CN109659587B - Flow battery capacity decay control system and method - Google Patents

Flow battery capacity decay control system and method Download PDF

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CN109659587B
CN109659587B CN201710947899.1A CN201710947899A CN109659587B CN 109659587 B CN109659587 B CN 109659587B CN 201710947899 A CN201710947899 A CN 201710947899A CN 109659587 B CN109659587 B CN 109659587B
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flow battery
hydrogen evolution
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高新亮
张华民
邹毅
姚启博
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Dalian Rongke Power Co Ltd
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    • HELECTRICITY
    • H01ELECTRIC ELEMENTS
    • H01MPROCESSES OR MEANS, e.g. BATTERIES, FOR THE DIRECT CONVERSION OF CHEMICAL ENERGY INTO ELECTRICAL ENERGY
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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

液流电池容量衰减控制系统及方法Flow battery capacity decay control system and method

技术领域technical field

本发明属于液流电池领域,涉及一种液流电池控制系统及方法。The invention belongs to the field of liquid flow batteries, and relates to a liquid flow battery control system and method.

背景技术Background technique

液流电池在长时间充放电运行后,系统的放电容量会逐渐衰减,电解液的综合价态会偏离3.5价(电解液的初始平衡价态),逐渐升高。如何从不同技术角度发现电池系统的衰减原因并进行实施监测同时采取控制措施,是抑制系统放电容量衰减,减少系统维护频率,保证系统长时间稳定运行的有力手段。After the flow battery is charged and discharged for a long time, the discharge capacity of the system will gradually decay, and the comprehensive valence state of the electrolyte will deviate from 3.5 valence (the initial equilibrium valence state of the electrolyte) and gradually increase. How to find the reasons for the attenuation of the battery system from different technical perspectives, implement monitoring and take control measures, is a powerful means to restrain the attenuation of the discharge capacity of the system, reduce the frequency of system maintenance, and ensure the long-term stable operation of the system.

而现有的方法一是根据系统表观显示的放电容量衰减程度达到客户接受下限时采用容量恢复手段,二是通过对电池系统正负极电解液进行综合价态测定,来判断系统实际理论的衰减程度,以上两种方法只能观测到衰减结果,而不能提前预知并采取抗容量衰减的措施,且前两种方法耗时长,测试结果误差较大。In the existing methods, one is to use a capacity recovery method when the discharge capacity decay degree displayed on the surface of the system reaches the lower limit accepted by customers; The attenuation degree, the above two methods can only observe the attenuation results, but cannot predict in advance and take anti-capacity attenuation measures, and the first two methods take a long time, and the test results have large errors.

全钒液流电池由于其安全性高,寿命高,功率容量独立及方便规模化的优势使其成为大规模储能的首选方案。All-vanadium redox flow batteries are the first choice for large-scale energy storage due to their high safety, long life, independent power capacity and convenient scale.

然而全钒液流电池负极电解液存在析氢副反应:However, there is a side reaction of hydrogen evolution in the negative electrolyte of all-vanadium redox flow battery:

2H++2V2+=2V3++H22H + +2V 2+ = 2V 3+ +H 2

由于此反应属于负极的自放电反应,析氢副反应的长期累积将导致系统放电容量的持续衰减,是全钒液流电池容量衰减的主要原因之一。Since this reaction belongs to the self-discharge reaction of the negative electrode, the long-term accumulation of the hydrogen evolution side reaction will lead to the continuous attenuation of the discharge capacity of the system, which is one of the main reasons for the capacity attenuation of the all-vanadium redox flow battery.

但在全钒液流电池容量衰减监控与控制上却鲜有报道,而通过测试电池系统总体价态偏移,需要配置专业仪器及配备操作人员,增加维护成本。However, there are few reports on the capacity attenuation monitoring and control of all-vanadium redox flow batteries. By testing the overall valence state deviation of the battery system, professional instruments and operators are required, which increases maintenance costs.

目前,当系统放电容量衰减到要求下限时,可通过调平系统总价态对系统容量进行恢复,但不论采用加入还原剂或者使用在线电解的方法,始终没有对容量衰减监视的报道,而监视这种衰减,可以在前期通过更为方便和低成本的调节方式初步控制,现有的检测方法都会带来人力、物力及设备和系统停用的投入和损失,维护成本居高不下,以一个1MW/2MWh系统为例,系统价态偏离30%,带来的年维护费用接近3万元。At present, when the discharge capacity of the system decays to the required lower limit, the system capacity can be recovered by leveling the total valence state of the system. However, whether by adding a reducing agent or using on-line electrolysis, there has never been any report on monitoring capacity decay. This attenuation can be preliminarily controlled by a more convenient and low-cost adjustment method in the early stage. The existing detection methods will bring the investment and loss of manpower, material resources, and equipment and system deactivation, and the maintenance cost will remain high. Take the 1MW/2MWh system as an example, the system price deviates by 30%, and the annual maintenance cost is close to 30,000 yuan.

申请公布号CN103733409A的中国专利申请公开了一种用于感测和减少液流电池系统内的氢析出的系统和方法,其利用与反应物反应产生的电流来检测氢气,为实时检测氢气含量,但由于氢气含量的波动性,实时检测氢气浓度误差很大。The Chinese patent application with application publication number CN103733409A discloses a system and method for sensing and reducing hydrogen evolution in a flow battery system, which utilizes the current generated by reacting with the reactant to detect hydrogen, in order to detect the hydrogen content in real time, However, due to the fluctuation of hydrogen content, the real-time detection of hydrogen concentration has a large error.

发明内容SUMMARY OF THE INVENTION

为了解决全钒液流电池容量衰减维护成本高的问题,本发明提出如下技术方案:In order to solve the problem of high maintenance cost of all-vanadium redox flow battery capacity decay, the present invention proposes the following technical solutions:

一种液流电池容量衰减控制系统,包括:A capacity decay control system for a flow battery, comprising:

气相色谱,测算负极电解液储罐内氢气的浓度;Gas chromatography to measure the concentration of hydrogen in the negative electrolyte storage tank;

总析氢量计算装置,周期性的由所述氢气的浓度计算总析氢量;a total hydrogen evolution calculation device, which periodically calculates the total hydrogen evolution from the concentration of the hydrogen;

监视设备,监测液流电池充放电状态;Monitoring equipment to monitor the state of charge and discharge of flow batteries;

容量恢复装置,在液流电池放电终止状态下将容量恢复剂添加到正极电解液储罐以控制液流电池容量衰减。The capacity recovery device adds a capacity recovery agent to the positive electrode electrolyte storage tank to control the capacity decay of the flow battery when the discharge of the flow battery is terminated.

