CN104882620B - Method and device for realizing self protection on high-low temperature halt of flow battery system - Google Patents
Method and device for realizing self protection on high-low temperature halt of flow battery system Download PDFInfo
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- CN104882620B CN104882620B CN201510203230.2A CN201510203230A CN104882620B CN 104882620 B CN104882620 B CN 104882620B CN 201510203230 A CN201510203230 A CN 201510203230A CN 104882620 B CN104882620 B CN 104882620B
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- H01M—PROCESSES OR MEANS, e.g. BATTERIES, FOR THE DIRECT CONVERSION OF CHEMICAL ENERGY INTO ELECTRICAL ENERGY
- 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
The invention discloses a method and a device for realizing self protection on high-low temperature halt of a flow battery system. The method comprises the following steps: judging whether the flow battery system receives a halt command or is in a halt state, and monitoring environment temperature T if the flow battery system receives a halt command or is in a halt state; determining the normal range of SOC (state of charge) of an electrolyte in a positive electrode storage or a negative electrode storage tank according to the environment temperature T; and judging whether the SOC of the electrolyte in the positive electrode storage or the negative electrode storage tank is within respective corresponding normal range, and reducing the SOC of the electrolyte in the positive electrode storage or the SOC of the electrolyte in the negative electrode storage tank if the SOC of the electrolyte in the positive electrode storage or the negative electrode storage tank is not within the respective corresponding normal range. The method and the device are capable of improving the electrolyte stability of the flow battery system under a high-low temperature halt condition, improving the self protection capability of the flow battery system, reducing the capacitance loss under a high-low temperature condition, prolonging the service life and improving the performance of a flow battery.
Description
Technical field
The present invention relates to a kind of flow battery system high/low temperature shuts down self-protection method and its device.
Background technology
Flow battery has that flexible design (power and capacity can independent design), long service life, charge-discharge performance be good, choosing
Location freedom, energy efficiency height, safety and environmental protection, maintenance cost are low and easily realize not available for other conventional batteries such as scale electric power storage
Plurality of advantages.During practical application, flow battery can be widely applied to the renewable energy systems such as wind energy, solar energy work
For energy-storage system, the output of the electric power continuous-stable of generation is enable；May also be used for carrying out peak load shifting to electrical network, by electricity consumption
The electric power of low ebb is stored, and is exported in peak of power consumption, is carried out balancing electric power supply and demand with this；Furthermore it is also possible to urgent telegram is answered in conduct
Origin system and stand-by station etc., it is considered to be most one of energy storage technology of Commercial Prospect.At present, multiple countries are built in succession
Into the flow battery demonstration system of kW～MW levels, it is matched in the renewable energy systems such as solar energy, wind energy and plays smooth defeated
Go out, tracking plan generating, the effect such as balanced load and peak load shifting.
In the actual application of flow battery system, can occur shutdown situation according to actual needs, and shut down sometimes
Time is longer；The SOC of flow battery system during appearance shutdown situation is often random, and the SOC between 0～100% has
May, in order to avoid flow battery system it is powered in the case of shut down when, the situation of pile is damaged due to internal self discharge, it is existing
The electrolyte in pile is discharged by way of outer meeting resistance in technology, so as to reach the work of protection flow battery system
With, and the electrolyte in both positive and negative polarity electrolyte storage tank does not have the passage of self discharge due to the stopping of circulating pump, it is impossible to realize shutting down
Electric discharge；But flow battery system after shutting down is under low temperature environment, in prolonged storage such as in the winter time, due to 2
The toleration of valency vanadium ion is poor, then the situation for divalent vanadium ion crystallization precipitation in electrolyte easily occur, the crystal of precipitation exist
Flow battery system carries out starting and will be partially into damaging ion-conducting membrane material in pile during charge and discharge cycles；Equally
Ground, flow battery system after shutdown under the hot environment, as 5 valency vanadium ions cannot bear higher temperature, then when
Higher than after uniform temperature, 5 valency vanadium ions can form Precipitation to ambient temperature, so as to can substantially reduce the property of flow battery system
Energy and life-span.Temperature tolerance based on different SOC electrolyte --- electrolyte liquid low-temperature stability and anode electrolyte are high
Temperature stability is different, therefore it is very necessary to develop a kind of general flow battery system high/low temperature shutdown self-shield scheme.
The content of the invention
Proposition of the present invention for problem above, and develop a kind of flow battery system high/low temperature shut down self-protection method and
Its device.
