CN118156571A - A zinc-bromine flow battery performance recovery method - Google Patents
A zinc-bromine flow battery performance recovery method Download PDFInfo
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- ZRXYMHTYEQQBLN-UHFFFAOYSA-N [Br].[Zn] Chemical compound [Br].[Zn] ZRXYMHTYEQQBLN-UHFFFAOYSA-N 0.000 title claims abstract description 42
- 238000000034 method Methods 0.000 title claims abstract description 30
- 238000011084 recovery Methods 0.000 title abstract description 33
- 239000003792 electrolyte Substances 0.000 claims abstract description 69
- HCHKCACWOHOZIP-UHFFFAOYSA-N Zinc Chemical compound [Zn] HCHKCACWOHOZIP-UHFFFAOYSA-N 0.000 claims abstract description 16
- WKBOTKDWSSQWDR-UHFFFAOYSA-N Bromine atom Chemical compound [Br] WKBOTKDWSSQWDR-UHFFFAOYSA-N 0.000 claims abstract description 15
- GDTBXPJZTBHREO-UHFFFAOYSA-N bromine Substances BrBr GDTBXPJZTBHREO-UHFFFAOYSA-N 0.000 claims abstract description 15
- 229910052794 bromium Inorganic materials 0.000 claims abstract description 15
- 239000007788 liquid Substances 0.000 claims description 15
- 239000007864 aqueous solution Substances 0.000 claims description 10
- VNDYJBBGRKZCSX-UHFFFAOYSA-L zinc bromide Chemical compound Br[Zn]Br VNDYJBBGRKZCSX-UHFFFAOYSA-L 0.000 claims description 6
- 239000000203 mixture Substances 0.000 claims description 4
- 229940102001 zinc bromide Drugs 0.000 claims description 3
- KNBFEGHMAKJNRX-UHFFFAOYSA-N 1-ethyl-2-methylpyrrolidin-1-ium bromide Chemical compound [Br-].C(C)[NH+]1C(CCC1)C KNBFEGHMAKJNRX-UHFFFAOYSA-N 0.000 claims 1
- 239000008139 complexing agent Substances 0.000 claims 1
- 239000002904 solvent Substances 0.000 claims 1
- 239000003115 supporting electrolyte Substances 0.000 claims 1
- XLYOFNOQVPJJNP-UHFFFAOYSA-N water Substances O XLYOFNOQVPJJNP-UHFFFAOYSA-N 0.000 claims 1
- 239000013543 active substance Substances 0.000 description 11
- 239000011701 zinc Substances 0.000 description 7
- 229910052725 zinc Inorganic materials 0.000 description 7
- 238000009825 accumulation Methods 0.000 description 6
- 238000004146 energy storage Methods 0.000 description 6
- OKTJSMMVPCPJKN-UHFFFAOYSA-N Carbon Chemical compound [C] OKTJSMMVPCPJKN-UHFFFAOYSA-N 0.000 description 5
- 229910052799 carbon Inorganic materials 0.000 description 5
- 238000002474 experimental method Methods 0.000 description 5
- CURLTUGMZLYLDI-UHFFFAOYSA-N Carbon dioxide Chemical compound O=C=O CURLTUGMZLYLDI-UHFFFAOYSA-N 0.000 description 4
- 239000003795 chemical substances by application Substances 0.000 description 4
- BDAGIHXWWSANSR-UHFFFAOYSA-N methanoic acid Natural products OC=O BDAGIHXWWSANSR-UHFFFAOYSA-N 0.000 description 4
- 238000007086 side reaction Methods 0.000 description 4
- 230000000052 comparative effect Effects 0.000 description 3
- 238000007599 discharging Methods 0.000 description 3
- 239000000243 solution Substances 0.000 description 3
- 239000000126 substance Substances 0.000 description 3
- BMYNFMYTOJXKLE-UHFFFAOYSA-N 3-azaniumyl-2-hydroxypropanoate Chemical compound NCC(O)C(O)=O BMYNFMYTOJXKLE-UHFFFAOYSA-N 0.000 description 2
- OSWFIVFLDKOXQC-UHFFFAOYSA-N 4-(3-methoxyphenyl)aniline Chemical compound COC1=CC=CC(C=2C=CC(N)=CC=2)=C1 OSWFIVFLDKOXQC-UHFFFAOYSA-N 0.000 description 2
- CPELXLSAUQHCOX-UHFFFAOYSA-N Hydrogen bromide Chemical compound Br CPELXLSAUQHCOX-UHFFFAOYSA-N 0.000 description 2
- 229910002092 carbon dioxide Inorganic materials 0.000 description 2
- 238000006243 chemical reaction Methods 0.000 description 2
- 238000005516 engineering process Methods 0.000 description 2
- 235000019253 formic acid Nutrition 0.000 description 2
- 239000007789 gas Substances 0.000 description 2
- 239000005431 greenhouse gas Substances 0.000 description 2
