity number at DEG C；Finally, positive and negative anodes experimental data is arranged respectively, using non-linear regression method, is fitted positive and negative anodes respectively
The data model of SOC=f (T, μ)；In formula, T is electrolyte temperature (DEG C), and μ is electrolysis fluid viscosity (Pas).
(2) porous media disposes.Contain VO as shown in Fig. 2, being equipped in positive fluid reservoir 12+/VO2 +Anode electrolyte, bear
It is equipped in pole fluid reservoir 2 and contains V2+/V3+Electrolyte liquid, connected respectively by pipeline between anode electrolyte and electrolyte liquid
Pile 3 is connect, the input terminal of flowmeter FM, temperature sensor TT and pressure sensor PT are connected with the pipeline respectively, full vanadium liquid
Galvanic battery control system (SOC on-line checkings) output end with flowmeter FM, temperature sensor TT and pressure sensor PT respectively
It is connected, the liquid stream that porous media 1 and pump 1 are placed in anode electrolyte is flowed through on route, by porous media 25 and pump two
7 liquid streams for being placed in electrolyte liquid flow through on route.
Wherein, porous media can choose electrode material for all-vanadium flow battery (such as：Graphite felt etc.), the geometry of porous media
Shape is unlimited with size, but need to meet electrolyte and be flowed through completely by porous media cross section.A kind of simple design scheme can be adopted
It takes the liquid flow path direction in electrolyte to be arranged and draws a flow branch, one is installed on branch road by deflector, porous electrode
The structure of approximate half-cell with end plate composition and by bolt fastening realizes that electrolyte is complete in branch and uniform flows
Porous graphite electrode.
(3) online SOC computational methods.Pressure sensor, flowmeter and temperature are installed in positive and negative anodes porous media pipeline
Sensor, and connect with battery management system or control system, realize real-time data collection, as shown in Figure 2；It will be in step (1)
The data model of fitting is input in battery management system or control system, is electrolysed using the pressure and flow rate calculation acquired in real time
Fluid viscosity, formula are as follows：
In formula, the Δ P is pressure difference (kPa), and L is the length (m) that electrolyte flows through porous media, and S is electrolysis liquid stream
Cross the cross-sectional area (m of porous media2), κ is porous media infiltration coefficient, and Q is the volume flow (m for flowing through porous media3/ s), μ
To be electrolysed fluid viscosity；And viscosity and temperature are substituted into data model, the real-time SOC value of positive and negative anodes is calculated, formula is as follows：
SOC=f (T, μ)
In order to keep technical scheme of the present invention and advantage clearer, retouched in detail below in conjunction with specific embodiment
It states.
Embodiment 1
In the present embodiment, all-vanadium redox flow battery system adds 2.6mol/L sulfuric acid as just using the vanadic sulfate of 1.6mol/L
Electrolyte liquid.First, the vanadic sulfate of 1.6mol/L is added in the sulfuric acid of 2.6mol/L, is stirred evenly, be configured to original
Beginning electrolyte；Then, electrolyte is electrolysed, obtains the positive and negative anodes electrolyte sample of corresponding different SOC；Further, by each
The electrolyte sample of corresponding specific SOC is respectively placed in insulating box, adjusting temperature, and electrolyte is viscous under acquisition series of temperature
Angle value；Finally, it using the numerical value of SOC, temperature and viscosity, is fitted using nonlinear neural network method and obtains positive and negative anodes electrolyte
The data model of SOC and electrolyte temperature and viscosity.
Above-mentioned data model is input in battery management or control system, porous medium arranged is in the suitable position of liquid stream pipeline
It sets, all-vanadium redox flow battery system and pressure, temperature and flow sensor is built, to real time data acquisition.Wherein, porous media oozes
Saturating rate is 2.8 × 10-8m2, cross-sectional area is 3.14 × 10-4m2, length 0.1m.
All-vanadium redox flow battery system is run, it is 2kPa to measure a certain moment anode porous media pressure at both sides difference, and cathode is more
Hole medium pressure at both sides difference is 2.4kPa, is 5.18 × 10 by the volume flow of anode and cathode porous media-5m3/ s, then it is sharp
It is 3.637 × 10 to be calculated with Darcy's law and obtain this moment viscosity of anode electrolyte-3Pas, this moment viscosity of electrolyte liquid
It is 4.064 × 10-3Pas, while it by anode and the electrolyte temperature of cathode porous media is 30 DEG C to measure this moment, electricity
Pond manage system by using returns offline obtained data model be calculated this moment anode electrolyte SOC for 50%, bear
Pole electrolyte SOC is 50%.
