阅读说明：本技术 一种水系锌离子液流电池 (Water-based zinc ion flow battery ) 是由 魏春光 王静霞 梁燕 黄德水 李柯 于 2021-02-01 设计创作，主要内容包括：本发明公开一种水系锌离子液流电池,包括电池槽主体、储液罐、循环泵,储液罐中的液体通过循环泵经管道流入电池槽主体,然后经过管道流回储液罐中实现流动循环,电池槽主体设置有正电极板和负电极板,电池槽主体底部设置有沉淀板和可闭合排泄口,沉淀产物沉积后通过沉淀板堆积到排泄口后排出。本发明采用简单巧妙的结构设计,将电池充放电过程中产生的副产物、脱落物在沉积板上充分汇集并及时排出电池体系外,保证电解液循环过程中维持清澈、稳定的状态,同时保证正、负电极发生反应的活性位点不受沉淀物的影响,从而提高水系锌离子液流电池的倍率性能和循环寿命,具有高效节能、安全环保、成本低廉等优点,有利于市场化应用。(The invention discloses a water system zinc ion flow battery, which comprises a battery jar main body, a liquid storage tank and a circulating pump, wherein liquid in the liquid storage tank flows into the battery jar main body through the circulating pump through a pipeline, then flows back into the liquid storage tank through the pipeline to realize flowing circulation, the battery jar main body is provided with a positive electrode plate and a negative electrode plate, the bottom of the battery jar main body is provided with a precipitation plate and a closable discharge port, and precipitated products are deposited and then are accumulated to the discharge port through the precipitation plate and then are discharged. The invention adopts simple and ingenious structural design, fully collects byproducts and fallen matters generated in the battery charging and discharging process on the deposition plate and timely discharges the byproducts and the fallen matters out of a battery system, ensures that a clear and stable state is maintained in the electrolyte circulating process, and simultaneously ensures that active sites of positive and negative electrodes which react are not influenced by the sediments, thereby improving the rate performance and the cycle life of the water system zinc ion flow battery, having the advantages of high efficiency, energy conservation, safety, environmental protection, low cost and the like, and being beneficial to marketization application.)

1. The utility model provides a river system zinc ion redox flow battery, includes battery jar main part, liquid storage pot, circulating pump, liquid in the liquid storage pot passes through the circulating pump is in the pipeline flows in the battery jar main part, then passes through the pipeline flows back to realize the circulation that flows in the liquid storage pot, the battery jar main part is provided with positive electrode plate and negative electrode plate, its characterized in that: the bottom of the battery jar main body is provided with a precipitation plate and a closable drain hole, and precipitated products are deposited and then are discharged after being accumulated to the drain hole through the precipitation plate.

2. The aqueous zinc ion flow battery of claim 1, wherein the angle between the settling plate and the inner side wall of the battery jar body is 5-95 °.

3. The aqueous zinc ion flow battery of claim 2, wherein a flow guide plate is further arranged at the upper end of the top of the settling plate, and the bottom of the flow guide plate is parallel to the settling plate.

4. The aqueous zinc ion flow battery of claim 3, wherein the surface of the settling plate is a smooth hydrophobic material.

5. The aqueous zinc ion flow battery of claim 1, wherein the positive electrode plate and the negative electrode plate are disposed opposite each other and are higher than the highest point of the settling plate, and the distance from the negative electrode plate to the settling plate is greater than or equal to the distance from the positive electrode plate to the settling plate.

6. The aqueous zinc ion flow battery of claim 1, wherein a throttling device is further arranged at the bottom of the battery jar body, and the throttling device comprises a throttling plate and a sliding rail.

7. The aqueous zinc ion flow battery of claim 1, wherein the battery cell body is further provided with an adjustable drain valve.

8. The aqueous zinc ion flow battery according to any one of claims 1 to 7, wherein the active material of the positive electrode plate is one or more of a manganese oxide compound, a metal composite oxide, a metal oxide, or a carbon material.