The technological means of the present invention are as follows：
A kind of flow battery system high/low temperature shuts down self-protection method, and the flow battery system includes that at least one is electric
Heap, positive pole storage tank, negative pole storage tank and circulating pump, methods described comprise the steps：
Step 1：Judge whether flow battery system receives halt instruction or in stopped status, be then execution step 2,
Step 1 is continued executing with otherwise；
Step 2：Monitoring of environmental temperature T；
Step 3：Judge that ambient temperature T, whether optionally greater than the first temperature threshold or less than equal to second temperature threshold value, is
Then execution step 4, otherwise return to step 2；
Step 4：Electrolyte state-of-charge in monitoring positive pole storage tank and negative pole storage tank；
Step 5：The normal model of the electrolyte state-of-charge in determining positive pole storage tank or negative pole storage tank according to ambient temperature T
Enclose；
Step 6：Judge positive pole storage tank or the electrolyte state-of-charge in negative pole storage tank whether in each self-corresponding normal
In the range of, it is then return to step 2, otherwise execution step 7；
Step 7：Reduce the electrolyte state-of-charge and/or the electrolyte state-of-charge in negative pole storage tank in positive pole storage tank；
Further, the step 7 is specially：
Electrolyte in electrolyte in positive pole storage tank and negative pole storage tank is delivered in a mixing storage tank and is mixed；
Mixed electrolyte is returned and is delivered to positive pole storage tank and negative pole storage tank；
Further, the step 7 is specially：
Connection positive pole storage tank and negative pole storage tank；
Electrolyte in positive pole storage tank is delivered to into negative pole storage tank, and/or the electrolyte in negative pole storage tank is just delivered to
Pole storage tank；
Further, the step 7 is specially：
Apply additive in positive pole storage tank and/or negative pole storage tank；
Further, the step 4 is specially：
When ambient temperature T is optionally greater than the first temperature threshold, the electrolyte state-of-charge in positive pole storage tank is monitored；
When ambient temperature T is less than equal to second temperature threshold value, the electrolyte state-of-charge in negative pole storage tank is monitored.
A kind of flow battery system high/low temperature shuts down self-protecting device, and the flow battery system includes that at least one is electric
Heap, positive pole storage tank, negative pole storage tank and circulating pump, described device include：
For judging whether flow battery system receives halt instruction or the self-shield judge module in stopped status；
Connect the self-shield judge module, for halt instruction or flow battery system being received when flow battery system
The temperature monitoring module of monitoring of environmental temperature T after shutdown；
Connection temperature monitoring module, is equal to for judging whether ambient temperature T is optionally greater than the first temperature threshold or is less than
The temperature judge module of second temperature threshold value；
Connection temperature judge module, for when ambient temperature T is optionally greater than the first temperature threshold, monitoring in positive pole storage tank
Electrolyte state-of-charge monitoring modular I；
Connection temperature judge module, for when ambient temperature T is less than equal to second temperature threshold value, monitoring in negative pole storage tank
Electrolyte state-of-charge monitoring modular II；
Connection temperature monitoring module, for the electrolyte lotus in determining positive pole storage tank or negative pole storage tank according to ambient temperature T
The acquisition module of the normal range of electricity condition；
Connection monitoring modular I, monitoring modular II and acquisition module, for the electrolysis in judging positive pole storage tank or negative pole storage tank
Whether liquid state-of-charge is in the state-of-charge judge module in each self-corresponding normal range；
Connection state-of-charge judge module, for be not at which corresponding just when electrolyte state-of-charge in positive pole storage tank
Often in scope, or the electrolyte state-of-charge in negative pole storage tank is when being not in its corresponding normal range, control liquid stream electricity
Cell system carries out electrolyte state-of-charge and reduces the control module of operation；
In addition, described device also includes：
Connect the positive pole storage tank and negative pole storage tank, for entering to the electrolyte that positive pole storage tank and the conveying of negative pole storage tank come
The mixing storage tank of row mixing；In the mixing storage tank, mixed electrolyte is returned and is delivered to positive pole storage tank and negative pole storage tank；
Be placed in positive pole storage tank and mixing storage tank between, and be placed in negative pole storage tank and mixing storage tank between transfer pipeline；
For the electrolyte in positive pole storage tank and negative pole storage tank to be delivered to the delivery pump of the mixing storage tank respectively；When just
Electrolyte state-of-charge in the storage tank of pole was not in its corresponding normal range, or the charged shape of the electrolyte in negative pole storage tank
When state was not in its corresponding normal range, the control module controls the transfer pipeline connection and the delivery pump is opened
Open；When the electrolyte state-of-charge in positive pole storage tank is within its corresponding normal range, or the electrolyte in negative pole storage tank
When state-of-charge is within its corresponding normal range, the control module controls the transfer pipeline and disconnects and the delivery pump
Close；
Further, the volume of the mixing storage tank is the 10%～30% of positive pole flask volume or negative pole flask volume；
The delivery pump rated power is the 10%～50% of the circulating pump rated power；
In addition, described device also includes：
The connecting pipeline being arranged between positive pole storage tank and negative pole storage tank；The control module is when the electrolysis in positive pole storage tank
Liquid state-of-charge was not in its corresponding normal range, or the electrolyte state-of-charge in negative pole storage tank is not at its correspondence
Normal range in when, control the connecting pipeline and connect；
In addition, described device also includes：
According to the electrolyte state-of-charge in positive pole storage tank and negative pole storage tank, the calculating mould of institute's expense additive is calculated
Block；
Apply the add module of the additive in positive pole storage tank and/or negative pole storage tank；The control module works as positive pole
Electrolyte state-of-charge in storage tank was not in its corresponding normal range, or the electrolyte state-of-charge in negative pole storage tank
When being not in its corresponding normal range, controlling the computing module carries out institute's expense additive calculating operation, and control
Making the add module carries out the consumption additive addition operation.