- IDQXZLKEWHBPCA-UHFFFAOYSA-N 2-ethyl-1-methylpyrrolidine Chemical compound CCC1CCCN1C IDQXZLKEWHBPCA-UHFFFAOYSA-N 0.000 description 1
- UFHFLCQGNIYNRP-UHFFFAOYSA-N Hydrogen Chemical compound [H][H] UFHFLCQGNIYNRP-UHFFFAOYSA-N 0.000 description 1
- PTFCDOFLOPIGGS-UHFFFAOYSA-N Zinc dication Chemical compound [Zn+2] PTFCDOFLOPIGGS-UHFFFAOYSA-N 0.000 description 1
- 239000011149 active material Substances 0.000 description 1
- 230000002238 attenuated effect Effects 0.000 description 1
- 230000009286 beneficial effect Effects 0.000 description 1
- 239000001569 carbon dioxide Substances 0.000 description 1
- 125000003178 carboxy group Chemical group [H]OC(*)=O 0.000 description 1
- 230000002860 competitive effect Effects 0.000 description 1
- 125000002485 formyl group Chemical class [H]C(*)=O 0.000 description 1
- 231100001261 hazardous Toxicity 0.000 description 1
- 229910052739 hydrogen Inorganic materials 0.000 description 1
- 239000001257 hydrogen Substances 0.000 description 1
- 125000002887 hydroxy group Chemical group [H]O* 0.000 description 1
- 239000011259 mixed solution Substances 0.000 description 1
- 230000010287 polarization Effects 0.000 description 1
- 238000010248 power generation Methods 0.000 description 1
- 150000003384 small molecules Chemical class 0.000 description 1
Classifications
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- H—ELECTRICITY
- H01—ELECTRIC ELEMENTS
- H01M—PROCESSES OR MEANS, e.g. BATTERIES, FOR THE DIRECT CONVERSION OF CHEMICAL ENERGY INTO ELECTRICAL ENERGY
- H01M8/00—Fuel cells; Manufacture thereof
- H01M8/18—Regenerative fuel cells, e.g. redox flow batteries or secondary fuel cells
- H01M8/184—Regeneration by electrochemical means
- H01M8/188—Regeneration by electrochemical means by recharging of redox couples containing fluids; Redox flow type batteries
-
- H—ELECTRICITY
- H01—ELECTRIC ELEMENTS
- H01M—PROCESSES OR MEANS, e.g. BATTERIES, FOR THE DIRECT CONVERSION OF CHEMICAL ENERGY INTO ELECTRICAL ENERGY
- H01M8/00—Fuel cells; Manufacture thereof
- H01M8/04—Auxiliary arrangements, e.g. for control of pressure or for circulation of fluids
- H01M8/04298—Processes for controlling fuel cells or fuel cell systems
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Abstract
Description
技术领域Technical Field
本发明涉及液流电池技术领域，特别涉及锌溴液流电池领域。The present invention relates to the technical field of liquid flow batteries, in particular to the field of zinc-bromine liquid flow batteries.
背景技术Background technique
风能、太阳能等可再生能源具有不连续、不稳定的特点，其这一特性会使其在并网过程中对电网造成冲击，影响电网安全稳定运行。储能技术则可以保证可再生能源发电并网的高效稳定运行。储能技术主要分为物理储能和化学储能两大类。化学储能中适用于大规模、大容量储能的氧化还原液流电池因其具有电池功率和容量相互独立、响应迅速、结构简单、易于设计等优点而受到广泛关注。锌溴液流电池作为氧化还原液流电池的一种，除具有上述优点外，还具有高开路电压(1.85V),高理论能量密度(435Wh/Kg),电解液、隔膜价格低廉等诸多优势。这些优势也使其与其它液流电池相比更具竞争力。Renewable energy sources such as wind power and solar energy are discontinuous and unstable, which will cause impacts on the power grid during the grid connection process, affecting the safe and stable operation of the power grid. Energy storage technology can ensure the efficient and stable operation of renewable energy power generation and grid connection. Energy storage technology is mainly divided into two categories: physical energy storage and chemical energy storage. Among chemical energy storage, redox flow batteries suitable for large-scale and large-capacity energy storage have attracted widespread attention because of their advantages such as independent battery power and capacity, rapid response, simple structure, and easy design. As a type of redox flow battery, zinc-bromine flow battery has many advantages in addition to the above advantages, such as high open circuit voltage (1.85V), high theoretical energy density (435Wh/Kg), low electrolyte and diaphragm prices, etc. These advantages also make it more competitive than other flow batteries.