9. The aqueous zinc ion flow battery according to any one of claims 1 to 7, wherein the active material of the negative electrode plate is an active material mainly containing zinc element or carbon element, the active material mainly containing zinc element is one of zinc powder, zinc foil and zinc sheet, and the active material mainly containing carbon element is one or more of graphene, carbon nanotube, artificial graphite, natural graphite and mesocarbon microbeads.

10. The aqueous zinc ion flow battery of any one of claims 1-7, wherein the liquid in the liquid storage tank comprises one or more of an electrolyte, a pH regulator, a temperature-resistant regulator, a corrosion-inhibiting additive, and a surfactant.

Technical Field

The invention belongs to the technical field of zinc ion batteries, and particularly relates to a water system zinc ion flow battery.

Background

The redox flow battery is one of the largest energy storage batteries in the world on a large scale, and is flexible in design, lowest in whole life cost and suitable for various energy storage occasions, so that the redox flow battery is strong in competitiveness and very wide in application prospect, and is one of the necessary technologies for renewable energy utilization and smart grid development. At present, the development of renewable energy sources such as wind energy, solar energy, biomass energy and the like is accelerated, and the development of efficient large-scale energy storage technology is very significant.

Flow batteries can be broadly classified into an all-liquid-phase double-flow battery and a deposition-type single-flow battery according to the difference in energy storage mechanism. The mature full-liquid-phase double-flow battery is an all-vanadium flow battery, but the vanadium price rises, and an expensive ion exchange membrane is needed, so that the difficulty is increased for the popularization and the application of the battery. The deposition type single flow battery system is characterized in that a charging (discharging) product of at least one pair of electrodes is deposited on (or originally on) an electrode in a charging (discharging) process, so that the problems of solution cross contamination, water transfer, use of expensive membrane materials and the like of the full-liquid-phase double flow battery are effectively solved, but the existing deposition type single flow battery, such as a zinc-nickel single flow battery (CN200610109424.7) anode adopts a nickel electrode, so that the cost is higher; PbO₂The Cu (Cd) single-flow battery (CN200810104996.5) contains toxic elements and has potential environmental pollution.

Chinese invention patent (CN 101540417) discloses a zinc ion battery, which uses manganese dioxide as the positive active material, zinc as the negative electrode, and an aqueous solution containing zinc ions as the electrolyte to form a rechargeable zinc ion battery. Such a rechargeable zinc-ion battery can be used several hundred times, while having a high power density and a high energy density. However, in this type of rechargeable zinc ion battery, on the one hand, as the electrochemical process proceeds, water in the electrolyte is gradually decomposed into hydrogen gas and oxygen gas, which volatilize, and the amount of electrolyte gradually decreases, resulting in a decrease in battery performance. On the other hand, the battery is prone to zinc dendrites and basic zinc sulfate precipitates (Zn) during cycling₄SO₄(OH)₆·5H₂O), and the like. Hard zinc dendrites greatly increase the risk of cell shorting, while inactive basic zinc sulfate precipitates deposit on the separator. The risk of short circuit of the battery is further increased by the continuous expansion of the volume of the diaphragm along with the continuous deposition of the byproducts; in addition to this, the present invention is,the porosity of the diaphragm is obviously reduced, the material transmission in the electrochemical reaction is blocked, and the reaction rate is slowed down, so that the capacity of the secondary zinc ion battery is reduced, and the cycle performance is poor.

Chinese invention patent (CN 201510621596.1) discloses a water system zinc-manganese single flow battery and a preparation method thereof, wherein active substances of a positive electrode and a negative electrode are stored in a flowing electrolyte in the form of soluble salts without being separated by an ion exchange membrane, meanwhile, the active substances in an oxidation state of the positive electrode and the active substances in a reduction state of the negative electrode can also be partially attached to current collectors of the positive electrode and the negative electrode, the mass transfer and diffusion of ions are accelerated by the flowing of the electrolyte, the risk of short circuit caused by the fact that the dendritic crystal of the zinc negative electrode punctures a diaphragm is effectively inhibited, and therefore the performances of the positive electrode and the negative electrode of the battery are improved. However, the flow of the electrolyte also aggravates side reactions in the system, byproducts such as basic zinc sulfate precipitate are continuously generated, and in addition, partial falling of electrode materials in the reaction process causes the problems of electrolyte turbidity, battery capacity attenuation, short circuit of the battery caused by connection of a positive electrode and a negative electrode after a large amount of deposits are formed at the bottom, and the like.

