WO2021243774A1 - High-specific-energy zinc-nickel flow battery having one negative electrode and multiple positive electrodes - Google Patents

High-specific-energy zinc-nickel flow battery having one negative electrode and multiple positive electrodes Download PDF

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WO2021243774A1
WO2021243774A1 PCT/CN2020/098453 CN2020098453W WO2021243774A1 WO 2021243774 A1 WO2021243774 A1 WO 2021243774A1 CN 2020098453 W CN2020098453 W CN 2020098453W WO 2021243774 A1 WO2021243774 A1 WO 2021243774A1
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battery
positive
zinc
negative
negative electrode
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PCT/CN2020/098453
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Chinese (zh)
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WO2021243774A9 (en
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侯腾腾
张益宁
朱明华
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苏州沃泰丰能电池科技有限公司
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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
    • Y—GENERAL TAGGING OF NEW TECHNOLOGICAL DEVELOPMENTS; GENERAL TAGGING OF CROSS-SECTIONAL TECHNOLOGIES SPANNING OVER SEVERAL SECTIONS OF THE IPC; TECHNICAL SUBJECTS COVERED BY FORMER USPC CROSS-REFERENCE ART COLLECTIONS [XRACs] AND DIGESTS
    • Y02—TECHNOLOGIES OR APPLICATIONS FOR MITIGATION OR ADAPTATION AGAINST CLIMATE CHANGE
    • Y02E—REDUCTION OF GREENHOUSE GAS [GHG] EMISSIONS, RELATED TO ENERGY GENERATION, TRANSMISSION OR DISTRIBUTION
    • Y02E60/00—Enabling technologies; Technologies with a potential or indirect contribution to GHG emissions mitigation
    • Y02E60/30—Hydrogen technology
    • Y02E60/50—Fuel cells

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  • the utility model relates to the field of zinc ion batteries, in particular to a high specific energy one-negative poly-positive zinc-nickel flow battery.
  • Nickel-zinc secondary battery Humans’ research on nickel-zinc secondary battery (Nickel-zinc secondary battery) has a history of more than one hundred years. Due to people’s concern about environmental issues, zinc-nickel batteries have considerable advantages as a clean energy source; zinc-nickel batteries have With the advantages of high working voltage, high energy density, good safety, and low cost, domestic zinc-nickel battery production has been industrialized. It is said that the United States Nengjie and China State Construction Group have reached an agreement to establish the world's largest nickel-zinc battery research and development and development in Huainan, Anhui. The production base, with a total investment of more than 10 billion U.S. dollars, shows that nickel-zinc batteries have aroused great interest from investors. Jilin Zall Technology Co., Ltd.
  • the first problem is the energy density of the battery.
  • zinc-nickel batteries are generally limited by the energy density of the electrodes.
  • the specific energy of the overall battery is 30Wh/Kg-50Wh/Kg, and the overall energy density is relatively low.
  • the second problem is the deformation of the electrode and the formation of zinc dendrites that occur at the negative electrode.
  • the metal zinc of the anode is oxidized to zinc ions and moves into the electrolyte. Then, due to the poor solubility of zinc ions in the alkaline electrolyte, these ions are deposited as zinc oxide particles at almost the same time.
  • zinc oxide particles are transformed into zinc particles. These zinc particles can move downwards in long-term cycles due to gravity, and this can cause changes in the shape of the anode.
  • Zinc particles can also form zinc dendrites on the anode. Changes in the shape of the anode can cause energy attenuation, and zinc dendrites can cause sudden failure of the battery.
  • the main technical problem solved by the utility model is to provide a high specific energy one-negative multiple positive zinc-nickel flow battery, which solves the problem of low specific energy of traditional zinc-nickel batteries and the problem of low cycle times caused by zinc dendrites.
  • the utility model adopts the following technical schemes:
  • a high specific energy negative multi-positive zinc-nickel flow battery comprising a positive electrode, a negative electrode, a separator, an electrolyte, a supporting material, and a battery casing.
  • the positive and negative electrodes are filled with a supporting material, and the separator is in the positive electrode.
  • the single positive electrode is composed of a plurality of positive electrodes in parallel.
  • multiple positive plates are designed in parallel to form the positive electrode of the battery.
  • a negative-to-multiple positive battery structure doubles the specific energy of the battery.
  • the specific energy can reach 100Wh/Kg-200Wh/Kg, which solves the traditional zinc-nickel battery. It’s a question of confession than energy.
  • the electrolyte concentration in the battery can be evenly distributed, inhibit the generation of zinc dendrites, and at the same time, the generated zinc oxide and other deposits will be washed away with the flow of electrolyte to avoid
  • the production of zinc crystal branches solves the problem that the zinc crystal branches will cause the battery to suddenly fail, and improves the service life of the battery.
  • the single positive electrode is designed to be composed of sintered nickel positive electrode sheets, and the number of the positive electrode sheets in the single positive electrode is 2-5 pieces.
  • the number of positive plates is too small to significantly increase the specific energy of the battery.
  • the number of positive plates is too large, too much zinc ions are oxidized in the electrolyte, and the solubility of zinc ions in alkaline electrolyte is poor, and they will be deposited as zinc oxide particles, which will move downward by gravity during long-term cycles. , Will cause changes in the shape of the anode, and zinc particles can also form zinc dendrites on the anode.
  • the number of positive plates in the single positive electrode designed in this application is three.
  • the specific energy of the battery can be significantly increased, and excessive zinc ions can be avoided to form zinc dendrites.
  • the positive electrode plates are designed to be separated by a support material.
  • the support material is used to ensure the filling of the electrolyte between the positive electrodes, and at the same time to fix and space the positive electrodes.
  • the support material designed in this application is an alkali-resistant PP or PE three-dimensional porous support material, and the thickness is 0.5 mm-1 mm.
  • the support material Since the electrolyte is an alkaline solution, the support material must have alkali resistance; at the same time, the use of porous three-dimensional support materials can enable the negative electrode to bear more zinc deposition. In addition, due to its three-dimensional structure, the electrolyte can be deposited on the positive electrode sheet. It can flow smoothly between the positive and negative poles.
