技术领域technical field
本发明属于物理化学领域，具体而言，涉及金属空气燃料电池系统及其应用。The invention belongs to the field of physical chemistry, and in particular relates to a metal-air fuel cell system and its application.
背景技术Background technique
金属空气燃料电池是一种将金属(或合金)与氧化剂自身的化学能通过电化学反应转化为电能的能量转换装置，反应在电解质中进行，总反应式M+1/2 H2O+1/4 O2＝M(OH)i，其中每摩尔金属M失去i摩尔电子，与i/4摩尔氧气发生反应。电化学反应的动力性不仅与催化剂的活性有关，还与电极表面与电解质状态紧密相关。一般的金属空气燃料电池是由金属阳极、电解液、空气阴极构成，其中，金属或其合金的颗粒、平板或其他特殊结构作为阳极，在反应中提供电子，空气膜电极作为阴极，催化氧气与水反应成为氢氧根离子，电解液一般由中性的盐水溶液或一定浓度的碱性溶液构成，从电解液中析出的金属氧化物沉积容易吸附在电极表面，是金属电极钝化的主要因素，并且积累的沉积物会占据很大电池内部空间。在阳极表面金属失去电子并与氢氧根结合以离子态进入电解液。在膜电极催化层的三相界面，氧气分子得到电子与水反应生成氢氧根离子进入电解液。总反应是金属与氧气反应为金属氧化物并溶解在电解液中，随着放电的进行，当电解液中金属氧化物浓度达到饱和时，反应产物逐渐从电解液中析出。金属氧化物沉积在电解液中逐渐增多，形成悬浊液，该悬浊液的颗粒物粒径均为纳米级，难以用普通的过滤方式去除，悬浮的沉积物将覆盖在电极表面，对于阳极，阻碍了金属失去电子的过程并增加了电极表面的阻抗，对于空气膜电极，减小了有效反应面积，阻碍后续的电化学反应，另外，随着放电的进行，反应产物积累量增大，一般反应产物的体积都会大于反应燃料的体积，严重挤占电解质的空间，在密封条件下甚至会增大电池内部压力，降低了电池性能甚至损坏膜电极与其他相关设备。Metal-air fuel cell is an energy conversion device that converts the chemical energy of metal (or alloy) and oxidant itself into electrical energy through electrochemical reaction. The reaction is carried out in the electrolyte. The total reaction formula is M+1/2 H2 O+1 /4 O2 =M(OH)i , where every mole of metal M loses i moles of electrons and reacts with i/4 moles of oxygen. The kinetics of the electrochemical reaction is not only related to the activity of the catalyst, but also closely related to the state of the electrode surface and electrolyte. A general metal-air fuel cell is composed of a metal anode, an electrolyte, and an air cathode. Among them, particles, flat plates, or other special structures of metal or its alloys are used as the anode to provide electrons in the reaction, and the air film electrode is used as the cathode to catalyze the exchange of oxygen and oxygen. Water reacts to become hydroxide ions. The electrolyte is generally composed of a neutral saline solution or a certain concentration of alkaline solution. The deposition of metal oxides precipitated from the electrolyte is easily adsorbed on the surface of the electrode, which is the main factor for the passivation of the metal electrode. , and the accumulated deposits will occupy a large internal space of the battery. The metal loses electrons on the surface of the anode and combines with hydroxide to enter the electrolyte in an ion state. At the three-phase interface of the membrane electrode catalytic layer, oxygen molecules get electrons and react with water to form hydroxide ions and enter the electrolyte. The overall reaction is that the metal and oxygen react to form metal oxides and dissolve in the electrolyte. As the discharge progresses, when the concentration of metal oxides in the electrolyte reaches saturation, the reaction products gradually precipitate from the electrolyte. The deposition of metal oxides in the electrolyte gradually increases to form a suspension. The particle size of the suspension is nano-scale, which is difficult to remove by ordinary filtration. The suspended sediment will cover the surface of the electrode. For the anode, It hinders the process of metal losing electrons and increases the impedance of the electrode surface. For air film electrodes, it reduces the effective reaction area and hinders the subsequent electrochemical reaction. In addition, as the discharge progresses, the accumulation of reaction products increases. The volume of the reaction product will be larger than the volume of the reaction fuel, seriously occupying the space of the electrolyte, and even increasing the internal pressure of the battery under sealed conditions, reducing the performance of the battery and even damaging the membrane electrode and other related equipment.
因此，有效去除在电解液中积累的金属氧化物沉积对于维持金属空气燃料电池的正常工作至关重要。Therefore, effective removal of metal oxide deposits accumulated in the electrolyte is crucial to maintain the normal operation of metal-air fuel cells.
溶液中沉积物的去除主要通过物理沉降、过滤和吸附，以及化学反应成大颗粒沉降和化学吸附或将沉积物转化为其他性质的产物的方式实现。在金属空气燃料电池电解液中，需要考虑整体燃料电池工作环境的稳定以及反应产物的回收难度，以便能实现金属耗材的再生、燃料的二次使用。The removal of sediment in the solution is mainly achieved by physical sedimentation, filtration and adsorption, as well as chemical reaction into large particle sedimentation and chemical adsorption or conversion of sediment into products of other properties. In the metal-air fuel cell electrolyte, it is necessary to consider the stability of the overall fuel cell working environment and the difficulty of recycling reaction products, so as to realize the regeneration of metal consumables and the secondary use of fuel.
