CN110718709A - A single-liquid film-free full-deposition type lead-acid flow battery device and its working method - Google Patents
A single-liquid film-free full-deposition type lead-acid flow battery device and its working method Download PDFInfo
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- 239000007788 liquid Substances 0.000 title claims abstract description 44
- 239000002253 acid Substances 0.000 title claims abstract description 18
- 238000000034 method Methods 0.000 title claims abstract description 14
- 239000003792 electrolyte Substances 0.000 claims abstract description 34
- 239000003381 stabilizer Substances 0.000 claims abstract description 27
- 238000007599 discharging Methods 0.000 claims description 15
- AFVFQIVMOAPDHO-UHFFFAOYSA-N Methanesulfonic acid Chemical compound CS(O)(=O)=O AFVFQIVMOAPDHO-UHFFFAOYSA-N 0.000 claims description 10
- 229940098779 methanesulfonic acid Drugs 0.000 claims description 5
- 150000002500 ions Chemical class 0.000 claims description 4
- 239000011259 mixed solution Substances 0.000 claims description 4
- 238000006479 redox reaction Methods 0.000 claims description 4
- 238000000151 deposition Methods 0.000 claims 3
- AFVFQIVMOAPDHO-UHFFFAOYSA-M Methanesulfonate Chemical compound CS([O-])(=O)=O AFVFQIVMOAPDHO-UHFFFAOYSA-M 0.000 claims 1
- 238000001802 infusion Methods 0.000 abstract description 9
- 238000012864 cross contamination Methods 0.000 abstract description 3
- 239000003014 ion exchange membrane Substances 0.000 abstract description 3
- 230000008569 process Effects 0.000 description 7
- 238000004146 energy storage Methods 0.000 description 5
- 238000011161 development Methods 0.000 description 4
- LLABTCPIBSAMGS-UHFFFAOYSA-L lead(2+);methanesulfonate Chemical compound [Pb+2].CS([O-])(=O)=O.CS([O-])(=O)=O LLABTCPIBSAMGS-UHFFFAOYSA-L 0.000 description 4
- 230000006872 improvement Effects 0.000 description 3
- 239000000243 solution Substances 0.000 description 3
- 241000282414 Homo sapiens Species 0.000 description 2
- XEEYBQQBJWHFJM-UHFFFAOYSA-N Iron Chemical compound [Fe] XEEYBQQBJWHFJM-UHFFFAOYSA-N 0.000 description 2
- GDTBXPJZTBHREO-UHFFFAOYSA-N bromine Chemical compound BrBr GDTBXPJZTBHREO-UHFFFAOYSA-N 0.000 description 2
- 238000006243 chemical reaction Methods 0.000 description 2
- 238000005260 corrosion Methods 0.000 description 2
- 230000007797 corrosion Effects 0.000 description 2
- 238000003411 electrode reaction Methods 0.000 description 2
- 238000012986 modification Methods 0.000 description 2
- 230000004048 modification Effects 0.000 description 2
- 238000010248 power generation Methods 0.000 description 2
- 230000000087 stabilizing effect Effects 0.000 description 2
- VYZAMTAEIAYCRO-UHFFFAOYSA-N Chromium Chemical compound [Cr] VYZAMTAEIAYCRO-UHFFFAOYSA-N 0.000 description 1
- 229910052794 bromium Inorganic materials 0.000 description 1
- 229910052804 chromium Inorganic materials 0.000 description 1
- 239000011651 chromium Substances 0.000 description 1
- 230000008021 deposition Effects 0.000 description 1
- 238000013461 design Methods 0.000 description 1
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- 238000004090 dissolution Methods 0.000 description 1
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- 238000005265 energy consumption Methods 0.000 description 1
- 238000005516 engineering process Methods 0.000 description 1
- 238000003912 environmental pollution Methods 0.000 description 1
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- 229910052742 iron Inorganic materials 0.000 description 1
- 230000007246 mechanism Effects 0.000 description 1
- 239000000203 mixture Substances 0.000 description 1
