Process and equipment for recycling metals from waste lithium-ion batteries by mechanical activation and synergistic extraction photolysis

Abstract

This invention provides a process and equipment for the synergistic recovery of metals from waste lithium-ion batteries through mechanical activation and photolysis extraction, relating to the field of metal material recycling technology. The process includes the following steps: Step S1, mixing ternary cathode material and lithium iron phosphate cathode material, washing and drying to remove surface dirt and residual electrolyte, obtaining a mixed cathode material; Step S2, homogenizing the mixed cathode material and ball milling to obtain a pretreated cathode material. This scheme ultimately achieves the destruction of the cathode material's crystal structure through mechanical force, increasing reactivity and metal leaching rate, reducing the amount of chemical reagents used, and utilizing the photosensitivity of ferric oxalate complexes to achieve efficient separation and recovery of iron under light conditions, avoiding the use of additional precipitants, reducing secondary pollution, and featuring advantages such as simple operation, low energy consumption, and no secondary pollution. It effectively achieves efficient separation and purification of multiple metal elements in waste lithium-ion batteries, realizing high-value recovery of valuable metals.

Description

Technical Field

[0001] This invention relates to the field of metal material recycling, and in particular to a process and equipment for the synergistic recycling of metals from waste lithium-ion batteries through mechanical activation and extraction-photolysis. Background Technology

[0002] Used lithium-ion batteries refer to lithium-ion batteries that have reached their designed service life or have lost their usability due to physical damage, cell failure, overcharging, or over-discharging, and can no longer be used in their original applications. The core components of these batteries include metallic elements such as lithium, cobalt, nickel, manganese, copper, and aluminum, as well as organic electrolytes, binders, separators, and plastic casings. If not recycled and disposed of according to regulations, they will cause multi-dimensional and continuous environmental harm to soil, water bodies, the atmosphere, and ecosystems, while also posing resource waste and safety hazards.

[0003] With the widespread use of electric vehicles and portable electronic devices, the number of used lithium-ion batteries has increased dramatically. If these batteries are not properly disposed of, they will not only cause serious environmental pollution but also waste valuable metal resources. Currently, the main methods for recycling used lithium-ion batteries include pyrometallurgy, hydrometallurgy, and biometallurgy; however, these methods suffer from high energy consumption, severe secondary pollution, and low metal recovery rates.

[0004] Therefore, it is necessary to provide a process for the synergistic recycling of metals from waste lithium-ion batteries through mechanical activation and extraction-photolysis to solve the above-mentioned technical problems. Summary of the Invention

[0005] This invention provides a process for the synergistic recovery of metals from waste lithium-ion batteries through mechanical activation and extraction-photolysis, which solves the problems of high energy consumption, serious secondary pollution, and low metal recovery rate in current waste lithium-ion battery recycling methods.

[0006] To address the aforementioned technical problems, the present invention provides a process for the synergistic recycling of metals from waste lithium-ion batteries through mechanical activation and extraction-photolysis, comprising the following steps:

[0007] Step S1: Mix the ternary cathode material and the lithium iron phosphate cathode material, wash and dry them to remove surface dirt and residual electrolyte, and obtain the mixed cathode material.

[0008] Step S2: Homogenize the mixed cathode material by ball milling to obtain pretreated cathode material;

[0009] Step S3: Slowly add the pretreated positive electrode material into the reaction vessel containing dilute sulfuric acid. After the reaction is completed, keep it warm and mature to obtain a lithium-containing nickel-cobalt-manganese solution and iron phosphate slag.

[0010] Step S4: Add the extractant bis(2,4,4-trimethylpentyl)phosphonic acid to the lithium-containing nickel-cobalt-manganese solution for extraction to obtain a cobalt organic phase, a nickel organic phase and an aqueous phase. The cobalt organic phase can be further purified by promoting the cation exchange reaction between cobalt and impurities present in the organic phase with cobalt sulfate solution. The separated and recovered aqueous phase 1 can be added to the nickel extraction process for extraction together.

[0011] Step S5: The cobalt organic phase and the nickel organic phase are back-extracted with sulfuric acid, evaporated and crystallized to obtain cobalt sulfate and nickel sulfate;

[0012] Step S6: Adjust the pH of the aqueous phase obtained in step S4, filter it, and obtain manganese hydroxide precipitate and lithium-containing solution;

[0013] Step S7: Add the ferric phosphate residue obtained in step S3 to an oxalic acid solution, then add hydrogen peroxide to react, filter, and obtain leachate and filter residue.

[0014] Step S8: Place the leachate in a photolysis reaction apparatus for reaction, filter, and obtain ferrous oxalate precipitate and filtrate;

[0015] Step S9: Mix the filtrate and the lithium-containing solution obtained in step S6, and heat to obtain lithium dihydrogen phosphate. The lithium-containing solution can be purified before being mixed with the filtrate.

[0016] Equipment for the synergistic recycling of metals from waste lithium-ion batteries through mechanical activation and photolysis extraction includes a reaction vessel, vessel cover, separator, drive mechanism, and feeding mechanism;

[0017] The driving mechanism includes a slider slidably connected inside the partition, a guide rail fixedly provided at the bottom of the slider, an electric telescopic rod fixedly provided at the top of the partition, and the output end of the electric telescopic rod fixedly connected to the top of the slider.

[0018] The feeding mechanism includes two sliding seats slidably connected to the surface of the guide rail. A movable plate is fixedly mounted on the bottom of each of the two sliding seats. A hopper is fixedly mounted on the front of the guide rail. The bottom of the hopper contacts the top of the two movable plates. A rotating shaft is rotatably connected longitudinally inside the guide rail. A drive disk is fixedly mounted on the circumferential side of the rotating shaft. A drive gear is fixedly mounted on the circumferential side of the rotating shaft and on the back of the drive disk. Drive gear plates are fixedly mounted on both sides of the bottom of the partition plate. A tension spring is fixedly mounted on the opposite side of the bottom of the two movable plates. A drive wheel is fixedly mounted on the back of each of the two movable plates. The opposite side of the two drive wheels contacts the circumferential side of the drive disk.

