Metal electrolyte flow battery system

Abstract

The utility model belongs to the technical field of electrochemical energy storage, and discloses a metal electrolyte flow battery system which comprises a metal electrolyte storage module, a metal electrolyte battery module, a metal electrolyte regeneration electrolytic bath module and metal electrolyte, and the metal electrolyte is used for circulating in the metal electrolyte storage module, the metal electrolyte flow battery and the metal electrolyte regeneration electrolytic cell module, and can be discharged in the metal battery and charged in the metal electrolyte regeneration electrolytic cell. According to the utility model, metal oxidation products generated by reaction and reduced metal particles are taken out of the battery reaction chamber by flowing electrolyte, so that the metal electrolyte is more uniformly distributed in a flow field, and the deposition and retention of metal powder in the flow field are obviously improved; the problems of metal dendrites and metal passivation generated in the charge-discharge cycle of a metal electrolyte flow battery are solved, the stability of the metal battery is enhanced, and the voltage efficiency and charge-discharge capacity of the metal battery are improved.

Description

Technical Field

[0001] The utility model belongs to the technical field of electrochemical energy storage, and specifically relates to a battery system. Background Art

[0002] Metal-based batteries are a new type of electrochemical energy storage battery that uses metal as the negative electrode, combined with suitable positive electrode active materials and positive electrode reactions. Metal batteries are favored by various industries due to their large capacity, high energy utilization efficiency, low cost, safety and wide range of applications.

[0003] According to different charging methods, common metal-based batteries are mainly divided into two types: mechanical charging type and electrolyte flow circulation type. The mechanical charging type has a simple structure and low device cost, but it is troublesome to replace the metal fuel and the utilization rate of the metal fuel is low. The electrolyte flow circulation type generally circulates alkaline liquid, and the metal fuel layer is fixed in the battery and is not frequently replaced. When charging, the metal is reduced on the metal fuel layer. Its development is mainly restricted by the accumulation of negative electrode metal dendrites and metal passivation during the battery's charge and discharge cycle, and the battery's cycle stability faces great obstacles. Utility Model Content

[0004] In order to solve the above technical problems, the utility model provides a metal electrolyte flow battery system, which greatly reduces the impact of metal passivation and metal dendrites on the stable operation of the battery and greatly improves the cycle stability of the metal battery.

[0005] The utility model is realized by the following technical solutions:

[0006] The utility model provides a metal electrolyte flow battery system, comprising a metal electrolyte storage module, a metal electrolyte battery module, a metal electrolyte regeneration electrolytic cell module and a metal electrolyte; the metal electrolyte is used to circulate in the metal electrolyte storage module, the metal electrolyte flow battery and the metal electrolyte regeneration electrolytic cell module;

[0007] The metal electrolyte storage module comprises a metal electrolyte storage tank and a metal electrolyte stirring device; the metal electrolyte storage tank stores metal electrolyte and is provided with a liquid inlet, a liquid outlet, and a gas outlet; the metal electrolyte stirring device is used to stir the metal electrolyte in the metal electrolyte storage tank;

[0008] The metal electrolyte battery module includes a first electrolyte pump, a first electrolyte buffer tank, a second electrolyte pump, and a metal battery; the metal battery includes a membrane electrode, a negative electrode cavity and a positive electrode cavity, the negative electrode cavity is provided with a negative electrode electrolyte inlet and a negative electrode electrolyte outlet connected to the interior thereof, and the positive electrode cavity is provided with a positive electrode inlet and a positive electrode outlet connected to the interior thereof; the membrane electrode includes a first ion exchange membrane, a negative electrode reaction conductive diffusion layer and a positive electrode reaction catalyst layer, the negative electrode reaction conductive diffusion layer is located in the negative electrode cavity, and the positive electrode reaction catalyst layer is located in the positive electrode cavity; the liquid outlet of the metal electrolyte storage tank is connected to the inlet of the first electrolyte buffer tank through the first electrolyte pump, and the outlet of the first electrolyte buffer tank is connected to the negative electrode electrolyte inlet of the metal battery through the second electrolyte pump; the negative electrode electrolyte outlet of the metal battery is connected to the liquid inlet of the metal electrolyte storage tank;

