CN107195932B - Flow battery capacity stabilization control method, system and flow battery - Google Patents
Flow battery capacity stabilization control method, system and flow battery Download PDFInfo
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- 238000000034 method Methods 0.000 title claims abstract description 29
- 230000006641 stabilisation Effects 0.000 title claims description 16
- 238000011105 stabilization Methods 0.000 title claims description 16
- 239000003792 electrolyte Substances 0.000 claims abstract description 309
- 239000003795 chemical substances by application Substances 0.000 claims abstract description 22
- 238000011084 recovery Methods 0.000 claims abstract description 22
- 230000033228 biological regulation Effects 0.000 claims abstract description 8
- 239000007788 liquid Substances 0.000 claims description 93
- 238000002474 experimental method Methods 0.000 claims description 20
- 238000012544 monitoring process Methods 0.000 claims description 13
- 229910001456 vanadium ion Inorganic materials 0.000 claims description 13
- 238000005070 sampling Methods 0.000 claims description 10
- 229910052720 vanadium Inorganic materials 0.000 claims description 8
- 238000007599 discharging Methods 0.000 claims description 7
- LEONUFNNVUYDNQ-UHFFFAOYSA-N vanadium atom Chemical compound [V] LEONUFNNVUYDNQ-UHFFFAOYSA-N 0.000 claims description 7
- 230000001276 controlling effect Effects 0.000 claims 5
- 230000001105 regulatory effect Effects 0.000 claims 4
- 230000014759 maintenance of location Effects 0.000 abstract description 2
- 239000008151 electrolyte solution Substances 0.000 description 4
- 238000005562 fading Methods 0.000 description 4
- 238000011217 control strategy Methods 0.000 description 3
- 230000007774 longterm Effects 0.000 description 3
- 239000000243 solution Substances 0.000 description 3
- 230000000087 stabilizing effect Effects 0.000 description 3
- 239000011149 active material Substances 0.000 description 2
- 238000001514 detection method Methods 0.000 description 2
- 238000010586 diagram Methods 0.000 description 2
- 238000005516 engineering process Methods 0.000 description 2
- 238000004458 analytical method Methods 0.000 description 1
- 238000005868 electrolysis reaction Methods 0.000 description 1
- 238000004146 energy storage Methods 0.000 description 1
- 150000002500 ions Chemical class 0.000 description 1
- 238000012423 maintenance Methods 0.000 description 1
- 238000007726 management method Methods 0.000 description 1
- 239000000463 material Substances 0.000 description 1
- 238000013508 migration Methods 0.000 description 1
- 230000005012 migration Effects 0.000 description 1
- XLYOFNOQVPJJNP-UHFFFAOYSA-N water Substances O XLYOFNOQVPJJNP-UHFFFAOYSA-N 0.000 description 1
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- H—ELECTRICITY
- H01—ELECTRIC ELEMENTS
- H01M—PROCESSES OR MEANS, e.g. BATTERIES, FOR THE DIRECT CONVERSION OF CHEMICAL ENERGY INTO ELECTRICAL ENERGY
- H01M8/00—Fuel cells; Manufacture thereof
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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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- H01M8/188—Regeneration by electrochemical means by recharging of redox couples containing fluids; Redox flow type batteries
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Abstract
Description
技术领域technical field
本发明属于液流电池技术领域，具体涉及一种液流电池容量稳定调控方法、系统及液流电池。The invention belongs to the technical field of liquid flow batteries, and in particular relates to a method and system for stabilizing the capacity of a liquid flow battery and a liquid flow battery.
背景技术Background technique
液流电池是大规模储能应用的首选技术之一，参考图1所示，现有技术中的液流电池通常包括由电池单体或多个电池单体串联组成的电堆6、正极电解液储罐3、负极电解液储罐4、循环泵5和液体输送管路1，其中电池单体包括正极、负极、正极电解液和负极电解液；正极电解液储罐3经循环泵5通过液体输送管路1与电堆6的正极电解液入口63相连，电堆6的正极电解液出口61经液体输送管路1与正极电解液储罐3相连，负极电解液储罐4经循环泵5通过液体输送管路1与电堆6的负极电解液入口64相连，电堆6的负极电解液出口62经液体输送管路1与负极电解液储罐4相连；所述液体输送管路1上设置有电动阀2；现有技术中的这种液流电池存在如下问题：在液流电池充放电循环过程中，由于正负极之间的离子和水迁移，会导致电解液逐渐失衡，使得电池效率及容量降低，现有技术中对于液流电池的容量衰减程度的检测手段，通常通过暂停液流电池的运行，然后进行电解液取样，进而得出电解液的钒离子浓度状态，从而获知液流电池的容量衰减程度，进一步地，对于出现容量衰减程度后液流电池的容量调控方案，国内的现有技术还存在一定的空白，美国专利US6764789提出了两种替代方法：分批液体调整法和溢流法，但需要额外的电能和/或设备来重新分配混合电解液；美国专利US20110300417提出了正负极电解液储罐联通的方法，长时间保持液面的水平使得液流电池容量保持长时间稳定，但是研究发现，长期保持正负极联通会造成漏电的产生，降低系统效率，而且在不同的运行时间后，对于获得最好的液流电池性能和容量稳定性来说，正负极电解液液面差是变化的，通过上述内容可知，现有技术中无法实现容量衰减程度的在线监测和调控，影响系统运行效率，同时对于针对不同的容量衰减程度来采用不同的调控方式，现有技术中尚未存在有效的解决方案。Flow batteries are one of the preferred technologies for large-scale energy storage applications. Referring to Figure 1, flow batteries in the prior art usually include a battery cell or multiple battery cells connected in series. Liquid storage tank 3, negative electrode electrolyte storage tank 4, circulation pump 5 and liquid delivery pipeline 1, wherein the battery cell includes positive electrode, negative electrode, positive electrode electrolyte and negative electrode electrolyte; positive electrode electrolyte storage tank 3 passes through circulation pump 5 The liquid delivery pipeline 1 is connected to the positive electrolyte inlet 63 of the stack 6, the positive electrolyte outlet 61 of the stack 6 is connected to the positive electrolyte storage tank 3 through the liquid delivery pipeline 1, and the negative electrolyte storage tank 4 is connected to the circulation pump 5. Connect to the negative electrode electrolyte inlet 64 of the cell stack 6 through the liquid delivery pipeline 1, and the negative electrode electrolyte outlet 62 of the battery stack 6 is connected to the negative electrode electrolyte storage tank 4 through the liquid delivery pipeline 1; the liquid delivery pipeline 1 An electric valve 2 is arranged on it; the flow battery in the prior art has the following problems: during the charging and discharging cycle of the flow battery, due