锌溴液流电池在充放电运行过程中存在正负极活性物质累积的问题，而活性物质累积会使电池极化变大造成电池性能衰减，影响电池使用寿命。现有技术中锌溴液流电池恢复方法中一种是在电池运行性能下降后，于正极电解液和/或负极电解液中添加恢复剂，该恢复剂为含有羟基、醛基、羧基的与锌溴电池电解液互溶的一类具有还原性的有机或无机物，该恢复剂可以被正极溴单质氧化生成质子与有机或无机小分子产物，质子穿透隔膜到达负极与负极锌单质反应生成锌离子，从而将锌溴或锌溴单液流电池电解液恢复至初始状态(ZL201611089121.3)；另一种是在电池运行一段时间后，将正极腔室内的正极电解液导入负极储罐内与负极电解液混合，然后将部分混合液再次填充至正极腔室内，通过正负极电解液互混使电池性能恢复(ZL201711213349.3)。第一种恢复方法添加恢复剂后会产生氢气，影响系统的安全稳定运行，同时由于氢溴酸的生成会使负极恢复后首圈充电过程生成的锌与氢溴酸发生化学反应，造成电池首圈充放电库伦效率偏低，此外还会产生温室气体二氧化碳；第二种方法中通过电解液互混进行电池性能恢复不会产生有害气体，但是随着活性物质浓度的增加锌负极副反应加剧，导致电解液互混后会存在正极活性物质溴的累积问题。正极活性物质溴的累积导致首圈充放电循环过程中负极充电生成的锌首先与电解液中溴发生化学反应，导致电池首圈库伦效率偏低。Zinc-bromine flow batteries have the problem of accumulation of active substances at the positive and negative electrodes during the charging and discharging process. The accumulation of active substances will increase the polarization of the battery, causing the battery performance to deteriorate and affecting the battery life. In the prior art, one method for restoring zinc-bromine flow batteries is to add a restoring agent to the positive electrode electrolyte and/or the negative electrode electrolyte after the battery operating performance declines. The restoring agent is a type of reducing organic or inorganic substance containing hydroxyl, aldehyde, or carboxyl groups that is miscible with the zinc-bromine battery electrolyte. The restoring agent can be oxidized by the positive electrode bromine element to generate protons and organic or inorganic small molecule products. The protons penetrate the diaphragm to reach the negative electrode and react with the negative electrode zinc element to generate zinc ions, thereby restoring the zinc-bromine or zinc-bromine single flow battery electrolyte to its initial state (ZL201611089121.3); the other method is to introduce the positive electrode electrolyte in the positive electrode chamber into the negative electrode storage tank and mix it with the negative electrode electrolyte after the battery has been running for a period of time, and then fill part of the mixed solution into the positive electrode chamber again, and restore the battery performance by mixing the positive and negative electrode electrolytes (ZL201711213349.3). The first recovery method generates hydrogen after adding a recovery agent, which affects the safe and stable operation of the system. At the same time, the generation of hydrobromic acid will cause the zinc generated in the first charging process after the negative electrode is restored to react chemically with hydrobromic acid, resulting in a low coulombic efficiency of the battery's first charge and discharge cycle. In addition, greenhouse gas carbon dioxide will be produced. In the second method, battery performance recovery by mixing electrolytes will not produce harmful gases, but as the concentration of active substances increases, the side reaction of zinc at the negative electrode intensifies, resulting in the accumulation of bromine, the active substance at the positive electrode, after the electrolytes are mixed. The accumulation of bromine, the active substance at the positive electrode, causes the zinc generated by the negative electrode charging during the first charge and discharge cycle to react chemically with bromine in the electrolyte first, resulting in a low coulombic efficiency of the battery's first cycle.