As a result of above-mentioned technical proposal, the flow battery system high/low temperature that the present invention is provided shut down self-protection method and
Its device, can according to the electrolyte state-of-charge in the change adjust automatically electrolyte storage tank of ambient temperature, when temperature it is too high
Or when too low, the electrolyte state-of-charge or the electrolyte state-of-charge in negative pole storage tank in positive pole storage tank, and root are monitored respectively
The normal range of electrolyte state-of-charge is determined according to the corresponding relation of ambient temperature and electrolyte state-of-charge, when the electricity for monitoring
Solution liquid state-of-charge was not in aforementioned normal range, then the self discharge passage of the electrolyte set up in both positive and negative polarity storage tank is realized
High/low temperature self-shield after flow battery system is shut down is operated, it is possible to increase the electrolysis that flow battery system is shut down under high/low temperature
Liquid stability, lifts the self-shield ability of flow battery system, reduces the loss of capacitance in the case of high/low temperature, put forward high liquid flow
Battery life and performance, during the realization of protected mode, electrolyte is not passed through pile, it is to avoid the secondary shutdown electric discharge of pile
Process.
Description of the drawings
Fig. 1 is the flow chart of the method for the invention；
Fig. 2 is the apparatus structure schematic diagram of the embodiment of the present invention 1；
Fig. 3 is the apparatus structure schematic diagram of the embodiment of the present invention 2；
Fig. 4 is the apparatus structure schematic diagram of the embodiment of the present invention 3；
Fig. 5-a are the relation curves of state of charge of anode electrolyte (SOC) and anode electrolyte current potential；
Fig. 5-b are the relation curves of electrolyte liquid state-of-charge (SOC) and electrolyte liquid current potential；
In figure：1st, pile, 2, positive pole storage tank, 3, negative pole storage tank, 4, circulating pump, 5, mixing storage tank, 6, transfer pipeline, 7, defeated
Send pump, 8, valve, 9, connecting pipeline, 10, add module, the 101, first additive storage apparatus, 102, Second addition stores
Device.
Specific embodiment
As shown in figure 1, a kind of flow battery system high/low temperature shuts down self-protection method, the flow battery system include to
Few pile, positive pole storage tank, negative pole storage tank and a circulating pump, methods described comprise the steps：
Step 1：Judge whether flow battery system receives halt instruction or in stopped status, be then execution step 2,
Step 1 is continued executing with otherwise；
Step 2：Monitoring of environmental temperature T；
Step 3：Judge that ambient temperature T, whether optionally greater than the first temperature threshold or less than equal to second temperature threshold value, is
Then execution step 4, otherwise return to step 2；
Step 4：Electrolyte state-of-charge in monitoring positive pole storage tank and negative pole storage tank；
Step 5：The normal model of the electrolyte state-of-charge in determining positive pole storage tank or negative pole storage tank according to ambient temperature T
Enclose；
Step 6：Judge positive pole storage tank or the electrolyte state-of-charge in negative pole storage tank whether in each self-corresponding normal
In the range of, it is then return to step 2, otherwise execution step 7；
Step 7：Reduce the electrolyte state-of-charge and/or the electrolyte state-of-charge in negative pole storage tank in positive pole storage tank；
Further, the step 7 is specially：
Electrolyte in electrolyte in positive pole storage tank and negative pole storage tank is delivered in a mixing storage tank and is mixed；
Mixed electrolyte is returned and is delivered to positive pole storage tank and negative pole storage tank；
Further, the step 7 is specially：
Connection positive pole storage tank and negative pole storage tank；
Electrolyte in positive pole storage tank is delivered to into negative pole storage tank, and/or the electrolyte in negative pole storage tank is just delivered to
Pole storage tank；
Further, the step 7 is specially：
Apply additive in positive pole storage tank and/or negative pole storage tank；
Further, the step 4 is specially：
When ambient temperature T is optionally greater than the first temperature threshold, the electrolyte state-of-charge in positive pole storage tank is monitored；
When ambient temperature T is less than equal to second temperature threshold value, the electrolyte state-of-charge in negative pole storage tank is monitored.