to the migration of ions and water between the positive and negative electrodes, the electrolyte will gradually become unbalanced, The efficiency and capacity of the battery are reduced. In the prior art, the detection method for the degree of capacity decay of the flow battery is usually by suspending the operation of the flow battery, and then sampling the electrolyte to obtain the concentration of vanadium ions in the electrolyte. Knowing the degree of capacity fading of the flow battery, further, there is still a certain gap in the domestic existing technology for the capacity regulation scheme of the flow battery after the degree of capacity fading occurs. The US patent US6764789 proposes two alternative methods: batch liquid Adjustment method and overflow method, but additional electrical energy and/or equipment are required to redistribute the mixed electrolyte; US Patent US20110300417 proposes a method of connecting the positive and negative electrolyte storage tanks to maintain the level of the liquid level for a long time so that the flow battery The capacity remains stable for a long time, but studies have found that keeping the positive and negative electrodes connected for a long time will cause leakage and reduce system efficiency, and after different operating times, for obtaining the best performance and capacity stability of the flow battery, The liquid level difference of the positive and negative electrolytes changes. From the above, it can be seen that the online monitoring and regulation of the degree of capacity fading cannot be realized in the prior art, which affects the operating efficiency of the system. At the same time, different regulation is adopted for different degrees of capacity fading way, there is no effective solution in the prior art.
发明内容Contents of the invention
本发明针对以上问题的提出，而研制一种能够实现液流电池容量和性能长时间保持稳定的液流电池容量稳定调控方法、系统及液流电池。In view of the above problems, the present invention develops a flow battery capacity stabilization control method, system and flow battery capable of maintaining the capacity and performance of the flow battery stable for a long time.
本发明的技术手段如下：Technical means of the present invention is as follows:
一种液流电池容量稳定调控方法，包括如下步骤：A method for stabilizing the capacity of a flow battery, comprising the steps of:
步骤1：获得液流电池当前的电解液容量衰减率；Step 1: Obtain the current electrolyte capacity decay rate of the flow battery;
步骤2：判断液流电池当前的电解液容量衰减率是否低于第一预设衰减率，是则返回步骤1，否则执行步骤3；Step 2: Determine whether the current electrolyte capacity decay rate of the flow battery is lower than the first preset decay rate, if yes, return to step 1, otherwise perform step 3;
步骤3：判断液流电池当前的电解液容量衰减率是否低于第二预设衰减率，是则执行步骤4，否则执行步骤5；Step 3: Determine whether the current electrolyte capacity decay rate of the flow battery is lower than the second preset decay rate, if yes, perform step 4, otherwise perform step 5;
步骤4：调节正极电解液和负极电解液的液面高度，使正极电解液与负极电解液之间的液位差小于预设值或者正极电解液与负极电解液中总钒比例保持在预设比例范围；Step 4: Adjust the liquid level height of the positive electrolyte and the negative electrolyte so that the liquid level difference between the positive electrolyte and the negative electrolyte is less than the preset value or the ratio of the total vanadium in the positive electrolyte to the negative electrolyte is kept at the preset Scale range;
步骤5：向正极电解液储罐和负极电解液储罐内添加所需用量的容量恢复剂；Step 5: Add the required amount of capacity recovery agent to the positive electrode electrolyte storage tank and the negative electrode electrolyte storage tank;
进一步地，所述步骤1具体包括如下步骤：Further, the step 1 specifically includes the following steps:
步骤11：监测液流电池运行状态参数；Step 11: Monitor the operating state parameters of the flow battery;
步骤12：根据所监测的液流电池运行状态参数，结合所述液流电池运行状态参数与电解液容量衰减率之间的对应关系，获得液流电池当前的电解液容量衰减率；Step 12: According to the monitored operating state parameters of the flow battery, combined with the corresponding relationship between the operating state parameters of the flow battery and the electrolyte capacity decay rate, the current electrolyte capacity decay rate of the flow battery is obtained;
进一步地，在步骤11之前还具有如下步骤：Further, before step 11, there are also the following steps:
确定液流电池运行状态参数与电解液容量衰减率之间的对应关系并存储；Determine and store the corresponding relationship between the operating state parameters of the flow battery and the electrolyte capacity decay rate;
进一步地，所述确定液流电池运行状态参数与电解液容量衰减率之间的对应关系步骤具体包括：Further, the step of determining the corresponding relationship between the operating state parameters of the flow battery and the electrolyte capacity decay rate specifically includes:
获得初始液流电池运行状态参数；Obtain the initial flow battery operating state parameters;
对液流电池进行充放电实验，获取充放电实验过程中的不同液流电池运行状态参数；Conduct charge and discharge experiments on the flow battery, and obtain the operating state parameters of different flow batteries during the charge and discharge experiment;
随着液流电池运行状态参数在充放电实验过程中的变化，进行多次正极电解液和负极电解液的取样，并获知取样的正极电解液和负极电解液的钒离子浓度；As the operating state parameters of the flow battery change during the charge-discharge experiment, the positive and negative electrolytes are sampled multiple times, and the vanadium ion concentrations of the sampled positive and negative electrolytes are obtained;
根据获知的正极电解液和负极电解液的钒离子浓度情况，计算出相应的电解液容量衰减率情况；According to the known vanadium ion concentration of positive electrolyte and negative electrolyte, calculate the corresponding electrolyte capacity decay rate;
得出液流电池运行状态参数与电解液容量衰减率之间的对应关系；The corresponding relationship between the operating state parameters of the flow battery and the electrolyte capacity decay rate is obtained;
进一步地，根据液流电池当前的电解液容量衰减率，以及正极电解液、负极电解液的体积，计算所需容量恢复剂的用量。Further, according to the current electrolyte capacity decay rate of the flow battery, and the volumes of the positive electrolyte and the negative electrolyte, the required amount of the capacity recovery agent is calculated.
