CN109659587A - Flow battery capacity attenuation control system and method - Google Patents
Flow battery capacity attenuation control system and method Download PDFInfo
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- CN109659587A CN109659587A CN201710947899.1A CN201710947899A CN109659587A CN 109659587 A CN109659587 A CN 109659587A CN 201710947899 A CN201710947899 A CN 201710947899A CN 109659587 A CN109659587 A CN 109659587A
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- H—ELECTRICITY
- H01—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
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- 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
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- H01M8/00—Fuel cells; Manufacture thereof
- H01M8/18—Regenerative fuel cells, e.g. redox flow batteries or secondary fuel cells
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Abstract
A redox flow battery capacity attenuation control system and method belong to the field of redox flow batteries and solve the problem of high maintenance cost of all-vanadium redox flow batteries, and the technical key points are as follows: gas chromatography, measuring and calculating the concentration of hydrogen in the cathode electrolyte storage tank; a total hydrogen evolution amount calculation device for periodically calculating a total hydrogen evolution amount from the concentration of the hydrogen gas; the monitoring equipment is used for monitoring the charging and discharging states of the flow battery; and the capacity recovery device is used for replenishing the positive electrolyte storage tank with a corresponding amount of capacity recovery agent in the discharging end state of the flow battery so as to control the capacity attenuation of the flow battery. The effect is as follows: the maintenance frequency is reduced, the labor cost is also reduced, and meanwhile, the abnormal phenomenon of the hydrogen evolution speed of the system can be found in real time, and measures can be taken in real time.
Description
Technical field
The invention belongs to flow battery field, it is related to a kind of flow battery control system and method.
Background technique
After long-time charge and discharge electricity operation, the discharge capacity of system can gradually decay flow battery, the synthesis valence of electrolyte
State can deviate 3.5 valences (the initial balance valence state of electrolyte), gradually rise.How from different technical standpoints discovery battery system
The reason of decay simultaneously carries out implementing monitoring while taking control measure, is to inhibit system discharge capacity attenuation, reduces system maintenance frequency
Rate guarantees the powerful measure of system long-time steady operation.
And existing method is first is that the discharge capacity attenuation degree apparently shown according to system reaches client when receiving lower limit
Using capacity restoration means, second is that by carrying out comprehensive valence state measurement to battery system positive and negative anodes electrolyte, to judge system reality
The attenuation degree of border theory, both the above method can only observe attenuation results, and cannot predict in advance and anti-capacity is taken to decline
The measure subtracted, and time-consuming for first two method, test result error is larger.
For all-vanadium flow battery since its is highly-safe, the service life is high, power capacity independence and the advantage of scale is facilitated to make it
Preferred option as extensive energy storage.
However there are liberation of hydrogen side reactions for all-vanadium flow battery electrolyte liquid:
2H++2V2+=2V3++H2↑
Since this reaction belongs to the self discharge reaction of cathode, the long-term accumulated of liberation of hydrogen side reaction will lead to system discharge capacity
Continuous decrement, one of the main reason for being all-vanadium flow battery capacity attenuation.
But it is rarely reported in the monitoring of all-vanadium flow battery capacity attenuation and control, and it is overall by test battery system
Valence state offset needs to configure special instrument and is equipped with operator, increases maintenance cost.
Currently, when system discharge capacity attenuation is to when requiring lower limit, can by the total valence state of leveling system to power system capacity into
Row restores, however, using the method that reducing agent is added or uses On-line electrolytic dissolution, always not to the report of capacity attenuation monitoring
Road, and monitor this decaying, it can tentatively be controlled in early period by more convenient and inexpensive regulative mode, existing detection
The investment and loss that method can all bring human and material resources and equipment and system to deactivate, maintenance cost is high, with a 1MW/
For 2MWh system, system valence state deviates 30%, and bring year, maintenance cost was close to 30,000 yuan.
The Chinese patent application of application publication number CN103733409A discloses a kind of for sensing and reducing flow battery
The system and method that hydrogen in system is precipitated, using hydrogen is detected with electric current generated by the reaction, for real-time detection
Hydrogen content, but due to the fluctuation of hydrogen content, real-time detection density of hydrogen error is very big.