[0009] The metal electrolyte regeneration electrolytic cell module comprises a third electrolyte pump, a second electrolyte buffer tank, a fourth electrolyte pump and a metal electrolyte regeneration electrolytic cell; the metal electrolyte regeneration electrolytic cell comprises a membrane electrode, a cathode cavity and an anode cavity, the cathode cavity is provided with a cathode electrolyte inlet and a cathode electrolyte outlet connected to the interior thereof, and the anode cavity is provided with an anode inlet and an anode outlet connected to the interior thereof; the membrane electrode comprises a second ion exchange membrane and an anode reaction catalyst layer, the anode reaction catalyst layer is disposed in the anode cavity, and the cathode cavity is a cavity; the liquid outlet of the metal electrolyte storage tank is connected to the inlet of the second electrolyte buffer tank through the third electrolyte pump, and the outlet of the second electrolyte buffer tank is connected to the cathode electrolyte inlet of the metal electrolyte regeneration electrolytic cell through the fourth electrolyte pump; the cathode electrolyte outlet of the metal electrolyte regeneration electrolytic cell is connected to the liquid inlet of the metal electrolyte storage tank.

[0010] Furthermore, the metal electrolyte is an iron metal electrolyte or a zinc metal electrolyte.

[0011] Furthermore, the liquid inlet, the liquid outlet, and the gas outlet are respectively arranged on the tank wall, the bottom, and the top of the metal electrolyte storage tank.

[0012] Furthermore, the metal electrolyte storage tank is equipped with a temperature sensor for monitoring the temperature of the metal electrolyte in the metal electrolyte storage tank.

[0013] Furthermore, the metal electrolyte storage tank is equipped with a liquid level sensor for monitoring the liquid level of the metal electrolyte in the metal electrolyte storage tank.

[0014] Furthermore, the negative electrode cavity of the metal battery adopts a direct current field or a serpentine flow field, and the cathode cavity of the metal electrolyte regeneration electrolytic cell can adopt a direct current field or a serpentine flow field.

[0015] Furthermore, the negative electrode cavity and flow field material of the metal battery are at least one of gold, silver, copper, iron, nickel, titanium, iron-nickel alloy, copper-nickel alloy, magnesium alloy or graphite; the flow field material of the cathode cavity of the metal electrolyte regeneration electrolytic cell is at least one of gold, silver, copper, iron, nickel, titanium, iron-nickel alloy, copper-nickel alloy, magnesium alloy or graphite.

[0016] Furthermore, when the negative electrode reaction conductive diffusion layer of the metal battery is a metal material, its structure is a mesh or foam structure, and the material is one of alkali corrosion-resistant metals such as nickel, iron, iron-nickel alloy, copper, copper-nickel alloy, titanium, etc.; when the negative electrode reaction conductive layer diffusion is a non-metallic material, the material is one of carbon paper or carbon felt.

[0017] Furthermore, pressure sensors are installed at the outlets of the first electrolyte pump, the second electrolyte pump, the third electrolyte pump, and the fourth electrolyte pump.

[0018] The beneficial effects of the utility model are:

[0019] The utility model provides a metal electrolyte flow battery system, which is different from the two common metal-based batteries. The metal fuel is distributed in the metal electrolyte, and the metal electrolyte circulates in the battery system. Most of the metal oxidation products and reduced metal particles generated by the reaction can be carried out of the battery reaction chamber by the flowing electrolyte, so that the metal electrolyte can be distributed more evenly in the flow field. Therefore, the utility model can significantly improve the deposition and retention problems of metal powder in the metal electrolyte in the flow field, thereby overcoming the problems of metal dendrites and metal passivation generated in the charge and discharge cycle of the metal electrolyte flow battery, enhancing the stability of the metal battery, extending the life of the metal battery, and improving the voltage efficiency and charge and discharge capacity of the metal battery. At the same time, the battery capacity of the metal electrolyte flow battery depends on the electrolyte storage capacity in the electrolyte storage tank, and the battery capacity can be adjusted according to actual conditions. BRIEF DESCRIPTION OF THE DRAWINGS