  • the negative electrode designed in this application is composed of a stretched copper mesh and a stretched stainless steel mesh, and the thickness is 0.1 mm-1 mm.
  • the negative electrode receives the electric ions in the electrolyte through the copper mesh, and a reduction reaction occurs to maintain the balance of the electric ions in the electrolyte.
  • the supporting material between the positive electrode plates is designed as a single piece, and the number of supporting materials on the surface of the negative electrode is 2-3 pieces.
  • the surface of the negative electrode is provided with 2-3 pieces of support material to increase the capacity of the negative electrode, so that more zinc can be deposited inside the three-dimensional support material when the battery is charged to ensure capacity matching with multiple positive electrodes.
  • the present application designs the internal positive and negative electrodes of the battery to be arranged at intervals, and the internal electrodes of the battery are in a parallel structure. All the negative electrodes and all the single positive electrodes in the battery are connected in parallel through the positive electrode current collector and the negative electrode current collector to form the total positive and total negative of the external circuit, which further improves the specific energy of the battery.
  • the electrolyte enters from the bottom of the battery through a pump, flows out from the upper part, and continuously circulates inside the battery during charging and discharging, forming a liquid flow system.
  • the use of a flowing electrolyte makes the electrolyte concentration distribution in the battery uniform, inhibits the generation of zinc dendrites, and at the same time washes away the generated zinc oxide and other deposits along with the flow of the electrolyte, without causing the problem of zinc dendrites.
  • the positive electrode of the battery is composed of multiple positive plates in parallel, which doubles the specific energy of a battery with a positive-to-negative battery structure.
  • the specific energy can reach 100Wh/Kg-200Wh/Kg;
  • the use of flowing electrolyte makes the electrolyte concentration distribution in the battery uniform, inhibits the generation of zinc dendrites, and at the same time causes the zinc oxide and other deposits produced to follow the electrolyte It can be washed away by the flow and wash away, and the problem of zinc crystal branches will not occur; (3)
  • the use of porous three-dimensional support materials allows the negative electrode to bear more zinc deposition.
  • the electrolyte can be between the positive and negative electrodes.
  • the space can flow smoothly.
  • the zinc-air battery of the present invention does not contain any materials that can easily cause combustion or explosion, has high safety, low cost, and has great promotion value.
  • Figure 1 is a schematic diagram of a high-specific energy-negative multi-positive zinc-nickel flow battery of the present invention.
  • the main technical problem solved by the utility model is to provide a high specific energy one-negative multi-positive zinc-nickel flow battery, which solves the problem of low specific energy of the traditional zinc-nickel battery and the problem of low cycle times caused by zinc dendrites.
  • the utility model adopts the following technical schemes:
  • the present utility model designs a high specific energy one-negative poly-positive zinc-nickel flow battery, which includes a positive electrode, a negative electrode 3, a separator 6, an electrolyte 5, a support material, and a battery casing 1.
  • the positive electrode and The negative electrode 3 is filled with a support material, the separator 6 is between the positive electrode and the negative electrode 3, and the single positive electrode is composed of multiple positive electrodes in parallel.
  • multiple positive plates are designed in parallel to form the positive electrode of the battery.
  • a negative-to-multiple positive battery structure doubles the specific energy of the battery.
  • the specific energy can reach 100Wh/Kg-200Wh/Kg, which solves the traditional zinc-nickel battery. It’s a question of confession than energy.
  • the concentration distribution of the electrolyte 5 in the battery can be evenly distributed, and the generation of zinc dendrites can be suppressed.
  • the present invention designs that the single positive electrode 7 is composed of sintered nickel positive plates, and the number of positive plates in the single positive electrode 7 is 2-5 pieces.
  • the number of positive plates is too small to significantly increase the specific energy of the battery.
  • the number of positive plates is too large, too much zinc ions are oxidized in electrolyte 5, and the solubility of zinc ions in alkaline electrolyte 5 is poor, and they will be deposited as zinc oxide particles, which will be affected by gravity during long-term cycles. Moving down will cause the shape of the anode to change, and zinc particles can also form zinc dendrites on the anode.
  • the number of positive plates in the single positive electrode 7 designed by the present invention is 3 pieces.
  • the specific energy of the battery can be significantly increased, and excessive zinc ions can be avoided to form zinc dendrites.
  • the present invention designs the positive electrode plates to be separated by a support material.
  • the support material is used to ensure the filling of the electrolyte 5 between the positive electrodes, and at the same time, is used to fix and separate the positive electrodes.
  • the support material of the present invention is designed to be an alkali-resistant three-dimensional porous support material of PP or PE, and the thickness is 0.5 mm-1 mm.
  • the support material Since the electrolyte 5 is an alkaline solution, the support material must have alkali resistance; at the same time, the use of a porous three-dimensional support material can enable the negative electrode 3 to bear more zinc deposition. In addition, due to its three-dimensional structure, the electrolyte 5 can It can flow smoothly between the positive plates and between the positive electrode and the negative electrode 3.
  • the negative electrode 3 of the present invention is designed to be composed of a stretched copper mesh and a stretched stainless steel mesh, and the thickness is 0.1 mm-1 mm.
  • the negative electrode 3 receives the electric ions in the electrolyte 5 through the copper mesh, and a reduction reaction occurs to maintain the balance of the electric ions in the electrolyte 5.
  • the present invention designs a single piece of supporting material between the positive electrode sheets, and the number of supporting materials on the surface of the negative electrode 3 is 2-3 pieces.
  • the surface of the negative electrode 3 is provided with 2-3 pieces of support material to increase the capacity of the negative electrode 3, so that more zinc can be deposited inside the three-dimensional support material when the battery is charged to ensure capacity matching with multiple positive electrodes.
  • the present invention designs the internal positive electrode and negative electrode 3 of the battery to be arranged at intervals, and the internal electrodes of the battery are in a parallel structure. All the negative electrodes 3 and all the single positive electrodes 7 in the battery are connected in parallel through the positive electrode current collector 8 and the negative electrode current collector 9 to form the total positive and total negative of the external circuit, which further improves the specific energy of the battery.