为解决金属空气燃料电池中反应产物过量沉积，进而阻碍后续的电化学反应的问题，已有的一种通过更换电解液及其沉积物与设置较高工作温度来维持燃料电池正常运行，即提高金属空气燃料电池的温度到75℃，以提高反应产物在电解液中的溶解度，并根据放电容量，当反应产物沉积量比较多时，用液压泵将新的氢氧化钾溶液更换电池中的悬浊液，从而保证电池的正常工作。这种技术简单易行，但需要额外的电解液，而且为了保证较高的温度需要保温系统，增加燃料电池系统的体积与重量。In order to solve the problem of excessive deposition of reaction products in metal-air fuel cells, which hinders the subsequent electrochemical reaction, an existing method maintains the normal operation of the fuel cell by replacing the electrolyte and its deposits and setting a higher operating temperature, that is, increasing The temperature of the metal-air fuel cell is 75°C to increase the solubility of the reaction product in the electrolyte, and according to the discharge capacity, when the deposition of the reaction product is relatively large, use a hydraulic pump to replace the suspension in the battery with a new potassium hydroxide solution liquid, so as to ensure the normal operation of the battery. This technology is simple and easy, but requires additional electrolyte, and in order to ensure a higher temperature, an insulation system is required, which increases the volume and weight of the fuel cell system.
另一种基于化学沉淀反应的方法促进金属氧化物生成稳定的沉淀物，通过简单的过滤实现了反应产物的分离，主要通过向悬浮的电解液中添加一定量的Ca(OH)2，促进悬浊液的沉降，在通过简单的过滤将这些较大的沉降物分离出来，使得电解液的放电容量提升了30％。这种技术需要在放电过程中不断加入添加剂，改变了电解液成分，而且形成的产物增加了金属还原的成本。Another method based on chemical precipitation reaction promotes the formation of stable precipitates of metal oxides, and the separation of reaction products is achieved by simple filtration, mainly by adding a certain amount of Ca(OH)2 The sedimentation of the turbid liquid and the separation of these larger sediments by simple filtration have increased the discharge capacity of the electrolyte by 30%. This technology requires continuous addition of additives during the discharge process, which changes the composition of the electrolyte, and the products formed increase the cost of metal reduction.
综上，目前对处理电解液中反应产物的研究比较少，已有技术主要采用化学沉降或整体更换的方法，效果明显，但是依旧需要额外的电解液与添加剂，成本较大。对应的辅助模块对整个燃料电池系统的结构有较大的要求。To sum up, there are relatively few studies on the treatment of reaction products in the electrolyte. The existing technologies mainly adopt the method of chemical precipitation or overall replacement. The effect is obvious, but additional electrolyte and additives are still required, and the cost is relatively high. The corresponding auxiliary modules place great demands on the structure of the entire fuel cell system.
发明内容Contents of the invention
本发明旨在至少在一定程度上解决相关技术中的技术问题之一。为此，本发明的一个目的在于提出金属空气燃料电池系统及其应用，利用该系统不仅能解决金属氧化物的过量积累问题，还能抑制反应产物在电极表面的吸附，同时收集反应产物，使金属还原过程更加简单，实现了长时稳定的放电，提高了燃料电池系统的能量密度与使用寿命。The present invention aims to solve one of the technical problems in the related art at least to a certain extent. For this reason, an object of the present invention is to propose metal air fuel cell system and application thereof, utilize this system not only to solve the excessive accumulation problem of metal oxide, also can suppress the adsorption of reaction product on electrode surface, collect reaction product simultaneously, make The metal reduction process is simpler, realizing long-term stable discharge, and improving the energy density and service life of the fuel cell system.
根据本发明的一个方面，本发明提出了一种金属空气燃料电池系统，包括：According to one aspect of the present invention, the present invention proposes a metal-air fuel cell system, comprising:
电池堆，所述电池堆具有电解液出口和电解液入口；a battery stack having an electrolyte outlet and an electrolyte inlet;
过滤装置，所述过滤装置内具有多孔介质，所述过滤装置分别与所述电解液出口和电解液入口相连。A filter device, the filter device has a porous medium inside, and the filter device is respectively connected to the electrolyte outlet and the electrolyte inlet.
根据本发明上述实施例的金属空气燃料电池系统，包括电池堆和过滤装置，其中，在过滤装置内设置多孔介质可以对金属空气燃料电池的反应产物进行有效过滤和收集。由此，通过采用本发明提出的金属空气燃料电池系统不仅能够有效解决反应产物在电解液中过量积累的问题，还能抑制反应产物在电极表面的吸附并收集反应产物，实现电解液的再生和循环利用，使电解液成分与电极工作环境稳定，并使金属还原过程更加简单，实现长时稳定的放电，显著提高燃料电池系统的能量密度与使用寿命。The metal-air fuel cell system according to the above-mentioned embodiments of the present invention includes a cell stack and a filter device, wherein a porous medium is provided in the filter device to effectively filter and collect the reaction products of the metal-air fuel cell. Therefore, by adopting the metal-air fuel cell system proposed by the present invention, not only can effectively solve the problem of excessive accumulation of reaction products in the electrolyte, but also inhibit the adsorption of reaction products on the electrode surface and collect the reaction products, so as to realize the regeneration of the electrolyte and Recycling can stabilize the electrolyte composition and electrode working environment, simplify the metal reduction process, achieve long-term stable discharge, and significantly improve the energy density and service life of the fuel cell system.
另外，根据本发明上述实施例的金属空气燃料电池系统还可以具有如下附加的技术特征：In addition, the metal-air fuel cell system according to the above-mentioned embodiments of the present invention may also have the following additional technical features:
在本发明的一些实施例中，所述多孔介质为多孔钛滤芯、多孔镍滤芯或者多孔不锈钢滤芯。由此，可以显著提高多孔介质的结构稳定性以及过滤装置的过滤效果。In some embodiments of the present invention, the porous medium is a porous titanium filter element, a porous nickel filter element or a porous stainless steel filter element. As a result, the structural stability of the porous medium and the filtering effect of the filter device can be significantly improved.
在本发明的一些实施例中，所述多孔介质的平均孔径不大于10微米。由此，可以进一步提高过滤装置的过滤效果。In some embodiments of the present invention, the average pore diameter of the porous medium is not greater than 10 microns. Thereby, the filtering effect of the filtering device can be further improved.
