Liquid metal battery electrode material separation device and use method

Abstract

The invention discloses a liquid metal battery electrode material separation device, and relates to the technical field of energy storage batteries, the liquid metal battery electrode material separation device comprises a fixed seat, a reaction cavity, a corundum crucible, a temperature control assembly, an electrolysis structure, an anti-dissipation structure, a collection structure, a negative electrode extraction pipe and a positive electrode extraction pipe; the fixed seat comprises a bottom plate and a heat insulation supporting seat; the heat insulation supporting seat is mounted at the top of the bottom plate; the invention also discloses a use method of the liquid metal battery electrode material separation device. According to the liquid metal battery electrode material separation device, through cooperation of the annular anode basket and the cathode rod in the center, the electric field edge effect can be eliminated, and the electrolysis uniformity is improved; in addition, directional separation of the dual-electrode metal is achieved through efficient conduction of the Mg-stabilized zirconia diaphragm on lithium ions and efficient blocking of the Mg-stabilized zirconia diaphragm on antimony and bismuth ions, and efficient and directional separation and recovery of the high-purity positive and negative electrode metal can be achieved by combining the density difference of the positive and negative electrode metal and a designed bimetal exclusive extraction path.

Description

Technical Field

[0001] This invention relates to the field of energy storage battery technology, and more specifically, to a liquid metal battery electrode material separation device and its usage method. Background Technology

[0002] Liquid metal batteries are a novel electrochemical energy storage technology that uses liquid metal as the electrode material and molten inorganic salt as both the electrolyte and the separator. Thanks to the significant density differences between the components, a stable layered structure can be spontaneously formed inside the battery. This technology has advantages such as long cycle life, high safety, low cost, and easy scalability, showing broad application prospects and is considered a highly promising large-scale power storage solution.

[0003] With technological advancements and widespread application, the issue of resource recycling of spent liquid metal batteries has become increasingly prominent. These batteries contain high-value metals such as lithium, bismuth, and antimony, making efficient recycling of electrode materials crucial for cost control and resource recycling.

[0004] Existing electrolytic recycling technologies face the following bottlenecks in this scenario. First, uneven electric fields lead to the co-deposition of impurities. Traditional flat electrode plates exhibit edge effects, resulting in large fluctuations in current density (±10%). Trace impurities in waste materials are prone to co-deposition at the cathode, leading to lithium purity below 98%. Second, low-density lithium has a high recovery loss rate. The lithium density (0.534 g / cm³) is much lower than that of molten electrolyte (1~3 g / cm³), resulting in a floating state. Existing scraping or simple siphon mechanisms are difficult to collect completely, and lithium is easily oxidized upon contact with air.

[0005] Therefore, developing an integrated electrolysis device that adapts to the characteristics of waste electrode materials from liquid metal batteries and combines the advantages of high-efficiency separation, long-term corrosion resistance, and low-loss recycling has become an urgent need for the industry. Summary of the Invention

[0006] In view of this, the purpose of this invention is to provide a liquid metal battery electrode material separation device and method, which eliminates the edge effect of the electric field and improves the electrolysis uniformity by cooperating with the annular anode basket and the central cathode rod; and achieves directional separation of the two electrode metals by using the Mg-stabilized zirconium oxide membrane for efficient conduction of lithium ions and efficient blocking of antimony and bismuth ions. Thus, by combining the density difference of the positive and negative electrode metals and the designed dual-metal exclusive extraction path, the recovery efficiency is greatly improved while achieving precise separation.

[0007] To achieve the above objectives, the present invention provides a liquid metal battery electrode material separation device, comprising:

[0008] The fixed base includes a base plate and a heat-insulating support base mounted on top of the base plate; the heat-insulating support base includes a flat plate mounted on the top surface of the base plate and a support cylinder mounted on the top surface of the flat plate. The reaction chamber includes an outer shell installed inside the support cylinder, a cover plate installed on the top opening side of the outer shell, and a fastening assembly for connecting the cover plate and the outer shell; a temperature control assembly for adjusting the ambient temperature inside the outer shell is provided between the outer shell and the support cylinder. A corundum crucible is provided inside the outer shell. An electrolytic structure includes an anode basket installed inside the housing, a cathode rod installed on the cover plate and located inside the anode basket, and a Mg-stabilized zirconium oxide diaphragm installed in an annular tubular shape inside the anode basket; the top of the cathode rod is provided with a cathode terminal extending to the top of the cover plate, and the top of the anode basket is provided with two anode terminals extending to the top of the cover plate. The anti-escape structure includes a flow guide installed on the outside of the cathode terminal and corresponding to the top of the cathode rod, and a liquid collection crucible disposed inside the corundum crucible and corresponding to the position of the anode basket; The collection structure includes two heating bases symmetrically mounted on both sides of the top surface of the plate and a vacuum tank mounted on top of the heating bases; The support cylinder is provided with a negative electrode extraction pipe for connecting the flow guide shroud and one of the two vacuum tanks, and the support cylinder is also provided with a positive electrode extraction pipe for connecting the liquid collecting crucible and the other vacuum tank.