Summary of the invention
In order to solve the problems, such as that all-vanadium flow battery capacity attenuation maintenance cost is high, the following technical solutions are proposed by the present invention:
A kind of flow battery capacity attenuation control system, comprising:
Gas-chromatography calculates the concentration of hydrogen in cathode electrolyte storage tank；
Total liberation of hydrogen device for calculating, periodically by the total hydrogen-separating quantity of concentration calculation of the hydrogen；
Supervision equipment monitors flow battery charging and discharging state；
Capacity restoration agent is added to anolyte liquid storage tank under flow battery discharge off state by capacity restoration device
To control flow battery capacity attenuation.
Further, the system also includes gas sampling assemblies, are located in cathode electrolyte storage tank, negative for acquiring
Gas in the electrolyte storage tank of pole, is connected with gas-chromatography, and the gas in cathode electrolyte storage tank is periodically sent into gas
The gas-detecting device of phase chromatography.
Further, the system also includes control cabinets, connect, are also attached to the vent valve of cathode electrolyte storage tank
Total liberation of hydrogen device for calculating.
Further, the system also includes control cabinets, connect with positive and negative electrode electrolyte storage tank coupling cock.
Further, the liberation of hydrogen device for calculating is stored with a plurality of instruction, and described instruction is suitable for processor and loads and hold
Row: by the hydrogen-separating quantity in the concentration calculation electrolyte storage tank of the hydrogen；
The hydrogen-separating quantity calculation formula is as follows:
M=C*VMark
M: the gross mass of hydrogen in storage tank；
C: the hydrogen quality volumetric concentration on tank body upper layer；
VMark: the gas volume of tank body upper space；
VMark=P1V1T1/PMarkTMark；
V1: the gas volume of tank body upper space；
P1: atmospheric pressure value in tank body；
PMark: 1 standard atmospheric pressure；
T1: temperature in storage tank；
TMark=273K.
Further, the gas volume of the tank body upper space is obtained by electrolyte storage tank liquidometer automatic data collection
, the gas temperature of the tank body upper space is obtained by electrolyte storage tank temperature sensor automatic data collection；And it will adopt
Collection data are transmitted to liberation of hydrogen device for calculating, and capacity restoration agent additive amount is determined by hydrogen-separating quantity and the unbalance relationship of electrolyte, by vanadium
Ion and the receiving and losing electrons ratio of capacity restoration agent obtain.
It is continuous according to flow battery system parameter setting the invention further relates to a kind of flow battery capacity attenuation control method
Hydrogen under charge and discharge electricity operation generates velocity amplitude, detects the practical generation speed of hydrogen with the analysis of continuous two charge and discharge cycles of determination
In the fluctuation range in front and back ratio section, fluctuation range transfinites hydrogen speed, and corresponding measure is taken to adjust.
Further, electrolyte periodically is converted to total hydrogen-separating quantity by concentration calculation total hydrogen-separating quantity of the hydrogen
Total valence state offset is to obtain the discharge capacity of flow battery system, when the discharge capacity numerical value of flow battery system is down to requirement
Discharge capacity recovery is carried out when lower limit.
Further, the hydrogen generation velocity perturbation range transfinites and adjusting method is: when the latter cycle period
Liberation of hydrogen speed and the fluctuation range of the ratio between the liberation of hydrogen speed of previous cycle period are more than limit value, if the analysis of the latter cycle period
Hydrogen speed is larger, then part anode electrolyte is imported cathode electrolyte storage tank to reduce electrolyte liquid SOC, while passing through electricity
Solution is adjusted temperature and reduced by the heat exchanger of cell system；If the liberation of hydrogen speed of the latter cycle period is smaller, cathode SOC mistake is confirmed
After low, to positive and negative anodes electrolyte status adjustment, negative solution is imported into anode a part, so that next charge and discharge cycles
SOC increases.Further, the fluctuation range transfinites and adjusting method is: when the liberation of hydrogen speed of the latter cycle period is greater than
At 1.3 times of previous cycle period liberation of hydrogen speed, i.e. when A >=1.3, part anode electrolyte is imported into cathode electrolyte storage tank,
To reduce the state-of-charge (State of Charge, SOC) of electrolyte liquid, until electrolyte liquid SOC is lower than 70%, together
When the temperature of electrolyte is adjusted to lower than 35 DEG C by the heat exchanger of battery system；As A≤0.7, and confirm that cathode SOC is low
When 50%, to positive and negative anodes electrolyte status adjustment.