在本发明的一些实施例中，所述多孔介质与所述过滤装置的电解液入口端之间限定有适于容纳沉淀物的过滤腔。由此，可以对金属空气燃料电池的反应产物进行有效收集。In some embodiments of the present invention, a filter cavity suitable for containing sediment is defined between the porous medium and the electrolyte inlet port of the filter device. Thus, the reaction products of the metal-air fuel cell can be efficiently collected.
在本发明的一些实施例中，金属空气燃料电池系统进一步包括：液压泵，所述液压泵设置在所述电解液出口和所述过滤装置之间，且适于对电解液进行加压过滤。由此，可以对进入过滤装置之前的过饱和电解液进行加压处理并进一步提高过滤装置的过滤效率。In some embodiments of the present invention, the metal-air fuel cell system further includes: a hydraulic pump, the hydraulic pump is arranged between the outlet of the electrolyte and the filtering device, and is suitable for filtering the electrolyte under pressure. Thus, the supersaturated electrolyte before entering the filter device can be pressurized and the filtration efficiency of the filter device can be further improved.
在本发明的一些实施例中，所述液压泵为蠕动泵。由此，可以进一步提高过滤效率。In some embodiments of the present invention, the hydraulic pump is a peristaltic pump. Thereby, filtration efficiency can be further improved.
根据本发明的第二个方面，本发明还提出了一种利用上述金属空气燃料电池系统实现稳定发电的方法，包括：According to the second aspect of the present invention, the present invention also proposes a method for realizing stable power generation by utilizing the above-mentioned metal-air fuel cell system, including:
使电池堆排出的饱和电解液进入过滤装置，在所述过滤装置内经过多孔介质过滤出沉淀物，以便得到净化电解液；The saturated electrolyte discharged from the battery stack enters the filter device, and the precipitate is filtered out through a porous medium in the filter device, so as to obtain a purified electrolyte;
使所述净化电解液进入电池堆。The purified electrolyte is passed into the stack.
由此，通过采用本发明上述实施例的实现金属空气燃料电池稳定发电的方法，不仅可以有效解决反应产物在电解液中过量积累的问题，还能抑制反应产物在电极表面的吸附并收集反应产物，实现电解液的再生和循环利用，使电解液成分与电极工作环境稳定，并使金属还原过程更加简单，实现长时稳定的放电，显著提高燃料电池系统的能量密度与使用寿命。Therefore, by adopting the method for realizing stable power generation of a metal-air fuel cell according to the above-mentioned embodiments of the present invention, not only the problem of excessive accumulation of reaction products in the electrolyte can be effectively solved, but also the adsorption of reaction products on the electrode surface can be inhibited and the reaction products can be collected. , realize the regeneration and recycling of the electrolyte, stabilize the electrolyte composition and electrode working environment, simplify the metal reduction process, realize long-term stable discharge, and significantly improve the energy density and service life of the fuel cell system.
另外，根据本发明上述实施例的实现金属空气燃料电池稳定发电的方法还可以具有如下附加的技术特征：In addition, the method for realizing stable power generation of a metal-air fuel cell according to the above-mentioned embodiments of the present invention may also have the following additional technical features:
在本发明的一些实施例中，实现金属空气燃料电池稳定发电的方法进一步包括：利用液压泵将所述饱和电解液泵入所述过滤层装置内。由此，可以对进入过滤装置之前的过饱和电解液进行加压处理并进一步提高过滤装置的过滤效率。In some embodiments of the present invention, the method for achieving stable power generation by a metal-air fuel cell further includes: using a hydraulic pump to pump the saturated electrolyte into the filter layer device. Thus, the supersaturated electrolyte before entering the filter device can be pressurized and the filtration efficiency of the filter device can be further improved.
在本发明的一些实施例中，所述饱和电解液在所述过滤层装置内过滤速度不应超过100cm/min，且过滤压力不应超过1MPa。由此，可以进一步提高过滤效果。In some embodiments of the present invention, the filtration speed of the saturated electrolyte in the filter layer device should not exceed 100 cm/min, and the filtration pressure should not exceed 1 MPa. Thereby, the filtering effect can be further improved.
在本发明的一些实施例中，实现金属空气燃料电池稳定发电的方法进一步包括：对所述过滤装置进行再生处理，所述再生处理包括：向所述过滤装置内逆向泵入水，以便对多孔介质进行解吸；利用弱酸或者弱碱溶液对经过所述解吸后的多孔介质进行清洗，以便获得再生后过滤装置。由此，不仅能够实现电解液的再生和循环利用，还能使过滤装置得到反复利用，整个循环使用过程不产生排放物。In some embodiments of the present invention, the method for realizing stable power generation of a metal-air fuel cell further includes: performing regeneration treatment on the filter device, and the regeneration treatment includes: reversely pumping water into the filter device, so that the porous medium performing desorption; using a weak acid or weak base solution to clean the desorbed porous medium so as to obtain a regenerated filter device. In this way, not only the regeneration and recycling of the electrolyte can be realized, but also the filtering device can be used repeatedly, and no discharge is generated during the whole recycling process.
附图说明Description of drawings
图1是根据本发明一个实施例的金属空气燃料电池系统的结构示意图。FIG. 1 is a schematic structural diagram of a metal-air fuel cell system according to an embodiment of the present invention.
图2是根据本发明又一个实施例的金属空气燃料电池系统的结构示意图。Fig. 2 is a schematic structural diagram of a metal-air fuel cell system according to yet another embodiment of the present invention.
图3是根据本发明一个实施例的过滤装置在过滤和再生过程中的液体流动方向示意图。Fig. 3 is a schematic diagram of the liquid flow direction during the filtration and regeneration process of the filter device according to an embodiment of the present invention.
图4是根据本发明一个实施例的过饱和电解液的过滤前后效果图。Fig. 4 is an effect diagram before and after filtration of a supersaturated electrolyte according to an embodiment of the present invention.