[0009] Preferably, the temperature control assembly includes a heating rod installed between the support cylinder and the outer shell, and a thermocouple installed on the cover plate and extending into the inner side of the corundum crucible; the heating rod is configured to adjust the ambient temperature inside the outer shell based on monitoring data from the thermocouple.

[0010] Preferably, an alumina ceramic fiber insulation layer is provided between the outer wall of the outer shell and the inner wall of the support cylinder; an insulating ceramic gasket is provided between the top surface of the outer shell and the bottom surface of the cover plate.

[0011] Preferably, a positioning groove adapted to the size of the outer wall of the liquid collecting crucible is formed at the center of the inner bottom wall of the corundum crucible, and the liquid collecting crucible is fitted into the positioning groove.

[0012] Preferably, a vertical guide groove is provided on the outer side of the cathode terminal.

[0013] Preferably, the vacuum tank is provided with an equipment interface, and a three-way valve is installed on the equipment interface. The other two ends of the three-way valve away from the equipment interface are respectively connected to the vacuum unit and the inert gas filling equipment, and the two vacuum tanks share the same vacuum unit.

[0014] Preferably, a shut-off valve is installed inside the negative electrode extraction tube and the positive electrode extraction tube, and the portions of the negative electrode extraction tube and the positive electrode extraction tube located outside the support cylinder and the vacuum tank are fitted with heat insulation sleeves, and the outer sides of both vacuum tanks are fitted with jacketed heating sleeves.

[0015] Preferably, the cover plate is equipped with a first feeding pipe, a second feeding pipe, and two exhaust valves. The second feeding pipe is used to introduce material into the annular inner cavity of the anode basket, and the first feeding pipe is used to introduce material between the corundum crucible and the anode basket.

[0016] This invention also proposes a method for using a liquid metal battery electrode material separation device, comprising the following steps: Step S1: Fill the waste material into the annular inner cavity of the anode basket through the second feeding pipe, and fill the electrolyte between the corundum crucible and the anode basket through the first feeding pipe. After filling, seal the first feeding pipe and the second feeding pipe. Step S2: Activate the heating rod to adjust the temperature inside the outer shell to the set target system temperature, introduce inert gas and maintain the gas pressure inside the outer shell at the set slight positive pressure; connect the positive and negative terminals of the DC power supply to the anode terminal and the cathode terminal respectively; Step S3: Connect the DC power supply and adjust the potential to the target value. The waste material undergoes an oxidation reaction in the anode basket. Negative electrode metal ions migrate through the Mg-stabilized zirconium oxide membrane to the cathode terminal, deposit as negative electrode metal in the flow channel, and gather in the flow hood. Positive electrode metal ions are blocked by the Mg-stabilized zirconium oxide membrane, reduced, and form molten positive electrode that flows to the liquid collection crucible. Step S4: Adjust the temperatures of the two vacuum tanks, the negative electrode extraction tube, and the positive electrode extraction tube to preset values ​​using the jacketed heating sleeve. Start the vacuum unit and adjust the gas pressure of the two vacuum tanks to set values ​​respectively. After the extraction reminder is reached, first open the shut-off valve on the negative electrode extraction tube to extract the negative electrode metal into the vacuum tank, and then open the shut-off valve on the positive electrode extraction tube to extract the positive electrode metal into the vacuum tank. The extraction time periods of the negative electrode metal and the positive electrode metal do not overlap, but after the extraction of either the negative electrode metal or the positive electrode metal is completed, it is necessary to refill the outer shell with inert gas.

[0017] Preferably, the method of using the liquid metal battery electrode material separation device further includes: Step S5: After the temperature inside the outer shell stabilizes, stop heating, remove the thermocouple to check the electrolyte level, and replenish electrolyte according to the electrolyte consumption. Then, repeat steps S1-S4 for continuous operation. Step S6: After the operation is completed, turn off the DC power supply and the vacuum unit, continue to introduce inert gas and gradually cool down. After the device cools down to room temperature, open the cover plate and take out the anode basket and the liquid collection crucible to clean up the residue and check the status of each component for maintenance.

[0018] Compared with the prior art, the present invention has the following advantages and effects: 1. The liquid metal battery electrode material separation device and method of the present invention eliminates the edge effect of the flat electrode by adopting a ring-shaped synergistic electrode structure, resulting in a uniform electric field distribution and a stable and efficient electrolysis process. Combined with the high selective permeability of the Mg-stabilized zirconium oxide membrane to target ions and the timed extraction design based on the dual-metal exclusive extraction path of density difference, it not only shortens the separation cycle, but also achieves high-purity directional separation of positive and negative electrode metals, with a recovery rate of not less than 98% and a purity of over 99.2%, which can significantly improve the recovery efficiency while achieving precise separation.