- 230000010287 polarization Effects 0.000 description 1
- HYHCSLBZRBJJCH-UHFFFAOYSA-N sodium polysulfide Chemical compound [Na+].S HYHCSLBZRBJJCH-UHFFFAOYSA-N 0.000 description 1
- 230000004083 survival effect Effects 0.000 description 1
- 229910052720 vanadium Inorganic materials 0.000 description 1
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Abstract
本发明公开了一种单液无膜全沉积型铅酸液流电池装置及其工作方法，包括：入口稳流器、反应器、交直流电转换器、负载、电能装置、出口稳流器和储液罐，所述储液罐出口通过输液管与入口稳流器相连，所述入口稳流器位于反应器入口处，在反应器出口处设有出口稳流器，所述出口稳流器通过输液管连回至储液罐进口；在反应器中设有并行连接且交替排列的正负电极板，正电极板通过导线与交直流电转换器一端连接，负电极板通过导线与交直流电转换器另一端连接，所述交直流电转换器还分别与负载、电能装置相连。本申请避免了电解液交叉污染和昂贵的离子交换膜问题；降低了电解液在电极板间的流动阻力，满足提高液流电池充放电性能的要求。
The invention discloses a single-liquid film-free full-deposition type lead-acid liquid flow battery device and a working method thereof. Liquid tank, the outlet of the liquid storage tank is connected with the inlet flow stabilizer through the infusion pipe, the inlet flow stabilizer is located at the inlet of the reactor, and an outlet flow stabilizer is arranged at the reactor outlet, and the outlet flow stabilizer passes through The infusion tube is connected back to the inlet of the liquid storage tank; positive and negative electrode plates are arranged in parallel and alternately arranged in the reactor, the positive electrode plate is connected to one end of the AC-DC converter through a wire, and the negative electrode plate is connected to the AC-DC converter through a wire. The other end is connected, and the AC/DC converter is also connected with the load and the power device respectively. The present application avoids the problems of electrolyte cross-contamination and expensive ion exchange membranes; reduces the flow resistance of electrolyte between electrode plates, and meets the requirements for improving the charge-discharge performance of flow batteries.
Description
技术领域technical field
本发明涉及一种氧化还原液流电池装置，特别是涉及一种单液无膜全沉积铅酸液流电池装置，属于能源科学技术新能源与节能领域。The invention relates to a redox flow battery device, in particular to a single-liquid film-free full-deposition lead-acid flow battery device, which belongs to the fields of new energy and energy saving in energy science and technology.
背景技术Background technique
能源危机与环境污染已经威胁到人类的生存和发展，大规模开发和应用无碳清洁分布式能源已经成为当今和今后人类社会生活的主题。在无碳清洁分布式能源中，储量最为丰富和最具规模化应用前景的是太阳能和风能等分布式能源。但是自然界中的太阳能和风能能量密度低，在时间和地域分布上极不均匀，随时间和季节波动性、地域差异性很大，这些都是限制其规模化开发应用的瓶颈。The energy crisis and environmental pollution have threatened the survival and development of human beings. The large-scale development and application of carbon-free and clean distributed energy has become the theme of human social life today and in the future. Among the carbon-free and clean distributed energy sources, the ones with the most abundant reserves and the most large-scale application prospects are distributed energy sources such as solar energy and wind energy. However, the energy density of solar energy and wind energy in nature is low, the time and geographical distribution are extremely uneven, and the fluctuations with time and season, and the geographical differences are very large. These are the bottlenecks that limit their large-scale development and application.
氧化还原液流电池作为新型的蓄电储能装置，具有诸多潜在的优良性能，如储能容量大、可超深度放电、使用寿命长、浓差极化小等，而且不受地理条件限制，可以作为太阳能、风能等分布式清洁能源的配套储能设备，还可以作为电网的调峰装置，提高输电质量，保障电网安全。As a new type of power storage device, redox flow battery has many potential excellent properties, such as large energy storage capacity, ultra-deep discharge, long service life, small concentration polarization, etc., and is not limited by geographical conditions. It can be used as a supporting energy storage device for distributed clean energy such as solar energy and wind energy.