具体实施方式detailed description
下面详细描述本发明的实施例，所述实施例的示例在附图中示出，其中自始至终相同或类似的标号表示相同或类似的元件或具有相同或类似功能的元件。下面通过参考附图描述的实施例是示例性的，旨在用于解释本发明，而不能理解为对本发明的限制。Embodiments of the present invention are described in detail below, examples of which are shown in the drawings, wherein the same or similar reference numerals designate the same or similar elements or elements having the same or similar functions throughout. The embodiments described below by referring to the figures are exemplary and are intended to explain the present invention and should not be construed as limiting the present invention.
根据本发明的一个方面，本发明提出了一种金属空气燃料电池系统，如图1所示，包括：电池堆10和过滤装置20。其中，电池堆10具有电解液出口11和电解液入口12；过滤装置20内具有多孔介质21，过滤装置10分别与电解液出口11和电解液入口12相连。According to one aspect of the present invention, the present invention proposes a metal-air fuel cell system, as shown in FIG. 1 , comprising: a cell stack 10 and a filter device 20 . Wherein, the battery stack 10 has an electrolyte outlet 11 and an electrolyte inlet 12; a filter device 20 has a porous medium 21 inside, and the filter device 10 is connected to the electrolyte outlet 11 and the electrolyte inlet 12 respectively.
根据本发明上述实施例的金属空气燃料电池系统，包括电池堆10和过滤装置20，其中，在过滤装置20内设置多孔介质21可以对金属空气燃料电池的反应产物进行有效过滤和收集。具体地，将过饱和电解液送入过滤装置20后，电解液中的反应产物被吸附在多孔介质21中，该固体反应产物依靠相互吸附作用形成较大颗粒，并在多孔介质21的过滤作用下从电解液中分离出来，得到澄清的电解液。由此，通过采用本发明提出的金属空气燃料电池系统不仅能够有效解决反应产物在电解液中过量积累的问题，还能抑制反应产物在电极表面的吸附并收集反应产物，实现电解液的再生和循环利用，使电解液成分与电极工作环境稳定，并使金属还原过程更加简单，实现长时稳定的放电，显著提高燃料电池系统的能量密度与使用寿命。The metal-air fuel cell system according to the above embodiments of the present invention includes a cell stack 10 and a filter device 20, wherein the porous medium 21 is provided in the filter device 20 to effectively filter and collect the reaction products of the metal-air fuel cell. Specifically, after the supersaturated electrolyte is sent into the filter device 20, the reaction product in the electrolyte is adsorbed in the porous medium 21, and the solid reaction product forms larger particles by mutual adsorption, and is filtered by the porous medium 21. separated from the electrolyte to obtain a clear electrolyte. Therefore, by adopting the metal-air fuel cell system proposed by the present invention, not only can effectively solve the problem of excessive accumulation of reaction products in the electrolyte, but also inhibit the adsorption of reaction products on the electrode surface and collect the reaction products, so as to realize the regeneration of the electrolyte and Recycling can stabilize the electrolyte composition and electrode working environment, simplify the metal reduction process, achieve long-term stable discharge, and significantly improve the energy density and service life of the fuel cell system.
下面参考图1-3对本发明上述实施例的金属空气燃料电池系统进行详细描述。The metal-air fuel cell system of the above embodiment of the present invention will be described in detail below with reference to FIGS. 1-3 .
根据本发明的具体实施例，多孔介质21可以为多孔钛滤芯、多孔镍滤芯或者多孔不锈钢滤芯。多孔介质的材料对金属空气燃料电池反应产物的过滤效果有很大影响，例如，一般滤纸和镍网海绵滤芯的过滤效果差并且不利于过滤物回收，碳纸、碳布、玻璃纤维的过滤效果不佳且石英成分在强碱环境下稳定性差，不锈钢滤网过滤效果差且在强碱环境下自身耐腐蚀性差，泡沫镍过滤效果不佳且不耐高压、结构稳定性差等。由此，本发明选用的上述滤芯在中性、强碱性环境下均具有较好的稳定性，并能有效吸附、过滤沉淀物。由此，不仅可以显著提高多孔介质的结构稳定性，还能显著提高过滤装置20的过滤效果。此外，本发明采用的上述滤芯一定的过滤速度下还能耐受正、反向高压水流，并可通过弱酸或弱碱条件反复清洗，由此，还可以实现滤芯的反复利用。According to a specific embodiment of the present invention, the porous medium 21 may be a porous titanium filter element, a porous nickel filter element or a porous stainless steel filter element. The material of the porous medium has a great influence on the filtration effect of the metal air fuel cell reaction product. For example, the filtration effect of general filter paper and nickel mesh sponge filter element is poor and is not conducive to the recovery of filtrate. The filtration effect of carbon paper, carbon cloth and glass fiber Poor and quartz components have poor stability in strong alkaline environment, stainless steel filter has poor filtering effect and poor corrosion resistance in strong alkaline environment, foam nickel has poor filtering effect and is not resistant to high pressure, poor structural stability, etc. Therefore, the above-mentioned filter element selected by the present invention has better stability in neutral and strongly alkaline environments, and can effectively absorb and filter sediment. In this way, not only the structural stability of the porous medium can be significantly improved, but also the filtering effect of the filtering device 20 can be significantly improved. In addition, the above-mentioned filter element used in the present invention can withstand forward and reverse high-pressure water flow at a certain filtration speed, and can be repeatedly cleaned under weak acid or weak alkali conditions, thereby realizing the repeated use of the filter element.
根据本发明的具体实施例，可以选用钛粉作为原材料并烧结成多孔钛滤芯，由此，可以进一步提高对反应产物的过滤效果，实现电解液的反复清洁利用。According to a specific embodiment of the present invention, titanium powder can be selected as a raw material and sintered into a porous titanium filter element, thereby further improving the filtering effect on the reaction product and realizing repeated cleaning and utilization of the electrolyte.