Further, by computer program control gas-chromatography when each adjacent two recycles discharge off, to negative electricity
The gas sample in liquid storage tank is solved, air pressure in storage tank is detected, when in the storage tank being negative pressure, extremely using argon gas or nitrogen ftercompction
Equal to external atmosphere pressure.
Further, the hydrogen-separating quantity calculation formula in electrolyte storage tank is as follows:
M=C*VMark
M: the gross mass of hydrogen in storage tank；
C: the hydrogen quality volumetric concentration on tank body upper layer；
VMark: the gas volume of tank body upper space；
VMark=P1V1T1/(PMarkTMark)；
V1: the gas volume of tank body upper space；
P1: atmospheric pressure value in tank body；
PMark: 1 standard atmospheric pressure；
T1: temperature in storage tank；
TMark:=273K.
Discharge capacity reverts to addition capacity restoration agent, and additive amount is determined by hydrogen-separating quantity and the unbalance relationship of electrolyte, by
V electrolyte and the receiving and losing electrons ratio of capacity restoration agent obtain.The capacity restoration agent is commercially available glycerol, oxalic acid, EDTA, wine
The reproducibilities small organic molecule such as stone acid.
The utility model has the advantages that hydrogen, which is precipitated, in the present invention carries out real-time monitoring, it is made to maintain fixed reaction level, according to declining
Subtract requirement, take regulation measure, so that it is safeguarded primary (2~3 years primary) in fixed term, reduce frequency of maintenance, also reduce
Human cost, while can find the liberation of hydrogen velocity anomaly phenomenon of system immediately, it takes measures immediately.
For the cited patent application in background technique: firstly, vanadium flow battery is due to for water system battery, electrolyte liquid
Liberation of hydrogen problem and principle are common knowledges, and following is to compare the application and the technical solution of cited patent application:
1. the test equipment and method of liang scheme compare
Cited patent application uses electrode detection hydrogen, detects hydrogen with electric current generated by the reaction using it,
For real-time detection hydrogen content, equipment precision is unknown, but due to the fluctuation of hydrogen content, real-time detection density of hydrogen error
Very big, experimental data shows that two kinds of gases are thoroughly mixed uniformly needs 2 hours or more；And hydrogen speed of separating out is in electrolyte SOC
It is not in exact linear relationship during from low to high, the error that takes measures in real time is very big.
Present invention application portable gas chromatography directly accurately surveys hydrogen content at each charge and discharge cycles end
It is fixed.To judge the liberation of hydrogen situation of previous cyclic process and be adjusted in time to subsequent cycle.
Simultaneously as evolving hydrogen reaction is the principal element for causing battery system electrolyte valence state unbalance, equipment in this patent
By summing up calculating to the total hydrogen-separating quantity of system, after certain amount recycles, by addition capacity restoration agent to the electricity after decaying
The discharge capacity of cell system is restored.
2. liberation of hydrogen inhibits means to compare
The operation of cited patent application be during the charging process, when system SOC it is excessively high i.e. there are when overcharge danger, pass through
Power converter reduces charge power to reduce current density, it is known that liberation of hydrogen speed has with electrolyte SOC height and temperature
Direct relation, reducing current density not can be reduced liberation of hydrogen, charge under low current density, as long as SOC still rises, electrolyte
Liquation hydrogen speed just still will increase.
And this patent concern theme be influence electrolyte SOC potential problems --- positive and negative anodes electrolyte volume migration or
Valence state is unbalance, prevents the unbalance needs of the total Vanadium valence of positive and negative anodes from inhibiting the generation of the high SOC of electrolyte from root.