由于氧化还原液流电池的种类不同，其反应机理不同。在传统的全钒体系、多硫化钠/溴体系和铁/铬体系等氧化还原液流电池中，存在两个主要不足之处：一个是关键组件隔膜，其性能不是很稳定，而且隔膜价格昂贵，这是传统液流储能电池发展的瓶颈。另外一个需要两套输液系统，使得系统结构复杂，成本增加。而现有的铅酸液流电池是由一块正极板和一块负极板通过螺纹固定在一起，电解液流经两电极板间的缝隙。这种电池的容量比较低，电解液在狭小的缝隙中流动阻力比较大，从而使得电池内阻较大，电池能耗较高，效率较低，而且电池使用过程中，电极板更换麻烦。Due to the different types of redox flow batteries, their reaction mechanisms are different. In traditional redox flow batteries such as all-vanadium system, sodium polysulfide/bromine system and iron/chromium system, there are two main shortcomings: one is the key component diaphragm, whose performance is not very stable, and the diaphragm is expensive , which is the bottleneck of the development of traditional liquid flow energy storage batteries. The other one requires two sets of infusion systems, which makes the system structure complex and the cost increases. In the existing lead-acid flow battery, a positive plate and a negative plate are fixed together by screws, and the electrolyte flows through the gap between the two electrode plates. The capacity of this kind of battery is relatively low, and the flow resistance of the electrolyte in the narrow gap is relatively large, so that the internal resistance of the battery is relatively large, the energy consumption of the battery is relatively high, and the efficiency is relatively low.
因此设计适合液流电池稳定充放电的反应器，去除液流电池在充放电过程中电极板数量和间距、电解液流动阻力对电池性能的影响因素，对全沉积型铅酸液流电池和其它单液无膜氧化还原液流电池极为必要。Therefore, a reactor suitable for stable charging and discharging of flow batteries is designed, and the number and spacing of electrode plates and the flow resistance of electrolyte during the charging and discharging process of the flow battery are removed. Single-liquid membraneless redox flow batteries are extremely necessary.
发明内容SUMMARY OF THE INVENTION
针对现有技术存在的上述问题，本申请提供一种单液无膜全沉积型铅酸液流电池装置及其工作方法，避免了电解液交叉污染和昂贵的离子交换膜问题；降低了电解液在电极板间的流动阻力，满足提高液流电池充放电性能的要求。In view of the above problems existing in the prior art, the present application provides a single-liquid membrane-free full-deposition type lead-acid flow battery device and a working method thereof, which avoid the problems of electrolyte cross-contamination and expensive ion exchange membranes; The flow resistance between the electrode plates meets the requirements for improving the charge and discharge performance of the flow battery.
为实现上述目的，本申请的技术方案为：一种单液无膜全沉积型铅酸液流电池装置，包括：入口稳流器、反应器、交直流电转换器、负载、电能装置、出口稳流器和储液罐，所述储液罐出口通过输液管与入口稳流器相连，所述入口稳流器位于反应器入口处，在反应器出口处设有出口稳流器，所述出口稳流器通过输液管连回至储液罐进口；在反应器中设有并行连接且交替排列的正负电极板，正电极板通过导线与交直流电转换器一端连接，负电极板通过导线与交直流电转换器另一端连接，所述交直流电转换器还分别与负载、电能装置相连。In order to achieve the above purpose, the technical solution of the present application is: a single-liquid film-free full-deposition lead-acid flow battery device, comprising: an inlet current stabilizer, a reactor, an AC/DC converter, a load, an electrical energy device, and an outlet stabilizer. A flow device and a liquid storage tank, the outlet of the liquid storage tank is connected with an inlet flow stabilizer through a transfusion pipe, the inlet flow stabilizer is located at the inlet of the reactor, and an outlet flow stabilizer is arranged at the reactor outlet, and the outlet The current stabilizer is connected back to the inlet of the liquid storage tank through the infusion pipe; positive and negative electrode plates are arranged in parallel and alternately arranged in the reactor, the positive electrode plate is connected with one end of the AC-DC converter through a wire, and the negative electrode plate is connected with The other end of the AC-DC converter is connected, and the AC-DC converter is also connected with the load and the power device respectively.
