由于锌溴液流电池需要循环泵、贮液槽等电解液循环系统所需的设备，导致了锌溴液流电池的能量密度由于系统损耗的影响而降低，另一方面这些电池辅助设备使得锌溴液流电池系统结构复杂，不利于小型化。Since zinc-bromine flow batteries require equipment required for electrolyte circulation systems such as circulation pumps and liquid storage tanks, the energy density of zinc-bromine flow batteries is reduced due to the impact of system losses. On the other hand, these battery auxiliary equipment make zinc The complex structure of bromine flow battery system is not conducive to miniaturization.

专利CN99245261.9介绍了一种锌溴蓄电池，它取消了锌溴液流电池的循环泵，贮液槽等电解液循环系统，使电池结构简单而紧凑，降低了系统能耗。但是，该系统未提出适合锌溴蓄电池使用的电极而是直接采用锌溴液流储能电池使用的碳毡电极，导致了系统的能量效率较低，并且由于未考虑电池析氢的抑制问题，导致系统需要设置排气孔，系统设计复杂，不利于密封。Patent CN99245261.9 introduces a zinc-bromine storage battery, which cancels the circulation pump of the zinc-bromine flow battery, the electrolyte circulation system such as the storage tank, makes the battery structure simple and compact, and reduces the energy consumption of the system. However, this system did not propose an electrode suitable for zinc-bromine batteries, but directly used carbon felt electrodes for zinc-bromine flow energy storage batteries, resulting in low energy efficiency of the system, and because the suppression of hydrogen evolution in batteries was not considered, resulting in The system needs to be equipped with vent holes, and the system design is complicated, which is not conducive to sealing.

随着人类经济和社会的发展，对能源的需求越来越多，使得化石能源保障压力越来越大；而且化石能源转化过程产生诸多环境问题：例如，排放氮和硫的氧化物引发酸雨，排放温室气体加速全球变暖的进程。因此，发展可再生能源，扩大其在能源结构中的比重，提高能源利用效率，将推动社会可持续发展。With the development of human economy and society, the demand for energy is increasing, which makes the pressure of fossil energy security increasing; and the process of fossil energy conversion produces many environmental problems: for example, the emission of nitrogen and sulfur oxides causes acid rain, Emissions of greenhouse gases accelerate the process of global warming. Therefore, developing renewable energy, expanding its proportion in the energy structure, and improving energy efficiency will promote sustainable social development.

电能作为清洁高效的二次能源，与人类日常生产生活密切相关，而不断增长的电能需求以及对电力品质的要求，需要频繁的对电网系统进行扩容和升级，大力发展太阳能、风能等可再生能源发电是解决这一问题的重要途径。然而，太阳能、风能具有明显的不连续、不稳定特性，对电网的稳定可靠运行提出了巨大挑战，成为阻碍其进一步发展的瓶颈。为此发展高效储能技术，用以平滑和稳定可再生能源发电的输出以及解决发电与用电的时差矛盾，提高电力品质和电网可靠性，具有十分重要的意义。As a clean and efficient secondary energy source, electric energy is closely related to the daily production and life of human beings. The ever-increasing demand for electric energy and the requirements for power quality require frequent expansion and upgrading of the power grid system, and vigorously develop renewable energy such as solar energy and wind energy. Power generation is an important way to solve this problem. However, solar energy and wind energy have obvious discontinuous and unstable characteristics, which pose a huge challenge to the stable and reliable operation of the power grid and become a bottleneck hindering their further development. Therefore, it is of great significance to develop high-efficiency energy storage technology to smooth and stabilize the output of renewable energy power generation, solve the time difference between power generation and power consumption, and improve power quality and grid reliability.