[0019] Preferably, the bottom of the hopper is provided with a discharge hole, the drive disc is elliptical and, after cooperating with the drive wheel, is used to adjust the distance between the two moving plates, thereby controlling the addition of pretreated positive electrode material, the lid is set on the top of the reactor and is fixedly connected to the reactor by bolts, the partition is fixed to the inner wall of the reactor, and the partition has multiple ventilation holes inside.

[0020] Preferably, a pre-wetting mechanism is fixedly provided at the bottom of the partition. The pre-wetting mechanism includes a storage cylinder fixedly provided at the bottom of the partition. A reciprocating frame is vertically slidably connected inside the storage cylinder. A first piston is fixedly provided at the top of the reciprocating frame and inside the storage cylinder. A first return spring is sleeved on the surface of the reciprocating frame and at the bottom of the storage cylinder. A trigger wheel is rotatably connected to the inner side of the bottom of the reciprocating frame. A trigger plate is fixedly provided at the top of each of the two moving plates. The two trigger plates are mirror images of each other and staggered front to back.

[0021] Preferably, the interior of the reactor is longitudinally rotatably connected to a spraying mechanism, which includes a spray pipe longitudinally rotatably connected to the interior of the reactor. The surface of the spray pipe is connected to multiple atomizing nozzles. An adjusting gear is fixedly provided on the surface of the spray pipe, and an adjusting toothed plate is fixedly provided at the bottom of the right-side movable plate. The spray pipe is connected to the storage cylinder through a flexible hose.

[0022] Preferably, a sampling mechanism is fixedly provided on the left side of the inner wall of the reactor. The sampling mechanism includes a mounting bracket fixedly provided on the left side of the inner wall of the reactor. A sliding rod is vertically slidably connected inside the mounting bracket. A second return spring is sleeved on the circumferential side of the sliding rod and at the top of the mounting bracket. A rotating seat is fixedly provided at the top of the sliding rod. A pressure roller is rotatably connected inside the rotating seat. A sampling cylinder is fixedly provided at the bottom of the mounting bracket. A second piston is fixedly provided at the bottom of the sliding rod and inside the sampling cylinder. A protruding plate is fixedly provided at the bottom of the moving plate on the right side.

[0023] Preferably, the inside of the vessel lid is vertically rotatably connected to a mixing mechanism, the mixing mechanism including a rotating shaft vertically rotatably connected to the inside of the vessel lid, the rotating shaft being rotatably connected to a partition, three sets of mixing paddles being fixed on the surface of the rotating shaft, and a drive motor for driving the rotating shaft to rotate being provided on the top of the vessel lid.

[0024] Preferably, a feed pipe is provided on the right side of the top of the partition, the top of the hopper is in contact with the bottom of the partition, and the feed pipe is connected to the hopper after the hopper is moved to the rightmost working position.

[0025] Preferably, the left side of the reactor is connected to a liquid inlet pipe, the top of the reactor cover is connected to an exhaust pipe, the bottom of the reactor is connected to a discharge pipe, and four support seats are arranged in a ring array on the periphery of the reactor, with support legs fixed at the bottom of each of the four support seats.

[0026] Compared with related technologies, the process for synergistic recycling of metals from waste lithium-ion batteries through mechanical activation and extraction-photolysis provided by this invention has the following beneficial effects:

[0027] By disrupting the crystal structure of the cathode material through mechanical force, the reactivity is improved, the metal leaching rate is increased, and the amount of chemical reagents used is reduced. Utilizing the photosensitivity of ferric oxalate complexes, iron can be efficiently separated and recovered under light conditions, avoiding the use of additional precipitants and reducing secondary pollution. It has the advantages of simple operation, low energy consumption, and no secondary pollution, effectively achieving the efficient separation and purification of multiple metal elements in waste lithium-ion batteries, realizing the high-value recovery of valuable metals, and improving resource utilization. Attached Figure Description

[0028] To more clearly illustrate the technical solutions in the embodiments of the present invention or the prior art, the drawings used in the description of the embodiments or the prior art will be briefly introduced below. Obviously, the drawings described below are only some embodiments of the present invention. For those skilled in the art, other drawings can be obtained based on the structures shown in these drawings without creative effort.

[0029] Figure 1 The optimal structural schematic diagram provided for this invention;

[0030] Figure 2 This is a schematic diagram of the cross-sectional view of the reaction vessel provided by the present invention;

[0031] Figure 3 for Figure 2 The diagram shows a structural schematic of the bottom view of the partition.

[0032] Figure 4 This is a schematic diagram of the drive mechanism and feeding mechanism provided by the present invention;

[0033] Figure 5 for Figure 4 The diagram shows the structure of the feeding mechanism;

[0034] Figure 6 for Figure 5 The diagram shows the structural schematic of the bottom view of the movable plate.

[0035] Figure 7 A schematic diagram showing the state in which the drive disc rotates 180 degrees and the two moving plates move to opposite sides via the drive wheel, as provided by the present invention.

[0036] Figure 8 Schematic diagram of the pre-wetting mechanism and spraying mechanism provided by the present invention;

[0037] Figure 9 forFigure 8 The diagram shows a cross-sectional view of the storage cylinder.

[0038] Figure 10 The diagram shows two movable plates moving from the left working position to the right, the right trigger plate lifting the reciprocating frame upwards via the trigger wheel, and the adjusting tooth plate driving the spray pipe to rotate clockwise via the adjusting gear.