发明内容Summary of the invention
高浓度锌溴液流电池随着活性物质浓度的增加锌负极副反应加剧，导致电解液互混后会存在正极活性物质溴的累积问题，正极活性物质溴的累积导致首圈充放电循环过程中负极充电生成的锌首先与电解液中溴发生化学反应，导致电池首圈库伦效率偏低。In high-concentration zinc-bromine flow batteries, as the concentration of active substances increases, the side reactions of the zinc negative electrode intensify, resulting in the accumulation of bromine, the active substance at the positive electrode, after the electrolytes are mixed. The accumulation of bromine, the active substance at the positive electrode, causes the zinc generated by the negative electrode charging during the first charge and discharge cycle to react chemically with the bromine in the electrolyte first, resulting in a low coulombic efficiency in the first cycle of the battery.
本发明中提出一种高浓度锌溴液流电池性能恢复方法，即在电池需要恢复时，首先将电池电解液进行互混，然后向电解液中添加锌粉，消除累积的溴。该方法可以使锌溴液流电池电解液完全恢复至初始状态，电池在恢复后首圈具有较高的库伦效率，降低电池恢复频率，同时不会产生H2和CO2,提高系统安全性，环境友好。The present invention proposes a method for restoring the performance of a high-concentration zinc-bromine flow battery, that is, when the battery needs to be restored, the battery electrolyte is first mixed, and then zinc powder is added to the electrolyte to eliminate the accumulated bromine. The method can completely restore the zinc-bromine flow battery electrolyte to its initial state, and the battery has a higher coulombic efficiency in the first cycle after restoration, reducing the battery restoration frequency, and at the same time does not produce H2 and CO2 , thereby improving system safety and being environmentally friendly.
本发明提供的完整技术方案为，所述锌溴液流电池性能恢复方法为在电池需要恢复时，首先对正负极电解液进行流经电池正负极的互混。待电池电压降为0V时，向正负极储液罐内分别加入锌粉，直至正负极储液罐电解液均变为无色。The complete technical solution provided by the present invention is that the performance recovery method of the zinc-bromine flow battery is to first mix the positive and negative electrolytes flowing through the positive and negative electrodes of the battery when the battery needs to be restored. When the battery voltage drops to 0V, zinc powder is added to the positive and negative electrode storage tanks respectively until the electrolytes in the positive and negative electrode storage tanks become colorless.
所述锌溴液流电池正负极电解液初始组成相同。The initial compositions of the positive and negative electrolytes of the zinc-bromine flow battery are the same.
所述锌溴液流电池电解液中溴化锌浓度为3-7M。The zinc bromide concentration in the zinc-bromine flow battery electrolyte is 3-7M.
本发明技术方案带来的有益效果Beneficial effects brought by the technical solution of the present invention
1.该恢复方法可以使高浓度锌溴液流电池在恢复后首圈即具有较高的库伦效率，解决现有技术中恢复后首圈库伦效率偏低的问题。1. The recovery method can make the high-concentration zinc-bromine flow battery have a higher coulombic efficiency in the first cycle after recovery, solving the problem of low coulombic efficiency in the first cycle after recovery in the prior art.
2.通过提高恢复后首圈库伦效率，降低电池恢复频率。2. Reduce the battery recovery frequency by improving the first cycle coulomb efficiency after recovery.
3.该恢复方法操作简单、安全可靠、环境友好，恢复过程中不会产生产生危险性气体(H2)、温室气体(CO2)。3. The recovery method is simple to operate, safe, reliable, and environmentally friendly, and no hazardous gas (H 2 ) or greenhouse gas (CO 2 ) is generated during the recovery process.
具体实施方式Detailed ways
包括锌溴液流电池、装有正极电解液的正极储液罐、装有负极电解液的负极储液罐，It includes a zinc-bromine flow battery, a positive electrode storage tank filled with a positive electrode electrolyte, and a negative electrode storage tank filled with a negative electrode electrolyte.