3. the features of the present invention
Battery system liberation of hydrogen is an inevitable process, can only test table by taking measures to control or inhibit
It is bright only when electrolyte is in high SOC (i.e. SOC > 70%), liberation of hydrogen can just aggravate.Reduction electric current is taken in cited patent application
The method of density theoretically and is not suitable for.The present invention reduces the technical solution of electrolyte SOC in practical large-scale MW grade battery
Can effectively reduce liberation of hydrogen speed in system, and then reduce the discharge capacity of battery system, inhibit rate of decay and reduce maintenance at
This.
Detailed description of the invention
Fig. 1 is the structural schematic block diagram of control system described in embodiment 2.
Specific embodiment
Embodiment 1:
A kind of flow battery capacity attenuation control system, including
Gas-chromatography calculates the concentration of hydrogen in cathode electrolyte storage tank；
Total liberation of hydrogen device for calculating, periodically by the total hydrogen-separating quantity of concentration calculation of the hydrogen；It is measured according to total liberation of hydrogen
Determine electrolyte valence state offset, certainly, total liberation of hydrogen device for calculating can be the embedded system or gas phase color of gas-chromatography
The concentration data of spectrum measuring and calculating can be transmitted to host computer by wired or wireless way, and to total liberation of hydrogen meter in host computer
It calculates.
Supervision equipment monitors flow battery charging and discharging state；
The capacity restoration agent of corresponding amount is added to positive electricity under flow battery discharge off state by capacity restoration device
Liquid storage tank is solved to control flow battery capacity attenuation.Discharge off state, that is, discharge off state, if being added in discharge condition
Restorative will affect discharge capacity, thus need to monitor discharge condition, and add restorative under discharge off state, to avoid
Influence electric discharge.In one embodiment, the flow battery capacity attenuation control system further includes gas sampling assembly, described
Gas sampling assembly can be the sub-device or a dress being independently set for belonging to total liberation of hydrogen device for calculating
It sets, is located in cathode electrolyte storage tank, for acquiring the gas in cathode electrolyte storage tank, be connected with gas-chromatography, it is all
The gas-detecting device that the gas in cathode electrolyte storage tank is sent into gas-chromatography of phase property.
In one embodiment, the flow battery capacity attenuation control system further includes control cabinet, the control cabinet
It can be the sub-device or a device being independently set for belonging to capacity restoration device, with electrolyte liquid
The vent valve of storage tank connects, and total liberation of hydrogen device for calculating is also attached to, by total liberation of hydrogen device for calculating output negative pole hydrogen total amount
The data of (total volume) are to control cabinet, when the data for the cathode hydrogen total amount that control cabinet obtains approach compared with the overall space of workshop
When explosion limit, control cabinet outputs control signals to vent valve, opens vent valve and hydrogen is exported outdoor, as a result, vent valve
Preferably solenoid valve, connection type therein are signal connection.
In one embodiment, the flow battery capacity attenuation control system further includes control cabinet, with positive and negative electrode
Electrolyte storage tank coupling cock connection, by the opening and closing of coupling cock with the SOC level to the electrolyte in cathode electrolyte storage tank into
Row is adjusted, i.e., is opened by coupling cock, part anode electrolyte is imported cathode electrolyte storage tank, to reduce electrolyte liquid
SOC completes SOC and adjusts.
In one embodiment, the liberation of hydrogen device for calculating is stored with a plurality of instruction, and described instruction adds suitable for processor
It carries and executes: by the hydrogen-separating quantity in the concentration calculation electrolyte storage tank of the hydrogen；
The hydrogen-separating quantity calculation formula is as follows:
M=C*VMark
M: the gross mass of hydrogen in storage tank
C: the hydrogen quality volumetric concentration on tank body upper layer, unit mg/L.