[0039] Figure 11 A schematic diagram showing the state in which the two movable plates provided by the present invention move from the right working position to the left, and the left trigger plate pushes the reciprocating frame upward through the trigger wheel;

[0040] Figure 12 The diagram shows the state in which the two movable plates provided by the present invention continuously move from the right working position to the left, the reciprocating frame is reset downwards, and the adjusting tooth plate drives the spray pipe to rotate counterclockwise through the adjusting gear.

[0041] Figure 13 A schematic diagram of the sampling mechanism provided by the present invention;

[0042] Figure 14 for Figure 13 The diagram shows a cross-sectional view of the sampling tube.

[0043] Figure 15 This is a schematic diagram of the structure of the hybrid mechanism provided by the present invention.

[0044] Explanation of icon numbers:

[0045] 1. Reactor; 2. Reactor lid; 3. Baffle plate;

[0046] 4. Drive mechanism; 41. Slider; 42. Guide rail; 43. Electric telescopic rod;

[0047] 5. Feeding mechanism; 51. Sliding seat; 52. Moving plate; 53. Hopper; 54. Rotating shaft; 55. Drive disc; 56. Drive gear; 57. Drive gear plate; 58. Tension spring; 59. Drive wheel;

[0048] 6. Pre-wetting mechanism; 61. Storage cylinder; 62. Reciprocating frame; 63. First piston; 64. First return spring; 65. Trigger wheel; 66. Trigger plate;

[0049] 7. Spraying mechanism; 71. Spray pipe; 72. Atomizing nozzle; 73. Adjusting gear; 74. Adjusting tooth plate;

[0050] 8. Sampling mechanism; 81. Mounting bracket; 82. Sliding rod; 83. Second return spring; 84. Rotating seat; 85. Pressure roller; 86. Sampling cylinder; 87. Second piston; 88. Protruding plate;

[0051] 9. Mixing mechanism; 91. Rotating shaft; 92. Mixing propeller; 93. Drive motor;

[0052] 10. Feed pipe; 11. Liquid inlet pipe; 12. Exhaust pipe; 13. Discharge pipe; 14. Support base; 15. Support leg. Detailed Implementation

[0053] The technical solutions of the embodiments of the present invention will be clearly and completely described below with reference to the accompanying drawings. Obviously, the described embodiments are only a part of the embodiments of the present invention, and not all of the embodiments. Based on the embodiments of the present invention, all other embodiments obtained by those of ordinary skill in the art without creative effort are within the scope of protection of the present invention.

[0054] This invention provides a process for the synergistic recycling of metals from waste lithium-ion batteries through mechanical activation and extraction-photolysis.

[0055] The process for the synergistic recycling of metals from waste lithium-ion batteries through mechanical activation and extraction-photolysis includes the following steps:

[0056] Step S1: Mix the ternary cathode material and the lithium iron phosphate cathode material, wash and dry them to remove surface dirt and residual electrolyte, and obtain the mixed cathode material.

[0057] Step S2: Homogenize the mixed cathode material by ball milling to obtain pretreated cathode material;

[0058] Step S3: Slowly add the pretreated positive electrode material to the reaction vessel 1 containing dilute sulfuric acid. After the reaction is completed, keep it warm and mature to obtain a lithium-containing nickel-cobalt-manganese solution and iron phosphate slag.

[0059] Step S4: Add the extractant bis(2,4,4-trimethylpentyl)phosphonic acid to the lithium-containing nickel-cobalt-manganese solution for extraction to obtain a cobalt organic phase, a nickel organic phase and an aqueous phase. The cobalt organic phase can be further purified by promoting the cation exchange reaction between cobalt and impurities present in the organic phase with cobalt sulfate solution. The separated and recovered aqueous phase 1 can be added to the nickel extraction process for extraction together.

[0060] Step S5: The cobalt organic phase and the nickel organic phase are back-extracted with sulfuric acid, evaporated and crystallized to obtain cobalt sulfate and nickel sulfate;

[0061] Step S6: Adjust the pH of the aqueous phase obtained in step S4, filter it, and obtain manganese hydroxide precipitate and lithium-containing solution;

[0062] Step S7: Add the ferric phosphate residue obtained in step S3 to an oxalic acid solution, then add hydrogen peroxide to react, filter, and obtain leachate and filter residue.

[0063] Step S8: Place the leachate in a photolysis reaction apparatus for reaction, filter, and obtain ferrous oxalate precipitate and filtrate;

[0064] Step S9: Mix the filtrate and the lithium-containing solution obtained in step S6, and heat to obtain lithium dihydrogen phosphate. The lithium-containing solution can be purified before being mixed with the filtrate.

[0065] Preferably, in step S2, the mixed cathode material is homogenized using a zirconium oxide mortar and then transferred to a planetary ball mill for ball milling. The milling is interrupted every 30 minutes and restarted in reverse rotation at a speed of 750 rpm for a total milling time of 7 hours to obtain the pretreated cathode material. The molar ratio of ternary lithium to lithium iron phosphate in the mixed cathode material is 1:1.

[0066] Preferably, in step S4, the extractant bis(2,4,4-trimethylpentyl)phosphonic acid is added to the lithium-containing nickel-cobalt-manganese solution for extraction. Cobalt is extracted at pH 5, O / A ratio 1:1, and time 15 min, and nickel is extracted at pH 7, O / A ratio 1:1, and time 15 min, to obtain a cobalt organic phase, a nickel organic phase, and an aqueous phase (containing lithium and manganese).