一种液流电池容量稳定调控系统，包括：A flow battery capacity stabilization control system, comprising:
获得液流电池当前电解液容量衰减率的获取单元；An acquisition unit for obtaining the current electrolyte capacity decay rate of the flow battery;
连接获取单元，用于判断液流电池当前电解液容量衰减率是否低于第一预设衰减率的第一判断单元；connected to the acquisition unit, a first judging unit for judging whether the current electrolyte capacity decay rate of the flow battery is lower than the first preset decay rate;
连接第一判断单元，用于当液流电池当前电解液容量衰减率高于等于第一预设衰减率时，判断液流电池当前的电解液容量衰减率是否低于第二预设衰减率的第二判断单元；当液流电池当前电解液容量衰减率高于等于第二预设衰减率时，执行向正极电解液储罐和负极电解液储罐内添加所需用量的容量恢复剂的操作；Connecting the first judging unit for judging whether the current electrolyte capacity decay rate of the flow battery is lower than the second preset decay rate when the current electrolyte capacity decay rate of the liquid flow battery is higher than or equal to the first preset decay rate The second judging unit; when the current electrolyte capacity decay rate of the flow battery is higher than or equal to the second preset decay rate, perform the operation of adding a required amount of capacity recovery agent to the positive electrolyte storage tank and the negative electrolyte storage tank ;
连接第二判断单元的控制单元，所述控制单元用于当液流电池当前电解液容量衰减率低于第二预设衰减率，同时高于等于第一预设衰减率时，调节正极电解液和负极电解液的液面高度，使正极电解液与负极电解液之间的液位差小于预设值或者正极电解液与负极电解液中总钒比例保持在预设比例范围；A control unit connected to the second judging unit, the control unit is used to adjust the positive electrode electrolyte when the current electrolyte capacity decay rate of the flow battery is lower than the second preset decay rate and at the same time higher than or equal to the first preset decay rate and the liquid level height of the negative electrode electrolyte, so that the liquid level difference between the positive electrode electrolyte and the negative electrode electrolyte is less than the preset value or the ratio of the total vanadium in the positive electrode electrolyte and the negative electrode electrolyte remains within the preset ratio range;
另外，所述容量稳定调控系统还包括：In addition, the capacity stabilization control system also includes:
用于监测液流电池运行状态参数的监测单元；所述获取单元根据所监测的液流电池运行状态参数，结合所述液流电池运行状态参数与电解液容量衰减率之间的对应关系，获得液流电池当前的电解液容量衰减率。A monitoring unit for monitoring the operating state parameters of the liquid flow battery; the acquisition unit obtains according to the monitored operating state parameters of the liquid flow battery in combination with the corresponding relationship between the operating state parameters of the liquid flow battery and the electrolyte capacity decay rate The current electrolyte capacity decay rate of the flow battery.
一种液流电池，包括上述所述的液流电池容量稳定调控系统；A flow battery, including the above-mentioned flow battery capacity stabilization control system;
进一步地，所述液流电池包括：电堆、正极电解液储罐、负极电解液储罐、液体输送管路和循环泵；正极电解液储罐经循环泵通过液体输送管路与电堆的正极电解液入口相连，电堆的正极电解液出口分别经液体输送管路与正极电解液储罐和负极电解液储罐相连；负极电解液储罐经循环泵通过液体输送管路与电堆的负极电解液入口相连，电堆的负极电解液出口分别经液体输送管路与正极电解液储罐和负极电解液储罐相连；Further, the liquid flow battery includes: an electric stack, a positive electrode electrolyte storage tank, a negative electrode electrolyte storage tank, a liquid delivery pipeline and a circulation pump; the positive electrode electrolyte storage tank passes through the circulation pump through the liquid delivery pipeline and the battery The positive electrolyte inlet is connected, and the positive electrolyte outlet of the stack is respectively connected to the positive electrolyte storage tank and the negative electrolyte storage tank through the liquid delivery pipeline; the negative electrolyte storage tank is connected to the stack through the liquid delivery pipeline through the circulating pump The negative electrode electrolyte inlet is connected, and the negative electrode electrolyte outlet of the cell stack is respectively connected to the positive electrode electrolyte storage tank and the negative electrode electrolyte storage tank through the liquid delivery pipeline;
所述正极电解液储罐和负极电解液储罐上均设置有用于添加容量恢复剂的加料口；Both the positive electrode electrolyte storage tank and the negative electrode electrolyte storage tank are provided with feeding ports for adding a capacity recovery agent;
进一步地，所述电堆的正极电解液出口与正极电解液储罐之间的液体输送管路、电堆的正极电解液出口与负极电解液储罐之间的液体输送管路、电堆的负极电解液出口与正极电解液储罐之间的液体输送管路、以及电堆的负极电解液出口与负极电解液储罐之间的液体输送管路上均设置有用于开启或关闭液体输送管路的电动阀；所述控制单元通过控制所述电动阀的工作状态实现正极电解液和负极电解液的液面高度的调节。Further, the liquid delivery pipeline between the positive electrolyte outlet of the stack and the positive electrolyte storage tank, the liquid delivery pipeline between the positive electrolyte outlet of the stack and the negative electrolyte storage tank, the The liquid delivery pipeline between the negative electrode electrolyte outlet and the positive electrode electrolyte storage tank, and the liquid delivery pipeline between the negative electrode electrolyte solution outlet of the cell stack and the negative electrode electrolyte storage tank are all provided with a device for opening or closing the liquid delivery pipeline. The electric valve; the control unit realizes the adjustment of the liquid level height of the positive electrode electrolyte and the negative electrode electrolyte by controlling the working state of the electric valve.