Disclosure of Invention

The purpose of the invention is: aiming at the defects of the prior art, the water system zinc ion flow battery is provided, the advantages of a zinc-manganese ion secondary battery and a flow battery are integrated, a simple and ingenious structural design is adopted, byproducts and fallen matters generated in the charging and discharging processes of the battery are fully collected on a deposition plate and are timely discharged out of the battery system, the adverse effect caused by continuous generation of byproducts such as basic zinc sulfate precipitation is avoided, the clear and stable state of the electrolyte in the circulating process is ensured, and meanwhile, the active sites of the positive electrode and the negative electrode which react are not influenced by the precipitates are ensured, so that the rate capability and the circulating life of the water system zinc ion flow battery are improved, and the water system zinc ion flow battery has the advantages of high efficiency, energy conservation, safety, environmental protection, low cost and the like, and is favorable.

In order to achieve the purpose, the invention adopts the following technical scheme:

the utility model provides a river system zinc ion redox flow battery, includes battery jar main part, liquid storage pot, circulating pump, liquid in the liquid storage pot passes through the circulating pump is in the pipeline flows in the battery jar main part, then passes through the pipeline flows back to realize the circulation that flows in the liquid storage pot, the battery jar main part is provided with positive electrode plate and negative electrode plate, its characterized in that: the bottom of the battery jar main body is provided with a precipitation plate and a closable drain hole, and precipitated products are deposited and then are discharged after being accumulated to the drain hole through the precipitation plate.

Preferably, the included angle between the settling plate and the inner side wall of the battery jar main body is 5-95 degrees.

Preferably, the positive electrode plate and the negative electrode plate are arranged oppositely and are higher than the highest point of the settling plate, and the distance from the negative electrode plate to the settling plate is greater than or equal to the distance from the positive electrode plate to the settling plate.

Preferably, the upper end of the top of the settling plate is also provided with a guide plate, and the bottom of the guide plate is parallel to the settling plate.

Preferably, the surface of the sediment plate is made of smooth hydrophobic materials.

Preferably, the bottom of the battery jar main body is further provided with a throttling device, and the throttling device comprises a throttling plate and a sliding rail.

Preferably, the sum of the lengths of the throttle plates is equal to or greater than the distance required for throttling of the throttle plates.

Preferably, the battery jar main part is also provided with an adjustable liquid outlet valve.

Preferably, the active material of the positive electrode plate is one or more of a manganese oxide compound, a metal composite oxide, a metal oxide or a carbon material.

Preferably, the active substance of the negative electrode plate is an active substance mainly containing zinc element or carbon element, the active substance mainly containing zinc element is one of zinc powder, zinc foil and zinc sheet, and the active substance mainly containing carbon element is one or more of graphene, carbon nano tube, artificial graphite, natural graphite and mesocarbon microbeads.

Preferably, the liquid in the liquid storage tank comprises one or more of electrolyte, a pH regulator, a temperature-resistant regulator, a corrosion inhibition additive and a surfactant.

Compared with the prior art, the invention has the advantages that at least:

1. the invention adopts simple and ingenious structural design, collects the byproducts and the fallen substances generated in the charging and discharging processes of the water system zinc ion flow battery on the deposition plate and discharges the byproducts and the fallen substances out of the battery system in time, avoids the adverse effect caused by continuous generation of the byproducts such as basic zinc sulfate precipitation and the like, ensures that the clear and stable state is maintained in the circulating process of the electrolyte, simultaneously ensures that the active sites of the reaction of the positive electrode and the negative electrode are not influenced by side reaction products, and ensures that the active substances existing in the form of ions can fully react, thereby obviously improving the electrochemical performance of the water system zinc ion flow battery.

2. According to the invention, the inclination angle of the settling plate can be adjusted by setting the included angle between the settling plate and the inner side wall of the battery jar body, so that the accumulation speed of byproducts, fallen objects and the like under the action of gravity and the area of a settling area can be adjusted, the flexibility is high, and the design can be carried out as required.