[0067] Preferably, in step S6, the aqueous phase obtained in step S4 is adjusted to pH 11 with sodium hydroxide, stirred for 15 min, and filtered to obtain manganese hydroxide precipitate and lithium-containing solution.

[0068] Preferably, in step S7, the ferric phosphate residue obtained in step S3 is added to an oxalic acid solution, and then an appropriate amount of 30% hydrogen peroxide is added and reacted for 30 minutes. After filtration, leachate and filter residue are obtained.

[0069] Preferably, in step S9, the filtrate and the lithium-containing solution obtained in step S6 are mixed and heated at 200°C for 24 hours to obtain lithium dihydrogen phosphate.

[0070] In this embodiment, the crystal structure of the cathode material is destroyed by mechanical force, thereby improving the reactivity, increasing the metal leaching rate, and reducing the amount of chemical reagents used. By utilizing the photosensitivity of the ferric oxalate complex, iron can be efficiently separated and recovered under light conditions, avoiding the use of additional precipitants and reducing secondary pollution. It has the advantages of simple operation, low energy consumption, and no secondary pollution, effectively achieving efficient separation and purification of multiple metal elements in waste lithium-ion batteries, realizing high-value recovery of valuable metals, and improving resource utilization.

[0071] This invention also provides equipment for the synergistic recycling of metals from waste lithium-ion batteries through mechanical activation and extraction-photolysis.

[0072] First embodiment:

[0073] Please see Figures 1 to 7The equipment for the synergistic recycling of waste lithium-ion battery metals through mechanical activation and extraction photolysis includes a reaction vessel 1, a vessel cover 2, a partition 3, a drive mechanism 4, and a feeding mechanism 5.

[0074] The driving mechanism 4 includes a slider 41 slidably connected inside the partition 3. A guide rail 42 is fixedly provided at the bottom of the slider 41, and an electric telescopic rod 43 is fixedly provided at the top of the partition 3. The output end of the electric telescopic rod 43 is fixedly connected to the top of the slider 41.

[0075] The feeding mechanism 5 includes two sliding seats 51 slidably connected to the surface of the guide rail 42. The bottom of each of the two sliding seats 51 is fixedly provided with a movable plate 52. A hopper 53 is fixedly provided on the front of the guide rail 42. The bottom of the hopper 53 is in contact with the top of the two movable plates 52. A rotating shaft 54 ​​is rotatably connected longitudinally inside the guide rail 42. A drive disk 55 is fixedly provided on the circumferential side of the rotating shaft 54. A drive gear 56 is fixedly provided on the circumferential side of the rotating shaft 54 ​​and on the back of the drive disk 55. Drive gear plates 57 are fixedly provided on both sides of the bottom of the partition plate 3. A tension spring 58 is fixedly provided on the opposite side of the bottom of the two movable plates 52. A drive wheel 59 is fixedly provided on the back of each of the two movable plates 52. The opposite side of the two drive wheels 59 is in contact with the circumferential side of the drive disk 55.

[0076] The bottom of the hopper 53 is provided with a discharge hole. The drive disc 55 is elliptical and, after cooperating with the drive wheel 59, is used to adjust the distance between the two moving plates 52, thereby controlling the addition of pre-treated positive electrode material. The lid 2 is set on the top of the reactor 1 and is fixedly connected to the reactor 1 by bolts. The partition 3 is fixed on the inner wall of the reactor 1, and the partition 3 has multiple ventilation holes inside.

[0077] Please combine Figures 4 to 7 : Start the electric telescopic rod 43. The electric telescopic rod 43 retracts and drives the slider 41 to slide to the left inside the partition 3. The slider 41 moves to the left and drives the guide rail 42 to move to the left. During the leftward movement of the guide rail 42, the drive gear 56 contacts the drive tooth plate 57 on the right side. The drive gear 56 drives the drive disk 55 to rotate 180 degrees clockwise through the rotating shaft 54. The drive disk 55 rotates 180 degrees clockwise, thereby causing the two drive wheels 59 to drive the two moving plates 52 to move to the opposite side, canceling the seal on the discharge hole of the hopper 53, and allowing the pretreated positive electrode material to fall into the dilute sulfuric acid.

[0078] Furthermore, after the drive gear 56 moves to the left and contacts the right drive gear plate 57, and continues to move to the left, the rotation of the drive disk 55 will slowly drive the two moving plates 52 to move to opposite sides through the two drive wheels 59, thereby slowly opening the discharge port of the hopper 53. When the drive disk 55 rotates 180 degrees clockwise, the discharge port of the hopper 53 will be fully opened. During the process of the drive gear 56 moving to the left, the hopper 53 will also move to the right, thereby achieving the effect of feeding less pre-treated positive electrode material on the side and feeding more material closer to the mixing center.

[0079] Furthermore, the initial working position of hopper 53 is located on the left side of reactor 1, and the discharge port of hopper 53 is in a sealed state. When guide rail 42 moves to the right, after drive gear 56 contacts the left drive tooth plate 57 and continues to move to the right, drive gear 56 will drive drive disk 55 to rotate counterclockwise 180 degrees through shaft 54, thereby slowly opening the discharge port of hopper 53. When hopper 53 moves to the middle position, the discharge port of hopper 53 is fully open. When hopper 53 continues to move to the right, after drive gear 56 contacts the right drive tooth plate 57, drive gear 56 will drive drive disk 55 to continue rotating 180 degrees through shaft 54. During the rotation, the tension of tension spring 58 causes the two moving plates 52 to move to one side, thereby slowly sealing hopper 53. When hopper 53 is in the rightmost working position, the discharge port of hopper 53 is in a sealed state.

[0080] Preferably, the slider 41 can also be made of a bidirectional threaded screw and a motor, replacing the electric telescopic rod 43, to realize the left and right reciprocating movement of the slider 41.