Wherein, the electrolyte state-of-charge and/or the electrolyte state-of-charge in negative pole storage tank in positive pole storage tank is reduced, it is excellent
Elect as reduce positive pole storage tank in electrolyte state-of-charge and/or the electrolyte state-of-charge in negative pole storage tank to state-of-charge just
Often at the upper limit of scope, and then can ensure that the capacity reduced by flow battery system is relatively fewer, beneficial to flow battery system
More capacity can be released when being again started up or the capacity of needs is less.
The additive is glucose, Fructose, citric acid, ascorbic acid, EDTA, ethylene glycol, acetaldehyde, glycerol, oxygen, mistake
Hydrogen oxide etc.；Electrolyte state-of-charge in positive pole storage tank or negative pole storage tank can be obtained by potential monitoring mode.
Fig. 2 shows the apparatus structure schematic diagram of the embodiment of the present invention 1, as shown in Fig. 2 a kind of flow battery system height
Temperature shuts down self-protecting device, and the flow battery system includes at least one pile 1, positive pole storage tank 2, negative pole storage tank 3 and circulation
Pump 4, described device includes：For judging whether flow battery system receives halt instruction or the self-shield in stopped status
Judge module；Connect the self-shield judge module, for halt instruction or flow battery system being received when flow battery system
The temperature monitoring module of monitoring of environmental temperature T after system shutdown；Connection temperature monitoring module, for judging whether ambient temperature T is high
In equal to the first temperature threshold or less than the temperature judge module equal to second temperature threshold value；Connection temperature judge module, is used for
When ambient temperature T is optionally greater than the first temperature threshold, the monitoring modular I of the electrolyte state-of-charge in positive pole storage tank 2 is monitored；
Connection temperature judge module, for when ambient temperature T is less than second temperature threshold value, monitoring the electrolyte lotus in negative pole storage tank 3
The monitoring modular II of electricity condition；Connection temperature monitoring module, for determining positive pole storage tank 2 or negative pole storage tank 3 according to ambient temperature T
In electrolyte state-of-charge normal range acquisition module；Connection monitoring modular I, monitoring modular II and acquisition module, use
Whether the electrolyte state-of-charge in positive pole storage tank 2 or negative pole storage tank 3 is judged is in the lotus in each self-corresponding normal range
Electricity condition judge module；Connection state-of-charge judge module, for being not at which when the electrolyte state-of-charge in positive pole storage tank 2
In corresponding normal range, or the electrolyte state-of-charge in negative pole storage tank 3 is when being not in its corresponding normal range, control
Flow battery system processed carries out electrolyte state-of-charge and reduces the control module of operation；Described device also includes：Connection is described just
Pole storage tank 2 and negative pole storage tank 3, for the mixing storage mixed to the electrolyte that positive pole storage tank 2 and the conveying of negative pole storage tank 3 come
Tank 5；In the mixing storage tank 5, mixed electrolyte is returned and is delivered to positive pole storage tank 2 and negative pole storage tank 3；It is placed in positive pole storage
Tank 2 and mixing storage tank 5 between, and be placed in negative pole storage tank 3 and mixing storage tank 5 between transfer pipeline 6；For by positive pole storage tank
2 and negative pole storage tank 3 in electrolyte be delivered to respectively it is described mixing storage tank 5 delivery pump 7；Electrolyte in positive pole storage tank 2
State-of-charge was not in its corresponding normal range, or the electrolyte state-of-charge in negative pole storage tank 3 is not at its correspondence
Normal range in when, the control module controls that the transfer pipeline 6 is connected and the delivery pump 7 is opened；Further, when
Electrolyte state-of-charge in positive pole storage tank 2 is within its corresponding normal range, or the electrolyte in negative pole storage tank 3 is charged
When state is within its corresponding normal range, the control module controls the disconnection of transfer pipeline 6 and the delivery pump 7 is closed
Close；Further, the volume of the mixing storage tank 5 is the 10%～30% of positive pole flask volume or negative pole flask volume；It is described
7 rated power of delivery pump is the 10%～50% of the circulating pump rated power；The control module is by being placed in the conveying
Valve 8 on pipeline 6 is controlling switching on and off for transfer pipeline 6.