根据本发明的具体实施例，多孔介质21的平均孔径可以不大于10微米。由此，可以进一步提高过滤装置20的过滤效果。金属氧化物悬浮物的过滤效果与滤芯的平均孔径有关，孔径越大，过滤阻力越小，但过滤效果越低；孔径越小，过滤阻力越大，但过滤效果越好。发明人通过大量实验发现，当多孔介质的孔径不超过10微米时，过滤效果几乎为100％且过滤阻力适中。此外，发明人还发现，将滤芯制作成棒状结构可以进一步加快过滤速度，提高过滤效率。According to a specific embodiment of the present invention, the average pore diameter of the porous medium 21 may not be greater than 10 microns. Thereby, the filtering effect of the filtering device 20 can be further improved. The filtering effect of metal oxide suspension is related to the average pore size of the filter element. The larger the pore size, the smaller the filtering resistance, but the lower the filtering effect; the smaller the pore size, the greater the filtering resistance, but the better the filtering effect. The inventor found through a large number of experiments that when the pore diameter of the porous medium is not more than 10 microns, the filtering effect is almost 100% and the filtering resistance is moderate. In addition, the inventors also found that making the filter element into a rod-shaped structure can further speed up the filtering speed and improve the filtering efficiency.
根据本发明的具体示例，多孔介质可21以为直径为10厘米、厚度为2毫米的圆柱状多孔钛滤芯，由此，可以进一步提高过滤效率。According to a specific example of the present invention, the porous medium 21 may be a cylindrical porous titanium filter core with a diameter of 10 cm and a thickness of 2 mm, thereby further improving the filtration efficiency.
根据本发明的具体实施例，如图2所示，多孔介质21与过滤装置20的电解液入口端之间可以限定有适于容纳沉淀物的过滤腔22。本发明中通过在过滤装置20中设置过滤腔，可以使从电解液中分离出来的反应产物在过滤腔中堆积起来，由此，可以对过滤出来的反应产物进行有效回收，并用以金属还原，进而实现燃料的循环利用。According to a specific embodiment of the present invention, as shown in FIG. 2 , a filter cavity 22 suitable for containing sediment may be defined between the porous medium 21 and the electrolyte inlet end of the filter device 20 . In the present invention, by providing a filter chamber in the filter device 20, the reaction product separated from the electrolyte can be accumulated in the filter chamber, thereby effectively recovering the filtered reaction product and using it for metal reduction, And then realize the recycling of fuel.
根据本发明的具体实施例，如图2所示，金属空气燃料电池系统可以进一步包括：液压泵30，液压泵30设置在电解液出口11和过滤装置20之间，且适于对电解液进行加压过滤。本发明中通过设置液压泵30可以对进入过滤装置20之前的过饱和电解液进行加压处理，使过饱和电解液在一定的压力下进行过滤，由此，可以进一步提高过滤装置20的过滤效率。需要注意的是，在过滤过程中，不宜使用太高的压力，以防电解液中析出的固体产物被强制转移到过滤装置20的出口处。According to a specific embodiment of the present invention, as shown in FIG. 2, the metal-air fuel cell system may further include: a hydraulic pump 30, which is arranged between the electrolyte outlet 11 and the filter device 20, and is suitable for performing Pressure filtration. In the present invention, by setting the hydraulic pump 30, the supersaturated electrolyte solution before entering the filter device 20 can be pressurized, so that the supersaturated electrolyte solution can be filtered under a certain pressure, thus, the filtration efficiency of the filter device 20 can be further improved . It should be noted that, during the filtering process, it is not appropriate to use too high a pressure, so as to prevent the solid products precipitated in the electrolyte from being forcibly transferred to the outlet of the filtering device 20 .
根据本发明的具体实施例，液压泵30可以为蠕动泵。本发明中通过选用蠕动泵，不仅可以对进入过滤装置20之前的过饱和电解液进行加压处理，还能控制过饱和电解液的流量，进而有效控制过滤速度。由此，可以进一步提高过滤效率。此外，本发明中选用蠕动泵还可以借助流体逆行对多孔介质21进行清洗，进而使过滤装置20可以反复利用。According to a specific embodiment of the present invention, the hydraulic pump 30 may be a peristaltic pump. In the present invention, by using a peristaltic pump, not only can the supersaturated electrolyte before entering the filter device 20 be pressurized, but also the flow rate of the supersaturated electrolyte can be controlled, thereby effectively controlling the filtration speed. Thereby, filtration efficiency can be further improved. In addition, in the present invention, the peristaltic pump can also be used to clean the porous medium 21 by means of fluid retrograde, so that the filter device 20 can be used repeatedly.
根据本发明的具体实施例，饱和电解液在过滤层装置20内的过滤速度可以不超过100cm/min(过滤速度是指单位时间内通过单位面积的液体体积，单位可以为cm3/cm2×min)，优选为50cm/min，由此既满足了电池内部电解液循环的速度要求，又能避免过大的液压对滤芯造成破坏。According to a specific embodiment of the present invention, the filtration speed of the saturated electrolyte in the filter layer device 20 may not exceed 100 cm/min (the filtration speed refers to the liquid volume passing through a unit area per unit time, and the unit may be cm3 /cm2 × min), preferably 50 cm/min, which not only meets the speed requirement of the electrolyte circulation inside the battery, but also avoids damage to the filter element caused by excessive hydraulic pressure.