The calculated value obtained to above-mentioned SOC online test methods carries out test verification.This moment anode of online acquisition and
Electrolyte liquid sample carries out offline titrimetry test, after test result is accurate to one decimal place and is rounded up,
Test result is VO in anode electrolyte2+Concentration 0.8mol/L, VO2 +Concentration 0.8mol/L, i.e. anode SOC are 50%；Negative electricity
Solve V in liquid2+Concentration 0.8mol/L, V3+Concentration 0.8mol/L, i.e. cathode SOC are 50%.
Embodiment the result shows that, the method for the present invention can effectively to SOC states carry out on-line checking, due to only by using conjunction
Suitable porous media, and analysis is acquired to data using common temperature, pressure and flow sensor, it is online to calculate in real time
Positive and negative anodes SOC, present invention gives easy, the reliable and inexpensive advantages of all-vanadium redox flow battery system SOC on-line checkings, can fit
Application for extensive all-vanadium flow battery energy-storage system.
Claims (8)
1. a kind of all-vanadium redox flow battery system SOC online test methods, which is characterized in that dispose porous Jie in pipe-line system
Matter, by measuring the pressure difference of porous media both sides in real time and by the volumetric flow units of porous media, calculating and pass through porous Jie
The electrolysis fluid viscosity of matter, and then using the SOC obtained offline and the data of electrolysis fluid viscosity and temperature fitting black-box model, and lead to
The electrolyte temperature value for crossing porous media, calculates SOC value in real time.
2. all-vanadium redox flow battery system SOC online test methods described in accordance with the claim 1, which is characterized in that porous media
Material selection there is inoxidizability and corrosive graphite felt or carbon felt, porous media be placed in main liquid stream pipeline or
In branch's liquid stream pipeline, shape is random geometry.
3. all-vanadium redox flow battery system SOC online test methods described in accordance with the claim 1, which is characterized in that pressure sensing
Device is mounted on porous media both sides, and flow and temperature sensor are mounted on the arbitrary side of porous media, sensor and all-vanadium flow
Battery control system is connected, and can ensure to acquire pressure, flow and temperature data in real time.
4. all-vanadium redox flow battery system SOC online test methods described in accordance with the claim 1, which is characterized in that utilize acquisition
Porous media pressure at both sides is poor, temperature and the infiltration coefficient of flow value and porous media, length and interfacial area value, it is real
When calculate through the electrolyte viscosity number of porous media.
5. all-vanadium redox flow battery system SOC online test methods according to claim 4, which is characterized in that using as follows
Darcy's law calculates electrolyte viscosity number：
Or
In formula, Δ P is pressure difference, and L is the length that electrolyte flows through porous media, and S is that electrolyte flows through the transversal of porous media
Area, κ are porous media infiltration coefficient, and Q is the volume flow for flowing through porous media, and μ is electrolysis fluid viscosity.
6. all-vanadium redox flow battery system SOC online test methods described in accordance with the claim 1, which is characterized in that battery operation
Preceding off-line measurement concentration of electrolyte, temperature and viscosity, and the data model of SOC and electrolyte temperature and viscosity are established, form is such as
Under：
SOC=f (T, μ)
In formula, T is electrolyte temperature, and μ is electrolysis fluid viscosity.
7. all-vanadium redox flow battery system SOC online test methods according to claim 6, which is characterized in that establish SOC with
Electrolyte temperature and the data model of viscosity use nonlinear data fitting method.
8. the all-vanadium redox flow battery system SOC online test methods described in a kind of claim 1~7, which is characterized in that anode
The detection of SOC and cathode SOC needs to implement porous media to anode and cathode respectively and data acquire, and off-line measurement and quasi- respectively
It closes data model and calculates SOC.
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| CN110534775A (en) * | 2019-09-03 | 2019-12-03 | 中国科学院金属研究所 | A kind of flow battery positive and negative anodes electrolyte migration control method |
| CN117872167A (en) * | 2024-03-12 | 2024-04-12 | 深圳市杰维工业设备有限公司 | Battery performance influence factor analysis method |
| CN117872167B (en) * | 2024-03-12 | 2024-05-14 | 深圳市杰维工业设备有限公司 | Battery performance influence factor analysis method |
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