[0081] In this embodiment, the elliptical drive disk 55 is rotated by the cooperation of the drive gear 56 and the two drive tooth plates 57. After cooperating with the drive wheel 59, the opening and closing state of the two moving plates 52 is controlled, thereby controlling the amount of pretreated cathode material added. The stirring center of the reactor 1 is the area with the strongest turbulence of dilute sulfuric acid and the most thorough mixing. By controlling the discharge port of the hopper 53 to be fully opened in the central area, the added pretreated cathode material can be directly entrained into the liquid phase by the high-speed stirring liquid flow, which greatly reduces the floating material layer formed by the powder floating in the low turbulence area on the side. In addition, it can accelerate the further dissociation of the powder crystal structure. Combined with the leaching reaction of dilute sulfuric acid, the subsequent heat preservation and curing time is shortened. The turbulence of dilute sulfuric acid on both sides of the reactor 1 is relatively weak. By controlling the addition of a small amount of pretreated cathode material, the problem of excessive local powder concentration and incomplete reaction can be avoided.

[0082] Second embodiment:

[0083] Please see Figures 8 to 12The bottom of the partition 3 is fixedly provided with a pre-wetting mechanism 6. The pre-wetting mechanism 6 includes a storage cylinder 61 fixedly provided at the bottom of the partition 3. A reciprocating frame 62 is vertically slidably connected inside the storage cylinder 61. A first piston 63 is fixedly provided at the top of the reciprocating frame 62 and inside the storage cylinder 61. A first return spring 64 is sleeved on the surface of the reciprocating frame 62 and at the bottom of the storage cylinder 61. A trigger wheel 65 is rotatably connected to the inner side of the bottom of the reciprocating frame 62. A trigger plate 66 is fixedly provided at the top of each of the two moving plates 52. The two trigger plates 66 are mirror images of each other and staggered front to back.

[0084] The interior of the reactor 1 is longitudinally rotatably connected to a spraying mechanism 7. The spraying mechanism 7 includes a spray pipe 71 longitudinally rotatably connected to the interior of the reactor 1. The surface of the spray pipe 71 is connected to multiple atomizing nozzles 72. An adjusting gear 73 is fixedly provided on the surface of the spray pipe 71. An adjusting toothed plate 74 is fixedly provided at the bottom of the moving plate 52 on the right side. The spray pipe 71 is connected to the storage cylinder 61 through a hose.

[0085] Preferably, the top of the storage cylinder 61 is connected to a water suction pipe, and both the water suction pipe and the hose are provided with one-way valves. The storage cylinder 61 is used to store deionized water.

[0086] Please combine Figures 8 to 10 When the hopper 53 is in the initial working position on the left and moves to the right, the two moving plates 52 will simultaneously drive the two trigger plates 66 to move to the right. When the right trigger plate 66 moves to the right, it will drive the reciprocating frame 62 to move upward through the trigger wheel 65. The reciprocating frame 62 moves upward, which will drive the first piston 63 to move upward, thereby transporting the deionized water in the storage cylinder 61 to the spray pipe 71 through the hose and spraying it out through the atomizing nozzle 72. After the right trigger plate 66 contacts the trigger wheel 65 and continues to move to the right, the adjusting tooth plate 74 will drive the adjusting gear 73 to rotate clockwise. The adjusting gear 73 will drive the spray pipe 71 and the atomizing nozzle 72 to rotate clockwise. The spray direction of the atomizing nozzle 72 will then slowly rotate to align the liquid surface of the dilute sulfuric acid with the feeding position of the discharge hole of the hopper 53.

[0087] Furthermore, as the two moving plates 52 continue to move to the right, after the trigger wheel 65 contacts the trigger plate 66 on the left, the spring force of the first reset spring 64 will drive the reciprocating frame 62 and the first piston 63 to move downward, thereby causing the storage cylinder 61 to re-extract deionized water.

[0088] Please combine Figure 11 and Figure 12When the two moving plates 52 move to the right working position and then move to the left to reset, the two moving plates 52 will simultaneously drive the two trigger plates 66 to move to the left. When the trigger plate 66 on the left contacts the trigger wheel 65 and continues to move to the left, the trigger wheel 65 will then drive the reciprocating frame 62 and the first piston 63 to move upward, so that the deionized water in the storage cylinder 61 is transported to the spray pipe 71 through the hose and sprayed out through the atomizing nozzle 72 (at this time, the spraying direction of the atomizing nozzle 72 is towards the feeding direction of the material outlet of the hopper 53).

[0089] Furthermore, as the two moving plates 52 continue to move to the left, when the right trigger plate 66 contacts the trigger wheel 65, under the action of the first reset spring 64, the reciprocating frame 62 will drive the first piston 63 to move downward, causing the storage cylinder 61 to re-extract deionized water. During the extraction process, the adjusting tooth plate 74 will drive the adjusting gear 73 to rotate counterclockwise. The counterclockwise rotation of the adjusting gear 73 will drive the spray pipe 71 and the atomizing nozzle 72 to rotate counterclockwise, thereby resetting the spraying direction of the atomizing nozzle 72.

[0090] Preferably, the pretreated cathode material after ball milling adsorbs a large amount of air or nitrogen. When the pretreated cathode material is immersed in dilute sulfuric acid, the pores are quickly filled by the liquid, and the adsorbed gas is violently desorbed instantly, forming a boiling phenomenon. However, by directing the spray direction of the atomizing nozzle 72 toward the discharge port of the hopper 53, the pretreated cathode material can be pre-wetted, thereby avoiding the occurrence of this problem.