Fig. 3 shows the apparatus structure schematic diagram of the embodiment of the present invention 2, as shown in figure 3, a kind of flow battery system height
Temperature shuts down self-protecting device, and the flow battery system includes at least one pile 1, positive pole storage tank 2, negative pole storage tank 3 and circulation
Pump 4, described device includes：For judging whether flow battery system receives halt instruction or the self-shield in stopped status
Judge module；Connect the self-shield judge module, for halt instruction or flow battery system being received when flow battery system
The temperature monitoring module of monitoring of environmental temperature T after system shutdown；Connection temperature monitoring module, for judging whether ambient temperature T is high
In equal to the first temperature threshold or less than the temperature judge module equal to second temperature threshold value；Connection temperature judge module, is used for
When ambient temperature T is optionally greater than the first temperature threshold, the monitoring modular I of the electrolyte state-of-charge in positive pole storage tank 2 is monitored；
Connection temperature judge module, for when ambient temperature T is less than equal to second temperature threshold value, monitoring the electrolysis in negative pole storage tank 3
The monitoring modular II of liquid state-of-charge；Connection temperature monitoring module, for determining positive pole storage tank 2 or negative pole according to ambient temperature T
The acquisition module of the normal range of the electrolyte state-of-charge in storage tank 3；Connection monitoring modular I, monitoring modular II and acquisition mould
Block, for the electrolyte state-of-charge in judging positive pole storage tank 2 or negative pole storage tank 3 whether within each self-corresponding normal range
State-of-charge judge module；Connection state-of-charge judge module, for not locating when the electrolyte state-of-charge in positive pole storage tank 2
Within its corresponding normal range, or the electrolyte state-of-charge in negative pole storage tank 3 was not in its corresponding normal range
When, controlling flow battery system carries out the control module that electrolyte state-of-charge reduces operating；Described device also includes：It is arranged on
Connecting pipeline 9 between positive pole storage tank 2 and negative pole storage tank 3；The control module is when the electrolyte state-of-charge in positive pole storage tank 2
It is not in its corresponding normal range, or the electrolyte state-of-charge in negative pole storage tank 3 is not at its corresponding normal model
When enclosing interior, control the connecting pipeline 9 and connect；Further, when the electrolyte state-of-charge in positive pole storage tank 2 is in its correspondence
Normal range in, or the electrolyte state-of-charge in negative pole storage tank 3 within its corresponding normal range when, the control
Module controls the connecting pipeline 9 and disconnects；The control module is by the valve 8 that is placed on the connecting pipeline 9 come the company of control
Siphunculus road 9 switches on and off.
Fig. 4 is the apparatus structure schematic diagram of the embodiment of the present invention 3, as shown in figure 4, a kind of flow battery system high/low temperature is stopped
Machine self-protecting device, the flow battery system include at least one pile 1, positive pole storage tank 2, negative pole storage tank 3 and circulating pump 4,
Described device includes：For judging whether flow battery system receives halt instruction or self-shield in stopped status judges
Module；Connect the self-shield judge module, for halt instruction being received or flow battery system stops when flow battery system
The temperature monitoring module of monitoring of environmental temperature T after machine；Connection temperature monitoring module, for judge ambient temperature T whether higher than etc.
In the first temperature threshold or less than the temperature judge module equal to second temperature threshold value；Connection temperature judge module, for working as ring
When border temperature T is optionally greater than the first temperature threshold, the monitoring modular I of the electrolyte state-of-charge in positive pole storage tank 2 is monitored；Connection
Temperature judge module, for when ambient temperature T is less than equal to second temperature threshold value, monitoring the electrolyte lotus in negative pole storage tank 3
The monitoring modular II of electricity condition；Connection temperature monitoring module, for determining positive pole storage tank 2 or negative pole storage tank 3 according to ambient temperature T
In electrolyte state-of-charge normal range acquisition module；Connection monitoring modular I, monitoring modular II and acquisition module, use
Whether the electrolyte state-of-charge in positive pole storage tank 2 or negative pole storage tank 3 is judged is in the lotus in each self-corresponding normal range
Electricity condition judge module；Connection state-of-charge judge module, for being not at which when the electrolyte state-of-charge in positive pole storage tank 2
In corresponding normal range, or the electrolyte state-of-charge in negative pole storage tank 3 is when being not in its corresponding normal range, control
Flow battery system processed carries out electrolyte state-of-charge and reduces the control module of operation；Described device also includes：Stored up according to positive pole
Electrolyte state-of-charge in tank 2 and negative pole storage tank 3, calculates the computing module of institute's expense additive；To positive pole storage tank 2 and/
Or in negative pole storage tank 3, apply the add module 10 of the additive；The control module is charged when the electrolyte in positive pole storage tank 2
State was not in its corresponding normal range, or the electrolyte state-of-charge in negative pole storage tank 3 to be not at which corresponding just
When often in scope, controlling the computing module carries out institute's expense additive calculating operation, and controls the add module 10
Carry out the consumption additive addition operation；The computing module connects the monitoring modular I and monitoring modular II；Specifically,
Realization of the computing module according to the electrolyte state-of-charge expense additive to calculate in positive pole storage tank 2 and negative pole storage tank 3
Process may be referred to Application No. 201210591063.X filed in 29 days December in 2012 of the applicant, entitled
《Application of the organic molecule as all-vanadium flow battery capacity restoration additive》Patent application document content, capacity therein
Recover the additive that additive is in the application；The add module 10 includes the first additive storage apparatus 101 and second
Additive storage apparatus 102, the first additive storage apparatus 101 connect positive pole storage tank inlet, Second addition by pipeline
Storage apparatus 102 connect negative pole storage tank inlet by pipeline, the first additive storage apparatus 101 and positive pole storage tank inlet it
Between pipeline on, and the pipeline between Second addition storage apparatus 102 and negative pole storage tank inlet on be provided with electromagnetism
Valve, control module are realized adding additive the control of operation by using the break-make of solenoid valve control pipeline.