进一步的,所述系统还包括气体采样装置,其位于负极电解液储罐内,用于采集负极电解液储罐内的气体,其与气相色谱相连,周期性的将负极电解液储罐内的气体送入气相色谱的气体检测装置。Further, the system also includes a gas sampling device, which is located in the negative electrolyte storage tank, used to collect the gas in the negative electrolyte storage tank, which is connected with the gas chromatography, and periodically collects the gas in the negative electrolyte storage tank. The gas is fed into the gas detection device of the gas chromatograph.

进一步的,所述系统还包括控制柜,其与负极电解液储罐的放气阀连接,还连接于总析氢量计算装置。Further, the system further includes a control cabinet, which is connected to the air release valve of the negative electrolyte storage tank, and is also connected to the total hydrogen evolution amount calculation device.

进一步的,所述系统还包括控制柜,其与正、负极电解液储罐联通阀连接。Further, the system further includes a control cabinet, which is connected with the communication valves of the positive and negative electrolyte storage tanks.

进一步的,所述析氢量计算装置存储有多条指令,所述指令适于处理器加载并执行:由所述氢气的浓度计算电解液储罐内的析氢量;Further, the hydrogen evolution amount calculation device stores a plurality of instructions, and the instructions are suitable for the processor to load and execute: calculate the hydrogen evolution amount in the electrolyte storage tank by the concentration of the hydrogen gas;

所述析氢量计算公式如下:The formula for calculating the amount of hydrogen evolution is as follows:

M=C*V M=C*V standard

M:储罐中氢气的总质量;M: the total mass of hydrogen in the storage tank;

C:罐体上层的氢气质量体积浓度;C: the mass volume concentration of hydrogen in the upper layer of the tank;

V:罐体上层空间的气体体积;V mark : the gas volume in the upper space of the tank;

V=P1V1T1/PTV mark =P 1 V 1 T 1 /P mark T mark ;

V1:罐体上层空间的气体体积;V 1 : the gas volume in the upper space of the tank;

P1:罐体内气压值;P 1 : the air pressure value in the tank;

P:1个标准大气压;P mark : 1 standard atmospheric pressure;

T1:储罐内温度;T 1 : temperature in the storage tank;

T=273K。T- mark = 273K.

进一步的,所述的罐体上层空间的气体体积由电解液储罐液位计自动采集数据获得,所述的罐体上层空间的气体温度由电解液储罐温度传感器自动采集数据获得;并将采集数据传输至析氢量计算装置,容量恢复剂添加量由析氢量与电解液失衡关系确定,由钒离子与容量恢复剂的得失电子比例得出。Further, the gas volume of the upper space of the tank is obtained by automatically collecting data from the electrolyte storage tank level gauge, and the gas temperature of the upper space of the tank is obtained by automatically collecting data from the temperature sensor of the electrolyte storage tank; and The collected data is transmitted to the hydrogen evolution amount calculation device, and the added amount of the capacity recovery agent is determined by the unbalanced relationship between the hydrogen evolution amount and the electrolyte, and is obtained from the ratio of gain and loss of vanadium ions to the capacity recovery agent.

本发明还涉及一种液流电池容量衰减控制方法,根据液流电池系统参数设定连续充放电运行下的氢气产生速度值,检测氢气实际产生速度以确定连续两个充放电循环的析氢速度在前后比值区间的波动范围,波动范围超限则采取相应措施调节。The present invention also relates to a capacity decay control method for a flow battery. The hydrogen generation rate value under continuous charge-discharge operation is set according to system parameters of the flow battery, and the actual hydrogen generation rate is detected to determine that the hydrogen evolution rate of two consecutive charge-discharge cycles is within The fluctuation range of the ratio range before and after, if the fluctuation range exceeds the limit, corresponding measures will be taken to adjust.

进一步的,周期性的由所述氢气的浓度计算总析氢量,对总析氢量折算成电解液总价态偏移量以得到液流电池系统的放电容量,当液流电池系统的放电容量数值降至要求下限时进行放电容量恢复。Further, the total hydrogen evolution amount is calculated periodically from the hydrogen concentration, and the total hydrogen evolution amount is converted into the total valence state offset of the electrolyte to obtain the discharge capacity of the flow battery system. Discharge capacity recovery is performed when it falls to the required lower limit.

进一步的,所述氢气产生速度波动范围超限及调节方法是:当后一个循环周期的析氢速度与前一个循环周期的析氢速度之比的波动范围超过限值,若后一个循环周期的析氢速度较大,则将部分正极电解液导入负极电解液储罐以降低负极电解液SOC,同时通过电池系统的换热器将溶液调节温度降低;若后一个循环周期的析氢速度较小,确认负极SOC过低后,对正负极电解液状态调节,将负极溶液导入正极一部分,使得下一个充放电循环的SOC增加。进一步的,所述波动范围超限及调节方法是:当后一个循环周期的析氢速度大于当前循环周期析氢速度的1.3倍时,即A≥1.3时,将部分正极电解液导入负极电解液储罐,以降低负极电解液的荷电状态(State of Charge,SOC),直至负极电解液SOC低于70%,同时通过电池系统的换热器将电解液的温度调节至低于35℃;当A≤0.7时,且确认负极SOC低于50%时,对正负极电解液状态调节。

Figure BDA0001432172280000031
Further, the above-mentioned hydrogen generation speed fluctuation range exceeds the limit and the adjustment method is: when the fluctuation range of the ratio of the hydrogen evolution speed of the latter cycle to the hydrogen evolution speed of the previous cycle exceeds the limit value, if the hydrogen evolution speed of the latter cycle If it is larger, then introduce part of the positive electrolyte into the negative electrolyte storage tank to reduce the SOC of the negative electrolyte, and at the same time adjust the temperature of the solution through the heat exchanger of the battery system to reduce the temperature; if the hydrogen evolution rate in the latter cycle is small, confirm the negative SOC After it is too low, the state of the positive and negative electrolytes is adjusted, and the negative electrode solution is introduced into a part of the positive electrode, so that the SOC of the next charge-discharge cycle increases. Further, the fluctuation range exceeds the limit and the adjustment method is: when the hydrogen evolution rate of the next cycle is greater than 1.3 times the hydrogen evolution rate of the current cycle, that is, when A≥1.3, part of the positive electrolyte is introduced into the negative electrolyte storage tank. , to reduce the state of charge (SOC) of the negative electrolyte until the SOC of the negative electrolyte is lower than 70%, and at the same time, the temperature of the electrolyte is adjusted to be lower than 35 ℃ through the heat exchanger of the battery system; when A When ≤ 0.7, and it is confirmed that the SOC of the negative electrode is lower than 50%, the state of the electrolyte of the positive and negative electrodes is adjusted.
Figure BDA0001432172280000031