进一步的，正负电极板与反应器为插拔式连接。Further, the positive and negative electrode plates are connected with the reactor in a pluggable manner.
进一步的，所述储液罐内是1.5mol/L的甲基磺酸铅和0.9mol/L的甲基磺酸的混合液。Further, the liquid storage tank is a mixed solution of 1.5 mol/L lead methanesulfonate and 0.9 mol/L methanesulfonic acid.
进一步的，在储液罐出口与入口稳流器之间的输液管上依次设有循环泵、流量计。Further, a circulating pump and a flow meter are sequentially arranged on the infusion pipe between the outlet of the liquid storage tank and the inlet flow stabilizer.
本申请还提供一种单液无膜全沉积型铅酸液流电池装置工作方法，具体包括：循环泵将储液罐中的电解液通过输液管流入到入口稳定器中，电解液在入口稳定器中稳定后分流进入反应器中，电解液在反应器中的液面不断升高到达出口而从反应器中流入到出口稳定器，然后经过输液管流入到储液罐中而实现电解液的循环流动；The application also provides a working method of a single-liquid film-free full-deposition type lead-acid flow battery device, which specifically includes: a circulating pump flows the electrolyte in the liquid storage tank into the inlet stabilizer through the infusion pipe, and the electrolyte is stabilized at the inlet. After the stabilizer is stabilized, the flow is divided into the reactor, and the liquid level of the electrolyte in the reactor continuously rises to the outlet and flows into the outlet stabilizer from the reactor, and then flows into the liquid storage tank through the infusion pipe to realize the electrolyte. circulating flow;
充电时，将交直流电转换器中的档位调至充电档；这时，电流经过导线通入电极板中，在有电流通过的条件下，电解液中的Pb离子发生氧化还原反应而在正极板上沉积PbO2和负极板上沉积Pb；放电时，将交直流电转换器中的档位调至放电档；这时，正负极板上的PbO2和Pb沉积物发生氧化还原反应生成Pb离子而溶入到电解液中，同时在整个回路上产生电流输送给负载。在充放电过程中，需要根据充放电电流、电压的大小或反应器中电极板的数目不同通过流量计调整电解液流量的大小。When charging, adjust the gear in the AC/DC converter to the charging gear; at this time, the current is passed into the electrode plate through the wire, and under the condition of current passing, the Pb ion in the electrolyte undergoes a redox reaction and is in the positive electrode. PbO 2 is deposited on the plate and Pb is deposited on the negative plate; when discharging, the gear in the AC-DC converter is adjusted to the discharge gear; at this time, the PbO 2 and Pb deposits on the positive and negative plates undergo a redox reaction to generate Pb The ions are dissolved into the electrolyte, and at the same time, a current is generated on the entire circuit and sent to the load. During the charging and discharging process, it is necessary to adjust the flow rate of the electrolyte through the flowmeter according to the size of the charging and discharging current, voltage or the number of electrode plates in the reactor.
本发明由于采用以上技术方案，能够取得如下的技术效果：The present invention can obtain the following technical effects due to the adoption of the above technical solutions:
1.本申请由多组正负电极并行连接且交替排列，正、负电极板的数量可以根据电池容量进行调整，保证液流电池在充放电过程中液流电池反应器具有更大的单位容积电极反应面积，提高全沉积型铅酸液流电池的单位容积电容量。1. The application consists of multiple groups of positive and negative electrodes connected in parallel and arranged alternately. The number of positive and negative electrode plates can be adjusted according to the battery capacity to ensure that the flow battery reactor has a larger unit volume during the charging and discharging process. The electrode reaction area improves the unit volume capacity of the fully deposited lead-acid flow battery.
2.通过在电解液流经反应器的前后分别增加稳流器，在电解液流动过程中起到稳定和分流的作用，保证电池在充放电过程中，能提高电解液在反应器中正、负电极间的流动稳定性和均匀性，提高电极电流分布的均匀性，从而提高电池的充放电性能。2. By adding a current stabilizer before and after the electrolyte flows through the reactor, it plays a role of stabilizing and shunting during the flow of the electrolyte, ensuring that the battery is charged and discharged during the process, and the positive and negative values of the electrolyte in the reactor can be improved. The flow stability and uniformity between electrodes improves the uniformity of electrode current distribution, thereby improving the charge and discharge performance of the battery.