The present invention indicates the different minimum and highest tolerable temperature of electrolyte difference state-of-charge correspondence, and Fig. 5-a are illustrated
The relation curve of state of charge of anode electrolyte (SOC) and anode electrolyte current potential；Fig. 5-b show that electrolyte liquid is charged
The relation curve of state (SOC) and electrolyte liquid current potential；Table 1-a give state of charge of anode electrolyte and ambient temperature it
Between data relationship example, table 1-b gives the data relationship example between electrolyte liquid state-of-charge and ambient temperature；If
Fixed first temperature threshold is 30 DEG C, then when ambient temperature T is optionally greater than 30 DEG C optionally greater than the first temperature threshold, to positive pole
Electrolyte state-of-charge in storage tank is monitored, and sets second temperature threshold value as 20 DEG C, when ambient temperature T is less than equal to second
When temperature threshold is i.e. less than equal to 20 DEG C, the electrolyte state-of-charge in negative pole storage tank is monitored, for example current environment temperature
Spend for 10 DEG C, judge that the temperature less than 20 DEG C of second temperature threshold value, is then supervised to the electrolyte state-of-charge in negative pole storage tank
Survey, and be 0%～40% according to the normal range of 10 DEG C of electrolyte state-of-charges determined in negative pole storage tank of ambient temperature, enter
Whether one step judges current electrolyte state-of-charge in negative pole storage tank within the normal range, it is assumed that current in negative pole storage tank
Electrolyte state-of-charge is not in normal range for 80%, the i.e. value, then need to perform the electrolyte reduced in negative pole storage tank
State-of-charge is operated；For example current environmental temperature is 37 DEG C, judges that the temperature higher than 30 DEG C of the first temperature threshold, is then stored up to positive pole
Electrolyte state-of-charge in tank is monitored, and according to the charged shape of 37 DEG C of electrolyte determined in positive pole storage tank of ambient temperature
The normal range of state is 0%～65%, determines whether whether the current electrolyte state-of-charge in positive pole storage tank is normal at this
In the range of, it is assumed that the current electrolyte state-of-charge in positive pole storage tank is not in normal range for 80%, the i.e. value, then need
Perform the electrolyte state-of-charge operation reduced in positive pole storage tank.
Data relationship example between table 1-a. state of charge of anode electrolyte and ambient temperature.
| Ambient temperature | Electrolyte liquid state-of-charge normal range |
| 30℃ | 0%～85% |
| 37℃ | 0%～65% |
| 42℃ | 0%～52% |
| 45℃ | 0%～15% |
Data relationship example between table 1-b. electrolyte liquid state-of-charges and ambient temperature.
| Ambient temperature | State of charge of anode electrolyte normal range |
| 20℃ | 0%～85% |
| 15℃ | 0%～60% |
| 10℃ | 0%～40% |
| 5℃ | 0%～5% |
Data above is all directed to total 1.5 ± 0.1M of vanadium, SO4 2-The V electrolyte of=4.0 ± 0.1M.
Under normal circumstances, the electrolyte in positive pole storage tank is the vanadium ion solution of 4 valencys and the mixing of 5 valencys, in negative pole storage tank
Electrolyte is the vanadium ion solution that divalent and trivalent mix, of the invention by the electrolysis in the electrolyte in positive pole storage tank and negative pole storage tank
Liquid mixes in electrolyte container, or is mixed in positive pole storage tank or negative pole storage tank by connecting pipeline, during mixing：Negative electricity
Solution liquid reacts：V2++V4+→V3+, anode electrolyte reacts：V5++V3+→V4+, i.e., mixed electrolyte is V3+/V4 +Solution, pure V3+、V4+The theoretical electric potential difference of valency solution only has 0.2V.