由于采用了上述技术方案，和现有技术相比，本发明提供的液流电池容量稳定调控方法、系统及液流电池具有如下优点：Due to the adoption of the above technical solution, compared with the prior art, the flow battery capacity stabilization control method, system and flow battery provided by the present invention have the following advantages:
1、本发明能够根据容量衰减程度的不同而采用不同的调控策略，包括在较低的衰减程度下采用调节正负极电解液液位差方式，而在较高的衰减程度下采用添加容量恢复剂方式，针对不同衰减程度采用不同的调控策略，可以有效提高液流电池容量保持能力，降低容量恢复剂的成本，实现液流电池容量和性能长时间保持稳定。1. The present invention can adopt different control strategies according to the degree of capacity attenuation, including adjusting the liquid level difference between the positive and negative electrodes at a lower degree of attenuation, and adding capacity recovery at a higher attenuation degree The agent method, and adopting different control strategies for different attenuation degrees, can effectively improve the capacity retention ability of the flow battery, reduce the cost of the capacity recovery agent, and realize the long-term stability of the flow battery capacity and performance.
2、本发明结构简单、调控手段智能化程度高，仅需要将监测及判断模块简单集成到电池管理系统即可，并且省却了现有技术中在正负极电解液储罐之间设置联通管的结构，有效降低电池系统的漏电电流，大幅度提高电池系统的效率和安全性；2. The present invention has a simple structure and a high degree of intelligence in the control means. It only needs to simply integrate the monitoring and judgment modules into the battery management system, and saves the need for connecting pipes between the positive and negative electrolyte storage tanks in the prior art. The structure can effectively reduce the leakage current of the battery system and greatly improve the efficiency and safety of the battery system;
3、本发明实现了液流电池的容量衰减程度的在线监测，并根据液流电池多种运行状态参数与电解液容量衰减率之间的函数模型，轻松获知液流电池任意时刻和状态下的容量衰减情况，省略了前往液流电池项目现场进行电解液取样并分析步骤，操作便捷，实用性强，大幅度节省液流电池运行维护阶段的人力、物力和财力。3. The present invention realizes the on-line monitoring of the capacity decay degree of the flow battery, and according to the function model between various operating state parameters of the flow battery and the capacity decay rate of the electrolyte, it is easy to know the capacity decay rate of the flow battery at any time and state. In case of capacity attenuation, the steps of going to the flow battery project site for electrolyte sampling and analysis are omitted. The operation is convenient and practical, and the manpower, material and financial resources in the operation and maintenance stage of the flow battery are greatly saved.
附图说明Description of drawings
图1是现有技术中的液流电池的结构示意图；FIG. 1 is a schematic structural diagram of a flow battery in the prior art;
图2、图3是本发明液流电池容量稳定调控系统及液流电池的结构示意图；Fig. 2 and Fig. 3 are structural schematic diagrams of the flow battery capacity stabilization control system and the flow battery of the present invention;
图4是本发明所述容量稳定调控方法的流程图；Fig. 4 is a flow chart of the capacity stabilization control method of the present invention;
图5是本发明所述步骤1的方法流程图；Fig. 5 is the method flowchart of step 1 of the present invention;
图6是本发明所述确定液流电池运行状态参数与电解液容量衰减率之间的对应关系步骤的流程图；Fig. 6 is a flow chart of the steps of determining the corresponding relationship between the operating state parameters of the flow battery and the electrolyte capacity decay rate according to the present invention;
图中：1、液体输送管路，2、电动阀，3、正极电解液储罐，4、负极电解液储罐，5、循环泵，6、电堆，7、加料口，61、正极电解液出口，62、负极电解液出口，63、正极电解液入口，64、负极电解液入口。In the figure: 1. Liquid delivery pipeline, 2. Electric valve, 3. Positive electrode electrolyte storage tank, 4. Negative electrode electrolyte storage tank, 5. Circulation pump, 6. Electric stack, 7. Feed port, 61. Positive electrode electrolysis Liquid outlet, 62, negative electrode electrolyte outlet, 63, positive electrode electrolyte inlet, 64, negative electrode electrolyte inlet.