3.通过对液流电池反应器的改进，可以将正、负电极板设计为插拔式结构，能实时对电池的容量进行调整，同时也可以对电极板进行实时更换，进而提高电池的稳定性和可维护性。3. Through the improvement of the flow battery reactor, the positive and negative electrode plates can be designed as a plug-in structure, the capacity of the battery can be adjusted in real time, and the electrode plates can also be replaced in real time, thereby improving the stability of the battery performance and maintainability.
4.正负极使用同一种液体，均以甲基磺酸和甲基磺酸铅混合液为电解液，避免了电解液的交叉污染和昂贵的离子交换膜问题。4. The positive and negative electrodes use the same liquid, and the mixed solution of methanesulfonic acid and lead methanesulfonate is used as the electrolyte, which avoids the cross-contamination of the electrolyte and the problem of expensive ion exchange membranes.
附图说明Description of drawings
图1为一种单液无膜全沉积型铅酸液流电池装置结构示意图；1 is a schematic structural diagram of a single-liquid film-free full-deposition type lead-acid flow battery device;
图中序号说明：1.循环泵；2.流量计；3.输液管；4.入口稳流器；5.反应器；6.负电极板；7.交直流电转换器；8.负载；9.电能装置；10.正电极板；11.出口稳流器；12.储液罐。Description of the serial numbers in the figure: 1. Circulating pump; 2. Flow meter; 3. Infusion pipe; 4. Inlet flow stabilizer; 5. Reactor; 6. Negative electrode plate; 7. AC/DC converter; 8. Load; 9 . Electric energy device; 10. Positive electrode plate; 11. Outlet flow stabilizer; 12. Liquid storage tank.
具体实施方式Detailed ways
本发明的实施例是在以本发明技术方案为前提下进行实施的，给出了详细的实施方式和具体的操作过程，但本发明的保护范围不限于下述实施例。The embodiments of the present invention are implemented on the premise of the technical solutions of the present invention, and detailed implementations and specific operation procedures are given, but the protection scope of the present invention is not limited to the following embodiments.
实施例1Example 1
本实施例提供一种单液无膜全沉积型铅酸液流电池装置，包括循环泵1、流量计2、输液管3、入口稳流器4、反应器5、负电极板6、交直流电转换器7、负载8、电能装置9、正电极板10、出口稳流器11和储液罐12。所述的循环泵1具有优良的耐强酸腐蚀性，其最大流量为20L/min，循环泵的最大流量也可以根据电池容量和性能要求而变化。所述的流量计2具有优良的耐强酸腐蚀性，其量程为0.1L/min～20L/min，流量计2的量程也可以根据电池容量和性能要求而变化。电解液在流经反应器的前后分别增加能起到稳定和分流作用的入口稳流器4和出口稳流器11，提高电极电流分布的均匀性和电池的充放电性能。所述反应器5内正负电极板并行连接且交替排列，正负电极板数量可由电池容量大小确定。所述反应器5内正负电极板可设计为插拔式结构，可以实时调整电极板数量和更换电极板。所述的储液罐12容积为10L，储存的1.5mol/L的甲基磺酸铅和0.9mol/L的甲基磺酸的混合液。This embodiment provides a single-liquid film-free full-deposition lead-acid flow battery device, including a circulating
该装置充分利用流体流动、化学反应、电解液沉积和溶解等原理，实现正、负电极板数的可调性，保证在充放电过程中液流电池具有更大的单位容积电极反应面积，提高电池的单位容积电容量。通过在电解液流经反应器的前后分别增加稳流器，在电解液流动过程中起到稳定和均匀分流的作用，保证电池在充放电过程中，能提高电解液在反应器中正、负电极间的流动稳定性和均匀性，提高电极电流分布的均匀性，从而提高电池的充放电性能。The device makes full use of the principles of fluid flow, chemical reaction, electrolyte deposition and dissolution, etc., to realize the adjustability of the number of positive and negative electrode plates, to ensure that the flow battery has a larger electrode reaction area per unit volume during the charging and discharging process. The unit volume capacity of the battery. By adding a flow stabilizer before and after the electrolyte flows through the reactor, it plays a role of stable and uniform shunting during the flow of the electrolyte, so as to ensure that during the charging and discharging process of the battery, the positive and negative electrodes of the electrolyte in the reactor can be improved. The flow stability and uniformity between the electrodes can be improved, and the uniformity of the electrode current distribution can be improved, thereby improving the charging and discharging performance of the battery.