[0019] 2. The liquid metal battery electrode material separation device in this invention adopts a composite structure of corundum crucible and stainless steel shell, and is equipped with a high-temperature resistant and corrosion-resistant Mg-stabilized zirconium oxide membrane to ensure long-term stability in molten salt environment; at the same time, the whole process is carried out under inert atmosphere protection, combined with vacuum extraction and inert gas purging process, which effectively prevents metal oxidation and environmental pollution and can meet the requirements of green recycling.

[0020] 3. The liquid metal battery electrode material separation device of this invention adopts an integrated annular anode basket design, which facilitates rapid loading and cleaning. Combined with intelligent temperature control and preset timing operation, it greatly reduces the complexity and professional requirements of manual operation. In addition, by adjusting the heating temperature and operating parameters, the device can be adapted to recover liquid metal battery electrode materials with different melting point compositions, and has good prospects for industrial application. Attached Figure Description

[0021] Figure 1 This is a schematic diagram of the liquid metal battery electrode material separation device and its usage method in an embodiment of the present invention; Figure 2 This is a schematic diagram of the liquid metal battery electrode material separation device and its usage method in an embodiment of the present invention.

[0022] Explanation of reference numerals in the attached figures: 1. Fixed base; 11. Base plate; 12. Heat insulation support base; 121. Flat plate; 122. Support cylinder; 2. Reaction chamber; 21. Outer shell; 211. Alumina ceramic fiber insulation layer; 212. Insulating ceramic gasket; 22. Cover plate; 221. First feeding pipe; 222. Exhaust valve; 223. Second feeding pipe; 23. Fastening assembly; 3. Heating rod; 4. Corundum crucible; 5. Electrolytic structure; 51. Cathode rod; 511. Cathode terminal; 52. Mg-stabilized zirconia diaphragm; 53. Anode basket; 531. Anode terminal; 6. Anti-escape structure; 61. Flow guide; 62. Liquid collection crucible; 7. Collection structure; 71. Heating base; 72. Vacuum tank; 721. Equipment interface; 8. Negative electrode extraction tube; 9. Positive electrode extraction tube; 10. Thermocouple. Detailed Implementation

[0023] The technical solution of the present invention will now be clearly and completely described with reference to the accompanying drawings. Obviously, the described embodiments are only some, not all, of the embodiments of the present invention. Based on the embodiments of the present invention, all other embodiments obtained by those skilled in the art without creative effort are within the scope of protection of the present invention.

[0024] In the description of this invention, it should be noted that, unless otherwise explicitly specified and limited, the terms "installation," "connection," and "linking" should be interpreted broadly. For example, they can refer to a fixed connection, a detachable connection, or an integral connection; they can refer to a mechanical connection or an electrical connection; they can refer to a direct connection or an indirect connection through an intermediate medium; they can also refer to the internal connection of two components; and they can refer to a wireless connection or a wired connection. Those skilled in the art can understand the specific meaning of the above terms in this invention based on the specific circumstances.

[0025] Please see Figure 1-2 As shown, this embodiment of the invention provides a liquid metal battery electrode material separation device, including a fixed base 1, a reaction chamber 2, an alumina crucible 4, a temperature control component, an electrolysis structure 5, an anti-escape structure 6, a collection structure 7, a negative electrode extraction tube 8, and a positive electrode extraction tube 9.

[0026] The fixed base 1 includes a base plate 11 and a heat insulation support base 12, which is installed on the top of the base plate 11. The heat insulation support base 12 includes a flat plate 121 and a support cylinder 122, with the flat plate 121 installed on the top surface of the base plate 11 and the support cylinder 122 installed on the top surface of the flat plate 121.

[0027] The reaction chamber 2 includes an outer shell 21, a cover plate 22, and a fastening assembly 23. The outer shell 21 is installed inside the support cylinder 122, the cover plate 22 is installed on the top opening side of the outer shell 21, and the fastening assembly 23 is used to connect the cover plate 22 and the outer shell 21. A temperature control assembly for adjusting the internal ambient temperature of the outer shell 21 is provided between the outer shell 21 and the support cylinder 122.

[0028] As a further description of the above solution, the fastening assembly 23 includes a connecting screw, an insulating sleeve, and a connecting nut. The insulating sleeve is fitted over the outside of the connecting screw and is used to isolate the connecting screw from contact with the outer shell 21 and the cover plate 22. The connecting screw and the insulating sleeve pass through the outer shell 21 and the cover plate 22. The connecting nut is threaded onto the connecting screw. By tightening the connecting nut, the cover plate 22 can be fixed to the outer shell 21. Conversely, when the connecting nut is loosened and removed, the cover plate 22 can be separated from the outer shell 21. The insulating sleeve is an alumina ceramic tube to ensure insulation between the cover plate and the cavity.

[0029] As a preferred embodiment of the above solution, the outer shell 21 is made of stainless steel to provide strong mechanical strength and rigidity, providing essential mechanical support and safety protection for the brittle and expensive corrosion-resistant ceramic liner, bearing the weight of all contents and mechanical stress during operation, effectively improving the robustness and safety of the device.