根据本发明的具体实施例，可以对过滤装置20进行再生处理，再生处理可以包括：向过滤装置20内逆向泵入水，以便对多孔介质21进行解吸；利用弱酸或者弱碱溶液对经过解吸后的多孔介质21进行清洗，以便获得再生后过滤装置20。具体可以通过将过滤装置的入口与出口对调并利用液压泵对水进行加压，使水流逆向流动并使大部分吸附在多孔介质21中的过滤物排出来，再利用弱酸或者弱碱溶液对其进行进一步清洗。由此，不仅能够实现电解液的再生和循环利用，使电解液成分与电极工作环境稳定，还能使过滤装置20得到反复利用，整个循环使用过程不产生排放物。此外，再生过程后得到的液体为金属氧化物混合液，可以通过电解对其进行还原并得到金属单质，进而实现燃料的循环利用。According to a specific embodiment of the present invention, the filter device 20 can be regenerated. The regeneration process can include: reversely pump water into the filter device 20 to desorb the porous medium 21; The porous medium 21 is cleaned in order to obtain a regenerated filter device 20 . Specifically, by reversing the inlet and outlet of the filter device and using a hydraulic pump to pressurize the water, the water flow is reversed and most of the filtrate adsorbed in the porous medium 21 is discharged, and then the weak acid or weak base solution is used to clean it. For further cleaning. In this way, not only the regeneration and recycling of the electrolyte can be realized, the components of the electrolyte and the working environment of the electrodes can be stabilized, but also the filter device 20 can be used repeatedly, and no discharge is generated during the entire recycling process. In addition, the liquid obtained after the regeneration process is a mixed liquid of metal oxides, which can be reduced by electrolysis to obtain simple metals, thereby realizing the recycling of fuel.
综上所述，通过利用本发明上述实施例的金属空气燃料电池系统，有效解决反应产物在电解液中过量积累的问题，还能抑制反应产物在电极表面的吸附并收集反应产物，实现电解液的再生和循环利用，使电解液成分与电极工作环境稳定。同时，还能实现过滤装置的再生，使过滤装置可以反复利用，并将过滤回收的产物还能用以金属还原，实现燃料循环利用，整个循环使用过程中不产生排放物。其中，过滤和再生过程中的液体流动方向如图3所示。由此，本发明上述实施例的金属容器燃料电池系统可以实现长时稳定的放电，并显著提高燃料电池系统的能量密度与使用寿命，能够广泛应用于各种金属空气燃料电池、电解产物回收与再生管理，以及水质净化、废水处理、化工提纯等领域。In summary, by using the metal-air fuel cell system of the above-mentioned embodiments of the present invention, the problem of excessive accumulation of reaction products in the electrolyte can be effectively solved, and the adsorption of reaction products on the electrode surface can be inhibited and the reaction products can be collected to realize electrolyte The regeneration and recycling of the electrolyte make the electrolyte composition and electrode working environment stable. At the same time, it can also realize the regeneration of the filter device, so that the filter device can be used repeatedly, and the product recovered by filtration can also be used for metal reduction to realize fuel recycling, and no emissions are generated during the entire recycling process. Wherein, the liquid flow direction during the filtration and regeneration process is shown in FIG. 3 . Therefore, the metal container fuel cell system of the above embodiment of the present invention can realize long-term stable discharge, and significantly improve the energy density and service life of the fuel cell system, and can be widely used in various metal-air fuel cells, electrolysis product recovery and Regeneration management, as well as water purification, wastewater treatment, chemical purification and other fields.
根据本发明的第二个方面，本发明还提出了一种利用上述金属空气燃料电池系统实现稳定发电的方法，包括：使电池堆10排出的饱和电解液进入过滤装置20，在过滤装置20内经过多孔介质21过滤出沉淀物，以便得到净化电解液；使净化电解液进入电池堆10。According to the second aspect of the present invention, the present invention also proposes a method for realizing stable power generation by using the above-mentioned metal-air fuel cell system, including: allowing the saturated electrolyte discharged from the battery stack 10 to enter the filter device 20, and in the filter device 20 The precipitate is filtered out through the porous medium 21 so as to obtain the purified electrolyte; the purified electrolyte enters the battery stack 10 .
由此，通过采用本发明上述实施例的实现金属空气燃料电池稳定发电的方法，不仅可以有效解决反应产物在电解液中过量积累的问题，还能抑制反应产物在电极表面的吸附并收集反应产物，实现电解液的再生和循环利用，使电解液成分与电极工作环境稳定，并使金属还原过程更加简单，实现长时稳定的放电，并显著提高燃料电池系统的能量密度与使用寿命。Therefore, by adopting the method for realizing stable power generation of a metal-air fuel cell according to the above-mentioned embodiments of the present invention, not only the problem of excessive accumulation of reaction products in the electrolyte can be effectively solved, but also the adsorption of reaction products on the electrode surface can be inhibited and the reaction products can be collected. , realize the regeneration and recycling of the electrolyte, stabilize the electrolyte composition and electrode working environment, simplify the metal reduction process, achieve long-term stable discharge, and significantly improve the energy density and service life of the fuel cell system.
下面对本发明上述实施例的实现金属空气燃料电池稳定发电的方法进行详细描述。The method for realizing stable power generation of the metal-air fuel cell according to the above-mentioned embodiments of the present invention will be described in detail below.