VMark: the gas volume of tank body upper space
VMark=P1V1T1/(PMarkTMark)
V1: the gas volume of tank body upper space
P1: atmospheric pressure value in tank body
PMark: 1 standard atmospheric pressure
T1: temperature in storage tank
TMark: 273K
The gas volume of the tank body upper space is obtained by the liquidometer automatic data collection that electrolyte storage tank is equipped with,
The gas temperature of the tank body upper space is obtained by electrolyte storage tank temperature sensor automatic data collection；And number will be acquired
According to being transmitted to liberation of hydrogen device for calculating.
Capacity restoration agent additive amount is determined by hydrogen-separating quantity and the unbalance relationship of electrolyte, by V electrolyte and capacity restoration agent
Receiving and losing electrons ratio obtains.
In one embodiment, a kind of flow battery capacity attenuation control method is disclosed, continuous charge and discharge electricity operation is set
Under hydrogen generate velocity amplitude, detect the practical generation speed of hydrogen with the hydrogen-separating quantity of continuous two charge and discharge cycles of determination in front and back
The fluctuation range in ratio section, fluctuation range transfinite, and corresponding measure is taken to adjust, periodically to total liberation of hydrogen in the period
Amount statistics, total amounts of hydrogen are converted to electrolyte valence state offset, and discharge capacity recovery is carried out when its numerical value reaches lower limit.
The fluctuation range transfinites and adjusting method is: as A >=1.3, part anode electrolyte being imported electrolyte
Liquid storage tank is reduced with reducing electrolyte liquid SOC, while electrolyte being adjusted temperature by the heat exchanger of battery system；When A≤
0.7, and confirm electrolyte liquid SOC it is too low when, then to positive and negative anodes electrolyte status adjustment.
In the method, by computer program control gas-chromatography by the gas in set time sampling cathode electrolyte storage tank
Body detects air pressure in storage tank, when in the storage tank being negative pressure, uses argon gas or nitrogen ftercompction to equal than external atmosphere pressure.
Hydrogen-separating quantity calculation formula in electrolyte storage tank is as follows:
M=C*VMark
M: the gross mass of hydrogen in storage tank；
C: the hydrogen quality volumetric concentration on tank body upper layer, unit mg/L.
VMark: the gas volume of tank body upper space；
VMark=P1V1T1/(PMarkTMark)；
V1: the gas volume of tank body upper space；
P1: atmospheric pressure value in tank body；
PMark: 1 standard atmospheric pressure；
T1: temperature in storage tank；
TMark=273K.
Discharge capacity restoration methods are addition capacity restoration agent, and additive amount is true by hydrogen-separating quantity and the unbalance relationship of electrolyte
It is fixed, it is obtained by vanadium ion and the receiving and losing electrons ratio of capacity restoration agent.
Embodiment 2:
Technical solution in the present embodiment can be used as an independent scheme, or the benefit as scheme in embodiment 1
Fill: a kind of flow battery capacity attenuation control system, be applied to flow battery system negative side, to detect cathode system due to
Side reaction liberation of hydrogen or storage tank seal problem cause oxygen to enter electrolyte storage tank bring self discharge problem.Application mode is to pass through
Connection cathode electrolyte storage tank top tank air is detected with gas-chromatography, to grasp the capacity attenuation situation of system in real time,
System includes: battery system, capacity restoration device, restorative addition equipment, to maintain equipment, detection system and control device, entirely
Vanadium flow battery system includes anode and cathode electrolyte storage tank and the connecting pipeline for connecting battery and electrolyte.Capacity restoration dress
It sets: the hydrogen calculation procedure set in control equipment being calculated according to hydrogen and calculates total hydrogen-separating quantity, and then obtains required recovery dosage,
Anode electrolyte is added in a certain amount of capacity restoration agent by restorative addition equipment.Wherein control device includes: supervision equipment
With control cabinet equipment, supervision equipment is used for the charging and discharging state of monitoring system, the signal that will be provided system discharge and finish, electric discharge
Be added restorative under state, control cabinet equipment be used to control cathode vent valve open and positive and negative electrode electrolyte storage tank coupling cock and
Liquid pouring pump is opened, to adjust the hydrogen gas accumulation bring danger of cathode storage tank and adjust electrolyte liquid SOC.Detection system includes
Gas-chromatography, gas sampling assembly, gas shield device, gas sampling assembly is arranged in cathode electrolyte storage tank, for adopting
Collect the gas in cathode electrolyte storage tank, gas sampling assembly is connected by diameter 3mmPE hose with gas-chromatography, and interval is fixed
Gas in storage tank is squeezed into vapor detection unit by time aspiration pump as built in gas-chromatography.Hydrogen total amount gas-chromatography is for detecting
Calculate H in cathode electrolyte storage tank2Ppm concentration；Gas shield device one end is connected with the safety valve of cathode electrolyte storage tank,
When cathode hydrogen total amount near-by explosion limit compared with the overall space of workshop, judgement is opened the safety-valve and exports hydrogen by system
Outdoor, protective device are connected to switch valve of the PLC control cabinet to start negative gas, and control cabinet one end connects gas-chromatography
Computer manipulative procedure, for calculating total gas flow.