[0020] Figure 1 This is a schematic diagram of the structure of the metal electrolyte flow battery system provided by the utility model;

[0021] Figure 2 A top view of the flow field of the negative electrode cavity of a metal battery provided by an embodiment of the utility model;

[0022] Figure 3 A top view of the flow field of the cathode cavity of the metal electrolyte regeneration electrolytic cell provided in an embodiment of the utility model.

[0023] In the above figure: 1—metal electrolyte storage module; 101—liquid inlet; 102—liquid outlet; 103—gas outlet; 104—electrolyte stirring device; 105—metal electrolyte storage tank; 2—metal electrolyte battery module; 201—first electrolyte pump; 202—first electrolyte buffer tank; 203—second electrolyte pump; 204—metal battery; 3—metal electrolyte regeneration electrolytic cell module; 301—third electrolyte pump; 302—second electrolyte buffer tank; 303—fourth electrolyte pump; 304—metal electrolyte regeneration electrolytic cell. DETAILED DESCRIPTION

[0024] In order to make the technical problems, technical solutions and beneficial effects solved by the utility model more clearly understood, the utility model is further described below in conjunction with the accompanying drawings and embodiments. It should be understood that the embodiments described here are only used to explain the utility model and are not used to limit the utility model.

[0025] like Figure 1 As shown, the utility model provides a metal electrolyte flow battery system, including a metal electrolyte, a metal electrolyte storage module 1, a metal electrolyte battery module 2, and a metal electrolyte regeneration electrolytic cell module 3.

[0026] The metal electrolyte circulates in the metal electrolyte storage module 1, the metal electrolyte flow battery 2, and the metal electrolyte regeneration electrolytic cell module 3, discharges in the metal battery 204, and charges in the metal electrolyte regeneration electrolytic cell 304. The metal electrolyte is a mixture of metal powder, liquid, and other additives in a certain proportion, and has appropriate viscosity, so that the metal powder can be well transported in the pipeline. Preferably, the metal electrolyte is an iron metal electrolyte or a zinc metal electrolyte.

[0027] The metal electrolyte storage module 1 mainly includes a metal electrolyte storage tank 105 and a metal electrolyte stirring device 104. The metal electrolyte storage tank 105 stores metal electrolyte and is provided with a liquid inlet 101, a liquid outlet 102, and a gas outlet 103. The liquid inlet 101, the liquid outlet 102, and the gas outlet 103 are respectively arranged on the tank wall, the bottom, and the top of the metal electrolyte storage tank 105. The metal electrolyte is drawn out from the liquid outlet 102, and returns to the metal electrolyte storage tank 105 from the liquid inlet 101 after passing through the charging and discharging system. The metal electrolyte stirring device 104 is used to stir the metal electrolyte in the metal electrolyte storage tank 105 to prevent the metal powder from settling.

[0028] The metal electrolyte storage tank 105 is equipped with a temperature sensor for monitoring the temperature of the metal electrolyte in the metal electrolyte storage tank 105 .

[0029] The metal electrolyte storage tank 105 is equipped with a liquid level sensor for monitoring the liquid level of the metal electrolyte in the metal electrolyte storage tank 105 .

[0030] The metal electrolyte battery module 2 mainly includes a first electrolyte pump 201, a first electrolyte buffer tank 202, a second electrolyte pump 203, and a metal battery 204. The metal electrolyte is first transported to the first electrolyte buffer tank 202 by the first electrolyte pump 201, and after stabilization, it is transported to the metal battery 204 by the second electrolyte pump 203 for discharge.