正极储液罐内的正极电解液通过泵与锌溴液流电池正极进口相连，锌溴液流电池正极出口与正极储液罐相连通；负极储液罐内的负极电解液通过泵与锌溴液流电池负极进口相连，锌溴液流电池负极出口与负极储液罐相连通；The positive electrode electrolyte in the positive electrode storage tank is connected to the positive electrode inlet of the zinc-bromine liquid flow battery through a pump, and the positive electrode outlet of the zinc-bromine liquid flow battery is connected to the positive electrode storage tank; the negative electrode electrolyte in the negative electrode storage tank is connected to the negative electrode inlet of the zinc-bromine liquid flow battery through a pump, and the negative electrode outlet of the zinc-bromine liquid flow battery is connected to the negative electrode storage tank;
于锌溴液流电池正极出口与正极储液罐相连通的管路上设有第一互混分支管路，于第一互混分支管路上设有第一互混阀；于锌溴液流电池负极出口与负极储液罐相连通的管路上设有第二互混分支管路，于第二互混分支管路上设有第二互混阀；A first intermixing branch pipeline is provided on the pipeline connecting the positive electrode outlet of the zinc-bromine liquid flow battery and the positive electrode storage tank, and a first intermixing valve is provided on the first intermixing branch pipeline; a second intermixing branch pipeline is provided on the pipeline connecting the negative electrode outlet of the zinc-bromine liquid flow battery and the negative electrode storage tank, and a second intermixing valve is provided on the second intermixing branch pipeline;
正负极电解液进行互混时，将第一互混阀和第二互混阀打开，正极出口流出的正极电解液导入正极储液罐和负极储液罐中，负极出口流出的负极电解液导入正极储液罐和负极储液罐中；When the positive and negative electrolytes are mixed, the first mixing valve and the second mixing valve are opened, the positive electrolyte flowing out of the positive electrode outlet is introduced into the positive electrode storage tank and the negative electrode storage tank, and the negative electrolyte flowing out of the negative electrode outlet is introduced into the positive electrode storage tank and the negative electrode storage tank;
待电池电压降为0V时，向正负极储液罐内分别加入锌粉，直至正和负极储液罐中的电解液均变为无色。When the battery voltage drops to 0V, add zinc powder to the positive and negative electrode storage tanks respectively until the electrolyte in the positive and negative electrode storage tanks becomes colorless.
实施例1Example 1
以3MZnBr2+0.5M KCl+0.8M MEP(溴化N,乙基甲基吡咯烷)的水溶液分别为正负电解液进行锌溴液流电池循环性能实验，正负电极均为碳毡，电解液于正负电极腔窒内的流速均为60ml/min,电流密度为40mA/cm2，电极有效面积36cm2，电池充电截止电压2V,放电截止电压0.5V，正负极电解液体积分别各80ml。首圈库伦效率CE97.1％,VE85.4％，EE82.9％；The zinc-bromine flow battery cycle performance experiment was carried out with 3MZnBr 2 +0.5M KCl+0.8M MEP (N-bromide, ethylmethylpyrrolidine) aqueous solution as positive and negative electrolytes, respectively. Both positive and negative electrodes were carbon felt, the flow rate of electrolyte in the positive and negative electrode cavities was 60ml/min, the current density was 40mA/cm 2 , the electrode effective area was 36cm 2 , the battery charge cut-off voltage was 2V, the discharge cut-off voltage was 0.5V, and the positive and negative electrolyte volumes were 80ml each. The first cycle coulomb efficiency CE97.1%, VE85.4%, EE82.9%;
电池运行800循环后，电池能量效率衰减至70％时进行电解液互混。待电池互混至电压降至0V后，分别向正负极储液罐中加入锌粉，至正负极储液罐电解液均变为无色。采用该恢复方法电池，恢复后首圈电池CE97.2％,VE84.8％，EE82.4％。After the battery runs for 800 cycles, the battery energy efficiency decays to 70%, and the electrolytes are mixed. After the battery voltage drops to 0V, zinc powder is added to the positive and negative electrode storage tanks respectively until the electrolytes in the positive and negative electrode storage tanks become colorless. Using this recovery method, the battery has a CE of 97.2%, a VE of 84.8%, and an EE of 82.4% in the first cycle after recovery.
电池再次运行500循环进行一次恢复即可，恢复后首圈电池CE97.4％,VE84.2％，EE82.0％。The battery can be recovered by running 500 cycles again. After recovery, the first cycle battery CE is 97.4%, VE is 84.2%, and EE is 82.0%.