具体实施方式Detailed ways
如图4和图5所示的液流电池容量稳定调控方法，包括如下步骤：The flow battery capacity stabilization control method shown in Figure 4 and Figure 5 includes the following steps:
步骤1：获得液流电池当前的电解液容量衰减率；Step 1: Obtain the current electrolyte capacity decay rate of the flow battery;
步骤2：判断液流电池当前的电解液容量衰减率是否低于第一预设衰减率，是则返回步骤1，否则执行步骤3；Step 2: Determine whether the current electrolyte capacity decay rate of the flow battery is lower than the first preset decay rate, if yes, return to step 1, otherwise perform step 3;
步骤3：判断液流电池当前的电解液容量衰减率是否低于第二预设衰减率，是则执行步骤4，否则执行步骤5；Step 3: Determine whether the current electrolyte capacity decay rate of the flow battery is lower than the second preset decay rate, if yes, perform step 4, otherwise perform step 5;
步骤4：调节正极电解液和负极电解液的液面高度，使正极电解液与负极电解液之间的液位差小于预设值或者正极电解液与负极电解液中总钒比例保持在预设比例范围；Step 4: Adjust the liquid level height of the positive electrolyte and the negative electrolyte so that the liquid level difference between the positive electrolyte and the negative electrolyte is less than the preset value or the ratio of the total vanadium in the positive electrolyte to the negative electrolyte is kept at the preset Scale range;
步骤5：向正极电解液储罐3和负极电解液储罐4内添加所需用量的容量恢复剂；Step 5: Add a required amount of capacity recovery agent to the positive electrode electrolyte storage tank 3 and the negative electrode electrolyte storage tank 4;
进一步地，所述步骤1具体包括如下步骤：Further, the step 1 specifically includes the following steps:
步骤11：监测液流电池运行状态参数；Step 11: Monitor the operating state parameters of the flow battery;
步骤12：根据所监测的液流电池运行状态参数，结合所述液流电池运行状态参数与电解液容量衰减率之间的对应关系，获得液流电池当前的电解液容量衰减率；Step 12: According to the monitored operating state parameters of the flow battery, combined with the corresponding relationship between the operating state parameters of the flow battery and the electrolyte capacity decay rate, the current electrolyte capacity decay rate of the flow battery is obtained;
进一步地，在步骤11之前还具有如下步骤：Further, before step 11, there are also the following steps:
确定液流电池运行状态参数与电解液容量衰减率之间的对应关系并存储；Determine and store the corresponding relationship between the operating state parameters of the flow battery and the electrolyte capacity decay rate;
进一步地，所述确定液流电池运行状态参数与电解液容量衰减率之间的对应关系步骤具体包括：Further, the step of determining the corresponding relationship between the operating state parameters of the flow battery and the electrolyte capacity decay rate specifically includes:
获得初始液流电池运行状态参数；Obtain the initial flow battery operating state parameters;
对液流电池进行充放电实验，获取充放电实验过程中的不同液流电池运行状态参数；Conduct charge and discharge experiments on the flow battery, and obtain the operating state parameters of different flow batteries during the charge and discharge experiment;
随着液流电池运行状态参数在充放电实验过程中的变化，进行多次正极电解液和负极电解液的取样，并获知取样的正极电解液和负极电解液的钒离子浓度；As the operating state parameters of the flow battery change during the charge-discharge experiment, the positive and negative electrolytes are sampled multiple times, and the vanadium ion concentrations of the sampled positive and negative electrolytes are obtained;
根据获知的正极电解液和负极电解液的钒离子浓度情况，计算出相应的电解液容量衰减率情况；According to the known vanadium ion concentration of positive electrolyte and negative electrolyte, calculate the corresponding electrolyte capacity decay rate;
得出液流电池运行状态参数与电解液容量衰减率之间的对应关系；The corresponding relationship between the operating state parameters of the flow battery and the electrolyte capacity decay rate is obtained;
进一步地，根据液流电池当前的电解液容量衰减率，以及正极电解液、负极电解液的体积，计算所需容量恢复剂的用量。Further, according to the current electrolyte capacity decay rate of the flow battery, and the volumes of the positive electrolyte and the negative electrolyte, the required amount of the capacity recovery agent is calculated.
如图2和图3所示的一种液流电池容量稳定调控系统，包括：获得液流电池当前电解液容量衰减率的获取单元；连接获取单元，用于判断液流电池当前电解液容量衰减率是否低于第一预设衰减率的第一判断单元；连接第一判断单元，用于当液流电池当前电解液容量衰减率高于等于第一预设衰减率时，判断液流电池当前的电解液容量衰减率是否低于第二预设衰减率的第二判断单元；当液流电池当前电解液容量衰减率高于等于第二预设衰减率时，执行向正极电解液储罐3和负极电解液储罐4内添加所需用量的容量恢复剂的操作；连接第二判断单元的控制单元，所述控制单元用于当液流电池当前电解液容量衰减率低于第二预设衰减率，同时高于等于第一预设衰减率时，调节正极电解液和负极电解液的液面高度，使正极电解液与负极电解液之间的液位差小于预设值或者正极电解液与负极电解液中总钒比例保持在预设比例范围；另外，所述容量稳定调控系统还包括：用于监测液流电池运行状态参数的监测单元；所述获取单元根据所监测的液流电池运行状态参数，结合所述液流电池运行状态参数与电解液容量衰减率之间的对应关系，获得液流电池当前的电解液容量衰减率；液流电池运行状态参数与电解液容量衰减率之间的对应关系可以实现确定并存储。A flow battery capacity stabilization control system as shown in Figure 2 and Figure 3, including: an acquisition unit for obtaining the current electrolyte capacity decay rate of the flow battery; connecting the acquisition unit for judging the current electrolyte capacity decay of the flow battery rate is lower than the first preset attenuation rate of the first judging unit; connected to the first judging unit, when the flow battery current electrolyte capacity attenuation rate is higher than or equal to the first preset attenuation rate, judging the current flow battery The second judging unit whether the decay rate of the electrolyte capacity is lower than the second preset decay rate; and the operation of adding a required amount of capacity recovery agent in the negative electrode electrolyte storage tank 4; the control unit connected to the second judging unit, the control unit is used when the current electrolyte capacity decay rate of the flow battery is lower than the second preset When the attenuation rate is higher than or equal to the first preset attenuation rate, adjust the liquid level height of the positive electrode electrolyte and the negative electrode electrolyte so that the liquid level difference between the positive electrode electrolyte and the negative electrode electrolyte is less than the preset value or the positive electrode electrolyte The proportion of the total vanadium in the negative electrode electrolyte is kept within a preset ratio range; in addition, the capacity stabilization control system also includes: a monitoring unit for monitoring the operating state parameters of the flow battery; the acquisition unit is based on the monitored flow battery Operating state parameters, combined with the corresponding relationship between the operating state parameters of the flow battery and the electrolyte capacity decay rate, to obtain the current electrolyte capacity decay rate of the flow battery; the relationship between the operating state parameters of the flow battery and the electrolyte capacity decay rate The corresponding relationship among them can be determined and stored.