进一步的,由计算机程序控制气相色谱在每相邻两个循环放电完毕时,对负极电解液储罐内的气体取样,检测储罐内气压,当所述储罐内为负压时,使用氩气或氮气补压至等于外界大气压。Further, the gas chromatograph is controlled by the computer program to sample the gas in the negative electrolyte storage tank when the discharge of each adjacent two cycles is completed, and the gas pressure in the storage tank is detected, and when the storage tank is negative pressure, argon is used. Gas or nitrogen supplementary pressure equal to the outside atmospheric pressure.

进一步的,电解液储罐内的析氢量计算公式如下:Further, the formula for calculating the amount of hydrogen evolution in the electrolyte storage tank is as follows:

M=C*V M=C*V standard

M:储罐中氢气的总质量;M: the total mass of hydrogen in the storage tank;

C:罐体上层的氢气质量体积浓度;C: the mass volume concentration of hydrogen in the upper layer of the tank;

V:罐体上层空间的气体体积;V mark : the gas volume in the upper space of the tank;

V=P1V1T1/(PT);V standard =P 1 V 1 T 1 /(P standard T standard );

V1:罐体上层空间的气体体积;V 1 : the gas volume in the upper space of the tank;

P1:罐体内气压值;P 1 : the air pressure value in the tank;

P:1个标准大气压;P mark : 1 standard atmospheric pressure;

T1:储罐内温度;T 1 : temperature in the storage tank;

T:=273K。T- mark : = 273K.

放电容量恢复为添加容量恢复剂,其添加量由析氢量与电解液失衡关系确定,由钒电解液与容量恢复剂的得失电子比例得出。所述容量恢复剂,为市售甘油、草酸、EDTA、酒石酸等还原性小分子有机物。The discharge capacity is recovered by adding a capacity recovery agent, the amount of which is determined by the unbalanced relationship between the amount of hydrogen evolution and the electrolyte, and is obtained from the ratio of gain and loss of electrons between the vanadium electrolyte and the capacity recovery agent. The capacity recovery agent is commercially available glycerol, oxalic acid, EDTA, tartaric acid and other reducing small molecular organic compounds.

有益效果:本发明对氢气析出进行实时监测,使其维持在固定的反应水平,根据衰减要求,采取调控措施,使其在固定期限内维护一次(2~3年一次),降低维护频率,也降低了人力成本,同时可以即时发现系统的析氢速度异常现象,即时采取措施。Beneficial effects: the present invention monitors the hydrogen evolution in real time to keep it at a fixed reaction level, and takes control measures according to the attenuation requirements to maintain it once within a fixed period (once in 2-3 years), reducing the maintenance frequency, and also reduces the maintenance frequency. The labor cost is reduced, and at the same time, the abnormal phenomenon of the hydrogen evolution rate of the system can be found immediately, and measures can be taken immediately.

对于背景技术中的引述专利申请:首先,钒液流电池由于为水系电池,负极电解液析氢问题及原理是公知常识,下述为将本申请与引述专利申请的技术方案进行对比:For the cited patent application in the background art: first, the vanadium redox flow battery is an aqueous battery, and the problem of hydrogen evolution in the negative electrode electrolyte and the principle are common knowledge, and the following is to compare this application with the technical scheme of the cited patent application:

1.两方案的测试设备及方法比较1. Comparison of test equipment and methods of the two schemes

引述专利申请采用电极检测氢气,利用其与反应物反应产生的电流来检测氢气,为实时检测氢气含量,其设备精度未知,但由于氢气含量的波动性,实时检测氢气浓度误差很大,实验数据表明,两种气体彻底混合均匀需要2小时以上;且氢气析出速度在电解液SOC从低到高的过程中,并非呈严格线性关系,实时采取措施误差很大。Quoting the patent application, the electrode is used to detect hydrogen, and the current generated by its reaction with the reactant is used to detect hydrogen. In order to detect the hydrogen content in real time, the accuracy of the equipment is unknown, but due to the fluctuation of the hydrogen content, the real-time detection of hydrogen concentration has a large error. It shows that it takes more than 2 hours for the two gases to be thoroughly mixed evenly; and the hydrogen evolution rate is not strictly linear in the process of the electrolyte SOC from low to high, and the real-time measures are very error-prone.

本发明应用便携式气相色谱在每个充放电循环末尾直接对氢气含量进行精确测定。以判断前一个循环过程的析氢情况并及时对下一循环做出调整。The invention uses portable gas chromatography to directly determine the hydrogen content accurately at the end of each charge-discharge cycle. In order to judge the hydrogen evolution of the previous cycle and make adjustments to the next cycle in time.

同时,由于析氢反应是导致电池系统电解液价态失衡的主要因素,本专利中设备通过对系统总析氢量进行加和计算,一定数量循环后,通过添加容量恢复剂对衰减后的电池系统的放电容量进行恢复。At the same time, since the hydrogen evolution reaction is the main factor leading to the imbalance of the valence state of the electrolyte of the battery system, the device in this patent calculates the total hydrogen evolution amount of the system by summing up, and after a certain number of cycles, adding a capacity recovery agent to the decayed battery system. The discharge capacity is recovered.

2.析氢抑制手段比较2. Comparison of hydrogen evolution inhibition methods

引述专利申请的操作是在充电过程中,当系统SOC过高即存在过充电危险时,通过功率转换器降低充电功率来降低电流密度,众所周知析氢速度与电解液SOC高低及温度有直接关系,降低电流密度并不能减少析氢,低电流密度下充电,只要SOC仍然上升,负极电解液析氢速度就仍会增加。The operation cited in the patent application is that during the charging process, when the SOC of the system is too high, that is, there is a danger of overcharging, the power converter is used to reduce the charging power to reduce the current density. The current density does not reduce the hydrogen evolution. When charging at a low current density, as long as the SOC still rises, the hydrogen evolution rate of the negative electrolyte will still increase.