为保证太阳能、风能等可再生能源发电系统的稳定供电，就必须开发高效、廉价、污染少和安全可靠的储能技术。纵观各种不同类型的化学蓄电池，液流电池以其独特的优势而成为最适宜大规模储能的蓄电池之一。与所有电化学电池一样，液流储能电池也是通过活性物质发生氧化还原反应来实现电能和化学能相互转化的电池系统。与传统二次电池不同，液流储能电池的电极均为惰性电极，为电极反应提供反应场所，同时起到电催化剂的作用。通常液流储能电池在初始状态，活性物质以离子状态存储于电解液当中，正极和负极电解液分别装在两个储罐中，通过送液泵实现电解液在管路系统中的循环。运行过程中，有的电池体系氧化还原反应表现为离子价态的变化，有的表现为金属的沉积与溶出，通常把后者表现形式的电池统称为沉积型液流储能电池。目前研究认为锌作为在水溶液中稳定存在的金属中比能量密度最高的金属，最适合于作为沉积型液流储能电池负极使用，如：锌溴、锌镍、锌锰、锌空等液流储能电池。In order to ensure the stable power supply of solar energy, wind energy and other renewable energy power generation systems, it is necessary to develop efficient, cheap, less polluting, safe and reliable energy storage technologies. Throughout the various types of chemical batteries, flow batteries have become one of the most suitable batteries for large-scale energy storage due to their unique advantages. Like all electrochemical batteries, the flow energy storage battery is also a battery system that realizes the mutual conversion of electrical energy and chemical energy through the oxidation-reduction reaction of active materials. Different from traditional secondary batteries, the electrodes of liquid flow energy storage batteries are all inert electrodes, which provide a reaction site for the electrode reaction and also act as an electrocatalyst. Usually, in the initial state of the flow energy storage battery, the active material is stored in the electrolyte in an ionic state. The positive and negative electrolytes are respectively installed in two storage tanks, and the circulation of the electrolyte in the pipeline system is realized by a liquid delivery pump. During operation, the redox reaction of some battery systems manifests as changes in the valence state of ions, and some manifests as deposition and dissolution of metals. Batteries with the latter manifestations are usually collectively referred to as deposition-type flow energy storage batteries. Current studies believe that zinc, as the metal with the highest specific energy density among the metals that exist stably in aqueous solution, is most suitable for use as the negative electrode of deposition-type flow energy storage batteries, such as: zinc bromine, zinc nickel, zinc manganese, zinc air, etc. Energy storage battery.

锌溴液流储能电池(Zinc-bromineredoxflowbattery,ZBB)是一种低能耗、高效率、环境友好型的液流储能电池，具有能量密度和电流效率高、装置简单易操纵、使用寿命长、成本低廉等优点，主要应用于电网调峰、风能和太阳能等可再生能源发电、电动汽车等领域。Zinc-bromine redox flow battery (ZBB) is a low-energy, high-efficiency, environment-friendly liquid flow energy storage battery with high energy density and current efficiency, simple and easy to operate device, long service life, Low cost and other advantages, it is mainly used in power grid peak regulation, renewable energy power generation such as wind energy and solar energy, electric vehicles and other fields.

锌溴液流电池在充放电工作时，用循环泵驱动电解液在电池内循环流动。电池不工作时电解液从电池空腔中抽出，贮存于贮液槽内，使电池内部正负极之间实现电解液断路，可以防止正极充电态溴扩散到负极直接发生化学反应而引起自放电。循环电解液同时还可以防止充电时锌枝晶生长穿过隔膜使正负极短路。专利EPBIO167517,CN1087209A等就是这类循环电解液锌溴电池。When the zinc-bromine flow battery is charging and discharging, the circulation pump is used to drive the electrolyte to circulate in the battery. When the battery is not working, the electrolyte is extracted from the battery cavity and stored in the liquid storage tank, so that the electrolyte is disconnected between the positive and negative electrodes inside the battery, which can prevent the positive charged bromine from diffusing to the negative electrode to directly cause chemical reactions and cause self-discharge. . Circulating the electrolyte can also prevent zinc dendrites from growing through the separator and short-circuiting the positive and negative electrodes during charging. Patent EPBIO167517, CN1087209A etc. are exactly this kind of circulation electrolyte zinc-bromine battery.

目前锌溴液流电池均采用导电基体并附着催化材料的方法制备电池正极，一方面活性较差，另一方面增加了工序，不利于成本控制。而碳毡作为电极在全钒液流电池中有广泛的应用，而碳毡作为锌溴液流电池正极具有良好的催化活性，但是由于负极为锌的沉积溶解反应，使用碳毡会导致锌的累积，影响电池寿命。At present, zinc-bromine flow batteries use a conductive substrate and attach catalytic materials to prepare the positive electrode of the battery. On the one hand, the activity is poor, and on the other hand, the process is increased, which is not conducive to cost control. Carbon felt is widely used as an electrode in all-vanadium flow batteries, and carbon felt has good catalytic activity as a positive electrode of zinc-bromine flow battery, but due to the deposition and dissolution reaction of zinc at the negative electrode, the use of carbon felt will lead to the dissolution of zinc. Cumulatively, affect battery life.

本发明提供了一种可以使用碳毡作为电极材料的解决方案，在保证电池性能提高的同时，解决了锌的累积及循环寿命较低的问题。The invention provides a solution for using carbon felt as an electrode material, which solves the problems of zinc accumulation and low cycle life while ensuring improved battery performance.

发明内容Contents of the invention

本发明提供一种长寿命锌溴液流电池结构及电解液组成。The invention provides a long-life zinc-bromine liquid flow battery structure and electrolyte composition.