The combined amount of anode electrolyte of the present invention and electrolyte liquid can determine in the following manner：In flow battery system
After multiple circular flow, those skilled in the art pass through both positive and negative polarity electrolyte SOC (active material concentration is poor) of detection to system,
The surpluses of active substance can be known, according to both positive and negative polarity active substance average price, trim is directly carried out, you can know positive and negative
Pole storage tank needs the electrolyte volume of output.
The flow battery system high/low temperature that the present invention is provided shuts down self-protection method and its device, can be according to ambient temperature
Change adjust automatically electrolyte storage tank in electrolyte state-of-charge, when when too high or too low for temperature, respectively monitor positive pole storage
The electrolyte state-of-charge in electrolyte state-of-charge or negative pole storage tank in tank, and according to ambient temperature and the charged shape of electrolyte
The corresponding relation of state determines the normal range of electrolyte state-of-charge, when the electrolyte state-of-charge for monitoring be not at it is aforementioned just
Often in scope, then the self discharge passage of the electrolyte set up in both positive and negative polarity storage tank realizes the height after flow battery system shutdown
Warm self-shield operation, it is possible to increase the electrolyte stability that flow battery system is shut down under high/low temperature, lifts flow battery system
The self-shield ability of system, reduces the loss of capacitance in the case of high/low temperature, improves flow battery life-span and performance, protected mode
Realization during electrolyte be not passed through pile, it is to avoid the secondary shutdown discharge process of pile.
The above, the only present invention preferably specific embodiment, but protection scope of the present invention is not limited thereto,
Any those familiar with the art the invention discloses technical scope in, technology according to the present invention scheme and its
Inventive concept equivalent or change in addition, should all be included within the scope of the present invention.
Claims (10)
1. a kind of flow battery system high/low temperature shuts down self-protection method, the flow battery system include at least one pile,
Positive pole storage tank, negative pole storage tank and circulating pump, it is characterised in that methods described comprises the steps：
Step 1：Judge whether flow battery system receives halt instruction or in stopped status, be then execution step 2, otherwise
Continue executing with step 1；
Step 2：Monitoring of environmental temperature T；
Step 3：Judge that ambient temperature T, whether optionally greater than the first temperature threshold or less than equal to second temperature threshold value, is to hold
Row step 4, otherwise return to step 2；
Step 4：Electrolyte state-of-charge in monitoring positive pole storage tank and negative pole storage tank；
Step 5：The normal range of the electrolyte state-of-charge in determining positive pole storage tank or negative pole storage tank according to ambient temperature T；
Step 6：Judge positive pole storage tank or the electrolyte state-of-charge in negative pole storage tank whether in each self-corresponding normal range
It is interior, it is then return to step 2, otherwise execution step 7；
Step 7：Reduce the electrolyte state-of-charge and/or the electrolyte state-of-charge in negative pole storage tank in positive pole storage tank.
2. flow battery system high/low temperature according to claim 1 shuts down self-protection method, it is characterised in that the step 7
Specially：
Electrolyte in electrolyte in positive pole storage tank and negative pole storage tank is delivered in a mixing storage tank and is mixed；
Mixed electrolyte is returned and is delivered to positive pole storage tank and negative pole storage tank.
3. flow battery system high/low temperature according to claim 1 shuts down self-protection method, it is characterised in that the step 7
Specially：
Connection positive pole storage tank and negative pole storage tank；
Electrolyte in positive pole storage tank is delivered to into negative pole storage tank, and/or the electrolyte in negative pole storage tank is delivered to into positive pole storage
Tank.
4. flow battery system high/low temperature according to claim 1 shuts down self-protection method, it is characterised in that the step 7
Specially：
Apply additive in positive pole storage tank and/or negative pole storage tank.
5. flow battery system high/low temperature according to claim 1 shuts down self-protection method, it is characterised in that the step 4
Specially：
When ambient temperature T is optionally greater than the first temperature threshold, the electrolyte state-of-charge in positive pole storage tank is monitored；
When ambient temperature T is less than equal to second temperature threshold value, the electrolyte state-of-charge in negative pole storage tank is monitored.