而本专利关注的主题是影响电解液SOC的潜在问题——正负极电解液体积迁移或价态失衡,防止正负极总钒价态的失衡需要从根源抑制电解液高SOC的产生。The subject of this patent is the potential problem affecting the SOC of the electrolyte—the volume migration or valence imbalance of the positive and negative electrolytes. To prevent the imbalance of the total vanadium valence state of the positive and negative electrodes, it is necessary to suppress the high SOC of the electrolyte from the source.

3.本发明的特点3. Features of the present invention

电池系统析氢是一个不可避免的过程,只能通过采取措施控制或者抑制,实验表明只有在电解液处于高SOC(即SOC>70%)时,析氢才会加剧。引述专利申请中采取降低电流密度的方法从理论上并不适用。本发明降低电解液SOC的技术方案在实际大型的MW级电池系统中可有效减少析氢速度,进而降低电池系统的放电容量,抑制衰减速率和减少维护成本。Hydrogen evolution in battery systems is an unavoidable process that can only be controlled or suppressed by taking measures. Experiments show that hydrogen evolution will only intensify when the electrolyte is at a high SOC (ie, SOC>70%). The method of reducing the current density cited in the patent application is not theoretically applicable. The technical solution for reducing the SOC of the electrolyte of the present invention can effectively reduce the hydrogen evolution rate in an actual large-scale MW-level battery system, thereby reducing the discharge capacity of the battery system, suppressing the decay rate and reducing maintenance costs.

附图说明Description of drawings

图1为实施例2中所述控制系统的结构示意框图。FIG. 1 is a schematic block diagram of the structure of the control system described in Embodiment 2. FIG.

具体实施方式Detailed ways

实施例1:Example 1:

一种液流电池容量衰减控制系统,包括A capacity decay control system for a flow battery, comprising:

气相色谱,测算负极电解液储罐内氢气的浓度;Gas chromatography to measure the concentration of hydrogen in the negative electrolyte storage tank;

总析氢量计算装置,周期性的由所述氢气的浓度计算总析氢量;依据总析氢量测定电解液价态偏移量,当然,总析氢量计算装置可以为气相色谱的嵌入式系统,或者气相色谱测算的浓度数据可以通过有线或无线方式传输至上位机,并于上位机中对总析氢量计算。The total hydrogen evolution amount calculation device periodically calculates the total hydrogen evolution amount according to the concentration of the hydrogen; the electrolyte valence offset is determined according to the total hydrogen evolution amount. Of course, the total hydrogen evolution amount calculation device can be an embedded system of gas chromatography, or The concentration data measured by gas chromatography can be transmitted to the host computer by wire or wireless, and the total amount of hydrogen evolution can be calculated in the host computer.

监视设备,监测液流电池充放电状态;Monitoring equipment to monitor the state of charge and discharge of flow batteries;

容量恢复装置,在液流电池放电终止状态下将相应量的容量恢复剂添加到正极电解液储罐以控制液流电池容量衰减。放电终止状态即放电完毕状态,若处于放电状态添加恢复剂会影响放电量,因而需要对放电状态监测,并在放电完毕状态下添加恢复剂,以避免影响放电。在一个实施例中,所述的液流电池容量衰减控制系统还包括气体采样装置,所述气体采样装置可以是属于总析氢量计算装置的一个子装置,或者是一个被独立设置的装置,其位于负极电解液储罐内,用于采集负极电解液储罐内的气体,其与气相色谱相连,周期性的将负极电解液储罐内的气体送入气相色谱的气体检测装置。The capacity recovery device adds a corresponding amount of the capacity recovery agent to the positive electrode electrolyte storage tank when the discharge of the flow battery is terminated to control the capacity decay of the flow battery. The discharge termination state is the discharge completed state. If it is in the discharge state, adding a recovery agent will affect the discharge amount. Therefore, it is necessary to monitor the discharge state, and add a recovery agent in the discharge completed state to avoid affecting the discharge. In one embodiment, the flow battery capacity decay control system further includes a gas sampling device, and the gas sampling device may be a sub-device belonging to the total hydrogen evolution amount calculation device, or an independent device, which It is located in the negative electrolyte storage tank and is used to collect the gas in the negative electrolyte storage tank. It is connected with the gas chromatography and periodically sends the gas in the negative electrolyte storage tank to the gas detection device of the gas chromatography.

在一个实施例中,所述的液流电池容量衰减控制系统还包括控制柜,所述控制柜可以是属于容量恢复装置的一个子装置,或者是一个被独立设置的装置,其与负极电解液储罐的放气阀连接,还连接于总析氢量计算装置,由总析氢量计算装置输出负极氢气总量(总体积)的数据至控制柜,当控制柜得到的负极氢气总量的数据与车间总体空间相比接近爆炸极限时,控制柜输出控制信号至放气阀,使放气阀打开将氢气导出室外,由此,放气阀优选为电磁阀,其中的连接方式为信号连接。In one embodiment, the flow battery capacity decay control system further includes a control cabinet, and the control cabinet may be a sub-device of the capacity recovery device, or an independently set device, which is connected to the negative electrolyte solution. The air release valve of the storage tank is connected to the total hydrogen evolution calculation device, and the total hydrogen evolution calculation device outputs the data of the total amount of negative hydrogen (total volume) to the control cabinet. When the overall space of the workshop is close to the explosion limit, the control cabinet outputs a control signal to the vent valve, so that the vent valve is opened to lead the hydrogen out of the room. Therefore, the vent valve is preferably a solenoid valve, and the connection method is signal connection.

在一个实施例中,所述的液流电池容量衰减控制系统还包括控制柜,其与正、负极电解液储罐联通阀连接,通过联通阀的启闭以对负极电解液储罐中的电解液的SOC水平进行调节,即通过联通阀开启,将部分正极电解液导入负极电解液储罐,以降低负极电解液的SOC,完成SOC调节。In one embodiment, the flow battery capacity decay control system further includes a control cabinet, which is connected to the communication valve of the positive and negative electrolyte storage tanks. The SOC level of the liquid is adjusted, that is, the communication valve is opened, and part of the positive electrolyte is introduced into the negative electrolyte storage tank to reduce the SOC of the negative electrolyte and complete the SOC adjustment.