The control method of above-mentioned control system is as follows: 1) according to the operational mode of system, setting under continuous charge and discharge electricity operation
Hydrogen generate speed be 6L/100LNegtive Solution/ cycle, the speed are the gas body under the status of criterion after conversion
Product determines the calculation method and detection program of hydrogen liberation of hydrogen speed, determines the liberation of hydrogen of continuous two charge and discharge cycles of battery system
Whether velocity ratio A meets 0.7 < A < 1.3；
If 2) A≤0.7 or A >=1.3, show the liberation of hydrogen velocity perturbation of the more previous circulation of liberation of hydrogen speed of latter circulation
Range is more than ± 30%, then decision-making system hydrogen-separating quantity is exceeded or system electrolyte utilization rate is insufficient, and system control program is alarmed simultaneously
It takes measures.
Wherein the liberation of hydrogen velocity test period is per the test interval twice, and this patent test period is the electric discharge of each circulation
System afterwards shelves the stage.It is tested after i.e. each complete charge and discharge cycles primary.
System alarm takes measures are as follows:
As A >=1.3, a part of anode electrolyte is imported into cathode electrolyte storage tank, to reduce electrolyte liquid
SOC, so that the SOC of electrolyte liquid is down to 70% hereinafter, simultaneously by the heat exchanger of battery system by the temperature tune of electrolyte
Section is to 35 DEG C or less；
As A≤0.7, need to check whether electrolyte liquid SOC is too low, i.e., need to check whether electrolyte liquid SOC is lower than
50%, such as confirm that it lower than 50%, is then adjusted positive and negative anodes electrolysis liquid status: importing a part of electrolyte liquid just
Pole electrolyte storage tank makes under its same operational mode, SOC > 60% of latter circulation electrolyte liquid.
SOC definition:
Anode: 5 valence ion concentrations account for anode electrolyte total V density ratio；
Cathode: divalent ion concentration accounts for anode electrolyte total V density ratio；
3) periodically the total hydrogen-separating quantity of system is counted, total amounts of hydrogen is converted to the offset of system electrolyte valence state
Amount, when its numerical value reaches system requirements lower limit, system alarm prompt carries out discharge capacity recovery.The period, Ke Yigen
It according to the type of flow battery system, mode or is mainly dependent on the frequency of use of flow battery system and determines, if often
It uses, then can be set as 1 month, otherwise, can be set as 3 months, it is, of course, also possible to be other times section.
By above-mentioned, the scheme in the present embodiment may relate to hydrogen-separating quantity, liberation of hydrogen speed and liberation of hydrogen total amount.
Wherein, liberation of hydrogen speed is that the difference of hydrogen-separating quantity and the ratio of time obtain, and unit is L/ circulation, is able to reflect fixation
Hydrogen-separating quantity in time.Hydrogen-separating quantity is the volume of liberation of hydrogen in the set time, unit L.When liberation of hydrogen total amount refers to one section
The adduction of interior hydrogen-separating quantity, the period can be artificially defined, and for example 2 months or 3 months.
