CN-122013262-A - Electrolytic recovery device and method for liquid metal battery

Abstract

The invention discloses an electrolytic recovery device and method for a liquid metal battery, relates to the technical field of liquid metal battery recovery, comprises a reaction kettle, comprises a cabin body and a top cover arranged at the top of the cabin body; the anode component comprises a refractory salt reaction container and an anode conductive lead embedded in the side wall of the refractory salt reaction container, the cathode component comprises a conductive rod penetrating through a top cover and an active metal adsorption body, continuous feeding and cathode component replacement in an open environment are realized through integrating a feeding port, a cathode replacement port and an inert gas inlet and outlet in the top cover of the reaction kettle, dependence of a glove box is eliminated, a thermal isolation is formed through the cooling region surrounding the side wall of the upper part of the cabin body, a high-temperature electrolysis region and an operation region are effectively separated, safety is improved, rapid solidification of lithium products is promoted, and a detachable active metal adsorption body cathode component is combined with a net-shaped salvaging tool to efficiently separate deposited lithium and molten salt, so that recovery efficiency is remarkably improved.

Inventors

• FAN LEI
• Chen Yuchengye
• WANG MINGWEI
• PANG LINGRONG
• ZHU YONG
• TENG YANG
• WANG WEI
• JIANG KAI
• Yuan Xianmei

Assignees

• 贵州电网有限责任公司
• 华中科技大学

Dates

Publication Date

20260512

Application Date

20251231

Claims (10)

1. 1. An electrolytic recovery device for a liquid metal battery is characterized by comprising, The reaction kettle (1) comprises a cabin body (11) and a top cover (12) arranged at the top of the cabin body (11); A cooling zone (2) surrounding the upper part of the cabin (11); The anode assembly (3) is arranged in the reaction kettle (1) and comprises a refractory salt reaction container (31) and an anode conductive lead (32) embedded in the side wall of the refractory salt reaction container (31); A cathode assembly (4) suspended in the refractory salt reaction vessel (31) and comprising a conductive rod (41) penetrating through the top cover (12) and an active metal adsorbing body (42) arranged at one end of the conductive rod (41); the anode conductive lead (32) and the conductive rod (41) keep an electric isolation distance, and the anode conductive lead (32) and the conductive rod (41) are led out of the reaction kettle (1) through the top cover (12) respectively.
2. 2. The electrolytic recovery device for a liquid metal battery according to claim 1, wherein a molten salt layer (311) is provided in the molten salt resistant reaction vessel (31), and the active metal adsorbent (42) is immersed in the molten salt layer (311).
3. 3. The electrolytic recovery device for liquid metal batteries according to claim 1, wherein the outer wall of the top cover (12) is provided with an air inlet hole (121) and an air outlet hole (122), and the air inlet hole and the air outlet hole are respectively connected into an air supply pipeline (123) and an air outlet pipeline (124).
4. 4. The electrolytic recovery device for liquid metal batteries according to claim 3, wherein a feed port (125) is arranged between the air inlet hole (121) and the air outlet hole (122), and the conductive rod (41) penetrates through the feed port (125) to be connected with external power supply equipment (5).
5. 5. The electrolytic recovery device for liquid metal batteries according to claim 4, wherein an anode lead inlet (126) is arranged between the air inlet (121) and the feed port (125), and the anode conductive lead (32) penetrates through the anode lead inlet (126) and is connected with an external power supply device (5).
6. 6. The electrolytic recovery device for liquid metal batteries according to claim 5, wherein an observation port (128) is provided between the feed port (125) and the gas outlet hole (122).
7. 7. The electrolytic recovery device for liquid metal cells according to claim 6, wherein rubber plugs (129) are movably arranged in the feed port (125), the anode lead inlet and outlet (126) and the observation port (128).
8. 8. The electrolytic recovery device for the liquid metal battery according to claim 1, wherein the outer wall of the cooling area (2) is provided with a water inlet (21) and a water outlet (22).
9. 9. The liquid metal battery electrolysis recovery method is characterized by comprising the liquid metal battery electrolysis recovery device according to any one of claims 1-8, Adding molten salt electrolyte into a refractory salt reaction container (31), and introducing inert gas through an air inlet hole (121) and an air outlet hole (122), replacing air in a reaction kettle (1) and maintaining an inert atmosphere; Heating to melt the molten salt electrolyte, and adding the positive electrode alloy of the failed liquid metal battery into the molten salt resistant reaction container (31) through a feed port (125); The anode conductive lead (32) and the conductive rod (41) are respectively connected to an external power supply device (5), and electrochemical excitation is applied to an electrolysis system, so that active metals in the positive electrode alloy are reduced and deposited on the active metal adsorption body (42).
10. 10. The method for electrolytic recovery of liquid metal cells according to claim 9, characterized in that when the deposition product exceeds the adsorption capacity of the active metal adsorbent (42), electrolysis is suspended, the cathode assembly (4) is replaced through the feed port (125), and overflowed liquid metal is recovered from the molten salt surface by means of a separation tool.