在一个实施例中,所述析氢量计算装置存储有多条指令,所述指令适于处理器加载并执行:由所述氢气的浓度计算电解液储罐内的析氢量;In one embodiment, the hydrogen evolution amount calculation device stores a plurality of instructions, and the instructions are suitable for the processor to load and execute: calculate the hydrogen evolution amount in the electrolyte storage tank from the hydrogen concentration;

所述析氢量计算公式如下:The formula for calculating the amount of hydrogen evolution is as follows:

M=C*V M=C*V standard

M:储罐中氢气的总质量M: the total mass of hydrogen in the tank

C:罐体上层的氢气质量体积浓度,单位mg/L。C: The mass volume concentration of hydrogen in the upper layer of the tank, in mg/L.

V:罐体上层空间的气体体积V mark : the gas volume in the upper space of the tank

V=P1V1T1/(PT)V standard = P 1 V 1 T 1 /(P standard T standard )

V1:罐体上层空间的气体体积V 1 : the gas volume in the upper space of the tank

P1:罐体内气压值P 1 : Air pressure inside the tank

P:1个标准大气压P mark : 1 standard atmospheric pressure

T1:储罐内温度T 1 : Temperature inside the tank

T:273KT- mark : 273K

所述的罐体上层空间的气体体积由电解液储罐设有的液位计自动采集数据获得,所述的罐体上层空间的气体温度由电解液储罐温度传感器自动采集数据获得;并将采集数据传输至析氢量计算装置。The gas volume of the upper space of the tank body is obtained by automatically collecting data from the liquid level gauge provided in the electrolyte storage tank, and the gas temperature of the upper space of the tank body is obtained by automatically collecting data from the temperature sensor of the electrolyte storage tank; and The collected data is transmitted to the hydrogen evolution amount calculation device.

容量恢复剂添加量由析氢量与电解液失衡关系确定,由钒电解液与容量恢复剂的得失电子比例得出。The addition amount of the capacity recovery agent is determined by the unbalanced relationship between the hydrogen evolution and the electrolyte, and is obtained from the ratio of gain and loss of electrons between the vanadium electrolyte and the capacity recovery agent.

在一个实施例中,其公开一种液流电池容量衰减控制方法,设定连续充放电运行下的氢气产生速度值,检测氢气实际产生速度以确定连续两个充放电循环的析氢量在前后比值区间的波动范围,波动范围超限则采取相应措施调节,周期性的对该周期内的总析氢量统计,总氢气量折算成电解液价态偏移量,当其数值达到下限时进行放电容量恢复。In one embodiment, it discloses a capacity decay control method for a flow battery, setting a hydrogen generation rate value under continuous charge-discharge operation, and detecting the actual hydrogen generation rate to determine the ratio of the amount of hydrogen evolution in two consecutive charge-discharge cycles before and after The fluctuation range of the interval, if the fluctuation range exceeds the limit, corresponding measures will be taken to adjust, and the total hydrogen evolution in this period will be counted periodically, and the total hydrogen amount will be converted into the valence state offset of the electrolyte. recover.

所述波动范围超限及调节方法是:当A≥1.3时,将部分正极电解液导入负极电解液储罐以降低负极电解液SOC,同时通过电池系统的换热器将电解液调节温度降低;当A≤0.7,且确认负极电解液SOC过低时,则对正负极电解液状态调节。The fluctuation range exceeds the limit and the adjustment method is: when A ≥ 1.3, part of the positive electrolyte is introduced into the negative electrolyte storage tank to reduce the SOC of the negative electrolyte, and at the same time, the temperature of the electrolyte is adjusted by the heat exchanger of the battery system to reduce; When A≤0.7, and it is confirmed that the SOC of the negative electrode electrolyte is too low, the state of the positive and negative electrode electrolytes is adjusted.

在该方法中,由计算机程序控制气相色谱按固定时间取样负极电解液储罐内的气体,检测储罐内气压,当所述储罐内为负压时,使用氩气或氮气补压至等于外界大气压。In this method, the gas in the negative electrolyte storage tank is sampled at a fixed time by computer program-controlled gas chromatography, the air pressure in the storage tank is detected, and when the storage tank is under negative pressure, argon or nitrogen is used to supplement the pressure to equal outside atmospheric pressure.

电解液储罐内的析氢量计算公式如下:The formula for calculating the amount of hydrogen evolution in the electrolyte storage tank is as follows:

M=C*V M=C*V standard

M:储罐中氢气的总质量;M: the total mass of hydrogen in the storage tank;

C:罐体上层的氢气质量体积浓度,单位mg/L。C: The mass volume concentration of hydrogen in the upper layer of the tank, in mg/L.

V:罐体上层空间的气体体积;V mark : the gas volume in the upper space of the tank;

V=P1V1T1/(PT);V standard =P 1 V 1 T 1 /(P standard T standard );

V1:罐体上层空间的气体体积;V 1 : the gas volume in the upper space of the tank;

P1:罐体内气压值;P 1 : the air pressure value in the tank;

P:1个标准大气压;P mark : 1 standard atmospheric pressure;

T1:储罐内温度;T 1 : the temperature in the storage tank;

T=273K。T- mark = 273K.

放电容量恢复方法为添加容量恢复剂,其添加量由析氢量与电解液失衡关系确定,由钒离子与容量恢复剂的得失电子比例得出。The discharge capacity recovery method is to add a capacity recovery agent, the amount of which is determined by the relationship between the hydrogen evolution amount and the electrolyte imbalance, and is obtained from the ratio of gain and loss of vanadium ions to the capacity recovery agent.