[0030] An alumina crucible 4 is disposed inside the outer shell 21. Preferably, in this embodiment of the invention, the Al2O3 content of the alumina crucible 4 is greater than 99%, so as to utilize its intrinsic chemical inertness to ensure that the alumina crucible 4 is not corroded during long-term operation, while avoiding the introduction of impurity ions. In addition, the excellent high-temperature insulation of the alumina crucible 4 ensures the precise control of the current path. Thus, it is convenient to combine the outer insulation layer and the metal support structure to form a long-life, highly reliable, and low-pollution electrolytic reaction vessel.

[0031] The electrolytic structure 5 includes an anode basket 53, a cathode rod 51, and a Mg-stabilized zirconia diaphragm 52. The anode basket 53 is installed inside the outer casing 21, the cathode rod 51 is installed on the cover plate 22 and located inside the anode basket 53, and the Mg-stabilized zirconia diaphragm 52 is installed in an annular tube shape inside the anode basket 53. The top of the cathode rod 51 is provided with a cathode terminal 511 extending to the top of the cover plate 22, and the top of the anode basket 53 is equipped with two anode terminals 531 extending to the top of the cover plate 22.

[0032] As a preferred embodiment of the above scheme, the anode basket 53 is an integral annular titanium alloy basket (Ti≥99.8%), and an annular inner cavity is formed inside the basket. The annular inner cavity can be used to collect waste materials. Titanium alloy not only has good electrical conductivity, but also has extremely high corrosion resistance in high-temperature molten salt environments. Especially in electrolytes containing fluorides or chlorides, it is not easy to corrode, dissolve or passivate. As an anode structural material for long-term service, it helps to reduce the replacement frequency of the anode basket 53 while ensuring uniform current distribution and more complete oxidation reaction of waste materials.

[0033] As another preferred option of the above scheme, the cathode rod 51 is a high-purity nickel cylinder (Ni≥99.9%). Nickel has high electrochemical stability in common liquid metal battery electrolytes (such as LiCl-KCl eutectic salt) and is not prone to participating in side reactions. As an inert cathode substrate, it is conducive to the uniform deposition of lithium ions and the formation of a dense and easily peelable lithium metal layer. In addition, the nickel cathode is corrosion resistant and has a long lifespan, making it very suitable for long-term continuous operation.

[0034] As another preferred embodiment of the above scheme, the Mg-stabilized zirconium oxide membrane 52 used in this invention, through magnesium ion doping optimization, achieves a balance between densification, high ionic conductivity, and high ion selectivity; a density greater than 99.5% constitutes an intrinsic physical barrier; and a density greater than 5 × 10⁻⁶ - Li ³S / cm + The conductivity provides a fast track for the efficient recovery of lithium; while Bi³⁺ with a purity greater than 99.8% offers a high efficiency. + / Sb³ + The barrier effect acts like a precise ion filter, fundamentally preventing the migration of impurity metals to the cathode; the synergistic effect of these three factors enables the device to maintain a high-purity lithium recovery rate of over 99.2% while ensuring long-term stable operation.

[0035] In this embodiment, the Mg-stabilized zirconium oxide membrane 52 has a membrane density greater than 99.5%, and the Li... + Electrical conductivity greater than 5×10 - ³S / cm, Bi³ + / Sb³ + The barrier effect is greater than 99.8%.

[0036] As a further description of the above scheme, the anode terminal 531 and cathode terminal 511 are respectively used to connect the positive and negative terminals of the DC power supply, so that when the DC power supply is turned on, the waste material can react in the anode basket 53, causing the negative electrode metal ions to migrate through the Mg stabilized zirconia membrane 52 to the cathode rod 51 and deposit on the cathode rod 51, while the positive electrode metal particles are blocked by the Mg stabilized zirconia membrane 52, so as to reduce and form a molten positive electrode inside the anode basket 53. Due to the large density difference, the negative electrode metal deposited on the cathode rod 51 will float up along the cathode rod 51, while the molten positive electrode metal in the anode basket 53 will sink.

[0037] The anti-escape structure 6 includes a flow guide 61 and a liquid collection crucible 62. The flow guide 61 is installed on the outside of the cathode terminal 511 and corresponds to the top of the cathode rod 51. The liquid collection crucible 62 is located inside the corundum crucible 4 and corresponds to the position of the anode basket 53.

[0038] As a further description of the above scheme, the flow guide 61 is cup-shaped and inverted on the top of the cathode rod 51. The negative electrode metal floating along the axis of the cathode rod 51 will gather in the flow guide 61, so that the flow guide 61 restricts the outward diffusion of the negative electrode metal. Specifically, the flow guide 61 and the cathode rod 51 are made of the same high-purity nickel to maintain electrochemical stability.

[0039] In addition, the anode basket 53 is a mesh structure, and the molten positive electrode metal sinking in the anode basket 53 will fall through the anode basket 53 into the liquid collecting crucible 62, so as to collect the molten positive electrode metal through the liquid collecting crucible 62.

[0040] The collection structure 7 includes a heating base 71 and a vacuum tank 72. The two heating bases 71 are symmetrically installed on both sides of the top surface of the plate 121, and the vacuum tank 72 is installed on top of the heating base 71.