  • the electrolyte 5 enters from the bottom of the battery through a pump, flows out from the upper part, and continuously circulates inside the battery during charging and discharging, forming a liquid flow system.
  • the use of flowing electrolyte 5 makes the concentration distribution of electrolyte 5 in the battery uniform, inhibits the generation of zinc dendrites, and at the same time washes away the generated zinc oxide and other deposits along with the flow of electrolyte 5, without the problem of zinc dendrite .
  • a high specific energy one-negative multi-positive zinc-nickel flow battery is designed.
  • Three sintered nickel positive plates are connected in parallel to form a single positive electrode 7, and a positive electrode is added between the three positive plates.
  • the support material 4 is used to ensure the filling of the electrolyte 5 between the positive electrodes;
  • the negative electrode 3 is located on both sides of the single positive electrode 7, and the surface of the negative electrode 3 is attached to the negative electrode support material 2, which is used to increase the capacity of the negative electrode 3, so that the battery can be charged
  • a separator 6 separates the single positive electrode 7 and the negative electrode 3 to ensure that the positive electrode and the negative electrode 3 of the battery will not be caused by zinc particles or zinc dendrites
  • the electrolyte 5 is introduced from the bottom of the battery through the pump, and flows out from the top of the symmetry plane, forming a liquid flow system.
  • a single positive electrode 7 is composed of multiple pieces of sintered nickel electrodes in parallel. The number can be selected from 2 to 5 pieces. Its specific energy is 2-4 times that of 1 positive to 1 negative battery.
  • a single positive electrode 7 composed of multiple pieces of sintered nickel electrodes in parallel is All the negative electrodes 3 and all the single positive electrodes 7 are connected in parallel through the positive electrode current collector 8 and the negative electrode current collector 9 to form the total positive and total negative of the external circuit.

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Abstract

The present utility model provides a high-specific-energy zinc-nickel flow battery having one negative electrode and multiple positive electrodes. The present zinc-nickel flow battery uses multiple positive electrode pieces connected in parallel to form a single positive electrode, so as to correspond to a negative electrode, thereby forming a battery structure in which multiple positive electrodes correspond to one negative electrode. The total capacity of a battery is increased in a confined space, so that the specific energy of the battery is greatly increased; in addition, a flow system is used to make the capacity of an active material match the capacity of a positive electrode; moreover, a three-dimensional mesh support material is used on the surface of the negative electrode, so that the capacity of the negative electrode is greatly increased, and the capacity of the negative electrode of the battery also effectively matches the capacity of the multiple positive electrodes. In the zinc-nickel flow battery of the present utility model, the specific energy of the battery can reach 100 Wh/Kg to 200 Wh/Kg, and the number of cycles of the battery exceeds 2000.

Description

一种高比能量的一负多正锌镍液流电池A high specific energy one-negative multi-positive zinc-nickel flow battery 技术领域Technical field
本实用新型涉及锌离子电池领域，特别涉及一种高比能量的一负多正锌镍液流电池。The utility model relates to the field of zinc ion batteries, in particular to a high specific energy one-negative poly-positive zinc-nickel flow battery.
背景技术Background technique
在当今能源领域，开发利用太阳能、风能等可再生能源越来越受到人们的关注，为了实现供电的稳定性，需要开发高效的大规模储能技术。二次电池作为一种重要的储能技术，得到了研究开发，并逐步被推向市场。其中，锂离子电池是被广泛使用的一种电池，但是由于其潜在的安全性，限制了其大规模储能领域的发展，另外，铅酸电池由于比能量低和铅污染的问题，也难以被市场接受，第三种较为可能性的储能电池，全钒液流电池，克服了安全性的问题和能量的问题，但是由于其高昂的成本，在市场化过程中也举步维艰。In today's energy field, the development and utilization of renewable energy such as solar and wind energy has attracted more and more attention. In order to achieve the stability of power supply, it is necessary to develop high-efficiency large-scale energy storage technology. As an important energy storage technology, secondary batteries have been researched and developed and are gradually being introduced to the market. Among them, lithium-ion battery is a widely used battery, but due to its potential safety, it limits its development in the field of large-scale energy storage. In addition, lead-acid batteries are also difficult due to the problems of low specific energy and lead pollution. Accepted by the market, the third more possible energy storage battery, the all-vanadium flow battery, overcomes the safety and energy problems, but due to its high cost, it is also struggling in the process of marketization.
人类对于锌镍电池(Nickel-zinc secondary battery)的研究其实已经有一百多年的历史了，由于人们对环境问题的关注，锌镍电池作为一种清洁能源相当大的优势；锌镍电池具有工作电压高、能量密度高、安全性好、成本低等优点，国内锌镍电池生产已经产业化，据称美国能杰与中建集团达成协议，在安徽淮南建立全球最大的镍锌电池研发与生产基地，总投资超过100亿美元，可见镍锌电池已引起投资者的巨大兴趣。吉林卓尔科技有限公司是一家以生产锌镍二次电池的专业厂家，循环寿命可达400次以上，由此可见，随着技术的进步， 锌镍电池中原来存在的问题基本都得到了有效的解决。因其在替代一次碱性电池、镉镍和氢镍电池方面具有很明显的优势，许多工厂已经开始批量规模化生产。锌镍电池具有成本低，比能量高，安全环保，因此，作为动力电池优势明显，是铅酸电池理想的替代品。但由于充放电产生的锌枝晶、溶解等问题没有得到彻底解决，因此未能大规模应用。随着社会的发展，人们对高能、低廉价格、环保、安全电池的需求日益旺盛，尤其是最近几年内，国内外科研机构以及企业单位对锌镍电池的研究成果较为突出。Humans’ research on nickel-zinc secondary battery (Nickel-zinc secondary battery) has a history of more than one hundred years. Due to people’s concern about environmental issues, zinc-nickel batteries have considerable advantages as a clean energy source; zinc-nickel batteries have With the advantages of high working voltage, high energy density, good safety, and low cost, domestic zinc-nickel battery production has been industrialized. It is said that the United States Nengjie and China State Construction Group have reached an agreement to establish the world's largest nickel-zinc battery research and development and development in Huainan, Anhui. The production base, with a total investment of more than 10 billion U.S. dollars, shows that nickel-zinc batteries have aroused great interest from investors. Jilin Zall Technology Co., Ltd. is a professional manufacturer of zinc-nickel secondary batteries, with a cycle life of more than 400 times. It can be seen that with the advancement of technology, the original problems in zinc-nickel batteries have basically been effective The solution. Because of its obvious advantages in replacing primary alkaline batteries, nickel-cadmium and nickel-hydrogen batteries, many factories have begun mass production. Zinc-nickel batteries have low cost, high specific energy, safety and environmental protection. Therefore, they have obvious advantages as power batteries and are ideal substitutes for lead-acid batteries. However, since the problems of zinc dendrites and dissolution caused by charging and discharging have not been completely solved, it has not been applied on a large scale. With the development of society, people's demand for high-energy, low-cost, environmentally friendly, and safe batteries is growing. Especially in recent years, domestic and foreign scientific research institutions and enterprises have made outstanding research results on zinc-nickel batteries.