System restores dosage addition:
According to reaction equation: 2V2++2H+=2V3++H2↑, obtain hydrogen generating quantity and the unbalance relationship of system electrolyte, then
It is obtained by the receiving and losing electrons ratio of 5 valence V electrolytes and restorative:
Such as: learnt by calculating, every kg oxalic acid can make up 249L hydrogen be precipitated bring valence state it is unbalance, system is according to hydrogen
Total amount calculates the restorative weight that should be added automatically.
According to oxidation-electron equation, every mol oxalic acid exhaustive oxidation can provide two electronics to restore two vanadium ions.
System requirements lower limit: client can generally receive discharge capacity and decline 30%, H2The relationship root that total amount and valence state deviate
It is obtained according to following formula: 2V2++2H+=2V3++H2↑, i.e., there ought be 1mol hydrogen to release, divalent vanadium concentration reduces in electrolyte liquid
2mol.And so on, according to total hydrogen-separating quantity, the rise of you can get it the comprehensive valence state of electrolyte.
4) default program, interval unite to total density of hydrogen in system in positive and negative anodes electrolyte storage tank in one week
Meter, to determine whether to reach dangerous limit value, takes emptying process to system in time.
Dangerous limit value: when hydrogen total volume in storage tank and workshop space total volume reach explosion limit, it is defined as hydrogen
Dangerous limit value.The hydrogen explosion limit refers to hydrogen volume content 4%~72%.
Hydrogen is detected as fully automatic system, samples gas in cathode storage tank by the set time by process control gas-chromatography
Body, it is automatic to detect air pressure in storage tank, when in tank being negative pressure, automatically turn on argon gas or nitrogen ftercompction to equal than external atmosphere pressure.
5) amounts of hydrogen density of hydrogen according to measured by gas-chromatography in electrolyte storage tank substitutes into formula and system is calculated
Hydrogen total amount, it is specific as follows:
M=C*VMark
M: the gross mass of hydrogen in storage tank；
C: the hydrogen quality volumetric concentration on tank body upper layer, unit mg/L.(gas-chromatography calculates hydrogen in cathode electrolyte storage tank
The concentration of gas can directly be scaled the hydrogen quality volumetric concentration on tank body upper layer).
VMark: the gas volume of tank body upper space；
VMark=P1V1T1/(PMarkTMark)；
V1: the gas volume of tank body upper space；
P1: atmospheric pressure value in tank body；
PMark: 1 standard atmospheric pressure；
T1: temperature in storage tank；
TMark=273K.
The preferable specific embodiment of the above, only the invention, but the protection scope of the invention is not
It is confined to this, anyone skilled in the art is in the technical scope that the invention discloses, according to the present invention
The technical solution of creation and its inventive concept are subject to equivalent substitution or change, should all cover the invention protection scope it
It is interior.
Claims (11)
1. a kind of flow battery capacity attenuation control system, which is characterized in that including
Gas-chromatography calculates the concentration of hydrogen in cathode electrolyte storage tank；
Total liberation of hydrogen device for calculating, periodically by the total hydrogen-separating quantity of concentration calculation of the hydrogen；
Supervision equipment monitors flow battery charging and discharging state；
Capacity restoration agent is added to anolyte liquid storage tank under flow battery discharge off state to control by capacity restoration device
Flow battery capacity attenuation processed.
2. flow battery capacity attenuation control system as described in claim 1, which is characterized in that further include gas sampling dress
It sets, is located in cathode electrolyte storage tank, for acquiring the gas in cathode electrolyte storage tank, be connected with gas-chromatography, it is all
The gas-detecting device that the gas in cathode electrolyte storage tank is sent into gas-chromatography of phase property.
3. flow battery capacity attenuation control system as described in claim 1, which is characterized in that it further include control cabinet, with
The vent valve of cathode electrolyte storage tank connects, and is also attached to total liberation of hydrogen device for calculating.
4. flow battery capacity attenuation control system as claimed in claim 1 or 3, which is characterized in that it further include control cabinet,
It is connect with positive and negative electrode electrolyte storage tank coupling cock.