[0041] As a further description of the above scheme, the heating base 71 is provided to heat the vacuum tank 72 to maintain the temperature of the vacuum tank 72 within a set range, thereby preventing the solidification of the positive or negative electrode metal or local overcooling while inhibiting the volatilization and oxidation of the material.

[0042] The support cylinder 122 is provided with a negative electrode extraction pipe 8 for connecting the flow guide 61 and one of the two vacuum tanks 72, and the support cylinder 122 is also provided with a positive electrode extraction pipe 9 for connecting the liquid collection crucible 62 and the other vacuum tank 72.

[0043] As a further description of the above scheme, when extracting the negative electrode metal, the negative electrode extraction tube 8 is used to connect the flow guide shroud 61 and the corresponding vacuum tank 72, so that the negative electrode metal flows into the corresponding vacuum tank 72 along the negative electrode extraction tube 8; similarly, the provided positive electrode extraction tube 9 can connect the liquid collection crucible 62 and the corresponding vacuum tank 72 when extracting the positive electrode metal, so that the positive electrode metal flows into the corresponding vacuum tank 72 through the positive electrode extraction tube 9.

[0044] Please see Figure 1-2 As shown, the temperature control assembly includes a heating rod 3 and a thermocouple 10. The heating rod 3 is installed between the support cylinder 122 and the outer shell 21, and the thermocouple 10 is installed on the cover plate 22 and extends to the inside of the corundum crucible 4. The heating rod 3 is configured to adjust the ambient temperature inside the outer shell 21 according to the monitoring data of the thermocouple 10.

[0045] As a preferred embodiment of the above scheme, the heating rod 3 is a ring-shaped silicon carbide heating rod, the thermocouple 10 is a Pt100 temperature sensor, and the temperature control component also includes a PLC controller. After setting the ambient temperature value inside the outer casing 21, the thermocouple 10 can play the role of detecting the temperature. After receiving the detection data from the thermocouple 10, the PLC controller can adjust the operating power of the heating rod 3 to achieve the temperature regulation function and maintain the ambient temperature inside the outer casing 21 within the preset range.

[0046] Please see Figure 1 As shown, an alumina ceramic fiber insulation layer 211 is provided between the outer wall of the outer shell 21 and the inner wall of the support cylinder 122.

[0047] As a further description of the above scheme, the alumina ceramic fiber insulation layer 211 is suitable for blocking the outer shell 21 and the support cylinder 122 to reduce heat exchange, play a role in heat insulation, and effectively reduce the heat loss efficiency inside the outer shell 21.

[0048] Please see Figure 1 As shown, an insulating ceramic gasket 212 is provided between the top surface of the outer casing 21 and the bottom surface of the cover plate 22. The insulating ceramic gasket 212 between the outer casing 21 and the cover plate 22 not only maintains good sealing performance but also separates the outer casing 21 and the cover plate 22, maintaining good insulation and preventing short circuits between the positive and negative poles. Specifically, the insulating ceramic gasket 212 needs to withstand temperatures greater than 800℃ to prevent softening, melting, cracking, or failure under high temperatures.

[0049] Please see Figure 1As shown, a positioning groove adapted to the outer wall size of the liquid collecting crucible 62 is formed at the center of the inner bottom wall of the corundum crucible 4. The liquid collecting crucible 62 is fitted into the positioning groove. The positioning groove is designed to ensure the accurate positioning of the liquid collecting crucible 62 and prevent it from sliding inside the corundum crucible 4, thereby maintaining the coaxiality of the corundum crucible 4 and the anode basket 53 and avoiding the collection of molten cathode metal from being affected by relative displacement between the anode basket 53 and the corundum crucible 4.

[0050] Please see Figure 1 As shown, a vertical guide groove is provided on the outer side of the cathode terminal 511. The guide groove increases the contact surface between the cathode terminal 511 and the negative electrode metal ions, thereby improving the negative electrode metal deposition efficiency. When the negative electrode metal is located in the guide groove, the negative electrode metal will generate a high surface tension, thereby forming a self-constraining effect in the guide groove. This prevents the negative electrode metal from adhering to the cathode terminal 511 while keeping it moving along the guide groove.

[0051] Please see Figure 1 As shown, the vacuum tank 72 is provided with an equipment interface 721, and a three-way valve is installed on the equipment interface 721. The other two ends of the three-way valve away from the equipment interface 721 are connected to the vacuum unit and the inert gas filling equipment, respectively. The two vacuum tanks 72 share the same vacuum unit.

[0052] As a further description of the above scheme, when the three-way valve is controlled to connect the vacuum unit to the pipeline, the operation of the vacuum unit can be used to adjust the gas pressure inside the vacuum tank 72. When the three-way valve is controlled to connect the inert gas filling device to the pipeline, the inert gas filling device can fill the vacuum tank 72 with inert gas.