针对可再充锌镍电池的商业化，目前存在两个主要的技术问题：Regarding the commercialization of rechargeable zinc-nickel batteries, there are currently two main technical problems:
第一个问题是电池能量密度的问题，目前锌镍蓄电池，普遍由于电极的能量密度的限制，整体的电池比能量在30Wh/Kg-50Wh/Kg，整体能量密度较低。The first problem is the energy density of the battery. At present, zinc-nickel batteries are generally limited by the energy density of the electrodes. The specific energy of the overall battery is 30Wh/Kg-50Wh/Kg, and the overall energy density is relatively low.
第二个问题是在负极发生的电极形变和锌枝晶的形成。在传统的可再充电锌镍电池中，在放电阶段，阳极的金属锌被氧化为锌离子并移动到电解液中。然后，由于锌离子在碱性电解液中的差的溶解性，几乎在同时，这些离子被沉积为氧化锌粒子。在充电阶段，氧化锌粒子转变成锌粒子。这些锌粒子可由于重力在长期循环中向下移动，而这会导致阳极形状的变化。锌粒子也可以在阳极上形成锌枝晶。阳极的形状的变化可导致能量衰减，而锌枝晶会导致电池的突然失效。The second problem is the deformation of the electrode and the formation of zinc dendrites that occur at the negative electrode. In a conventional rechargeable zinc-nickel battery, during the discharge phase, the metal zinc of the anode is oxidized to zinc ions and moves into the electrolyte. Then, due to the poor solubility of zinc ions in the alkaline electrolyte, these ions are deposited as zinc oxide particles at almost the same time. During the charging phase, zinc oxide particles are transformed into zinc particles. These zinc particles can move downwards in long-term cycles due to gravity, and this can cause changes in the shape of the anode. Zinc particles can also form zinc dendrites on the anode. Changes in the shape of the anode can cause energy attenuation, and zinc dendrites can cause sudden failure of the battery.
实用新型内容Utility model content
本实用新型主要解决的技术问题是提供一种高比能量的一负多正锌镍液流电池，解决了传统锌镍电池比能量较低的问题和锌枝晶导致循环次数较低的问 题。本实用新型采用如下技术方案：The main technical problem solved by the utility model is to provide a high specific energy one-negative multiple positive zinc-nickel flow battery, which solves the problem of low specific energy of traditional zinc-nickel batteries and the problem of low cycle times caused by zinc dendrites. The utility model adopts the following technical schemes:
一种高比能量的一负多正锌镍液流电池，包括正极、负极、隔膜、电解液、支撑材料、电池外壳组成，所述正负极间有支撑材料进行填充，所述隔膜在正极和负极之间，所述单个正极由多片正极片并联组成。A high specific energy negative multi-positive zinc-nickel flow battery, comprising a positive electrode, a negative electrode, a separator, an electrolyte, a supporting material, and a battery casing. The positive and negative electrodes are filled with a supporting material, and the separator is in the positive electrode. Between the positive electrode and the negative electrode, the single positive electrode is composed of a plurality of positive electrodes in parallel.
本申请中通过设计多片正极片并联组成电池的正极，一负对多正的电池结构成倍提升了电池的比能量，比能量可以达到100Wh/Kg-200Wh/Kg，解决了传统锌镍电池比能量交底的问题。同时通过设计液流电池，采用流动的电解液，可以使电池内电解液浓度分布均匀，抑制锌枝晶的产生，同时将产生的氧化锌等沉积物随着电解液的流动而冲刷掉，避免产生锌晶枝，解决了锌晶枝会导致电池突然失效的问题，提高了电池的使用寿命。In this application, multiple positive plates are designed in parallel to form the positive electrode of the battery. A negative-to-multiple positive battery structure doubles the specific energy of the battery. The specific energy can reach 100Wh/Kg-200Wh/Kg, which solves the traditional zinc-nickel battery. It’s a question of confession than energy. At the same time, by designing a flow battery and using a flowing electrolyte, the electrolyte concentration in the battery can be evenly distributed, inhibit the generation of zinc dendrites, and at the same time, the generated zinc oxide and other deposits will be washed away with the flow of electrolyte to avoid The production of zinc crystal branches solves the problem that the zinc crystal branches will cause the battery to suddenly fail, and improves the service life of the battery.