根据本发明的具体实施例，多孔介质21可以为多孔钛滤芯、多孔镍滤芯或者多孔不锈钢滤芯。多孔介质的材料对金属空气燃料电池反应产物的过滤效果有很大影响，例如，一般滤纸和镍网海绵滤芯的过滤效果差并且不利于过滤物回收，碳纸、碳布、玻璃纤维的过滤效果不佳且石英成分在强碱环境下稳定性差，不锈钢滤网过滤效果差且在强碱环境下自身耐腐蚀性差，泡沫镍过滤效果不佳且不耐高压、结构稳定性差等。由此，本发明选用的上述滤芯在中性、强碱性环境下均具有较好的稳定性，并能有效吸附、过滤沉淀物。由此，不仅可以显著提高多孔介质的结构稳定性，还能显著提高过滤装置20的过滤效果。此外，本发明采用的上述滤芯一定的过滤速度下还能耐受正、反向高压水流，并可通过弱酸或弱碱条件反复清洗，由此，还可以实现滤芯的反复利用。According to a specific embodiment of the present invention, the porous medium 21 may be a porous titanium filter element, a porous nickel filter element or a porous stainless steel filter element. The material of the porous medium has a great influence on the filtration effect of the metal air fuel cell reaction product. For example, the filtration effect of general filter paper and nickel mesh sponge filter element is poor and is not conducive to the recovery of filtrate. The filtration effect of carbon paper, carbon cloth and glass fiber Poor and quartz components have poor stability in strong alkaline environment, stainless steel filter has poor filtering effect and poor corrosion resistance in strong alkaline environment, foam nickel has poor filtering effect and is not resistant to high pressure, poor structural stability, etc. Therefore, the above-mentioned filter element selected by the present invention has better stability in neutral and strongly alkaline environments, and can effectively absorb and filter sediment. In this way, not only the structural stability of the porous medium can be significantly improved, but also the filtering effect of the filtering device 20 can be significantly improved. In addition, the above-mentioned filter element used in the present invention can withstand forward and reverse high-pressure water flow at a certain filtration speed, and can be repeatedly cleaned under weak acid or weak alkali conditions, thereby realizing the repeated use of the filter element.
根据本发明的具体实施例，可以选用钛粉作为原材料并烧结成多孔钛滤芯，由此，可以进一步提高对反应产物的过滤效果，实现电解液的反复清洁利用。According to a specific embodiment of the present invention, titanium powder can be selected as a raw material and sintered into a porous titanium filter element, thereby further improving the filtering effect on the reaction product and realizing repeated cleaning and utilization of the electrolyte.
根据本发明的具体实施例，多孔介质21的平均孔径可以不大于10微米。由此，可以进一步提高过滤装置20的过滤效果。金属氧化物悬浮物的过滤效果与滤芯的平均孔径有关，孔径越大，过滤阻力越小，但过滤效果越低；孔径越小，过滤阻力越大，但过滤效果越好。发明人通过大量实验发现，当多孔介质的孔径不超过10微米时，过滤效果几乎为100％且过滤阻力适中。此外，发明人还发现，将滤芯制作成棒状结构可以进一步加快过滤速度，提高过滤效率。According to a specific embodiment of the present invention, the average pore diameter of the porous medium 21 may not be greater than 10 microns. Thereby, the filtering effect of the filtering device 20 can be further improved. The filtering effect of metal oxide suspension is related to the average pore size of the filter element. The larger the pore size, the smaller the filtering resistance, but the lower the filtering effect; the smaller the pore size, the greater the filtering resistance, but the better the filtering effect. The inventor found through a large number of experiments that when the pore diameter of the porous medium is not more than 10 microns, the filtering effect is almost 100% and the filtering resistance is moderate. In addition, the inventors also found that making the filter element into a rod-shaped structure can further speed up the filtering speed and improve the filtering efficiency.
根据本发明的具体示例，多孔介质21可以为直径为10厘米、厚度为2毫米的圆柱状多孔钛滤芯，由此，可以进一步提高过滤效率。According to a specific example of the present invention, the porous medium 21 may be a cylindrical porous titanium filter core with a diameter of 10 cm and a thickness of 2 mm, thereby further improving the filtration efficiency.
根据本发明的具体实施例，饱和电解液在的过滤层装置20内的过滤速度可以不超过100cm/min，优选为50cm/min，由此既能满足电池内部电解液循环的速度要求，又能避免过大的液压对滤芯造成破坏。According to a specific embodiment of the present invention, the filtration rate of the saturated electrolyte in the filter layer device 20 can be no more than 100 cm/min, preferably 50 cm/min, which can not only meet the speed requirements of the electrolyte circulation in the battery, but also Avoid damage to the filter element caused by excessive hydraulic pressure.
根据本发明的具体实施例，实现金属空气燃料电池稳定发电的方法可以进一步包括：利用液压泵将饱和电解液泵入过滤层装置20内。本发明中通过利用液压泵30可以对进入过滤装置20之前的过饱和电解液进行加压处理，使过饱和电解液在一定的压力下进行过滤，由此，可以进一步提高过滤效率。需要注意的是，在过滤过程中，不宜使用太高的压力，以防电解液中析出的固体产物被强制转移到过滤装置20的出口处。According to a specific embodiment of the present invention, the method for realizing stable power generation of the metal-air fuel cell may further include: using a hydraulic pump to pump the saturated electrolyte into the filter layer device 20 . In the present invention, the hydraulic pump 30 can be used to pressurize the supersaturated electrolyte before entering the filter device 20, so that the supersaturated electrolyte can be filtered under a certain pressure, thereby further improving the filtration efficiency. It should be noted that during the filtering process, it is not appropriate to use too high a pressure, so as to prevent the solid product precipitated in the electrolyte from being forcibly transferred to the outlet of the filtering device 20 .
根据本发明的具体实施例，液压泵30可以为蠕动泵。本发明中通过选用蠕动泵，不仅可以对进入过滤装置20之前的过饱和电解液进行加压处理，还能控制过饱和电解液的流量，进而有效控制过滤速度。由此，可以进一步提高过滤效率。此外，本发明中选用蠕动泵可以实现流体逆行，进而对多孔介质进行清洗再生。According to a specific embodiment of the present invention, the hydraulic pump 30 may be a peristaltic pump. In the present invention, by using a peristaltic pump, not only can the supersaturated electrolyte before entering the filter device 20 be pressurized, but also the flow rate of the supersaturated electrolyte can be controlled, thereby effectively controlling the filtration speed. Thereby, filtration efficiency can be further improved. In addition, the selection of a peristaltic pump in the present invention can realize fluid retrograde, and then clean and regenerate the porous medium.