[0053] Please see Figure 1 As shown, shut-off valves are installed inside the negative electrode extraction tube 8 and the positive electrode extraction tube 9. The portions of the negative electrode extraction tube 8 and the positive electrode extraction tube 9 located outside the support cylinder 122 and the vacuum tank 72 are fitted with heat insulation sleeves. The outer sides of both vacuum tanks 72 are fitted with jacketed heating sleeves.

[0054] As a further description of the above scheme, the provided jacketed heating jacket and insulation jacket are suitable for use with the heating base 71 to maintain the temperature of the vacuum tank 72 within the set range, and by controlling the opening of the shut-off valve, it can connect the vacuum tank 72 and the outer shell 21. When the shut-off valve is opened, the vacuum unit or inert gas filling equipment can control the gas pressure or inert atmosphere inside the outer shell 21.

[0055] Please see Figure 1-2As shown, the cover plate 22 is equipped with a first feeding pipe 221, a second feeding pipe 223, and two exhaust valves 222. The second feeding pipe 223 is used to introduce the material into the annular inner cavity of the anode basket 53, and the first feeding pipe 221 is used to introduce the material between the corundum crucible 4 and the anode basket 53.

[0056] As a further description of the above scheme, the top of the anode basket 53 is provided with a discharge port corresponding to the end position of the second feeding pipe 223. The second feeding pipe 223 is used to add waste material into the annular inner cavity of the anode basket 53 through the discharge port. The first feeding pipe 221 is used to add electrolyte between the corundum crucible 4 and the anode basket 53. The exhaust valve 222 is adapted to play the role of venting air when the inert gas filling device is filled into the outer shell 21 through the negative electrode extraction pipe 8 and the positive electrode extraction pipe 9, so as to form a filling and discharging circuit to ensure complete air discharge and fill the entire inner cavity of the outer shell 21 with inert gas.

[0057] Please see Figure 1-2 As shown, the present invention also proposes a method for using a liquid metal battery electrode material separation device, comprising the following steps: Step S1: Fill the waste material into the annular cavity of the anode basket 53 through the second feeding pipe 223, and fill the electrolyte between the corundum crucible 4 and the anode basket 53 through the first feeding pipe 221. After filling, seal the first feeding pipe 221 and the second feeding pipe 223. Step S2: Start the heating rod 3 to adjust the temperature inside the outer shell 21 to the set target system temperature, introduce inert gas and maintain the gas pressure inside the outer shell 21 at the set micro-positive pressure; connect the positive and negative terminals of the DC power supply to the anode terminal 531 and the cathode terminal 511 respectively. Step S3: Turn on the DC power supply and adjust the potential to the target value. The waste material undergoes an oxidation reaction in the anode basket 53. The negative electrode metal ions migrate through the Mg stabilized zirconium oxide membrane 52 to the cathode terminal 511, where they are deposited as negative electrode metal in the flow channel and gather in the flow guide shroud 61. The positive electrode metal ions are blocked by the Mg stabilized zirconium oxide membrane 52 and, after reduction, form molten positive electrode that flows to the liquid collection crucible 62. Step S4: Adjust the temperatures of the two vacuum tanks 72, the negative electrode extraction tube 8, and the positive electrode extraction tube 9 to the preset values ​​using the jacketed heating jacket. Start the vacuum unit and adjust the gas pressure of the two vacuum tanks to the set values ​​respectively. After the extraction reminder is reached, first open the shut-off valve on the negative electrode extraction tube 8 to extract the negative electrode metal into the vacuum tank 72, and then open the shut-off valve on the positive electrode extraction tube 9 to extract the positive electrode metal into the vacuum tank 72. The extraction time periods of the negative electrode metal and the positive electrode metal do not overlap, but after the extraction of the negative electrode metal or the positive electrode metal is completed, it is necessary to refill the outer shell 21 with inert gas.

[0058] As a preferred option, the extraction reminder can be a time-based reminder set according to experimental data, implemented by adding a time relay to the control system, or it can be a trigger-based reminder that is dynamically adjusted according to the electrolysis efficiency, implemented by adding a monitoring module.

[0059] Please see Figure 1-2 As shown, in step S5: after the temperature inside the outer shell 21 stabilizes, heating is paused. Thermocouple 10 is removed to check the electrolyte level. Electrolyte is replenished according to the electrolyte consumption. Then, steps S1-S4 can be repeated for continuous operation. Step S6: After the operation is completed, turn off the DC power supply and vacuum unit, continue to introduce inert gas and gradually cool down. After the device cools down to room temperature, open the cover plate 22 and take out the anode basket 53 and the liquid collection crucible 62 to clean up the residue and check the status of each component for maintenance.

[0060] As a further description of the above scheme, in step S5, the electrolyte level can be checked by looking at the wet / dry boundary line on the thermocouple 10.

[0061] It should be noted that the liquid metal battery waste material provided in this application is a solid composition consisting of granulated positive and negative electrode metals and electrolyte, with a particle size of 20-50 mm.