进一步的，本申请设计所述单个正极由烧结镍正极片组成，所述单个正极中正极片的数量为2-5片。正极片的数量过少，不能显著的提升电池的比能量。但是正极片的数量过多时，电解液中被氧化的锌离子过多，而锌离子在碱性电解液中的溶解性较差，会沉积为氧化锌粒子，在长期循环中受重力向下移动，会导致阳极形状的变化，锌粒子也可以在阳极上形成锌枝晶。Further, in the present application, the single positive electrode is designed to be composed of sintered nickel positive electrode sheets, and the number of the positive electrode sheets in the single positive electrode is 2-5 pieces. The number of positive plates is too small to significantly increase the specific energy of the battery. However, when the number of positive plates is too large, too much zinc ions are oxidized in the electrolyte, and the solubility of zinc ions in alkaline electrolyte is poor, and they will be deposited as zinc oxide particles, which will move downward by gravity during long-term cycles. , Will cause changes in the shape of the anode, and zinc particles can also form zinc dendrites on the anode.
进一步的，本申请设计所述单个正极中正极片数量为3片。正极片为3片时既可以显著的提升电池的比能量又可以避免产生过多的锌离子导致形成锌枝晶。Further, the number of positive plates in the single positive electrode designed in this application is three. When the number of positive plates is 3, the specific energy of the battery can be significantly increased, and excessive zinc ions can be avoided to form zinc dendrites.
进一步的，本申请设计所述正极片之间由支撑材料进行间隔隔开。支撑材料用来保证正极之间电解液的填充，同时用来固定并间隔开正极片。Further, in this application, the positive electrode plates are designed to be separated by a support material. The support material is used to ensure the filling of the electrolyte between the positive electrodes, and at the same time to fix and space the positive electrodes.
进一步的，本申请设计所述支撑材料为耐碱性的PP或PE三维多孔支撑材料，所述厚度为0.5mm-1mm。Further, the support material designed in this application is an alkali-resistant PP or PE three-dimensional porous support material, and the thickness is 0.5 mm-1 mm.
由于电解液为碱性溶液，因此支撑材料一定要具有耐碱性；同时采用多孔三维的支撑材料，可以使负极能够承担更多的锌沉积，此外由于其三维结构，使电解液能够在正极片间和正负极之间能够顺利流动，。Since the electrolyte is an alkaline solution, the support material must have alkali resistance; at the same time, the use of porous three-dimensional support materials can enable the negative electrode to bear more zinc deposition. In addition, due to its three-dimensional structure, the electrolyte can be deposited on the positive electrode sheet. It can flow smoothly between the positive and negative poles.
进一步的，本申请设计所述负极由拉伸铜网、拉伸不锈钢网组成，所述厚度为0.1mm-1mm。负极通过铜网接收电解液中电离子，发生还原反应，维持电解液中电离子平衡。Further, the negative electrode designed in this application is composed of a stretched copper mesh and a stretched stainless steel mesh, and the thickness is 0.1 mm-1 mm. The negative electrode receives the electric ions in the electrolyte through the copper mesh, and a reduction reaction occurs to maintain the balance of the electric ions in the electrolyte.
进一步的，本申请设计所述正极片之间支撑材料为单片，负极表面支撑材料数量为2-3片。Further, in the present application, the supporting material between the positive electrode plates is designed as a single piece, and the number of supporting materials on the surface of the negative electrode is 2-3 pieces.
正极片之间只需要保证电解液的填充就可以，同时为了现场正极区域，因此只需要单片支撑材料。而负极表面设置2-3片支撑材料，用来增加负极的容量，能够使电池在充电的时候在三维支撑材料内部沉积更多的锌，保证和多正极进行容量匹配。It is only necessary to ensure the electrolyte filling between the positive plates, and at the same time, only a single piece of support material is needed for the on-site positive electrode area. The surface of the negative electrode is provided with 2-3 pieces of support material to increase the capacity of the negative electrode, so that more zinc can be deposited inside the three-dimensional support material when the battery is charged to ensure capacity matching with multiple positive electrodes.
进一步的，本申请设计所述电池内部正极和负极间隔排列，所述电池内部电极为并联结构。电池中所有的负极和所有的单个正极进行并联，通过正极集流体和负极集流体进行连接，形成外电路的总正和总负，进一步的提升了电池的比能量。Further, the present application designs the internal positive and negative electrodes of the battery to be arranged at intervals, and the internal electrodes of the battery are in a parallel structure. All the negative electrodes and all the single positive electrodes in the battery are connected in parallel through the positive electrode current collector and the negative electrode current collector to form the total positive and total negative of the external circuit, which further improves the specific energy of the battery.
所述电解液通过泵从电池底部进入，从上部流出，充放电时在电池内部不断循环，形成液流***。采用流动的电解液，使电池内电解液浓度分布均匀， 抑制锌枝晶的产生，同时将产生的氧化锌等沉积物随着电解液的流动而冲刷掉，不会产生锌晶枝问题。The electrolyte enters from the bottom of the battery through a pump, flows out from the upper part, and continuously circulates inside the battery during charging and discharging, forming a liquid flow system. The use of a flowing electrolyte makes the electrolyte concentration distribution in the battery uniform, inhibits the generation of zinc dendrites, and at the same time washes away the generated zinc oxide and other deposits along with the flow of the electrolyte, without causing the problem of zinc dendrites.
由于上述技术方案的运用，本实用新型与现有技术相比具有下列优势效果：Due to the application of the above-mentioned technical solutions, the present utility model has the following advantages and effects compared with the prior art:
提供了一种高比能量的一负多正锌镍液流电池，(1)采用多片正极片并联的方式组成电池的正极，比一正对一负的电池结构电池比能量成倍提升，比能量能够达到100Wh/Kg-200Wh/Kg；(2)采用流动的电解液，使电池内电解液浓度分布均匀，抑制锌枝晶的产生，同时将产生的氧化锌等沉积物随着电解液的流动而冲刷掉，不会产生锌晶枝问题；(3)采用多孔三维的支撑材料，使负极能够承担更多的锌沉积，另外由于其三维结构，使电解液能够在正极片间和正负极之间能够顺利流动，(4)本实用新型锌空电池不含任何容易导致燃烧或***的材料，安全性高，成本低，有很大推广价值。Provides a high specific energy one-negative multi-positive zinc-nickel flow battery. (1) The positive electrode of the battery is composed of multiple positive plates in parallel, which doubles the specific energy of a battery with a positive-to-negative battery structure. The specific energy can reach 100Wh/Kg-200Wh/Kg; (2) The use of flowing electrolyte makes the electrolyte concentration distribution in the battery uniform, inhibits the generation of zinc dendrites, and at the same time causes the zinc oxide and other deposits produced to follow the electrolyte It can be washed away by the flow and wash away, and the problem of zinc crystal branches will not occur; (3) The use of porous three-dimensional support materials allows the negative electrode to bear more zinc deposition. In addition, due to its three-dimensional structure, the electrolyte can be between the positive and negative electrodes. The space can flow smoothly. (4) The zinc-air battery of the present invention does not contain any materials that can easily cause combustion or explosion, has high safety, low cost, and has great promotion value.