实施例2Example 2
将实施例提供的单液无膜全沉积型铅酸液流电池装置在小型的太阳能发电装置上试用，安装在太阳能发电装置的用电部位。电解液是1.5mol/L的甲基磺酸铅和0.9mol/L的甲基磺酸的混合液；储液罐的容积为10L，电解液的流量为2L/min；电极板数为50，其中正负极板各为25；充放电电流为20A，充放电时间为10h。The single-liquid film-free full-deposition type lead-acid flow battery device provided in the embodiment is tried on a small solar power generation device, and is installed in the power consumption part of the solar power generation device. The electrolyte is a mixture of 1.5mol/L lead methanesulfonate and 0.9mol/L methanesulfonic acid; the volume of the liquid storage tank is 10L, and the flow rate of the electrolyte is 2L/min; the number of electrode plates is 50, The positive and negative plates are 25 each; the charging and discharging current is 20A, and the charging and discharging time is 10h.
本申请电池装置运行了100个充放电循环，充放电过程中运行稳定，可靠，运行过程中没有发生沉积物脱落或沉积物粘连导致断路或短路的现象。停止充放电后，电极板上的沉积物比较致密和均匀，说明本发明的液流电池储能装置在此电解液流量和反应器结构设计条件下，电解液在反应器内流场分布非常均匀，而且与电极板之间的接触非常充分，使得液流电池储能装置具有稳定的充放电性能。The battery device of the present application has been operated for 100 charge-discharge cycles, and the operation is stable and reliable during the charge-discharge process, and no disconnection or short-circuit caused by deposit shedding or deposit adhesion occurs during the operation. After stopping charging and discharging, the deposits on the electrode plates are relatively dense and uniform, indicating that the flow field distribution of the electrolyte in the reactor is very uniform under the conditions of the electrolyte flow rate and the reactor structure design of the flow battery energy storage device of the present invention. , and the contact with the electrode plate is very sufficient, so that the flow battery energy storage device has stable charge and discharge performance.
以上所述仅是本发明的优选实施方式，并不用于限制本发明，应当指出，对于本技术领域的普通技术人员，在不脱离本发明技术原理的前提下，还可以做出若干改进和变型，这些改进和变型也应视为本发明的保护范围。The above are only preferred embodiments of the present invention and are not intended to limit the present invention. It should be pointed out that for those skilled in the art, without departing from the technical principles of the present invention, several improvements and modifications can also be made. , these improvements and modifications should also be regarded as the protection scope of the present invention.
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Citations (2)
| Publication number | Priority date | Publication date | Assignee | Title |
|---|---|---|---|---|
| CN104078695A (en) * | 2014-07-22 | 2014-10-01 | 沈阳工程学院 | Full-sedimentary type lead acid liquid current battery energy storing device |
| CN109065932A (en) * | 2018-08-09 | 2018-12-21 | 中南大学 | deposition flow battery |
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Patent Citations (2)
| Publication number | Priority date | Publication date | Assignee | Title |
|---|---|---|---|---|
| CN104078695A (en) * | 2014-07-22 | 2014-10-01 | 沈阳工程学院 | Full-sedimentary type lead acid liquid current battery energy storing device |
| CN109065932A (en) * | 2018-08-09 | 2018-12-21 | 中南大学 | deposition flow battery |
Non-Patent Citations (1)
| Title |
|---|
| 林仁荣等: ""无膜单液铅酸液流电池的制备与性能研究"", 《沈阳工程学院（自然科学版）》 * |
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