实施例2:Example 2:

本实施例中的技术方案可以作为一个独立的方案,或者作为实施例1中方案的补充:一种液流电池容量衰减控制系统,应用于液流电池系统负极侧,用以检测负极系统由于副反应析氢或储罐密封问题造成氧气进入电解液储罐带来的自放电问题。应用方式为通过联通负极电解液储罐上层气体与气相色谱进行检测,以便实时掌握系统的容量衰减情况,系统包括:电池系统、容量恢复装置、恢复剂添加设备、维护设备、检测系统和控制装置,全钒液流电池系统包括正极和负极电解液储罐及连接电池与电解液的连接管线。容量恢复装置:根据氢气计算控制设备内设的氢气计算程序计算总析氢量,进而得出所需的恢复剂量,由恢复剂添加设备将一定量的容量恢复剂加入正极电解液。其中控制装置包括:监视设备和控制柜设备,监视设备用于监视系统的充放电状态,其将给出系统放电完毕的信号,放电状态下加入恢复剂,控制柜设备用来控制负极放气阀开启和正、负极电解液储罐联通阀和倒液泵开启,用以调节负极储罐氢气累积带来的危险和调节负极电解液SOC。检测系统包括气相色谱、气体采样装置、气体保护装置,气体采样装置设置在负极电解液储罐内,用于采集负极电解液储罐内的气体,气体采样装置通过直径3mmPE软管与气相色谱相连,间隔固定时间由气相色谱内置抽气泵将储桶内气体打入气相检测单元。氢气总量气相色谱用于检测计算负极电解液储罐内H2的ppm浓度;气体保护装置一端与负极电解液储罐的安全阀相连,当负极氢气总量与车间总体空间相比接近爆炸极限时,系统将判断打开安全阀将氢气导出室外,保护装置连接到PLC控制柜用以启动负极气体的开关阀,控制柜一端连接气相色谱的电脑操控程序,用来计算总气体量。The technical solution in this embodiment can be used as an independent solution, or as a supplement to the solution in Embodiment 1: a flow battery capacity decay control system, applied to the negative side of the flow battery system, to detect the negative electrode system due to secondary The self-discharge problem caused by oxygen entering the electrolyte storage tank is caused by hydrogen evolution in the reaction or the sealing problem of the storage tank. The application method is to detect the upper layer gas of the anode electrolyte storage tank and gas chromatography, so as to grasp the capacity attenuation of the system in real time. The system includes: battery system, capacity recovery device, recovery agent adding equipment, maintenance equipment, detection system and control device , The all-vanadium redox flow battery system includes positive and negative electrolyte storage tanks and connecting pipelines connecting the battery and the electrolyte. Capacity recovery device: Calculate the total amount of hydrogen evolution according to the hydrogen calculation program built in the hydrogen calculation control device, and then obtain the required recovery dose. A certain amount of capacity recovery agent is added to the positive electrolyte by the recovery agent addition device. The control device includes: monitoring equipment and control cabinet equipment, the monitoring equipment is used to monitor the charging and discharging state of the system, it will give a signal that the system is discharged, and the recovery agent is added in the discharging state, and the control cabinet equipment is used to control the negative discharge valve. Open the communication valve and the liquid pouring pump of the positive and negative electrolyte storage tanks to adjust the danger caused by the accumulation of hydrogen in the negative storage tank and adjust the SOC of the negative electrolyte. The detection system includes a gas chromatography, a gas sampling device, and a gas protection device. The gas sampling device is arranged in the negative electrolyte storage tank and is used to collect the gas in the negative electrolyte storage tank. The gas sampling device is connected to the gas chromatography through a 3mm PE hose in diameter , and the gas in the storage barrel is pumped into the gas detection unit by the built-in air pump of the gas chromatography at a fixed time interval. The total hydrogen gas chromatography is used to detect and calculate the ppm concentration of H2 in the negative electrolyte storage tank; one end of the gas protection device is connected to the safety valve of the negative electrolyte storage tank, when the total negative hydrogen gas is close to the explosion limit compared with the overall space of the workshop At this time, the system will judge to open the safety valve to export the hydrogen to the outdoor, the protection device is connected to the PLC control cabinet to activate the on-off valve of the negative gas, and one end of the control cabinet is connected to the computer control program of the gas chromatograph to calculate the total gas volume.

上述控制系统的控制方法如下:1)根据系统的运行模式,设定连续充放电运行下的氢气产生速度为6L/100LNegtive Solution/cycle,该速度为折算后的标准状况下的气体体积,确定氢气析氢速度的计算方法和检测程序,判定电池系统连续两个充放电循环的析氢速度比值A是否满足0.7<A<1.3;The control method of the above-mentioned control system is as follows: 1) According to the operation mode of the system, the hydrogen generation speed under the continuous charge and discharge operation is set to be 6L/100L Negtive Solution /cycle, and this speed is the gas volume under the converted standard condition, determine The calculation method and detection procedure of the hydrogen evolution rate of hydrogen, to determine whether the hydrogen evolution rate ratio A of the battery system for two consecutive charge-discharge cycles satisfies 0.7<A<1.3;

2)如果A≤0.7或A≥1.3,表明后一循环的析氢速度较前一个循环的析氢速度波动范围超过±30%,则判定系统析氢量超标或系统电解液利用率不足,系统控制程序报警并采取措施。2) If A≤0.7 or A≥1.3, it means that the hydrogen evolution rate of the next cycle exceeds the fluctuation range of the hydrogen evolution rate of the previous cycle by more than ±30%, then it is judged that the amount of hydrogen evolution in the system exceeds the standard or the utilization rate of the system electrolyte is insufficient, and the system control program alarms and take action.

其中析氢速度测试周期为每两次测试间隔时间,本专利测试周期为每个循环放电后的系统搁置阶段。即每个完整充放电循环后测试一次。The hydrogen evolution rate test period is the interval between two tests, and the patent test period is the system shelving stage after each cycle of discharge. That is, one test after each complete charge-discharge cycle.

系统报警采取措施为:The system alarm takes the following measures:

当A≥1.3时,将一部分正极电解液导入负极电解液储罐,以降低负极电解液的SOC,使得负极电解液的SOC降至70%以下,同时通过电池系统的换热器将电解液的温度调节至35℃以下;When A≥1.3, a part of the positive electrolyte is introduced into the negative electrolyte storage tank to reduce the SOC of the negative electrolyte, so that the SOC of the negative electrolyte is reduced to less than 70%, and the Adjust the temperature to below 35°C;

当A≤0.7时,需检查负极电解液SOC是否过低,即需检查负极电解液SOC是否低于50%,如确认其低于50%,则对正负极电解液状态进行调节:即将一部分负极电解液导入正极电解液储罐,使其同一运行模式下,后一循环负极电解液的SOC>60%。When A≤0.7, it is necessary to check whether the SOC of the anode electrolyte is too low, that is, it is necessary to check whether the SOC of the anode electrolyte is lower than 50%. If it is confirmed that it is lower than 50%, adjust the state of the anode and cathode electrolytes: The negative electrolyte is introduced into the positive electrolyte storage tank, so that under the same operation mode, the SOC of the negative electrolyte in the subsequent cycle is >60%.