3. According to the invention, the guide plate with the bottom parallel to the settling plate is arranged, so that when liquid flows and circulates in a water system zinc ion flow battery system, the natural impact force of downward flowing of the liquid is utilized to flush the sediment at the inclined plane part at the upper end of the settling plate, and the sediment is further moved and accumulated towards the drainage outlet. Through the effect of cleaning while circulating and combining the advantage that the settling plate has a smooth and hydrophobic surface, the precipitates can be fully collected and discharged, the discharge degree of the precipitates is further ensured, and the rate performance and the cycle life of the water system zinc ion flow battery are improved.

4. The invention sets the positions of the positive electrode plate and the negative electrode plate to be higher than the highest point of the precipitation plate, and the distance between the negative electrode plate and the precipitation plate is larger than that between the positive electrode plate and the precipitation plate, because precipitation products such as basic zinc sulfate (Zn) precipitate₄SO₄(OH)₆·5H₂O), and the like, mainly generated and fallen by the negative electrode plate, thereby not only providing larger precipitation space for precipitation products, but also prolonging the distance between the positive electrode plate and the negative electrode plate for byproducts, fallen objects and the like, and avoiding the risk of short circuit of the battery.

5. According to the invention, the throttling device is arranged, the throttling plate in the sliding rail slides to open and close, when the throttling plate is opened, the throttling plate liquid circularly flows in the battery jar main body, when the discharging port needs to be opened to discharge sediment, the throttling plate can be closed, and the liquid passage at the upper end and the lower end of the throttling plate is cut off, so that the normal circular flow of the liquid at the upper end of the throttling plate is ensured, the outflow loss of the liquid when the discharging port is opened is reduced, meanwhile, the vicinity of the discharging port is conveniently washed and cleaned as required, and the sustainable development concept of fine chemical engineering, energy conservation and environmental protection is fully embodied.

Drawings

The invention and its advantageous effects are explained in detail below with reference to the accompanying drawings and the detailed description.

Fig. 1 is a schematic structural diagram of embodiment 1 of the present invention.

Fig. 2 is a schematic structural diagram of embodiment 2 of the present invention.

Fig. 3 is a charge-discharge curve of the aqueous zinc ion flow battery of example 1 of the present invention.

Fig. 4 is a coulombic efficiency curve of the aqueous zinc-ion flow battery of example 1 of the present invention.

Fig. 5 is a cycle curve of an aqueous zinc ion flow battery of example 2 of the present invention.

Fig. 6 is a curve of capacity retention rate of the aqueous zinc ion flow battery of example 2 of the present invention.

Reference symbol names: 1. a battery jar body; 2. a liquid storage tank; 3. a circulation pump; 4. A pipe 5, a positive electrode plate; 6. a negative electrode plate; 7. A settling plate; 8. a drain port; 9. a throttling device; 91. a throttle plate; 92. a slide rail; 10. a baffle; 11. a liquid outlet valve.

Detailed Description

The technical solutions of the present invention are described below with specific examples, but the scope of the present invention is not limited thereto.

Example 1

As shown in fig. 1, the aqueous zinc ion flow battery comprises a battery jar main body 1, a liquid storage tank 2 and a circulating pump 3, wherein liquid in the liquid storage tank 2 flows into the battery jar main body 1 through the circulating pump 3 via a pipeline 4, and then flows back into the liquid storage tank 2 via the pipeline 4 to realize flowing circulation, the battery jar main body 1 is provided with a positive electrode plate 5 and a negative electrode plate 6, the bottom of the battery jar main body 1 is provided with a precipitation plate 7 and a closable drain outlet 8, and precipitated products are deposited and then stacked on the drain outlet 8 through the precipitation plate 7 and then discharged.

Preferably, the angle between the settling plate 7 and the inner side wall of the battery jar body 1 is 60 degrees.

Preferably, the positive electrode plate 5 and the negative electrode plate 6 are arranged oppositely and are higher than the highest point of the settling plate 7, and the distance from the negative electrode plate 6 to the settling plate 7 is greater than the distance from the positive electrode plate 5 to the settling plate 7.