如图2和图3所示的一种液流电池，包括电堆6、正极电解液储罐3、负极电解液储罐4、液体输送管路1和循环泵5；正极电解液储罐3经循环泵5通过液体输送管路1与电堆6的正极电解液入口63相连，电堆6的正极电解液出口61分别经液体输送管路1与正极电解液储罐3和负极电解液储罐4相连；负极电解液储罐4经循环泵5通过液体输送管路1与电堆6的负极电解液入口64相连，电堆6的负极电解液出口62分别经液体输送管路1与正极电解液储罐3和负极电解液储罐4相连；所述正极电解液储罐3和负极电解液储罐4上均设置有用于添加容量恢复剂的加料口7；所述电堆6的正极电解液出口61与正极电解液储罐3之间的液体输送管路1、电堆6的正极电解液出口61与负极电解液储罐4之间的液体输送管路1、电堆6的负极电解液出口62与正极电解液储罐3之间的液体输送管路1、以及电堆6的负极电解液出口62与负极电解液储罐4之间的液体输送管路1上均设置有用于开启或关闭液体输送管路1的电动阀2；所述控制单元通过控制所述电动阀2的工作状态实现正极电解液和负极电解液的液面高度的调节。A liquid flow battery as shown in Figures 2 and 3, including a stack 6, a positive electrolyte storage tank 3, a negative electrolyte storage tank 4, a liquid delivery pipeline 1 and a circulation pump 5; the positive electrolyte storage tank 3 The circulation pump 5 is connected to the positive electrolyte inlet 63 of the stack 6 through the liquid delivery pipeline 1, and the positive electrolyte outlet 61 of the stack 6 is connected to the positive electrolyte storage tank 3 and the negative electrolyte storage tank 3 through the liquid delivery pipeline 1 respectively. The tank 4 is connected; the negative electrode electrolyte storage tank 4 is connected to the negative electrode electrolyte inlet 64 of the stack 6 through the circulation pump 5 through the liquid delivery pipeline 1, and the negative electrode electrolyte outlet 62 of the stack 6 is connected to the positive electrode through the liquid delivery pipeline 1 respectively. The electrolyte storage tank 3 is connected to the negative electrode electrolyte storage tank 4; the positive electrode electrolyte storage tank 3 and the negative electrode electrolyte storage tank 4 are all provided with a feed port 7 for adding a capacity recovery agent; the positive electrode of the stack 6 The liquid delivery pipeline 1 between the electrolyte outlet 61 and the positive electrolyte storage tank 3, the liquid delivery pipeline 1 between the positive electrolyte outlet 61 of the stack 6 and the negative electrolyte storage tank 4, and the negative electrode of the stack 6 The liquid delivery pipeline 1 between the electrolyte outlet 62 and the positive electrode electrolyte storage tank 3, and the liquid delivery pipeline 1 between the negative electrode electrolyte solution outlet 62 of the stack 6 and the negative electrode electrolyte storage tank 4 are all provided with The electric valve 2 of the liquid delivery pipeline 1 is opened or closed; the control unit realizes the adjustment of the liquid level of the positive electrode electrolyte and the negative electrode electrolyte by controlling the working state of the electric valve 2 .
本发明所述液流电池运行状态参数为荷电状态SOC和/或正负极液位差(正极电解液储罐3内的电解液与负极电解液储罐4内的电解液之间的液位差)，下面以液流电池运行状态参数为荷电状态SOC来对确定液流电池运行状态参数与电解液容量衰减率之间的对应关系步骤作具体说明：首先获得初始荷电状态SOC0(液流电池未进行下面的充放电实验之前的SOC，通常初始荷电状态可以为100％或0％)，然后对液流电池以额定功率进行连续充放电实验，在充放电实验过程中的不同SOC状态下截止充放电，并分别进行多次正极电解液和负极电解液的取样，同时获知取样的正极电解液和负极电解液的钒离子浓度；根据获知的正极电解液和负极电解液的钒离子浓度情况，计算出相应的电解液容量衰减率R；进一步地，得出在充放电实验过程中的不同SOC与电解液容量衰减率之间的对应关系，具体地，能够电解液容量衰减率R＝(xi-SOC0)/(1-SOC0)，这里的xi为电解液不同取样时刻i所对应的荷电状态SOC(多次截止充放电实验时的不同SOC)；下面以液流电池运行状态参数为正负极液位差来对确定液流电池运行状态参数与电解液容量衰减率之间的对应关系步骤作具体说明：首先获得正极电解液储罐3内的电解液与负极电解液储罐4内的电解液的初始液位高度L0；然后对液流电池以额定功率进行连续充放电实验，并获取在充放电实验过程中的不同正负极液位差；随着正负极液位差在充放电实验过程中的变化，分别进行多次正极电解液和负极电解液的取样，并获知取样的正极电解液和负极电解液的钒离子浓度；根据获知的正极电解液和负极电解液的钒离子浓度情况，计算出相应的电解液容量衰减率R；进一步地，得出在充放电实验过程中的不同正负极液位差与电解液容量衰减率之间的对应关系，具体地，得出电解液容量衰减率R＝yi/2L0，这里的yi为电解液不同取样时刻i所对应的正负极液位差；下面以液流电池运行状态参数为荷电状态SOC和正负极液位差来对确定液流电池运行状态参数与电解液容量衰减率之间的对应关系步骤作具体说明：首先获得初始荷电状态SOC0(液流电池未进行下面的充放电实验之前的SOC，通常初始荷电状态可以为100％或0％)、正极电解液储罐3内的电解液与负极电解液储罐4内的电解液的初始液位高度L0；然后对液流电池以额定功率进行连续充放电实验，在充放电实验过程中的不同SOC状态下截止充放电，同时获取截止充放电时的正负极液位差，并分别进行多次正极电解液和负极电解液的取样，以及获知取样的正极电解液和负极电解液的钒离子浓度；根据获知的正极电解液和负极电解液的钒离子浓度情况，计算出相应的电解液容量衰减率R；进一步地，得出在充放电实验过程中的不同的荷电状态SOC和正负极液位差与电解液容量衰减率之间的对应关系，具体地，得出电解液容量衰减率R＝(xi-SOC0)/(1-SOC0)+yi/2L0，这里的xi为电解液不同取样时刻i所对应的荷电状态SOC(多次截止充放电实验时的不同SOC)，yi为电解液不同取样时刻i所对应的正负极液位差；这里提到的初始荷电状态SOC0和充放电实验过程中的不同SOC的获得可以通过SOC检测装置直接获取，也可以通过本申请人于2014年11月3日申请的主题名称为《液流电池系统荷电状态监测方法及其系统》、申请号为201410613631.0的专利申请文件中记载的荷电状态监测系统来间接获取；本发明所述正极电解液指的是正极电解液储罐3内的电解液，负极电解液指的是负极电解液储罐4内的电解液。The operating state parameters of the flow battery in the present invention are the state of charge SOC and/or the liquid level difference between the positive and negative electrodes (the liquid between the electrolyte in the positive electrolyte storage tank 3 and the electrolyte in the negative electrolyte storage tank 4 ). Potential difference), the steps of determining the corresponding relationship between the flow battery operating state parameters and the electrolyte capacity decay rate will be described in detail below by taking the operating state parameters of the flow battery as the state of charge SOC: First, obtain the initial state of charge SOC 0 (the SOC of the flow battery before the following charge and discharge experiments, usually the initial state of charge can be 100% or 0%), then carry out continuous charge and discharge experiments with the rated power of the flow battery, during the charge