实施例2Example 2
分别以3MZnBr2+0.5M KCl+0.8MMEP的水溶液、4MZnBr2+0.5MKCl+0.8MMEP的水溶液、5MZnBr2+0.5M KCl+0.8MMEP的水溶液、6MZnBr2+0.5M KCl+0.8MMEP的水溶液、7MZnBr2+0.5M KCl+0.8MMEP的水溶液分别为正负电解液进行锌溴液流电池循环性能实验，电极为碳毡，电解液于正负电极腔窒内的流速60ml/min,电流密度为40mA/cm2，电极有效面积36cm2，电池充电截止电压2V,放电截止电压0.5V，正负极电解液体积分别各80ml。首圈和电池运行800循环恢复后的电池性能如下，The zinc-bromine flow battery cycle performance experiment was carried out using 3MZnBr 2 +0.5M KCl+0.8MMEP aqueous solution, 4MZnBr 2 +0.5MKCl+0.8MMEP aqueous solution, 5MZnBr 2 +0.5M KCl+0.8MMEP aqueous solution, 6MZnBr 2 +0.5M KCl+0.8MMEP aqueous solution, and 7MZnBr 2 +0.5M KCl+0.8MMEP aqueous solution as positive and negative electrolytes, respectively. The electrodes were carbon felt, the flow rate of the electrolyte in the positive and negative electrode cavities was 60ml/min, the current density was 40mA/cm 2 , the electrode effective area was 36cm 2 , the battery charge cut-off voltage was 2V, the discharge cut-off voltage was 0.5V, and the positive and negative electrolyte volumes were 80ml each. The battery performance in the first cycle and after the battery was restored after 800 cycles is as follows:
随着活性物质浓度的增加，电池CE、VE均有所下降，这主要是由于随着活性物质浓度的增加电池副反应加剧导致电池CE降低；电解液电导率下降导致电池VE降低所致。恢复后不同浓度溴化锌电解液CE均可达到初始水平。As the concentration of active substances increases, the battery CE and VE both decrease. This is mainly due to the intensification of battery side reactions as the concentration of active substances increases, which leads to a decrease in battery CE; the decrease in electrolyte conductivity leads to a decrease in battery VE. After recovery, the CE of zinc bromide electrolytes of different concentrations can reach the initial level.
对比例1Comparative Example 1
以3MZnBr2+0.5MKCl+0.8MMEP的水溶液为电解液进行锌溴液流电池循环性能实验，电极为碳毡，电解液流速60ml/min,电流密度为40mA/cm2，电极有效面积36cm2，电池充电截止电压2V,放电截止电压0.5V，正负极电解液体积各80ml。首圈CE97.1％,VE85.4％，EE82.9％电池运行800循环后，电池能量效率衰减至电池能量效率70％时进行电解液互混。待电池互混至电压降至0V后，进行正常充放电。采用该恢复方法电池，恢复后首圈电池CE90.1％,VE85.1％，EE76.7％。这主要是由于负极副反应的存在导致电池互混至0V后电解液中仍然有溴存在所致。The zinc-bromine flow battery cycle performance experiment was carried out with an aqueous solution of 3MZnBr 2 +0.5MKCl+0.8MMEP as the electrolyte. The electrode was carbon felt, the electrolyte flow rate was 60ml/min, the current density was 40mA/cm 2 , the electrode effective area was 36cm 2 , the battery charging cut-off voltage was 2V, the discharge cut-off voltage was 0.5V, and the volume of the positive and negative electrolytes was 80ml each. The first cycle CE was 97.1%, VE was 85.4%, and EE was 82.9%. After the battery ran for 800 cycles, the battery energy efficiency was attenuated to 70% and the electrolyte was mixed. After the battery was mixed until the voltage dropped to 0V, normal charging and discharging were performed. The battery using this recovery method had a first cycle CE of 90.1%, VE of 85.1%, and EE of 76.7% after recovery. This is mainly due to the presence of bromine in the electrolyte after the battery was mixed to 0V due to the presence of side reactions at the negative electrode.
此外，采用该种恢复方法电池再次运行200循环即需进行一次恢复，恢复后首圈电池CE89.2％,VE84.2％，EE75.1％。与采用互混后添加锌粉恢复方法相比，恢复后的电池首圈库伦效率CE偏低，电池恢复频率增加。In addition, the battery needs to be restored after running 200 cycles using this recovery method. After recovery, the first cycle battery CE is 89.2%, VE is 84.2%, and EE is 75.1%. Compared with the recovery method using zinc powder after mixing, the first cycle coulomb efficiency CE of the battery after recovery is lower, and the battery recovery frequency increases.