SOC定义:SOC Definition:

正极:5价离子浓度占正极电解液总钒浓度比例;Positive electrode: the proportion of 5-valent ion concentration in the total vanadium concentration of the positive electrode electrolyte;

负极:2价离子浓度占正极电解液总钒浓度比例;Negative electrode: the proportion of divalent ion concentration in the total vanadium concentration of the positive electrolyte;

3)周期性的对系统总析氢量进行统计,将总氢气量折算成系统电解液价态偏移量,当其数值达到系统要求下限时,系统报警提示进行放电容量恢复。所述的周期,可以根据液流电池系统的类型、模式或者主要依据于液流电池系统的使用频率来确定,如果经常使用,则可以设定为1个月,否则,可以设定为3个月,当然,还可以是其他时间区间。3) Periodically count the total hydrogen evolution of the system, and convert the total hydrogen amount into the valence offset of the system electrolyte. When the value reaches the lower limit required by the system, the system alarms and prompts the discharge capacity recovery. The cycle can be determined according to the type and mode of the flow battery system or mainly according to the frequency of use of the flow battery system. If it is used frequently, it can be set to 1 month, otherwise, it can be set to 3. Months, of course, can also be other time periods.

由上述,本实施例中的方案可能涉及析氢量、析氢速度与析氢总量。From the above, the solution in this embodiment may involve the amount of hydrogen evolution, the rate of hydrogen evolution and the total amount of hydrogen evolution.

其中,析氢速度是析氢量的差值与时间的比值获得,单位为L/循环,能够反映固定Among them, the hydrogen evolution rate is obtained by the ratio of the difference between the hydrogen evolution amount and the time, and the unit is L/cycle, which can reflect the fixed

时间内的析氢量。析氢量是固定时间内析氢的体积,单位为L。析氢总量指一段时The amount of hydrogen evolution over time. The amount of hydrogen evolution is the volume of hydrogen evolution in a fixed time, in L. The total amount of hydrogen evolution refers to a period of time

间内析氢量的加和,该时间段可以人为定义,如为2个月或者3个月。The sum of the amount of hydrogen evolution in the interval, the time period can be defined artificially, such as 2 months or 3 months.

系统恢复剂量添加:System Restoration Dose Addition:

根据反应方程式:2V2++2H+=2V3++H2↑,得出氢气产生量与系统电解液失衡关系,再由5价钒电解液与恢复剂的得失电子比例得出:According to the reaction equation: 2V 2+ +2H + =2V 3+ +H 2 ↑, the unbalanced relationship between the hydrogen production and the system electrolyte is obtained, and then the ratio of gain and loss electrons between the 5-valent vanadium electrolyte and the recovery agent is obtained:

例如:由计算得知,每kg草酸可弥补249L氢气析出带来的价态失衡,系统依照氢气总量自动计算出所应添加的恢复剂重量。For example, it is known from the calculation that each kg of oxalic acid can make up for the valence imbalance caused by the evolution of 249L of hydrogen, and the system automatically calculates the weight of the restoring agent that should be added according to the total amount of hydrogen.

根据氧化还原方程,每mol草酸彻底氧化可提供两个电子用以还原两个钒离子。According to the redox equation, the complete oxidation of oxalic acid can provide two electrons to reduce two vanadium ions per mol of oxalic acid.

系统要求下限:客户一般能接受放电容量下降30%,H2总量与价态偏离的关系根据下式得出:2V2++2H+=2V3++H2↑,即当有1mol氢气释放出,负极电解液中2价钒浓度降低2mol。以此类推,根据总析氢量,即可得出电解液综合价态的升高量。The lower limit of system requirements: customers can generally accept a 30% drop in discharge capacity, and the relationship between the total amount of H 2 and the valence deviation is obtained according to the following formula: 2V 2+ +2H + = 2V 3+ +H 2 ↑, that is, when there is 1mol of hydrogen released, and the concentration of divalent vanadium in the negative electrolyte decreased by 2 mol. By analogy, according to the total amount of hydrogen evolution, the increase in the comprehensive valence state of the electrolyte can be obtained.

4)系统设定程序,间隔一周对系统内正负极电解液储罐内的总氢气浓度进行统计,以确定是否达到危险限值,及时对系统采取排空处理。4) The system sets the program, and counts the total hydrogen concentration in the positive and negative electrolyte storage tanks of the system every one week to determine whether the dangerous limit is reached, and the system is emptied in time.

危险限值:当储罐内氢气总体积与车间空间总体积达到爆炸极限时,定义为氢气的危险限值。氢气爆炸极限指氢气体积含量4%~72%。Dangerous limit: When the total volume of hydrogen in the storage tank and the total volume of the workshop space reach the explosion limit, it is defined as the dangerous limit of hydrogen. The hydrogen explosion limit refers to the hydrogen volume content of 4% to 72%.

氢气检测为全自动系统,通过程序控制气相色谱按固定时间取样负极储罐内气体,自动检测储罐内气压,当罐内为负压时,自动开启氩气或氮气补压至等于外界大气压。The hydrogen detection is a fully automatic system. The gas in the negative electrode storage tank is sampled at a fixed time through the program control gas chromatography, and the pressure in the storage tank is automatically detected. When the tank is under negative pressure, the argon or nitrogen gas is automatically turned on to supplement the pressure until it is equal to the external atmospheric pressure.

5)电解液储罐内氢气量根据气相色谱所测得的氢气浓度,代入公式计算得到系统的氢气总量,具体如下:5) The amount of hydrogen in the electrolyte storage tank is based on the hydrogen concentration measured by gas chromatography, and is substituted into the formula to calculate the total amount of hydrogen in the system, as follows:

M=C*V M=C*V standard

M:储罐中氢气的总质量;M: the total mass of hydrogen in the storage tank;

C:罐体上层的氢气质量体积浓度,单位mg/L。(气相色谱测算负极电解液储罐内氢气的浓度可以直接被换算为罐体上层的氢气质量体积浓度)。C: The mass volume concentration of hydrogen in the upper layer of the tank, in mg/L. (The concentration of hydrogen in the negative electrolyte storage tank measured by gas chromatography can be directly converted into the mass volume concentration of hydrogen in the upper layer of the tank).