Preferably, a guide plate 10 is further arranged at the upper end of the top of the settling plate 7, and the bottom of the guide plate 10 is parallel to the settling plate 7.

Preferably, the surface of the precipitation plate 7 is made of smooth hydrophobic material.

Preferably, the bottom of the battery jar body 1 is further provided with a throttling device 9, and the throttling device 9 comprises a throttling plate 91 and a sliding rail 92.

Preferably, the length of the throttle plate 91 is greater than the distance required for throttle plate throttling.

Preferably, the battery jar body 1 is further provided with an adjustable liquid outlet valve 11.

Preferably, the active substance of the positive electrode plate 5 is manganese oxide, the active substance of the negative electrode plate 6 is zinc foil, and the liquid in the liquid storage tank 2 is zinc sulfate and manganese sulfate mixed aqueous solution electrolyte, a pH regulator and a temperature-resistant regulator.

The water-based zinc ion flow battery of example 1 was tested. As shown in FIG. 3, the open circuit voltage of the battery was about 1.2V, and constant voltage charging was performed at a voltage of 2.0 mA/cm²The current density of the discharge tube is discharged, the cut-off voltage is 0.2V, and the first-circle discharge specific capacity is about 3.1mAh/cm²The specific discharge capacity of the 100 th circle is about 3.9mAh/cm²(ii) a As shown in fig. 4, the average coulombic efficiency of the cell was greater than 90%.

Example 2

As shown in fig. 2, the aqueous zinc ion flow battery comprises a battery jar main body 1, a liquid storage tank 2 and a circulating pump 3, wherein liquid in the liquid storage tank 2 flows into the battery jar main body 1 through the circulating pump 3 via a pipeline 4, and then flows back into the liquid storage tank 2 via the pipeline 4 to realize flowing circulation, the battery jar main body 1 is provided with a positive electrode plate 5 and a negative electrode plate 6, the bottom of the battery jar main body 1 is provided with two settling plates 7 and a closable drain outlet 8, and settled products are accumulated to the drain outlet 8 through the settling plates 7 and then discharged.

Preferably, the angle between the settling plate 7 and the inner side wall of the battery jar body 1 is 45 degrees.

Preferably, the positive electrode plate 5 and the negative electrode plate 6 are oppositely arranged and are higher than the highest point of the settling plate 7, and the distance from the negative electrode plate 6 to the settling plate 7 is equal to the distance from the positive electrode plate 5 to the settling plate 7.

Preferably, a guide plate 10 is further arranged at the upper end of the top of the settling plate 7, and the bottom of the guide plate 10 is parallel to the settling plate 7.

Preferably, the surface of the precipitation plate 7 is made of smooth hydrophobic material.

Preferably, the bottom of the battery jar body 1 is further provided with a throttling device 9, and the throttling device 9 comprises a throttling plate 91 and a sliding rail 92.

Preferably, the sum of the lengths of the throttle plates 91 is greater than the distance required for throttle plate throttling.

Preferably, the battery jar body 1 is further provided with an adjustable liquid outlet valve 11.

Preferably, the active substance of the positive electrode plate 5 is a mixture of manganese oxide and artificial graphite, the active substance of the negative electrode plate 6 is zinc alloy, and the liquid in the liquid storage tank 2 is a mixed aqueous solution electrolyte of zinc sulfate and manganese sulfate, a pH regulator and a surfactant.

The water-based zinc ion flow battery of example 2 was tested. FIG. 5 shows 10mA/cm²A 500-cycle curve for the cell at current density; as shown in the capacity retention rate curve of the battery of fig. 6, the capacity retention rate of the battery was greater than 80%.

Variations and modifications to the above-described embodiments may occur to those skilled in the art, which fall within the scope and spirit of the above description. Therefore, the present invention is not limited to the specific embodiments disclosed and described above, and some modifications and variations of the present invention should fall within the scope of the claims of the present invention. Furthermore, although specific terms are employed herein, they are used in a generic and descriptive sense only and not for purposes of limitation.