[0091] Preferably, when some ultrafine hydrophobic particles in the pretreated cathode material come into contact with the acid surface, they cannot be wetted in time due to surface tension and float on the liquid surface, forming a layer of scum. The floating solids do not have sufficient contact with dilute sulfuric acid, and the reaction will be severely delayed. Furthermore, when they accumulate to a certain amount, they may be suddenly entrained by the mixing paddle 92, causing a violent local reaction. This problem can be avoided by aiming the spray direction of the atomizing nozzle 72 at the surface of the dilute sulfuric acid. The atomizing nozzle 72 can be used in conjunction with the defoaming paddle to press the floating matter into the liquid surface.

[0092] In this embodiment, the moving plate 52 drives the two trigger plates 66 to move left and right, and in conjunction with the trigger wheel 65, pushes the reciprocating frame 62 and the first piston 63 upward, thereby delivering the deionized water in the storage cylinder 61 to the reaction vessel 1 through the spray pipe 71 and the atomizing nozzle 72. In addition, during the movement of the right moving plate 52, it will simultaneously drive the adjusting tooth plate 74 to move, thereby adjusting the working angle of the atomizing nozzle 72 through the adjusting gear 73. By pre-wetting the pretreated positive electrode material, the boiling phenomenon caused by the instantaneous desorption of gas in the pores when the powder is immersed in dilute sulfuric acid is avoided. By adjusting the spraying direction of the atomizing nozzle 72 downward, the surface of the dilute sulfuric acid is sprayed. The atomized water droplets can reduce the surface tension of the acid liquid, break the surface gas film of the ultrafine hydrophobic particles, and allow the floating material to be quickly wetted and sink.

[0093] Third embodiment:

[0094] Please see Figure 1 , Figure 2 , Figures 13 to 15 A sampling mechanism 8 is fixedly provided on the left side of the inner wall of the reactor 1. The sampling mechanism 8 includes a mounting bracket 81 fixedly provided on the left side of the inner wall of the reactor 1. A sliding rod 82 is vertically slidably connected inside the mounting bracket 81. A second return spring 83 is sleeved on the circumferential side of the sliding rod 82 and located at the top of the mounting bracket 81. A rotating seat 84 is fixedly provided at the top of the sliding rod 82. A pressure roller 85 is rotatably connected inside the rotating seat 84. A sampling cylinder 86 is fixedly provided at the bottom of the mounting bracket 81. A second piston 87 is fixedly provided at the bottom end of the sliding rod 82 and located inside the sampling cylinder 86. A protruding plate 88 is fixedly provided at the bottom of the moving plate 52 on the right side.

[0095] The inside of the vessel lid 2 is vertically rotatably connected to a mixing mechanism 9. The mixing mechanism 9 includes a rotating shaft 91 vertically rotatably connected to the inside of the vessel lid 2. The rotating shaft 91 is rotatably connected to the partition plate 3. Three sets of mixing paddles 92 are fixed on the surface of the rotating shaft 91. A drive motor 93 for driving the rotating shaft 91 to rotate is provided on the top of the vessel lid 2.

[0096] A feed pipe 10 is provided on the right side of the top of the partition 3. The top of the hopper 53 is in contact with the bottom of the partition 3. After the hopper 53 moves to the rightmost working position, the feed pipe 10 is connected to the hopper 53.

[0097] The left side of the reactor 1 is connected to an inlet pipe 11, the top of the reactor cover 2 is connected to an exhaust pipe 12, the bottom of the reactor 1 is connected to a discharge pipe 13, and four support seats 14 are arranged in a ring array on the periphery of the reactor 1, and support legs 15 are fixed at the bottom of each of the four support seats 14.

[0098] Preferably, when the hopper 53 is in the initial working position on the left, the convex plate 88 will press the sliding rod 82 downward through the pressure roller 85, the second reset spring 83 is in the contracted state, the sliding rod 82 will drive the second piston 87 to move downward, and the sampling cylinder 86 is in an empty state.

[0099] Preferably, the bottom of the sampling cylinder 86 is connected to an extraction tube, and the left side of the sampling cylinder 86 is connected to a discharge tube. Valves are provided on the surface of both the extraction tube and the discharge tube.

[0100] Please combine Figure 13 and Figure 14 When the two moving plates 52 move from the initial working position on the left to the right, the left moving plate 52 will drive the convex plate 88 to move to the right, thereby slowly releasing the pressure on the pressure roller 85. Under the action of the second reset spring 83, the rotating seat 84 will drive the sliding rod 82 to move upward, and the sliding rod 82 will then drive the second piston 87 to move upward, thereby extracting the clear liquid at the top.

[0101] Furthermore, when it is necessary to sample the reactor 1, the two moving plates 52 move to the left, causing the convex plate 88 to move to the left. After the convex plate 88 moves to the left and contacts the pressure roller 85, and continues to move to the left, the pressure roller 85 will press the sliding rod 82 downward, causing the second reset spring 83 to contract. The sliding rod 82 will drive the second piston 87 to move downward, thereby discharging the sample in the sampling cylinder 86 through the discharge pipe. When it is not necessary to sample the reactor 1, the sample in the sampling cylinder 86 can be re-transported into the reaction solution by controlling the valves on the surface of the extraction pipe and the discharge pipe.

[0102] Please combine Figure 15 Start the drive motor 93. The drive motor 93 rotates and drives the rotating shaft 91 to rotate. The rotating shaft 91 rotates and drives the mixing paddle 92 to rotate. The rotating mixing paddle 92 mixes the dilute sulfuric acid with the pretreated positive electrode material.

[0103] In this embodiment, when it is necessary to take a sample from the reactor 1, the two moving plates 52 drive the convex plate 88 to move to the left. After the convex plate 88 moves to the left and contacts the pressure roller 85, and continues to move to the left, the pressure roller 85 will press the sliding rod 82 and the second piston 87 downward, thereby discharging the sample in the sampling tube 86 through the discharge pipe. The extracted clear liquid can be used to directly detect the leaching concentration of Li, Ni, Co and Mn, accurately reflecting the acid leaching reaction process.