[0062] Based on the principles of directional ion migration, high-efficiency electric field, density-adaptive timed operation, and green environmental protection, this invention achieves efficient oxidation of liquid metal battery waste materials at the annular anode, directional migration of negative electrode metal to the cathode for aggregation, and sedimentation of positive electrode metal to the bottom due to its high density during the recycling process. By setting each operation time node based on previous experimental data, efficient and green recycling of positive and negative electrodes is achieved.

[0063] Example 1: The following is a specific example of the basic structural dimensions of the present invention:

[0064] If the basic structure is configured with the dimensions in the table above, the single loading capacity of waste materials can reach 30-35 kg. When inert gas (argon) is filled into the outer shell 21, the outer shell 21 can maintain a slight positive pressure of 0.03 MPa. Before extracting the negative electrode metal, the vacuum tank 72 for storing the negative electrode metal needs to maintain a negative pressure of 0.025 MPa under the action of the vacuum unit so that the negative electrode metal can flow smoothly to the corresponding vacuum tank 72. Before extracting the positive electrode metal, the vacuum tank 72 for storing the positive electrode metal needs to maintain a negative pressure of 0.015 MPa under the action of the vacuum unit so that the positive electrode metal can flow smoothly to the corresponding vacuum tank 72.

[0065] During this process, after the negative electrode metal is extracted for 2-5 minutes, the connection between the vacuum unit and the negative electrode metal storage vacuum tank 72 needs to be blocked through a three-way valve, and the inert gas filling device needs to be connected to the negative electrode metal storage vacuum tank 72 to fill the vacuum tank 72 and the outer shell 21 with inert gas. After filling for 1-2 minutes, the connection between the inert gas filling device and the negative electrode metal storage vacuum tank 72 needs to be blocked through a three-way valve to maintain the inert atmosphere of the vacuum tank 72 and the outer shell 21. When extracting the positive electrode metal, the connection between the vacuum unit and the positive electrode metal storage vacuum tank 72 needs to be blocked after 8-10 minutes of extraction, and the connection between the inert gas filling device and the positive electrode metal storage vacuum tank 72 needs to be blocked after filling with inert gas for 1-2 minutes to maintain the inert atmosphere of the vacuum tank 72 and the outer shell 21.

[0066] In addition, after a period of use, thermocouple 10 needs to be removed to check the electrolyte level. If the electrolyte level is 20mm lower than the initial level, electrolyte needs to be added in time. When the waste material in the anode basket 53 has completed its reaction (the current drops to below 10% of the initial value), steps 1-4 can be repeated for the next batch of operation; 3-4 batches can be run continuously per day.

[0067] The above are merely preferred embodiments of the present invention and are not intended to limit the scope of protection of the present invention. Those skilled in the art can adjust the reminder parameters of the time relay, the anode basket filling amount, the feed port size of the integral anode basket, the spacing between the double terminals, the heating rod power, etc., based on the core design concept of the present invention. All equivalent modifications or substitutions under the concept of the present invention should be included within the scope of protection of the present invention.

[0068] While the present invention has been disclosed above, its scope of protection is not limited thereto. Those skilled in the art can make various changes and modifications without departing from the spirit and scope of this disclosure, and all such changes and modifications will fall within the scope of protection of this invention.

Claims

1. A device for separating electrode materials in a liquid metal battery, characterized in that, include: The fixed base (1) includes a base plate (11) and a heat-insulating support base (12) installed on the top of the base plate (11); the heat-insulating support base (12) includes a flat plate (121) installed on the top surface of the base plate (11) and a support cylinder (122) installed on the top surface of the flat plate (121). The reaction chamber (2) includes an outer shell (21) installed inside the support cylinder (122), a cover plate (22) installed on the top opening side of the outer shell (21), and a fastening assembly (23) for connecting the cover plate (22) and the outer shell (21); a temperature control assembly for adjusting the ambient temperature inside the outer shell (21) is provided between the outer shell (21) and the support cylinder (122); A corundum crucible (4) is provided on the inner side of the outer shell (21). The electrolytic structure (5) includes an anode basket (53) installed inside the outer casing (21), a cathode rod (51) installed on the cover plate (22) and located inside the anode basket (53), and a Mg-stabilized zirconium oxide diaphragm (52) installed in an annular tubular shape inside the anode basket (53); the top of the cathode rod (51) is provided with a cathode terminal (511) extending to the top of the cover plate (22), and the top of the anode basket (53) is equipped with two anode terminals (531) extending to the top of the cover plate (22); The anti-escape structure (6) includes a flow guide (61) installed on the outside of the cathode terminal (511) and corresponding to the top of the cathode rod (51) and a liquid collection crucible (62) disposed on the inside of the corundum crucible (4) and corresponding to the position of the anode basket (53). The collection structure (7) includes two heating bases (71) symmetrically mounted on both sides of the top surface of the plate (121) and a vacuum tank (72) mounted on the top of the heating bases (71). The support cylinder (122) is provided with a negative electrode extraction tube (8) for connecting the flow guide (61) and one of the two vacuum tanks (72), and the support cylinder (122) is also provided with a positive electrode extraction tube (9) for connecting the liquid collecting crucible (62) and the other vacuum tank (72).