V:罐体上层空间的气体体积;V mark : the gas volume in the upper space of the tank;

V=P1V1T1/(PT);V standard =P 1 V 1 T 1 /(P standard T standard );

V1:罐体上层空间的气体体积;V 1 : the gas volume in the upper space of the tank;

P1:罐体内气压值;P 1 : the air pressure value in the tank;

P:1个标准大气压;P mark : 1 standard atmospheric pressure;

T1:储罐内温度;T 1 : temperature in the storage tank;

T=273K。T- mark = 273K.

以上所述,仅为本发明创造较佳的具体实施方式,但本发明创造的保护范围并不局限于此,任何熟悉本技术领域的技术人员在本发明创造披露的技术范围内,根据本发明创造的技术方案及其发明构思加以等同替换或改变,都应涵盖在本发明创造的保护范围之内。The above description is only a preferred embodiment of the present invention, but the protection scope of the present invention is not limited to this. The equivalent replacement or modification of the created technical solution and its inventive concept shall be included within the protection scope of the present invention.

Claims (10)

1. A flow battery capacity fade control system is characterized by comprising
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;
the capacity recovery device is used for adding a capacity recovery agent to the positive electrolyte storage tank to control the capacity attenuation of the flow battery in the discharge termination state of the flow battery;
the total hydrogen evolution amount calculation device stores a plurality of instructions, and the instructions are suitable for a processor to load and execute: calculating the total hydrogen evolution amount in the electrolyte storage tank according to the concentration of the hydrogen;
the total hydrogen evolution quantity calculation formula is as follows:
M=C*Vsign board
M is the total mass of hydrogen in the storage tank;
c: mass volume concentration of hydrogen on the upper layer of the tank body;
Vsign board: the current temperature in the storage tank is TSign boardWhen the pressure value in the tank body is PSign boardThe gas volume of the upper space of the tank body;
Vsign board= P1V1T1/PSign boardTSign board
V1: the current temperature in the storage tank is T1When the pressure value in the tank body is P1The gas volume of the upper space of the tank body;
P1: the air pressure value in the tank body;
Psign board: 1 standard atmospheric pressure;
T1: the temperature in the storage tank;
Tsign board=273K。
2. The flow battery capacity fade control system of claim 1, further comprising a gas sampling device located in the negative electrolyte reservoir for collecting gas in the negative electrolyte reservoir, connected to the gas chromatograph, for periodically sending gas from the negative electrolyte reservoir to the gas detection device of the gas chromatograph.
3. The flow battery capacity fade control system of claim 1, further comprising a control cabinet connected to a purge valve of the negative electrolyte storage tank and further connected to the total hydrogen evolution volume calculation device.
4. The flow battery capacity fade control system of claim 1 or 3, further comprising a control cabinet connected to the positive and negative electrolyte tank communication valves.
5. The flow battery capacity fade control system of claim 1, wherein the gas volume in the tank headspace is obtained from automatically collected data from an electrolyte tank level gauge, and the gas temperature in the tank headspace is obtained from automatically collected data from an electrolyte tank temperature sensor; and transmitting the acquired data to a hydrogen evolution amount calculation device, wherein the addition amount of the capacity recovery agent is determined by the relation between the hydrogen evolution amount and the solution unbalance, and is obtained by the gain-loss electron ratio of the vanadium ions and the capacity recovery agent.
6. A method for controlling the capacity attenuation of a flow battery is characterized by comprising the following steps: setting a hydrogen generation speed value under continuous charge-discharge operation according to parameters of a flow battery system, detecting the actual hydrogen generation speed to determine the fluctuation range of the hydrogen evolution speed of two continuous charge-discharge cycles in a front-rear ratio interval, and taking corresponding measures to adjust if the fluctuation range exceeds the limit.
7. The method for controlling the capacity fading of the flow battery as claimed in claim 6, wherein the total hydrogen evolution amount is periodically calculated according to the concentration of the hydrogen, the total hydrogen evolution amount is converted into the total electrolyte valence offset to obtain the discharge capacity of the flow battery system, and the discharge capacity is recovered when the discharge capacity value of the flow battery system is reduced to the required lower limit.
8. The flow battery capacity fade control method of claim 6 or 7, wherein the hydrogen generation rate fluctuation range overrun and regulation method is: when the fluctuation range of the ratio of the hydrogen evolution speed of the next cycle period to the hydrogen evolution speed of the previous cycle period exceeds the limit value, if the hydrogen evolution speed of the next cycle period is higher, part of the positive electrolyte is led into a negative electrolyte storage tank to reduce the SOC of the negative electrolyte, and meanwhile, the solution is adjusted to reduce the temperature through a heat exchanger of the battery system; if the hydrogen evolution speed of the next cycle period is low, and the SOC of the negative electrode is determined to be too low, the state of the electrolyte of the positive electrode and the negative electrode is adjusted, and the negative electrode solution is introduced into a part of the positive electrode, so that the SOC of the next charge-discharge cycle is increased.
9. The flow battery capacity fading control method as claimed in claim 8, wherein the specific method for judging and adjusting the fluctuation range overrun is as follows: when A is more than or equal to 1.3, introducing part of the positive electrolyte into a negative electrolyte storage tank to reduce the charge state of the negative electrolyte until the SOC of the negative electrolyte is lower than 70%, and simultaneously adjusting the temperature of the electrolyte to be lower than 35 ℃ through a heat exchanger of a battery system; when A is less than or equal to 0.7 and the SOC of the negative electrode is confirmed to be lower than 50%, adjusting the state of the electrolyte of the positive electrode and the negative electrode, and introducing the negative electrode solution into a part of the positive electrode to increase the SOC of the next charge-discharge cycle, wherein: a = hydrogen evolution rate of the latter cycle/hydrogen evolution rate of the former cycle.
10. The method for controlling the capacity fade of a flow battery as claimed in claim 6 or 7, wherein the gas chromatography is controlled by a computer program to sample the gas in the negative electrolyte tank at a fixed time, detect the pressure in the tank, and when the pressure in the tank is negative, supplement the pressure to be equal to the external atmospheric pressure by using argon or nitrogen.
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