[0104] Please refer to the reference again. Figures 1 to 15 The working principle of the equipment for the synergistic recycling of metals from waste lithium-ion batteries through mechanical activation and extraction-photolysis provided by this invention is as follows:

[0105] Step S1: Calculate and measure the required volume of dilute sulfuric acid according to the preset liquid-solid ratio and target acid concentration, pump it into the reactor 1, turn on the drive motor 93, drive the rotating shaft 91 and mixing paddle 92 to rotate, and when the preset speed is reached, turn on the heating system of the jacket of the reactor 1 to preheat the sulfuric acid solution to the set initial leaching temperature.

[0106] In step S2, when the hopper 53 is in the initial working position on the left, the electric telescopic rod 43 extends and drives the slider 41 to move to the right. When the slider 41 drives the hopper 53 to the rightmost working position, the feed pipe 10 will connect with the hopper 53, and the discharge port of the hopper 53 will be in a sealed state at this time. Pre-treated positive electrode material is added into the hopper 53 through the feed pipe 10. After completion, the position of the hopper 53 is reset to the left. After the hopper 53 is reset, it will be in a closed state again.

[0107] Step S3: After resetting, the electric telescopic rod 43 extends again, driving the slider 41 and guide rail 42 to move to the right. When the guide rail 42 moves to the right, the drive gear 56 contacts the left drive tooth plate 57 and continues to move to the right. The drive gear 56 will drive the drive disk 55 to rotate counterclockwise by 180 degrees through the rotating shaft 54, thereby slowly opening the discharge hole of the hopper 53. When the hopper 53 moves to the middle position, the discharge hole of the hopper 53 is fully open. When the hopper 53 continues to move to the right, the drive gear 56 contacts the right drive tooth plate 57 and the drive gear 56 will drive the drive disk 55 to continue to rotate by 180 degrees through the rotating shaft 54. During the rotation, the tension of the tension spring 58 causes the two moving plates 52 to move to one side, thereby slowly sealing the hopper 53. When the hopper 53 is in the rightmost working position, the discharge hole of the hopper 53 is sealed.

[0108] In step S4, when the hopper 53 is in the initial working position on the left and moves to the right, the two moving plates 52 will simultaneously drive the two trigger plates 66 to move to the right. When the right trigger plate 66 moves to the right, it will drive the reciprocating frame 62 to move upward through the trigger wheel 65. The reciprocating frame 62 moves upward, which will drive the first piston 63 to move upward, thereby transporting the deionized water in the storage cylinder 61 to the spray pipe 71 through the hose and spraying it out through the atomizing nozzle 72. After the right trigger plate 66 contacts the trigger wheel 65 and continues to move to the right, the adjusting tooth plate 74 will drive the adjusting gear 73 to rotate clockwise. The adjusting gear 73 will drive the spray pipe 71 and the atomizing nozzle 72 to rotate clockwise. The spray direction of the atomizing nozzle 72 will then slowly rotate to align the liquid surface of the dilute sulfuric acid with the feeding position of the discharge hole of the hopper 53.

[0109] In step S5, when it is necessary to sample the reactor 1, the two moving plates 52 move to the left, causing the convex plate 88 to move to the left. After the convex plate 88 moves to the left and contacts the pressure roller 85, and continues to move to the left, the pressure roller 85 will press the sliding rod 82 downward, causing the second reset spring 83 to contract. The sliding rod 82 will drive the second piston 87 to move downward, thereby discharging the sample in the sampling cylinder 86 through the discharge pipe. When it is not necessary to sample the reactor 1, the sample in the sampling cylinder 86 can be re-transported into the reaction solution by controlling the valves on the surface of the extraction pipe and the discharge pipe.

[0110] The above description is only a preferred embodiment of the present invention and does not limit the patent scope of the present invention. All equivalent structural transformations made under the concept of the present invention using the contents of the present invention specification and drawings, or direct / indirect applications in other related technical fields, are included within the patent protection scope of the present invention.

Claims

1. A process for the synergistic recycling of metals from waste lithium-ion batteries through mechanical activation and extraction-photolysis, characterized in that, Includes the following steps: Step S1: Mix the ternary cathode material and the lithium iron phosphate cathode material, wash and dry them to remove surface dirt and residual electrolyte, and obtain the mixed cathode material. Step S2: Homogenize the mixed cathode material by ball milling to obtain pretreated cathode material; Step S3: Slowly add the pretreated positive electrode material into the reaction vessel containing dilute sulfuric acid. After the reaction is completed, keep it warm and mature to obtain a lithium-containing nickel-cobalt-manganese solution and iron phosphate slag. Step S4: Add the extractant bis(2,4,4-trimethylpentyl)phosphonic acid to the lithium-containing nickel-cobalt-manganese solution for extraction to obtain a cobalt organic phase, a nickel organic phase and an aqueous phase. The cobalt organic phase can be further purified by promoting the cation exchange reaction between cobalt and impurities present in the organic phase with cobalt sulfate solution. The separated and recovered aqueous phase 1 can be added to the nickel extraction process for extraction together. Step S5: The cobalt organic phase and the nickel organic phase are back-extracted with sulfuric acid, evaporated and crystallized to obtain cobalt sulfate and nickel sulfate; Step S6: Adjust the pH of the aqueous phase obtained in step S4, filter it, and obtain manganese hydroxide precipitate and lithium-containing solution; Step S7: Add the ferric phosphate residue obtained in step S3 to an oxalic acid solution, then add hydrogen peroxide to react, filter, and obtain leachate and filter residue. Step S8: Place the leachate in a photolysis reaction apparatus for reaction, filter, and obtain ferrous oxalate precipitate and filtrate; Step S9: Mix the filtrate and the lithium-containing solution obtained in step S6, and heat to obtain lithium dihydrogen phosphate. The lithium-containing solution can be purified before being mixed with the filtrate.