[0031] The metal battery 204 includes a membrane electrode, a negative electrode cavity and a positive electrode cavity. The negative electrode cavity is provided with a negative electrode electrolyte inlet and a negative electrode electrolyte outlet connected to the inside thereof, and the positive electrode cavity is provided with a positive electrode inlet and a positive electrode outlet connected to the inside thereof. The membrane electrode is the discharge core area of ​​the metal battery 204, including a first ion exchange membrane, a negative electrode reaction conductive diffusion layer and a positive electrode reaction catalyst layer; the negative electrode reaction conductive diffusion layer is located in the negative electrode cavity, and the positive electrode reaction catalyst layer is located in the positive electrode cavity.

[0032] The positive electrode inlet and the positive electrode outlet of the metal battery 204 are used to connect to the alkali solution storage tank for circulation. Specifically, the positive electrode inlet of the metal battery 204 is connected to the outlet of the gear pump for conveying pure liquid; the positive electrode outlet of the metal battery 204 is connected to the inlet of the alkali solution storage tank.

[0033] The inlet of the first electrolyte pump 201 is connected to the liquid outlet 102 of the metal electrolyte storage tank 105 through a pipeline, the outlet of the first electrolyte pump 201 is connected to the inlet of the first electrolyte buffer tank 202 through a pipeline, the outlet of the first electrolyte buffer tank 202 is connected to the inlet of the second electrolyte pump 203 through a pipeline, and the outlet of the second electrolyte pump 203 is connected to the negative electrolyte inlet of the metal battery 204 through a pipeline. The negative electrolyte outlet of the metal battery 204 is connected to the liquid inlet 101 of the metal electrolyte storage tank 105 through a pipeline.

[0034] The negative electrode cavity of the metal battery 204 may adopt a direct current field or a serpentine flow field to prevent the metal electrolyte from being retained in the flow field and the battery stack from being blocked due to the electrodeposition of the metal.

[0035] The flow field material of the negative electrode cavity of the metal battery 204 is at least one of gold, silver, copper, iron, nickel, titanium, iron-nickel alloy, copper-nickel alloy, magnesium alloy or graphite.

[0036] Among them, when the negative electrode reaction conductive diffusion layer is a metal material, its structure is a mesh or foam structure, and the material is one of alkali corrosion-resistant metals such as nickel, iron, iron-nickel alloy, copper, copper-nickel alloy, and titanium; when the negative electrode reaction conductive diffusion layer is a non-metallic material, the material is one of carbon paper or carbon felt.

[0037] The metal electrolyte regeneration electrolytic cell module 3 includes a third electrolyte pump 301, a second electrolyte buffer tank 302, a fourth electrolyte pump 303 and a metal electrolyte regeneration electrolytic cell 304. The metal electrolyte is first transported to the second electrolyte buffer tank 302 by the third electrolyte pump 301, and after stabilization, it is transported to the metal electrolyte regeneration electrolytic cell 304 by the fourth electrolyte pump 303 for charging.

[0038] The metal electrolyte regeneration electrolytic cell 304 includes a membrane electrode, a cathode cavity and an anode cavity, the cathode cavity is provided with a cathode electrolyte inlet and a cathode electrolyte outlet connected to the interior thereof, and the anode cavity is provided with an anode inlet and an anode outlet connected to the interior thereof. The membrane electrode includes a second ion exchange membrane and an anode reaction catalyst layer, the anode reaction catalyst layer is placed in the anode cavity, and the cathode cavity is a cavity.

[0039] The anode inlet and anode outlet of the metal electrolyte regeneration electrolytic cell 304 are used to connect to the alkali solution storage tank for circulation. Specifically, the anode inlet of the metal electrolyte regeneration electrolytic cell 304 is connected to the outlet of the gear pump for conveying pure liquid; the anode outlet of the metal battery 204 is connected to the inlet of the alkali solution storage tank.