and discharge experiments Cut off charging and discharging under different SOC states, and carry out sampling of positive electrode electrolyte and negative electrode electrolyte several times respectively, and obtain the vanadium ion concentration of sampled positive electrode electrolyte and negative electrode electrolyte at the same time; According to the concentration of vanadium ions, the corresponding electrolyte capacity decay rate R is calculated; further, the corresponding relationship between different SOCs and electrolyte capacity decay rates in the charging and discharging experiment process is obtained, specifically, the capacity decay rate of the electrolyte can be Rate R=( xi -SOC 0 )/(1-SOC 0 ), where xi is the state of charge SOC corresponding to different sampling time i of the electrolyte (different SOC during multiple cut-off charge and discharge experiments); the following Taking the operating state parameters of the flow battery as the positive and negative liquid level difference, the steps of determining the corresponding relationship between the operating state parameters of the flow battery and the electrolyte capacity decay rate are described in detail: first, the electrolytic solution in the positive electrolyte storage tank 3 is obtained liquid and the initial liquid level of the electrolyte in the negative electrode electrolyte storage tank 4 ; ; Along with the change of positive and negative liquid level difference in charge and discharge experiment process, carry out the sampling of multiple positive electrode electrolyte and negative electrode electrolyte respectively, and obtain the vanadium ion concentration of sampled positive electrode electrolyte and negative electrode electrolyte; The concentration of vanadium ions in the positive electrolyte and the negative electrolyte is calculated, and the corresponding electrolyte capacity decay rate R is calculated; further, the different positive and negative liquid level differences and electrolyte capacity decay rates Specifically, the capacity decay rate of the electrolyte is obtained R=y i /2L 0 , where y i is the liquid level difference between the positive and negative electrodes corresponding to different sampling times i of the electrolyte; the flow battery The operating state parameters are the state of charge SOC and the liquid level difference between the positive and negative electrodes to specifically describe the steps for determining the corresponding relationship between the operating state parameters of the flow battery and the electrolyte capacity decay rate: first obtain the initial state of charge SOC 0 (flow battery SOC before the following charge and discharge experiments, usually the initial state of charge can be 100% or 0%), the initial liquid level of the electrolyte in the positive electrode electrolyte storage tank 3 and the electrolyte in the negative electrode electrolyte storage tank 4 Height L 0 ; then conduct continuous charge and discharge experiments on the flow battery at rated power, under different SOC states during the charge and discharge experiments Stop charging and discharging, obtain the positive and negative liquid level difference when charging and discharging is stopped at the same time, and carry out the sampling of positive electrode electrolyte and negative electrode electrolyte several times respectively, and obtain the vanadium ion concentration of sampled positive electrode electrolyte and negative electrode electrolyte; According to Based on the known vanadium ion concentrations of the positive electrolyte and the negative electrolyte, the corresponding electrolyte capacity decay rate R is calculated; furthermore, the different state of charge SOC and the positive and negative liquid level difference and The corresponding relationship between the electrolyte capacity decay rate, specifically, the electrolyte capacity decay rate R = ( xi -SOC 0 )/(1-SOC 0 )+y i /2L 0 , where x i is the electrolytic The state of charge SOC corresponding to different sampling times i of the electrolyte (different SOCs during multiple cut-off charge and discharge experiments), y i is the positive and negative liquid level difference corresponding to different sampling times i of the electrolyte; the initial charge mentioned here The state of charge SOC 0 and the different SOCs in the charging and discharging experiment process can be obtained directly through the SOC detection device, and can also be obtained through the application of the applicant on November 3, 2014. Method and System thereof", the application number is 201410613631.0 The state of charge monitoring system recorded in the patent application documents is indirectly obtained; the positive electrolyte in the present invention refers to the electrolyte in the positive electrolyte storage tank 3, and the negative electrolyte Refers to the electrolyte in the negative electrode electrolyte storage tank 4 .