附图说明Description of the drawings
图1是本实用新型一种高比能量的一负多正锌镍液流电池示意图。Figure 1 is a schematic diagram of a high-specific energy-negative multi-positive zinc-nickel flow battery of the present invention.
附图说明：1、电池外壳；2、负极支撑材料；3、负极；4、正极支撑材料；5、电解液；6、隔膜；7、单个正极；8、正极集流体；9、负极集流体。Brief description of the drawings: 1. Battery case; 2. Negative electrode support material; 3. Negative electrode; 4. Positive electrode support material; 5. Electrolyte; 6. Separator; 7. Single positive electrode; 8. Positive electrode current collector; 9. Negative electrode current collector. .
具体实施方式detailed description
下面结合实施例对本实用新型做进一步的说明，以使本实用新型的优点和特征能更易于被本领域技术人员理解，从而对本实用新型的保护范围做出更为清楚明确的界定。Hereinafter, the present utility model will be further explained in conjunction with the embodiments, so that the advantages and features of the present utility model can be more easily understood by those skilled in the art, so as to make a clearer and clearer definition of the protection scope of the present utility model.
本实用新型主要解决的技术问题是提供一种高比能量的一负多正锌镍液流电池，解决了传统锌镍电池比能量较低的问题和锌枝晶导致循环次数较低的问题。本实用新型采用如下技术方案：The main technical problem solved by the utility model is to provide a high specific energy one-negative multi-positive zinc-nickel flow battery, which solves the problem of low specific energy of the traditional zinc-nickel battery and the problem of low cycle times caused by zinc dendrites. The utility model adopts the following technical schemes:
具体实施时，本实用新型设计了一种高比能量的一负多正锌镍液流电池，包括正极、负极3、隔膜6、电解液5、支撑材料、电池外壳1组成，所述正极和负极3间有支撑材料进行填充，所述隔膜6在正极和负极3之间，所述单个正极由多片正极片并联组成。In specific implementation, the present utility model designs a high specific energy one-negative poly-positive zinc-nickel flow battery, which includes a positive electrode, a negative electrode 3, a separator 6, an electrolyte 5, a support material, and a battery casing 1. The positive electrode and The negative electrode 3 is filled with a support material, the separator 6 is between the positive electrode and the negative electrode 3, and the single positive electrode is composed of multiple positive electrodes in parallel.
本申请中通过设计多片正极片并联组成电池的正极，一负对多正的电池结构成倍提升了电池的比能量，比能量可以达到100Wh/Kg-200Wh/Kg，解决了传统锌镍电池比能量交底的问题。同时通过设计液流电池，采用流动的电解液5，可以使电池内电解液5浓度分布均匀，抑制锌枝晶的产生，同时将产生的氧化锌等沉积物随着电解液5的流动而冲刷掉，避免产生锌晶枝，解决了锌晶枝会导致电池突然失效的问题，提高了电池的使用寿命。In this application, multiple positive plates are designed in parallel to form the positive electrode of the battery. A negative-to-multiple positive battery structure doubles the specific energy of the battery. The specific energy can reach 100Wh/Kg-200Wh/Kg, which solves the traditional zinc-nickel battery. It’s a question of confession than energy. At the same time, by designing the flow battery and using the flowing electrolyte 5, the concentration distribution of the electrolyte 5 in the battery can be evenly distributed, and the generation of zinc dendrites can be suppressed. At the same time, the generated zinc oxide and other deposits will be washed away with the flow of the electrolyte 5 To avoid the generation of zinc crystal branches, it solves the problem that the zinc crystal branches will cause the battery to fail suddenly, and improves the service life of the battery.
具体实施时，本实用新型设计所述单个正极7由烧结镍正极片组成，所述单个正极7中正极片的数量为2-5片。正极片的数量过少，不能显著的提升电池的比能量。但是正极片的数量过多时，电解液5中被氧化的锌离子过多，而锌离子在碱性电解液5中的溶解性较差，会沉积为氧化锌粒子，在长期循环中受重力向下移动，会导致阳极形状的变化，锌粒子也可以在阳极上形成锌枝晶。In specific implementation, the present invention designs that the single positive electrode 7 is composed of sintered nickel positive plates, and the number of positive plates in the single positive electrode 7 is 2-5 pieces. The number of positive plates is too small to significantly increase the specific energy of the battery. However, when the number of positive plates is too large, too much zinc ions are oxidized in electrolyte 5, and the solubility of zinc ions in alkaline electrolyte 5 is poor, and they will be deposited as zinc oxide particles, which will be affected by gravity during long-term cycles. Moving down will cause the shape of the anode to change, and zinc particles can also form zinc dendrites on the anode.
具体实施时，本实用新型设计所述单个正极7中正极片数量为3片。正极片为3片时既可以显著的提升电池的比能量又可以避免产生过多的锌离子导致 形成锌枝晶。In specific implementation, the number of positive plates in the single positive electrode 7 designed by the present invention is 3 pieces. When the number of positive plates is 3, the specific energy of the battery can be significantly increased, and excessive zinc ions can be avoided to form zinc dendrites.
具体实施时，本实用新型设计所述正极片之间由支撑材料进行间隔隔开。支撑材料用来保证正极之间电解液5的填充，同时用来固定并间隔开正极片。In specific implementation, the present invention designs the positive electrode plates to be separated by a support material. The support material is used to ensure the filling of the electrolyte 5 between the positive electrodes, and at the same time, is used to fix and separate the positive electrodes.