6. a kind of flow battery system high/low temperature shuts down self-protecting device, the flow battery system include at least one pile,
Positive pole storage tank, negative pole storage tank and circulating pump, it is characterised in that described device includes：
For judging whether flow battery system receives halt instruction or the self-shield judge module in stopped status；
Connect the self-shield judge module, for halt instruction or flow battery system shutdown being received when flow battery system
The temperature monitoring module of monitoring of environmental temperature T afterwards；
Connection temperature monitoring module, for judging ambient temperature T whether optionally greater than the first temperature threshold or less than equal to second
The temperature judge module of temperature threshold；
Connection temperature judge module, for when ambient temperature T is optionally greater than the first temperature threshold, monitoring the electricity in positive pole storage tank
The monitoring modular I of solution liquid state-of-charge；
Connection temperature judge module, for when ambient temperature T is less than equal to second temperature threshold value, monitoring the electricity in negative pole storage tank
The monitoring modular II of solution liquid state-of-charge；
Connection temperature monitoring module, for the charged shape of electrolyte in determining positive pole storage tank or negative pole storage tank according to ambient temperature T
The acquisition module of the normal range of state；
Connection monitoring modular I, monitoring modular II and acquisition module, for the electrolyte lotus in judging positive pole storage tank or negative pole storage tank
Whether electricity condition is in the state-of-charge judge module in each self-corresponding normal range；
Connection state-of-charge judge module, for being not at its corresponding normal model when the electrolyte state-of-charge in positive pole storage tank
In enclosing, or the electrolyte state-of-charge in negative pole storage tank is when being not in its corresponding normal range, controls flow battery system
System carries out electrolyte state-of-charge and reduces the control module of operation.
7. flow battery system high/low temperature according to claim 6 shuts down self-protecting device, it is characterised in that described device
Also include：
Connect the positive pole storage tank and negative pole storage tank, for mixing to the electrolyte that positive pole storage tank and the conveying of negative pole storage tank come
The mixing storage tank of conjunction；In the mixing storage tank, mixed electrolyte is returned and is delivered to positive pole storage tank and negative pole storage tank；
Be placed in positive pole storage tank and mixing storage tank between, and be placed in negative pole storage tank and mixing storage tank between transfer pipeline；
For the electrolyte in positive pole storage tank and negative pole storage tank to be delivered to the delivery pump of the mixing storage tank respectively；When positive pole is stored up
Electrolyte state-of-charge in tank was not in its corresponding normal range, or the electrolyte state-of-charge in negative pole storage tank is not
When within its corresponding normal range, the control module controls the transfer pipeline and connects and delivery pump unlatching；When
Electrolyte state-of-charge in positive pole storage tank is within its corresponding normal range, or the charged shape of the electrolyte in negative pole storage tank
When state is within its corresponding normal range, the control module controls the transfer pipeline and disconnects and delivery pump closing.
8. flow battery system high/low temperature according to claim 7 shuts down self-protecting device, it is characterised in that the mixing
The volume of storage tank is the 10%～30% of positive pole flask volume or negative pole flask volume；The delivery pump rated power is followed for described
The 10%～50% of ring pump rated power.
9. flow battery system high/low temperature according to claim 6 shuts down self-protecting device, it is characterised in that described device
Also include：
The connecting pipeline being arranged between positive pole storage tank and negative pole storage tank；The control module is when the electrolyte lotus in positive pole storage tank
Electricity condition was not in its corresponding normal range, or the electrolyte state-of-charge in negative pole storage tank to be not at which corresponding just
When often in scope, control the connecting pipeline and connect.
10. flow battery system high/low temperature according to claim 6 shuts down self-protecting device, it is characterised in that described device
Also include：
According to the electrolyte state-of-charge in positive pole storage tank and negative pole storage tank, the computing module of institute's expense additive is calculated；
Apply the add module of the additive in positive pole storage tank and/or negative pole storage tank；The control module works as positive pole storage tank
In electrolyte state-of-charge be not in its corresponding normal range, or the electrolyte state-of-charge in negative pole storage tank is not located
When within its corresponding normal range, control the computing module and carry out institute's expense additive to calculate operation, and control institute
Stating add module carries out the consumption additive addition operation.
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| US10991960B2 (en) | 2016-03-14 | 2021-04-27 | Dalian Rongkepower Co., Ltd | Electrolyte storage tank, flow battery, box-type flow battery system and charge-discharge control method of flow battery |
| BR112019020312A2 (en) * | 2017-03-27 | 2020-05-05 | Storen Tech Inc | advanced electrolyte mixing method for all vanadium flow batteries |
| CN109346756A (en) * | 2018-11-26 | 2019-02-15 | 上海电气集团股份有限公司 | A kind of flow battery system and its regeneration of electrolyte method of regeneration of electrolyte |
| CN111509278B (en) * | 2020-03-20 | 2023-03-17 | 香港科技大学 | Method for recovering capacity and efficiency of all-vanadium redox flow battery on line |
| CN112531192A (en) * | 2021-02-01 | 2021-03-19 | 深圳市寒暑科技新能源有限公司 | Zinc-manganese single flow battery |
| CN114335647A (en) * | 2021-12-31 | 2022-04-12 | 寰泰储能科技股份有限公司 | Shutdown protection system and method for liquid flow energy storage system |
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| CN102354761B (en) * | 2011-10-10 | 2013-12-25 | 中国东方电气集团有限公司 | Flow cell system and shutdown protection method as well as device thereof |
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