为实现上述目的，本发明的具体技术方案如下：To achieve the above object, the specific technical solutions of the present invention are as follows:

电池由一节或二节以上单电池串联而成的电池模块、电解液储液罐、循环泵和循环管路组成；单电池包括正极、隔膜、负极，其特征在于，正负极均采用活性碳毡作为电极材料。隔膜为多孔膜或离子交换膜。正负极电解液主盐均为溴化锌溶液，溴化锌浓度为1.0mol/L—5.0mol/L。正负极电解液均含有氯离子溶液，氯离子浓度为1.0mol/L—5.0mol/L。The battery is composed of a battery module connected in series by one or more single cells, an electrolyte storage tank, a circulation pump and a circulation pipeline; the single cell includes a positive electrode, a diaphragm, and a negative electrode. Carbon felt as electrode material. The diaphragm is a porous membrane or an ion exchange membrane. The main salt of the positive and negative electrolytes is zinc bromide solution, and the concentration of zinc bromide is 1.0mol/L-5.0mol/L. Both positive and negative electrode electrolytes contain chloride ion solution, and the chloride ion concentration is 1.0mol/L-5.0mol/L.

本发明的有益效果：Beneficial effects of the present invention:

1.该电池正负极均采用碳毡材料，简化了正极电极的制备过程。1. Both the positive and negative electrodes of the battery are made of carbon felt, which simplifies the preparation process of the positive electrode.

2.该电池及电解液组成提高了电池的能量密度。2. The composition of the battery and electrolyte improves the energy density of the battery.

3.该电池具有良好的循环稳定性。3. The battery has good cycle stability.

附图说明Description of drawings

图1为实施例锌溴蓄电池循环数据图；Fig. 1 is the cycle data figure of zinc-bromine storage battery of embodiment;

图2为对比例锌溴蓄电池循环数据图。Fig. 2 is a cycle data diagram of a zinc-bromine battery of a comparative example.

具体实施方式detailed description

实施例1Example 1

电极面积36cm²，充放电电流密度20mA/cm²,The electrode area is 36cm² , the charge and discharge current density is 20mA/cm² ,

电解液组成：正极和负极各40ml的2.0M溴化锌溶液+2.0M氯化钾溶液；Electrolyte composition: 40ml of 2.0M zinc bromide solution + 2.0M potassium chloride solution for positive and negative electrodes;

对比例1Comparative example 1

电解液组成：正负极各40ml的2.0M溴化锌溶液。Electrolyte composition: 40ml of 2.0M zinc bromide solution for positive and negative electrodes.

本发明电池正负极均采用活性碳毡作为电极材料，为了解决负极采用碳毡而引起的锌累积所导致的电池循环寿命偏低的问题，在正负极电解液中加入氯离子，一方面提高了电池的开路电压及能量密度，另一方面由于氯离子的加入，大大改善了锌沉积形貌及锌累积问题，解决了电池由于采用高活性碳毡所带来的循环稳定性较差的难题。Both the positive and negative electrodes of the battery of the present invention use activated carbon felt as the electrode material. In order to solve the problem of low battery cycle life caused by zinc accumulation caused by the use of carbon felt in the negative electrode, chloride ions are added to the positive and negative electrolytes. The open circuit voltage and energy density of the battery are improved. On the other hand, due to the addition of chloride ions, the zinc deposition morphology and zinc accumulation problems are greatly improved, and the problem of poor cycle stability caused by the use of highly active carbon felt is solved. problem.

由图可以看出：电解液中加入氯离子之后，电池的循环性能明显提高。未加入氯离子的传统电池循环10次左右，性能即明显出现衰减。It can be seen from the figure that after adding chloride ions to the electrolyte, the cycle performance of the battery is significantly improved. The performance of a traditional battery without chlorine ions is obviously attenuated after about 10 cycles.

Claims

1. a long-life zinc-bromine flow battery structure, it is characterized in that: include a joint monocell or by two battery modules saving above cells in series, monocell includes positive pole, barrier film, negative pole, it is characterised in that: the positive pole of monocell and negative pole all adopt activated carbon-fiber felt as electrode material.

2. battery structure according to claim 1, it is characterised in that: battery is saved monocell by one or the two joint battery modules of above cells in series, electrolyte fluid reservoir, circulating pump and circulation line form.

3. battery structure according to claim 1 and 2, it is characterised in that: barrier film is perforated membrane or ion exchange membrane.

4. battery structure according to claim 1 and 2, it is characterised in that: the positive pole of described zinc-bromine flow battery and electrolyte liquid are bromide solutions, and zinc bromide concentration is 1.0mol/L 5.0mol/L.

5. battery structure according to claim 4, it is characterised in that: positive pole and electrolyte liquid all contain Chloride Solution, and chlorine ion concentration is 1.0mol/L 5.0mol/L.