具体实施时，本实用新型设计所述支撑材料为耐碱性的PP或PE三维多孔支撑材料，所述厚度为0.5mm-1mm。In specific implementation, the support material of the present invention is designed to be an alkali-resistant three-dimensional porous support material of PP or PE, and the thickness is 0.5 mm-1 mm.
由于电解液5为碱性溶液，因此支撑材料一定要具有耐碱性；同时采用多孔三维的支撑材料，可以使负极3能够承担更多的锌沉积，此外由于其三维结构，使电解液5能够在正极片间和正极和负极3之间能够顺利流动，。Since the electrolyte 5 is an alkaline solution, the support material must have alkali resistance; at the same time, the use of a porous three-dimensional support material can enable the negative electrode 3 to bear more zinc deposition. In addition, due to its three-dimensional structure, the electrolyte 5 can It can flow smoothly between the positive plates and between the positive electrode and the negative electrode 3.
具体实施时，本实用新型设计所述负极3由拉伸铜网、拉伸不锈钢网组成，所述厚度为0.1mm-1mm。负极3通过铜网接收电解液5中电离子，发生还原反应，维持电解液5中电离子平衡。In specific implementation, the negative electrode 3 of the present invention is designed to be composed of a stretched copper mesh and a stretched stainless steel mesh, and the thickness is 0.1 mm-1 mm. The negative electrode 3 receives the electric ions in the electrolyte 5 through the copper mesh, and a reduction reaction occurs to maintain the balance of the electric ions in the electrolyte 5.
具体实施时，本实用新型设计所述正极片之间支撑材料为单片，负极3表面支撑材料数量为2-3片。In specific implementation, the present invention designs a single piece of supporting material between the positive electrode sheets, and the number of supporting materials on the surface of the negative electrode 3 is 2-3 pieces.
正极片之间只需要保证电解液5的填充就可以，同时为了现场正极区域，因此只需要单片支撑材料。而负极3表面设置2-3片支撑材料，用来增加负极3的容量，能够使电池在充电的时候在三维支撑材料内部沉积更多的锌，保证和多正极进行容量匹配。It is only necessary to ensure that the electrolyte 5 is filled between the positive plates. At the same time, for the on-site positive electrode area, only a single piece of supporting material is required. The surface of the negative electrode 3 is provided with 2-3 pieces of support material to increase the capacity of the negative electrode 3, so that more zinc can be deposited inside the three-dimensional support material when the battery is charged to ensure capacity matching with multiple positive electrodes.
具体实施时，本实用新型设计所述电池内部正极和负极3间隔排列，所述电池内部电极为并联结构。电池中所有的负极3和所有的单个正极7进行并联，通过正极集流体8和负极集流体9进行连接，形成外电路的总正和总负，进一 步的提升了电池的比能量。In specific implementation, the present invention designs the internal positive electrode and negative electrode 3 of the battery to be arranged at intervals, and the internal electrodes of the battery are in a parallel structure. All the negative electrodes 3 and all the single positive electrodes 7 in the battery are connected in parallel through the positive electrode current collector 8 and the negative electrode current collector 9 to form the total positive and total negative of the external circuit, which further improves the specific energy of the battery.
所述电解液5通过泵从电池底部进入，从上部流出，充放电时在电池内部不断循环，形成液流***。采用流动的电解液5，使电池内电解液5浓度分布均匀，抑制锌枝晶的产生，同时将产生的氧化锌等沉积物随着电解液5的流动而冲刷掉，不会产生锌晶枝问题。The electrolyte 5 enters from the bottom of the battery through a pump, flows out from the upper part, and continuously circulates inside the battery during charging and discharging, forming a liquid flow system. The use of flowing electrolyte 5 makes the concentration distribution of electrolyte 5 in the battery uniform, inhibits the generation of zinc dendrites, and at the same time washes away the generated zinc oxide and other deposits along with the flow of electrolyte 5, without the problem of zinc dendrite .
具体实施时，如附图所示，设计一种高比能量的一负多正锌镍液流电池，由三片烧结镍正极片并联组成单个正极7，三片正极片之间间隔加一片正极支撑材料4，用来保证正极之间电解液5的填充；负极3位于单个正极7两侧，负极3表面贴合负极支撑材料2，用来增加负极3的容量，能够使电池在充电的时候在三维支撑材料内部沉积更多的锌，保证和多正极进行容量匹配；单个正极7和负极3之间有隔膜6进行隔开，保证电池正极和负极3不会因为锌颗粒或者锌枝晶导致电池的短路，电解液5通过泵由电池底部通入，从对称面顶部流出，形成液流***。In specific implementation, as shown in the figure, a high specific energy one-negative multi-positive zinc-nickel flow battery is designed. Three sintered nickel positive plates are connected in parallel to form a single positive electrode 7, and a positive electrode is added between the three positive plates. The support material 4 is used to ensure the filling of the electrolyte 5 between the positive electrodes; the negative electrode 3 is located on both sides of the single positive electrode 7, and the surface of the negative electrode 3 is attached to the negative electrode support material 2, which is used to increase the capacity of the negative electrode 3, so that the battery can be charged Deposit more zinc inside the three-dimensional support material to ensure capacity matching with multiple positive electrodes; a separator 6 separates the single positive electrode 7 and the negative electrode 3 to ensure that the positive electrode and the negative electrode 3 of the battery will not be caused by zinc particles or zinc dendrites When the battery is short-circuited, the electrolyte 5 is introduced from the bottom of the battery through the pump, and flows out from the top of the symmetry plane, forming a liquid flow system.
单个正极7由多片烧结镍电极并联组成，数量可以选择2-5片，其比能量是1正对1负电池的2-4倍，多片烧结镍电极并联组成的单个正极7，电池中所有的负极3和所有的单个正极7进行并联，通过正极集流体8和负极集流体9进行连接，形成外电路的总正和总负。A single positive electrode 7 is composed of multiple pieces of sintered nickel electrodes in parallel. The number can be selected from 2 to 5 pieces. Its specific energy is 2-4 times that of 1 positive to 1 negative battery. A single positive electrode 7 composed of multiple pieces of sintered nickel electrodes in parallel is All the negative electrodes 3 and all the single positive electrodes 7 are connected in parallel through the positive electrode current collector 8 and the negative electrode current collector 9 to form the total positive and total negative of the external circuit.