根据本发明的具体实施例，实现金属空气燃料电池稳定发电的方法可以进一步包括：对过滤装置20进行再生处理，再生处理可以包括：向过滤装置20内逆向泵入水，以便对多孔介质21进行解吸；利用弱酸或者弱碱溶液对经过解吸后的多孔介质21进行清洗，以便获得再生后过滤装置20。具体可以通过将过滤装置20的入口与出口对调并利用液压泵对水进行加压，使水流逆向流动并使大部分吸附在多孔介质21中的过滤物排出来，再利用弱酸或者弱碱溶液对其进行进一步清洗。由此，通过采用上述方法可以有效实现过滤装置20的再生和重复利用，进而有效降低成本。此外，再生处理后，可以回收废液中的金属氧化物，并通过电解还原金属氧化物得到金属单质，进而实现燃料的循环利用。因此，本发明上述实施例的方法中整个循环过程不产生排放物。According to a specific embodiment of the present invention, the method for realizing stable power generation of a metal-air fuel cell may further include: performing regeneration treatment on the filter device 20, and the regeneration treatment may include: reversely pumping water into the filter device 20, so as to desorb the porous medium 21 ; Clean the desorbed porous medium 21 with a weak acid or weak base solution, so as to obtain the regenerated filter device 20 ; Specifically, the inlet and outlet of the filter device 20 can be reversed and the water can be pressurized by a hydraulic pump to make the water flow reverse and discharge most of the filtrate adsorbed in the porous medium 21, and then use a weak acid or weak base solution to It is further cleaned. Therefore, the regeneration and reuse of the filter device 20 can be effectively realized by adopting the above method, thereby effectively reducing the cost. In addition, after the regeneration treatment, the metal oxides in the waste liquid can be recovered, and the metal oxides can be electrolytically reduced to obtain simple metals, thereby realizing the recycling of fuels. Therefore, in the method of the above-mentioned embodiment of the present invention, no emissions are generated during the entire cycle.
实施例1Example 1
金属空气燃料电池系统，包括电池堆、过滤装置和可调流量及压力的蠕动泵，其中，过滤装置中，多孔介质为直径10厘米、厚度2毫米、空间为10微米的圆柱状多孔钛滤芯，滤芯上部空间是过滤腔，过饱和电解液是由30wt％氢氧化钾溶液溶解过量氧化锌构成。将过饱和电解液由蠕动泵送入过滤装置进行过滤，过滤压力为1个大气压，过滤速度为50cm/min，最终从过滤装置渗透出来澄清电解液。过滤前的过饱和电解液和过滤装置后的电解液分别如图4所示。A metal-air fuel cell system, including a battery stack, a filter device, and a peristaltic pump with adjustable flow and pressure, wherein, in the filter device, the porous medium is a cylindrical porous titanium filter element with a diameter of 10 cm, a thickness of 2 mm, and a space of 10 microns. The space above the filter element is a filter chamber, and the supersaturated electrolyte is formed by dissolving excess zinc oxide in 30 wt% potassium hydroxide solution. The supersaturated electrolyte is sent into the filter device by a peristaltic pump for filtration, the filter pressure is 1 atmosphere, the filter speed is 50cm/min, and finally the electrolyte is permeated from the filter device to clarify. The supersaturated electrolyte before filtration and the electrolyte after the filtration device are shown in Figure 4 respectively.
结论：从图4中可以看出，通过采用上述金属空气燃料电池系统，可以对过饱和电解液进行有效过滤，得到澄清电解液。Conclusion: It can be seen from Figure 4 that by adopting the above-mentioned metal-air fuel cell system, the supersaturated electrolyte can be effectively filtered to obtain a clarified electrolyte.
在本说明书的描述中，参考术语“一个实施例”、“一些实施例”、“示例”、“具体示例”、或“一些示例”等的描述意指结合该实施例或示例描述的具体特征、结构、材料或者特点包含于本发明的至少一个实施例或示例中。在本说明书中，对上述术语的示意性表述不必针对的是相同的实施例或示例。而且，描述的具体特征、结构、材料或者特点可以在任一个或多个实施例或示例中以合适的方式结合。此外，在不相互矛盾的情况下，本领域的技术人员可以将本说明书中描述的不同实施例或示例以及不同实施例或示例的特征进行结合和组合。In the description of this specification, descriptions referring to the terms "one embodiment", "some embodiments", "example", "specific examples", or "some examples" mean that specific features described in connection with the embodiment or example , structure, material or characteristic is included in at least one embodiment or example of the present invention. In this specification, the schematic representations of the above terms are not necessarily directed to the same embodiment or example. Furthermore, the described specific features, structures, materials or characteristics may be combined in any suitable manner in any one or more embodiments or examples. In addition, those skilled in the art can combine and combine different embodiments or examples and features of different embodiments or examples described in this specification without conflicting with each other.
尽管上面已经示出和描述了本发明的实施例，可以理解的是，上述实施例是示例性的，不能理解为对本发明的限制，本领域的普通技术人员在本发明的范围内可以对上述实施例进行变化、修改、替换和变型。Although the embodiments of the present invention have been shown and described above, it can be understood that the above embodiments are exemplary and should not be construed as limiting the present invention, those skilled in the art can make the above-mentioned The embodiments are subject to changes, modifications, substitutions and variations.
| Application Number | Priority Date | Filing Date | Title |
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| CN201710501489.4ACN107171007A (en) | 2017-06-27 | 2017-06-27 | Metal air fuel cell system and its application |
| Application Number | Priority Date | Filing Date | Title |
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| CN201710501489.4ACN107171007A (en) | 2017-06-27 | 2017-06-27 | Metal air fuel cell system and its application |
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| CN107171007Atrue CN107171007A (en) | 2017-09-15 |
| Application Number | Title | Priority Date | Filing Date |
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| CN201710501489.4APendingCN107171007A (en) | 2017-06-27 | 2017-06-27 | Metal air fuel cell system and its application |
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| CN (1) | CN107171007A (en) |
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