5. flow battery capacity attenuation control system as described in claim 1, which is characterized in that the liberation of hydrogen device for calculating
It is stored with a plurality of instruction, described instruction is suitable for processor and loads and execute: by the concentration calculation electrolyte storage tank of the hydrogen
Hydrogen-separating quantity；
The hydrogen-separating quantity calculation formula is as follows:
M=C*VMark
M: the gross mass of hydrogen in storage tank；
C: the hydrogen quality volumetric concentration on tank body upper layer；
VMark: the gas volume of tank body upper space；
VMark=P1V1T1/PMarkTMark；
V1: the gas volume of tank body upper space；
P1: atmospheric pressure value in tank body；
PMark: 1 standard atmospheric pressure；
T1: temperature in storage tank；
TMark=273K.
6. flow battery capacity attenuation control system as claimed in claim 5, which is characterized in that the tank body upper space
Gas volume by electrolyte storage tank liquidometer automatic data collection obtain, the gas temperature of the tank body upper space is by electricity
Liquid storage tank temperature sensor automatic data collection is solved to obtain；And acquisition data are transmitted to liberation of hydrogen device for calculating, capacity restoration
Agent additive amount is determined by hydrogen-separating quantity and the unbalance relationship of solution, is obtained by vanadium ion and the receiving and losing electrons ratio of capacity restoration agent.
7. a kind of flow battery capacity attenuation control method, it is characterised in that: continuously filled according to flow battery system parameter setting
Hydrogen under electric discharge operation generates velocity amplitude, detects the practical generation speed of hydrogen with the liberation of hydrogen of continuous two charge and discharge cycles of determination
In the fluctuation range in front and back ratio section, fluctuation range transfinites speed, and corresponding measure is taken to adjust.
8. flow battery capacity attenuation control method as claimed in claim 7, which is characterized in that periodically by the hydrogen
The total hydrogen-separating quantity of concentration calculation, the total valence state offset of electrolyte is converted to obtain the electric discharge of flow battery system to total hydrogen-separating quantity
Capacity carries out discharge capacity recovery when the discharge capacity numerical value of flow battery system, which is down to, requires lower limit.
9. flow battery capacity attenuation control method as claimed in claim 7 or 8, which is characterized in that the hydrogen generates speed
Degree fluctuation range transfinites and adjusting method is: when the liberation of hydrogen speed of the latter cycle period and the liberation of hydrogen speed of previous cycle period
The fluctuation range of the ratio between degree is more than that limit value leads part anode electrolyte if the liberation of hydrogen speed of the latter cycle period is larger
Enter cathode electrolyte storage tank to reduce electrolyte liquid SOC, while solution is adjusted by temperature drop by the heat exchanger of battery system
It is low；It,, will to positive and negative anodes electrolyte status adjustment after confirmation cathode SOC is too low if the liberation of hydrogen speed of the latter cycle period is smaller
Negative solution imports anode a part, so that the SOC of next charge and discharge cycles increases.
10. flow battery capacity attenuation control method as claimed in claim 9, which is characterized in that the fluctuation range transfinites
Judgement is with the specific method adjusted: when A >=1.3, part anode electrolyte being imported cathode electrolyte storage tank to reduce cathode
The state-of-charge of electrolyte until electrolyte liquid SOC is lower than 70%, while adjusting electrolyte by the heat exchanger of battery system
Temperature makes it below 35 DEG C；It, will to positive and negative anodes electrolyte status adjustment as A≤0.7, and when confirming that cathode SOC is lower than 50%
Negative solution imports anode a part, so that the SOC of next charge and discharge cycles increases, in which: A=the latter cycle period
Liberation of hydrogen speed/previous cycle period liberation of hydrogen speed.
11. flow battery capacity attenuation control method as claimed in claim 7 or 8, which is characterized in that by computer program control
Gas-chromatography processed detects air pressure in storage tank, when being in the storage tank by the gas in set time sampling cathode electrolyte storage tank
When negative pressure, argon gas or nitrogen ftercompction to equal than external atmosphere pressure are used.
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