2. The liquid metal battery electrode material separation device according to claim 1, characterized in that, The temperature control assembly includes a heating rod (3) installed between the support cylinder (122) and the outer shell (21) and a thermocouple (10) installed on the cover plate (22) and extending to the inside of the corundum crucible (4); the heating rod (3) is configured to adjust the ambient temperature inside the outer shell (21) based on the monitoring data of the thermocouple (10).

3. The liquid metal battery electrode material separation device according to claim 2, characterized in that, An alumina ceramic fiber insulation layer (211) is provided between the outer wall of the outer shell (21) and the inner wall of the support cylinder (122); an insulating ceramic gasket (212) is provided between the top surface of the outer shell (21) and the bottom surface of the cover plate (22).

4. The liquid metal battery electrode material separation device according to claim 1, characterized in that, The corundum crucible (4) has a positioning groove at the center of its inner bottom wall that is adapted to the size of the outer wall of the liquid collecting crucible (62), and the liquid collecting crucible (62) is fitted into the positioning groove.

5. The liquid metal battery electrode material separation device according to claim 1, characterized in that, A vertical guide groove is provided on the outside of the cathode terminal (511).

6. The liquid metal battery electrode material separation device according to claim 1, characterized in that, The vacuum tank (72) is provided with an equipment interface (721), and a three-way valve is installed on the equipment interface (721). The other two ends of the three-way valve away from the equipment interface (721) are respectively connected to the vacuum unit and the inert gas filling equipment. The two vacuum tanks (72) share the same set of vacuum units.

7. The liquid metal battery electrode material separation device according to claim 1, characterized in that, The negative electrode extraction tube (8) and the positive electrode extraction tube (9) are equipped with shut-off valves. The portions of the negative electrode extraction tube (8) and the positive electrode extraction tube (9) located outside the support cylinder (122) and the vacuum tank (72) are fitted with heat insulation sleeves. The outer sides of both vacuum tanks (72) are fitted with jacketed heating sleeves.

8. The liquid metal battery electrode material separation device according to claim 1, characterized in that, The cover plate (22) is equipped with a first feeding pipe (221), a second feeding pipe (223) and two exhaust valves (222). The second feeding pipe (223) is used to introduce material into the annular inner cavity of the anode basket (53), and the first feeding pipe (221) is used to introduce material between the corundum crucible (4) and the anode basket (53).

9. A method of using a liquid metal battery electrode material separation device based on any one of claims 1-8, characterized in that, Includes the following steps: Step S1: Fill the waste material into the annular cavity of the anode basket (53) through the second feeding pipe (223), and fill the electrolyte between the corundum crucible (4) and the anode basket (53) through the first feeding pipe (221). After filling, seal the first feeding pipe (221) and the second feeding pipe (223). Step S2: Start the heating rod (3) to adjust the temperature inside the outer shell (21) to the set target system temperature, introduce inert gas and maintain the gas pressure inside the outer shell (21) at the set micro positive pressure; connect the positive and negative terminals of the DC power supply to the anode terminal (531) and the cathode terminal (511) respectively. Step S3: Turn on the DC power supply and adjust the potential to the target value. The waste material undergoes an oxidation reaction in the anode basket (53). The negative electrode metal ions migrate through the Mg-stabilized zirconium oxide membrane (52) to the cathode terminal (511), are deposited as negative electrode metal in the flow channel, and gather in the flow guide shroud (61). The positive electrode metal ions are blocked by the Mg-stabilized zirconium oxide membrane (52), and after reduction, they form molten positive electrode that flows to the liquid collection crucible (62). Step S4: Adjust the temperatures of the two vacuum tanks (72), the negative electrode extraction tube (8), and the positive electrode extraction tube (9) to preset values ​​using the jacket heating sleeve, and start the vacuum unit to adjust the gas pressure of the two vacuum tanks to set values ​​respectively; after the extraction reminder is reached, first open the shut-off valve on the negative electrode extraction tube (8) to extract the negative electrode metal into the vacuum tank (72), and then open the shut-off valve on the positive electrode extraction tube (9) to extract the positive electrode metal into the vacuum tank (72). The extraction time periods of the negative electrode metal and the positive electrode metal do not overlap, but after the extraction of the negative electrode metal or the positive electrode metal is completed, it is necessary to refill the outer shell (21) with inert gas.

10. The method of using the liquid metal battery electrode material separation device according to claim 9, characterized in that, Also includes: Step S5: After the temperature inside the outer shell (21) stabilizes, stop heating. Remove the thermocouple (10) to check the electrolyte level. Replenish electrolyte according to electrolyte consumption. Then repeat steps S1-S4 for continuous operation. Step S6: After the operation is completed, turn off the DC power supply and the vacuum unit, continue to introduce inert gas and gradually cool down. After the device cools down to room temperature, open the cover plate (22) and take out the anode basket (53) and the liquid collection crucible (62) to clean up the residue and check the status of each component for maintenance.

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