[0040] The inlet of the third electrolyte pump 301 is connected to the liquid outlet 102 of the metal electrolyte storage tank 105 through a pipeline, the outlet of the third electrolyte pump 301 is connected to the inlet of the second electrolyte buffer tank 302 through a pipeline, the outlet of the second electrolyte buffer tank 302 is connected to the inlet of the fourth electrolyte pump 303 through a pipeline, and the outlet of the fourth electrolyte pump 303 is connected to the cathode electrolyte inlet of the metal electrolyte regeneration electrolytic cell 304 through a pipeline. The cathode electrolyte outlet of the metal electrolyte regeneration electrolytic cell 304 is connected to the liquid inlet 101 of the metal electrolyte storage tank 105 through a pipeline.

[0041] The cathode cavity of the metal electrolyte regeneration electrolytic cell 304 may adopt a DC field or a serpentine flow field to prevent the metal electrolyte from being retained in the flow field and the cell stack from being blocked due to the electrodeposition of the metal.

[0042] The flow field material of the cathode cavity of the metal electrolyte regeneration electrolytic cell 304 is at least one of gold, silver, copper, iron, nickel, titanium, iron-nickel alloy, copper-nickel alloy, magnesium alloy or graphite.

[0043] Furthermore, pressure sensors are installed at the outlets of the first electrolyte pump 201 , the second electrolyte pump 203 , the third electrolyte pump 301 , and the fourth electrolyte pump 303 .

[0044] The utility model discloses a metal electrolyte flow battery system, and its use process is as follows:

[0045] Confirm whether the metal electrolyte storage tank 105 has leakage and gas leakage. After eliminating the leakage and gas leakage, add the prepared metal electrolyte and observe the metal electrolyte level. The metal electrolyte level should be higher than the height of the liquid inlet 101 of the metal electrolyte storage tank 105, so as to reduce the electrolyte entrainment of gas in the metal electrolyte storage tank 105. After the liquid level is normal, start the electrolyte stirring device 104 to ensure that the metal electrolyte is evenly distributed in the metal electrolyte storage tank 105.

[0046] Start the first electrolyte pump 201 to store a certain amount of metal electrolyte in the first electrolyte buffer tank 202, and then start the second electrolyte pump 203 to pump the metal electrolyte into the metal battery 204. Check the sealing condition of the metal battery 204, the liquid level in the first electrolyte buffer tank 202 and the pressure in the delivery pipeline. After the inspection is normal, discharge the metal electrolyte.

[0047] Start the third electrolyte pump 301 to store a certain amount of metal electrolyte in the second electrolyte buffer tank 302, and then start the fourth electrolyte pump 303 to pump the metal electrolyte into the metal electrolyte regeneration electrolytic cell 303, check the sealing condition of the metal electrolyte regeneration electrolytic cell 303, the liquid level in the second electrolyte buffer tank 302 and the pressure in the delivery pipeline, and after the inspection is normal, charge the metal electrolyte.

[0048] Although the preferred embodiments of the present invention have been described above in conjunction with the accompanying drawings, the present invention is not limited to the above-mentioned specific implementation methods. The above-mentioned specific implementation methods are merely illustrative and not restrictive. Under the guidance of the present invention, ordinary technicians in this field can also make many forms of specific changes without departing from the scope of protection of the invention and the claims, all of which fall within the scope of protection of the present invention.