本发明提供的液流电池容量稳定调控方法、系统及液流电池，能够实现液流电池的容量衰减程度的在线监测，并针对容量衰减程度的不同，采用调节正负极电解液液位差和添加容量恢复剂的不同调控手段，保证液流电池的运行效率，调控简单智能，能够延缓液流电池容量衰减，实现液流电池容量和性能长时间保持稳定，本发明能够根据所监测的液流电池运行状态参数的情况直接得出当前的容量衰减率，直接在线获知液流电池的容量衰减情况，而避免了现有技术中必须暂停液流电池的运行来检测液流电池的容量衰减程度，造成影响系统运行效率，监测不便的问题，同时能够根据容量衰减程度的不同情况，分别采用不同的调控策略，具体为当液流电池当前电解液容量衰减率高于等于第二预设衰减率时，执行向正极电解液储罐3和负极电解液储罐4内添加所需用量的容量恢复剂的操作，其中所需容量恢复剂的用量，可以根据液流电池当前的电解液容量衰减率，以及正极电解液、负极电解液的体积计算得出，具体地，假设目前的电解液容量衰减率为R0、正极电解液储罐3内的电解液体积为L1、负极电解液储罐4内的电解液体积为L2，则需要增加的容量恢复剂的用量为其中Z为容量恢复剂分子量，M为活性物质总浓度，n0为1mol容量恢复剂可以还原n mol的活性物质，具体地，当液流电池为全钒液流电池时，M为1.65mol/L，容量恢复剂的添加具体可以通过设置在正极电解液储罐3和负极电解液储罐4上的加料口7来添加。The method and system for stabilizing the capacity of the flow battery and the flow battery provided by the present invention can realize online monitoring of the degree of capacity attenuation of the flow battery, and according to the difference in the degree of capacity attenuation, adjust the positive and negative electrolyte level difference and Adding different control methods of capacity recovery agent can ensure the operating efficiency of the flow battery, the control is simple and intelligent, can delay the capacity decay of the flow battery, and realize the long-term stability of the capacity and performance of the flow battery. The current capacity decay rate can be directly obtained from the battery operating state parameters, and the capacity decay of the flow battery can be obtained directly online, which avoids the need to suspend the operation of the flow battery to detect the capacity decay of the flow battery in the prior art. It will affect the system operation efficiency and inconvenient monitoring. At the same time, different control strategies can be adopted according to the different conditions of capacity decay. Specifically, when the current electrolyte capacity decay rate of the flow battery is higher than or equal to the second preset decay rate , perform the operation of adding a required amount of capacity recovery agent to the positive electrode electrolyte storage tank 3 and the negative electrode electrolyte storage tank 4, wherein the required amount of capacity recovery agent can be based on the current electrolyte capacity decay rate of the flow battery, and the volumes of the positive electrolyte and the negative electrolyte are calculated. Specifically, assuming that the current electrolyte capacity decay rate is R 0 , the volume of the electrolyte in the positive electrolyte storage tank 3 is L 1 , and the negative electrolyte storage tank is 4 The volume of the electrolyte solution inside is L 2 , then the amount of capacity recovery agent that needs to be increased is Wherein Z is the molecular weight of the capacity recovery agent, M is the total concentration of the active material, and n 0 is that 1mol of the capacity recovery agent can reduce n mol of the active material, specifically, when the flow battery is an all-vanadium flow battery, M is 1.65mol/ L, the addition of the capacity recovery agent can specifically be added through the feeding port 7 provided on the positive electrode electrolyte storage tank 3 and the negative electrode electrolyte storage tank 4 .
本发明当液流电池当前电解液容量衰减率低于第二预设衰减率，同时高于等于第一预设衰减率时，调节正极电解液和负极电解液的液面高度，使正极电解液与负极电解液之间的液位差小于预设值，具体可以为：当正极电解液的液面高度高于负极电解液的液面高度时，关闭正极电解液储罐3与电堆的正极电解液出口61之间的液体输送管路1，同时开启电堆的正极电解液出口61与负极电解液储罐4之间的液体输送管路1；当负极电解液的液面高度高于正极电解液的液面高度时，关闭负极电解液储罐4与电堆的负极电解液出口62之间的液体输送管路1，同时开启电堆的负极电解液出口62与正极电解液储罐3之间的液体输送管路1，通过在现有技术中的液流电池的基础上增设液体输送管路，使得从电堆出来的正极电解液能够返回到负极电解液储罐4，从电堆出来的负极电解液能够返回到正极电解液储罐3，不需要额外的动力辅助设备，且有利于保持液流电池容量和性能长时间稳定。本发明还可以通过调节正极电解液和负极电解液的液面高度，使正极电解液与负极电解液中总钒比例保持在预设比例范围，这里的预设比例范围为1：1.5～1：1.2。In the present invention, when the current electrolyte capacity attenuation rate of the flow battery is lower than the second preset attenuation rate and at the same time higher than or equal to the first preset attenuation rate, the liquid level heights of the positive electrode electrolyte and the negative electrode electrolyte are adjusted to make the positive electrode electrolyte The liquid level difference between the positive electrode electrolyte and the negative electrode electrolyte is less than the preset value, specifically: when the liquid level of the positive electrode electrolyte is higher than the liquid level of the negative electrode electrolyte, close the positive electrode of the positive electrode electrolyte storage tank 3 and the stack. The liquid delivery pipeline 1 between the electrolyte outlet 61, simultaneously open the liquid delivery pipeline 1 between the positive electrode electrolyte outlet 61 of the cell stack and the negative electrode electrolyte storage tank 4; when the liquid level of the negative electrode electrolyte is higher than the positive electrode When the liquid level of the electrolyte is high, close the liquid delivery pipeline 1 between the negative electrolyte storage tank 4 and the negative electrolyte outlet 62 of the stack, and simultaneously open the negative electrolyte outlet 62 and the positive electrolyte storage tank 3 of the stack. The liquid delivery pipeline 1 between them, by adding a liquid delivery pipeline on the basis of the liquid flow battery in the prior art, the positive electrode electrolyte from the stack can return to the negative electrode electrolyte storage tank 4, from the stack The discharged negative electrode electrolyte can be returned to the positive electrode electrolyte storage tank 3 without additional power auxiliary equipment, and is conducive to maintaining the long-term stability of the capacity and performance of the flow battery. In the present invention, the proportion of the total vanadium in the positive electrolyte and the negative electrolyte can be kept within a preset ratio range by adjusting the liquid level heights of the positive electrolyte and the negative electrolyte, where the preset ratio range is 1:1.5 to 1: 1.2.
以上所述，仅为本发明较佳的具体实施方式，但本发明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揭露的技术范围内，根据本发明的技术方案及其发明构思加以等同替换或改变，都应涵盖在本发明的保护范围之内。The above is only a preferred embodiment of the present invention, but the scope of protection of the present invention is not limited thereto, any person familiar with the technical field within the technical scope disclosed in the present invention, according to the technical solution of the present invention Any equivalent replacement or change of the inventive concepts thereof shall fall within the protection scope of the present invention.
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