2. A device for the synergistic recycling of metals from waste lithium-ion batteries through mechanical activation and extraction-photolysis, characterized in that, The equipment for recycling waste lithium-ion battery metal is used in the process for recycling waste lithium-ion battery metal as described in claim 1, and includes a reaction vessel, a vessel cover, a partition, a drive mechanism, and a feeding mechanism. The driving mechanism includes a slider slidably connected inside the partition, a guide rail fixedly provided at the bottom of the slider, an electric telescopic rod fixedly provided at the top of the partition, and the output end of the electric telescopic rod fixedly connected to the top of the slider. The feeding mechanism includes two sliding seats slidably connected to the surface of the guide rail. A movable plate is fixedly mounted on the bottom of each of the two sliding seats. A hopper is fixedly mounted on the front of the guide rail. The bottom of the hopper contacts the top of the two movable plates. A rotating shaft is rotatably connected longitudinally inside the guide rail. A drive disk is fixedly mounted on the circumferential side of the rotating shaft. A drive gear is fixedly mounted on the circumferential side of the rotating shaft and on the back of the drive disk. Drive gear plates are fixedly mounted on both sides of the bottom of the partition plate. A tension spring is fixedly mounted on the opposite side of the bottom of the two movable plates. A drive wheel is fixedly mounted on the back of each of the two movable plates. The opposite side of the two drive wheels contacts the circumferential side of the drive disk.

3. The equipment for the synergistic recycling of waste lithium-ion battery metals through mechanical activation and extraction-photolysis as described in claim 2, characterized in that, The bottom of the hopper has a discharge hole. The drive disc is elliptical and, when used in conjunction with the drive wheel, is used to adjust the distance between the two moving plates, thereby controlling the addition of pretreated cathode material. The lid is located on the top of the reactor and is fixedly connected to the reactor by bolts. The partition is fixed to the inner wall of the reactor, and the partition has multiple ventilation holes inside.

4. The equipment for the synergistic recycling of waste lithium-ion battery metals through mechanical activation and extraction-photolysis as described in claim 2, characterized in that, A pre-wetting mechanism is fixedly provided at the bottom of the partition. The pre-wetting mechanism includes a storage cylinder fixedly provided at the bottom of the partition. A reciprocating frame is vertically slidably connected inside the storage cylinder. A first piston is fixedly provided at the top of the reciprocating frame and inside the storage cylinder. A first return spring is sleeved on the surface of the reciprocating frame and at the bottom of the storage cylinder. A trigger wheel is rotatably connected to the inner side of the bottom of the reciprocating frame. A trigger plate is fixedly provided at the top of each of the two moving plates. The two trigger plates are mirror images of each other and staggered front to back.

5. The equipment for the synergistic recycling of waste lithium-ion battery metals through mechanical activation and extraction-photolysis as described in claim 4, characterized in that, The reactor is longitudinally rotatably connected to a spraying mechanism, which includes a spray pipe longitudinally rotatably connected to the reactor. The surface of the spray pipe is connected to multiple atomizing nozzles. An adjusting gear is fixed on the surface of the spray pipe. An adjusting toothed plate is fixed on the bottom of the moving plate on the right side. The spray pipe is connected to a storage cylinder through a hose.

6. The equipment for the synergistic recycling of waste lithium-ion battery metals through mechanical activation and extraction-photolysis as described in claim 2, characterized in that, A sampling mechanism is fixedly installed on the left side of the inner wall of the reactor. The sampling mechanism includes a mounting bracket fixedly installed on the left side of the inner wall of the reactor. A sliding rod is vertically slidably connected inside the mounting bracket. A second return spring is sleeved on the circumferential side of the sliding rod and at the top of the mounting bracket. A rotating seat is fixedly installed at the top of the sliding rod. A pressure roller is rotatably connected inside the rotating seat. A sampling cylinder is fixedly installed at the bottom of the mounting bracket. A second piston is fixedly installed at the bottom of the sliding rod and inside the sampling cylinder. A protruding plate is fixedly installed at the bottom of the moving plate on the right side.

7. The equipment for the synergistic recycling of waste lithium-ion battery metals through mechanical activation and extraction-photolysis as described in claim 2, characterized in that, The inside of the vessel lid is vertically rotatably connected to a mixing mechanism. The mixing mechanism includes a rotating shaft vertically rotatably connected to the inside of the vessel lid. The rotating shaft is rotatably connected to a partition plate. Three sets of mixing paddles are fixed on the surface of the rotating shaft. A drive motor for driving the rotating shaft to rotate is provided on the top of the vessel lid.

8. The equipment for the synergistic recycling of waste lithium-ion battery metals through mechanical activation and extraction-photolysis as described in claim 2, characterized in that, A feed pipe is provided on the right side of the top of the partition. The top of the hopper is in contact with the bottom of the partition. After the hopper moves to the rightmost working position, the feed pipe is connected to the hopper.

9. The equipment for the synergistic recycling of waste lithium-ion battery metals through mechanical activation and extraction-photolysis as described in claim 2, characterized in that, The left side of the reactor is connected to a liquid inlet pipe, the top of the reactor lid is connected to an exhaust pipe, the bottom of the reactor is connected to a discharge pipe, and four support seats are arranged in a ring array on the periphery of the reactor, with support legs fixed at the bottom of each of the four support seats.

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