Claims

1. A metal electrolyte flow battery system, characterized in that: It includes a metal electrolyte storage module, a metal electrolyte battery module, a metal electrolyte regeneration electrolytic cell module and a metal electrolyte; The metal electrolyte is used to circulate among the metal electrolyte storage module, the metal electrolyte flow battery, and the metal electrolyte regeneration electrolytic cell module; The metal electrolyte storage module includes a metal electrolyte storage tank and a metal electrolyte stirring device; The metal electrolyte storage tank stores metal electrolyte and is provided with a liquid inlet, a liquid outlet, and a gas outlet; The metal electrolyte stirring device is used to stir the metal electrolyte in the metal electrolyte storage tank; The metal electrolyte battery module includes a first electrolyte pump, a first electrolyte buffer tank, a second electrolyte pump, and a metal battery; the metal battery includes a membrane electrode, a negative electrode cavity and a positive electrode cavity, the negative electrode cavity is provided with a negative electrode electrolyte inlet and a negative electrode electrolyte outlet connected to the interior thereof, and the positive electrode cavity is provided with a positive electrode inlet and a positive electrode outlet connected to the interior thereof; the membrane electrode includes a first ion exchange membrane, a negative electrode reaction conductive diffusion layer and a positive electrode reaction catalyst layer, the negative electrode reaction conductive diffusion layer is located in the negative electrode cavity, and the positive electrode reaction catalyst layer is located in the positive electrode cavity; the liquid outlet of the metal electrolyte storage tank is connected to the inlet of the first electrolyte buffer tank through the first electrolyte pump, and the outlet of the first electrolyte buffer tank is connected to the negative electrode electrolyte inlet of the metal battery through the second electrolyte pump; the negative electrode electrolyte outlet of the metal battery is connected to the liquid inlet of the metal electrolyte storage tank; The metal electrolyte regeneration electrolytic cell module comprises a third electrolyte pump, a second electrolyte buffer tank, a fourth electrolyte pump and a metal electrolyte regeneration electrolytic cell; the metal electrolyte regeneration electrolytic cell comprises a membrane electrode, a cathode cavity and an anode cavity, the cathode cavity is provided with a cathode electrolyte inlet and a cathode electrolyte outlet connected to the interior thereof, and the anode cavity is provided with an anode inlet and an anode outlet connected to the interior thereof; the membrane electrode comprises a second ion exchange membrane and an anode reaction catalyst layer, the anode reaction catalyst layer is disposed in the anode cavity, and the cathode cavity is a cavity; the liquid outlet of the metal electrolyte storage tank is connected to the inlet of the second electrolyte buffer tank through the third electrolyte pump, and the outlet of the second electrolyte buffer tank is connected to the cathode electrolyte inlet of the metal electrolyte regeneration electrolytic cell through the fourth electrolyte pump; the cathode electrolyte outlet of the metal electrolyte regeneration electrolytic cell is connected to the liquid inlet of the metal electrolyte storage tank.

2. A metal electrolyte flow battery system according to claim 1, characterized in that: The metal electrolyte is an iron metal electrolyte or a zinc metal electrolyte.

3. A metal electrolyte flow battery system according to claim 1, characterized in that: The liquid inlet, the liquid outlet, and the gas outlet are respectively arranged on the tank wall, the bottom, and the top of the metal electrolyte storage tank.

4. A metal electrolyte flow battery system according to claim 1, characterized in that: The metal electrolyte storage tank is equipped with a temperature sensor for monitoring the temperature of the metal electrolyte in the metal electrolyte storage tank.

5. The metal electrolyte flow battery system according to claim 1, characterized in that: The metal electrolyte storage tank is equipped with a liquid level sensor for monitoring the liquid level of the metal electrolyte in the metal electrolyte storage tank.

6. A metal electrolyte flow battery system according to claim 1, characterized in that: The negative electrode cavity of the metal battery adopts a direct current field or a serpentine flow field, and the cathode cavity of the metal electrolyte regeneration electrolytic cell can adopt a direct current field or a serpentine flow field.

7. The metal electrolyte flow battery system according to claim 1, characterized in that: When the negative electrode reaction conductive diffusion layer of the metal battery is a metal material, its structure is a mesh or foam structure, and the material is one of nickel, iron, iron-nickel alloy, copper, copper-nickel alloy, and titanium; when the negative electrode reaction conductive layer diffusion is a non-metallic material, the material is one of carbon paper or carbon felt.

8. The metal electrolyte flow battery system according to claim 1, characterized in that: Pressure sensors are installed at the outlets of the first electrolyte pump, the second electrolyte pump, the third electrolyte pump, and the fourth electrolyte pump.

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