对比例2Comparative Example 2
以3MZnBr2+0.5MKCl+0.8MMEP的水溶液为电解液进行锌溴液流电池循环性能实验，电极为碳毡，电解液流速60ml/min,电流密度为40mA/cm2，电极有效面积36cm2，电池充电截止电压2V,放电截止电压0.5V，正负及电解液体积各80ml。首圈库伦效率CE97.2％,VE85.1％，EE82.7％；The zinc-bromine flow battery cycle performance experiment was carried out with an aqueous solution of 3MZnBr 2 +0.5MKCl+0.8MMEP as the electrolyte, the electrode was carbon felt, the electrolyte flow rate was 60ml/min, the current density was 40mA/cm 2 , the electrode effective area was 36cm 2 , the battery charge cut-off voltage was 2V, the discharge cut-off voltage was 0.5V, and the positive, negative and electrolyte volumes were 80ml each. The first cycle coulomb efficiency CE97.2%, VE85.1%, EE82.7%;
电池运行800循环后，电池能量效率衰减至68％时在电解液中加入甲酸至电解液由红色变为无色,进行正常充放电。采用该恢复方法电池，恢复后首圈电池CE92.1％,VE85.1％，EE78.4％。这主要是由于甲酸与累积的溴反应生成HBr，首圈充电过程中生成锌与HBr发生化学反应所致。After the battery ran for 800 cycles, when the battery energy efficiency decayed to 68%, formic acid was added to the electrolyte until the electrolyte changed from red to colorless, and normal charging and discharging was performed. Using this recovery method, the battery CE was 92.1%, VE was 85.1%, and EE was 78.4% after the first cycle of recovery. This is mainly due to the reaction of formic acid with accumulated bromine to generate HBr, and the chemical reaction of zinc generated during the first cycle of charging with HBr.
此外，采用该种恢复方法电池再次运行300循环即需进行一次恢复，恢复后首圈电池CE 91.8％,VE84.7％，EE77.8％。与采用添加锌粉恢复方法相比，此恢复方法首圈CE偏低，电池恢复频率增加。In addition, the battery needs to be restored after running 300 cycles. After restoration, the first cycle battery CE is 91.8%, VE is 84.7%, and EE is 77.8%. Compared with the recovery method using zinc powder, the first cycle CE of this recovery method is lower and the battery recovery frequency increases.
对比例3Comparative Example 3
以2MZnBr2+0.5M KCl+0.8MMEP的水溶液为正负电解液进行锌溴液流电池循环性能实验，电极为碳毡，电解液于正负电极腔窒内的流速60ml/min,电流密度为40mA/cm2，电极有效面积36cm2，电池充电截止电压2V,放电截止电压0.5V，正负极电解液体积分别各80ml。电池运行800循环后，电池能量效率衰减至69％时进行电解液互混。互混至0V后电解液变为无色，说明电解液中以无溴的存在。The zinc-bromine flow battery cycle performance experiment was carried out with an aqueous solution of 2MZnBr 2 +0.5M KCl+0.8MMEP as the positive and negative electrolytes. The electrodes were carbon felt, the flow rate of the electrolyte in the positive and negative electrode cavities was 60ml/min, the current density was 40mA/cm 2 , the electrode effective area was 36cm 2 , the battery charging cut-off voltage was 2V, the discharge cut-off voltage was 0.5V, and the positive and negative electrolyte volumes were 80ml each. After the battery ran for 800 cycles, the battery energy efficiency decayed to 69%, and the electrolytes were mixed. After mixing to 0V, the electrolyte became colorless, indicating that there was no bromine in the electrolyte.
当溶液中活性物质为2M时，电池首圈CE98.4％ VE86.1％When the active substance in the solution is 2M, the battery first cycle CE98.4% VE86.1%
EE84.5％，互混恢复后首圈CE 98.2％ VE 86.2％、EE84.6％。这也说明当活性物质浓度为2M时，仅互混就可将电池性能恢复到初始水平，不存在高浓度下仅互混首圈CE偏低及恢复频率增加的问题。EE84.5%, after intermixing recovery, the first cycle CE 98.2%, VE 86.2%, EE84.6%. This also shows that when the active material concentration is 2M, only intermixing can restore the battery performance to the initial level, and there is no problem of low first cycle CE and increased recovery frequency under high concentration.
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