以上仅为本实用新型的实施例，并非因此限制本实用新型的专利范围，凡是利用本实用新型说明书及附图内容所作的等效结构或等效流程变换，或直接或间接运用在其他相关的技术领域，均同理包括在本实用新型的专利保护范围 内。The above are only examples of the utility model, and do not limit the scope of the utility model's patents. Any equivalent structure or equivalent process transformation made using the content of the utility model description and drawings, or directly or indirectly applied to other related The technical field is similarly included in the scope of patent protection of this utility model.

Claims (9)

  1. 一种高比能量的一负多正锌镍液流电池，包括正极、负极、隔膜、电解液、支撑材料、电池外壳组成，其特征在于，所述正极和负极间有支撑材料进行填充，所述隔膜在正极和负极之间，单个正极由多片正极片并联组成。A high-specific energy negative poly-positive zinc-nickel flow battery, comprising a positive electrode, a negative electrode, a separator, an electrolyte, a supporting material, and a battery shell. It is characterized in that a supporting material is filled between the positive electrode and the negative electrode. The diaphragm is between the positive electrode and the negative electrode, and a single positive electrode is composed of multiple positive electrodes in parallel.
  2. 根据权利要求1所述的一种高比能量的一负多正锌镍液流电池，其特征在于，所述单个正极由烧结镍正极片组成，所述单个正极中正极片的数量为2-5片。The one-negative multi-positive zinc-nickel flow battery with high specific energy according to claim 1, wherein the single positive electrode is composed of sintered nickel positive plates, and the number of positive plates in the single positive electrode is 2 5 slices.
  3. 根据权利要求1或2所述的一种高比能量的一负多正锌镍液流电池，其特征在于，所述单个正极中正极片数量为3片。The one-negative multi-positive zinc-nickel flow battery with high specific energy according to claim 1 or 2, wherein the number of positive plates in the single positive electrode is three.
  4. 根据权利要求1所述的一种高比能量的一负多正锌镍液流电池，其特征在于，所述正极片之间由支撑材料进行间隔隔开。The negative poly-positive zinc-nickel flow battery with high specific energy according to claim 1, wherein the positive electrode plates are separated by a support material.
  5. 根据权利要求1所述的一种高比能量的一负多正锌镍液流电池，其特征在于，所述支撑材料为耐碱性的PP或PE三维多孔支撑材料，所述厚度为0.5mm-1mm。The high specific energy one-negative poly-positive zinc-nickel flow battery according to claim 1, wherein the support material is an alkali-resistant PP or PE three-dimensional porous support material, and the thickness is 0.5 mm -1mm.
  6. 根据权利要求1所述的一种高比能量的一负多正锌镍液流电池，其特征在于，所述负极由拉伸铜网、拉伸不锈钢网组成，所述厚度为0.1mm-1mm。The high specific energy one-negative poly-positive zinc-nickel flow battery according to claim 1, wherein the negative electrode is composed of a stretched copper mesh and a stretched stainless steel mesh, and the thickness is 0.1mm-1mm .
  7. 根据权利要求1所述的一种高比能量的一负多正锌镍液流电池，其特征在于，所述正极片之间支撑材料为单片，负极表面支撑材料数量为2-3片。A high specific energy negative poly-positive zinc-nickel flow battery according to claim 1, wherein the support material between the positive electrode sheets is a single sheet, and the number of support materials on the surface of the negative electrode is 2-3 sheets.
  8. 根据权利要求1所述的一种高比能量的一负多正锌镍液流电池，其特征在于，电池内部正极和负极间隔排列，电池内部电极为并联结构。The one-negative multi-positive zinc-nickel flow battery with high specific energy according to claim 1, wherein the positive electrode and the negative electrode in the battery are arranged at intervals, and the internal electrodes of the battery are in a parallel structure.
  9. 根据权利要求1所述的一种高比能量的一负多正锌镍液流电池，其特征在于，所述电解液通过泵从电池底部进入，从上部流出，充放电时在电池内部不断循环，形成液流***。The one-negative multi-positive zinc-nickel flow battery with high specific energy according to claim 1, wherein the electrolyte enters from the bottom of the battery through a pump, flows out from the upper part, and continuously circulates inside the battery during charging and discharging. , Forming a liquid flow system.
PCT/CN2020/098453 2020-05-30 2020-06-28 High-specific-energy zinc-nickel flow battery having one negative electrode and multiple positive electrodes WO2021243774A1 (en)

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WO2018229880A1 (en) * 2017-06-13 2018-12-20 日立化成株式会社 Aqueous solution secondary battery
CN110459791A (en) * 2019-07-30 2019-11-15 苏州沃泰丰能电池科技有限公司 The method and zinc ion flow battery that zinc ion flow battery prevents zinc from depositing
EP3641041A1 (en) * 2018-10-16 2020-04-22 LANXESS Deutschland GmbH Carbon electrode for dichromate redox flow batteries

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WO2018229880A1 (en) * 2017-06-13 2018-12-20 日立化成株式会社 Aqueous solution secondary battery
CN108023108A (en) * 2017-12-06 2018-05-11 合肥伏雷科技有限公司 A kind of large power redox flow cell cathode integral structure
CN108808053A (en) * 2018-06-22 2018-11-13 浙江裕源储能科技有限公司 A kind of Zn-Ni liquid energy-storage battery
EP3641041A1 (en) * 2018-10-16 2020-04-22 LANXESS Deutschland GmbH Carbon electrode for dichromate redox flow batteries
CN110459791A (en) * 2019-07-30 2019-11-15 苏州沃泰丰能电池科技有限公司 The method and zinc ion flow battery that zinc ion flow battery prevents zinc from depositing

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