Description

Electrolytic recovery device and method for liquid metal battery Technical Field The invention relates to the technical field of liquid metal battery recovery, in particular to an electrolytic recovery device and method for a liquid metal battery. Background The liquid metal battery has the advantages of high safety, long cycle life, low cost and the like due to the unique three-liquid-layer self-assembly structure, and is regarded as an important technical route of a large-scale energy storage system. The battery does not form a solid interface in the charge and discharge process, so that the problem of dendrite growth is avoided, meanwhile, the components of the battery are highly simplified, and a theoretical basis is provided for efficient closed-loop recovery of materials. In recent years, research on recycling of liquid metal batteries around lithium-bismuth, sodium-antimony and other systems is gradually developed, and a molten salt electrolysis method is mainly adopted to selectively reduce and separate active metals in a failure positive electrode alloy at high temperature, so that recycling of key resources is realized. However, the existing recovery technology is still limited to small-batch operation in a laboratory, and the defects of incapability of continuous operation, high energy consumption, severe environmental requirements and the like are generally overcome. Specifically, the traditional method is usually carried out in a closed inert environment such as a glove box, the single treatment capacity is only several to tens of grams, the electrolysis process is required to be interrupted for feeding, collecting products and replacing electrodes, and large-scale operation is difficult to realize. Based on the above problems, we propose an electrolytic recovery device and method for liquid metal batteries. Disclosure of Invention Therefore, the invention aims to solve the technical problem of realizing continuous, batch and low-energy consumption molten salt electrolysis recovery of the anode alloy of the failed liquid metal battery under an open system. The technical problem is solved by the technical scheme that the liquid metal battery electrolysis recovery device comprises a reaction kettle, a cooling zone, an anode assembly, a cathode assembly, a conductive rod and an active metal adsorption body, wherein the reaction kettle comprises a cabin body and a top cover arranged at the top of the cabin body, the cooling zone is arranged around the upper part of the cabin body, the anode assembly is arranged in the reaction kettle and comprises a refractory salt reaction container and an anode conductive lead embedded in the side wall of the refractory salt reaction container, the cathode assembly is suspended in the refractory salt reaction container and comprises a conductive rod penetrating through the top cover and an active metal adsorption body arranged at one end of the conductive rod, the anode conductive lead and the conductive rod keep an electric isolation distance, and the anode conductive lead and the conductive rod are led out of the reaction kettle through the top cover respectively. In a preferred embodiment of the liquid metal battery electrolysis recovery device, a molten salt layer is arranged in the molten salt resistant reaction container, and the active metal adsorbent is immersed in the molten salt layer. In an optimized implementation mode of the liquid metal battery electrolysis recovery device, an air inlet hole and an air outlet hole are formed in the outer wall of the top cover, and are respectively connected into an air supply pipeline and an air outlet pipeline. In a preferred embodiment of the liquid metal battery electrolysis recovery device, a feeding hole is arranged between the air inlet hole and the air outlet hole, and the conducting rod penetrates through the feeding hole to be connected with external power supply equipment. In a preferred embodiment of the liquid metal battery electrolysis recovery device, an anode lead inlet and an anode lead outlet are arranged between the air inlet and the feeding port, and the anode conductive lead penetrates through the anode lead inlet and the anode lead outlet to be connected with external power supply equipment. In a preferred embodiment of the liquid metal battery electrolysis recovery device, an observation port is arranged between the feeding port and the air outlet. In a preferred embodiment of the liquid metal battery electrolysis recovery device, rubber plugs are movably arranged in the feeding port, the anode lead inlet and outlet and the observation port. In a preferred embodiment of the liquid metal battery electrolysis recovery device, the outer wall of the cooling area is provided with a water inlet and a water outlet. The invention also provides a liquid metal battery electrolysis recovery method, which comprises the steps of adding molten salt electrolyte into a refractory salt reaction container, intro