A method for producing a battery material lithium carbonate, a method for preparing a collector, and an apparatus

Abstract

The application provides a battery material lithium carbonate production method, a collector preparation method and equipment, and relates to the field of battery material preparation.The battery material lithium carbonate production method comprises the following steps: S1, roughing: after ball milling treatment of lithium mica ore, the lithium mica ore is added to a flotation tank, after sedimentation and desliming, adjusting agents, collectors and MIBC foaming agents are added in sequence under stirring; wherein the chemical general formula of the collector is provided.The battery material lithium carbonate production method provided by the application exhibits excellent enrichment performance and stable recovery effect, and can effectively improve the quality and yield of the lithium mica concentrate; the phosphonic acid group in the structure has excellent complexing and adsorbing properties, so that it can still maintain good separation effect in a complex ion environment, greatly improving the stability and adaptability of the process, thereby improving the quality of the lithium mica concentrate, and laying a foundation for subsequent production of higher-quality lithium carbonate.

Description

Technical Field

[0001] This invention relates to the field of lithium carbonate preparation for battery materials, and particularly to a method for producing lithium carbonate for battery materials, a method for preparing a collector, and equipment. Background Technology

[0002] lithium carbonate Lithium carbonate is a crucial raw material in the lithium battery industry. It is a key lithium source for preparing cathode materials and electrolytes, and the raw materials for preparing lithium carbonate usually include lepidolite.

[0003] The current process for preparing lithium carbonate from lepidolite includes crushing and grinding the lepidolite ore, flotation of the lepidolite ore concentrate, and then roasting, leaching and filtering the concentrate lepidolite, purifying and removing impurities, and precipitating lithium.

[0004] Among them, lepidolite has poor buoyancy, and its sheet-like structure... and The coexistence of these factors makes the surface electrical properties of minerals complex and lacks effective active sites, making it difficult for traditional collectors (such as fatty acids and alkanolamines) to achieve efficient adsorption and selective separation during flotation, resulting in problems such as low lithium recovery rate and poor concentrate grade.

[0005] In acidic flotation systems, cationic collectors such as dodecylamine and fatty amines can form electrostatic adsorption with some mineral surfaces, but they have drawbacks such as poor water solubility, difficulty in emulsification, and weak foam control ability. In addition, they are not stable enough and are easily affected by factors such as pH and temperature of the system, which limits their application effect in the separation of lepidolite.

[0006] Therefore, it is necessary to provide a method for producing lithium carbonate, a battery material, to solve the above-mentioned technical problems. Summary of the Invention

[0007] This invention provides a method for producing lithium carbonate, a battery material, which solves the problems of low lithium recovery rate and poor concentrate grade caused by the difficulty in achieving efficient adsorption and selective separation of collectors in the flotation process in the existing technology.

[0008] To solve the above-mentioned technical problems, the present invention provides a method for producing lithium carbonate, a battery material, comprising the following steps:

[0009] S1. Roughing: After ball milling, the lepidolite is added to the flotation cell. After settling and desliming, the modifier, collector, and MIBC frother are added in sequence with stirring.

[0010] The general chemical formula of the collector is: The general structural formula is:

[0011] ;

[0012] Where R is Straight-chain or branched alkyl or benzyl groups; It is a quaternary ammonium group;

[0013] S2. Fine treatment: After roughing, rough concentrate and rough tailings are obtained. Three fine treatments and two scavengings are performed to obtain lithium concentrate and lithium tailings.

[0014] S3. Calcination: The lithium concentrate is fed into a rotary kiln and calcined at 500-800℃ for 2-3 hours.

[0015] S4. Leaching and filtration: After cooling the calcined solid product, it is added to a sulfuric acid solution with a mass fraction of 5% - 25% for leaching. Then, after filtration, lithium-containing leachate and leaching residue are obtained.

[0016] S5. Purification and impurity removal: Add a preset amount of hydrogen peroxide to the lithium-containing leachate, then adjust the pH of the solution to 5-13, filter the precipitate, and finally use the ion exchange resin method to remove the residual impurity ions in the solution to obtain the purified lithium-containing solution.

[0017] S6. Preparation of lithium carbonate: Add sodium carbonate or ammonium carbonate solution to the purified lithium-containing solution, control the reaction pH value at 8-11, and generate lithium carbonate precipitate. Then, after filtration, washing and drying, lithium carbonate is obtained.

[0018] Preferably, the modifier is at least one of water glass, oxalic acid, sodium hexametaphosphate, starch, and calcium lignosulfonate, and the dosage is 500-1000 g / t.

[0019] Preferably, the amount of the collector is 100-500 g / t, and the amount of the foaming agent is 10-50 g / t.

[0020] This invention also provides a method for preparing a collector, used in the lithium carbonate production method for the aforementioned battery material; comprising the following steps:

[0021] S11, Synthesis of Quaternary Ammonium Salts: This involves synthesizing amino compounds... With iodomethane A two-step nucleophilic substitution reaction is carried out to introduce two methyl groups, forming a stable [substance / form]. Type quaternary ammonium salt, namely ;

[0022] S12, Ring-opening addition of propylene oxide to construct a β-hydroxy intermediate: A nucleophilic addition reaction is performed between a quaternary ammonium cation and propylene oxide, introducing a β-hydroxypropyl substituent at the end of the quaternary ammonium structure, thus yielding... ;

[0023] S13, Mannich phosphonation reaction, introducing β-hydroxyphosphonic acid structure: Using the Mannich three-component condensation reaction, intermediate 2 is condensed with formaldehyde and phosphorous acid under acidic conditions to introduce the β-hydroxyphosphonic acid functional group, yielding the target product precursor, namely:

[0024] ;

[0025] S14. Ion exchange to prepare Cl⁻ type target product: The target product precursor was dissolved in an isopropanol-water mixed solution, 1.5 equivalents of NaCl were added, and the mixture was ultrasonically dispersed for 30 minutes and stirred at room temperature for 4 hours. After removing the generated NaI precipitate by filtration, the solution was concentrated under reduced pressure and vacuum dried at 50°C for 12 hours to obtain the final product.

[0026] .

[0027] The present invention also provides an apparatus for preparing a collector, which is used in a method for preparing a collector, comprising: a base on which a support is mounted;

[0028] A rotating device, comprising a motor and a right-angle plate, wherein the motor is mounted on the bracket and is used to drive the right-angle plate to rotate horizontally;

[0029] An ultrasonic disperser and a stirring device are respectively installed at both ends of the right-angle plate;

[0030] A lifting device for raising or lowering the right-angle plate.

[0031] Preferably, the rotating device further includes a connecting shaft, which includes a square shaft and a sleeve. The square shaft is mounted on the output shaft of the motor, and the sleeve is fitted onto the square shaft.

[0032] The right-angle plate is mounted on the sleeve.

[0033] Preferably, the stirring device includes a driving component, a stirring rod, and a stirring blade. The stirring rod passes through the right-angle plate and is rotatably connected to the right-angle plate. The stirring blade is installed at the bottom end of the stirring rod. The driving component is used to drive the stirring rod to rotate.

[0034] Preferably, the driving component is a driven gear, which is mounted on the top of the stirring rod. The rotating device also includes a main gear, which is mounted on the output shaft of the motor and located above the square shaft. The driving component is higher than the main gear.

[0035] The connecting shaft also includes a round shaft, which is installed at the bottom end of the square shaft, and the sleeve is fitted onto the round shaft and the square shaft.

[0036] Preferably, the lifting device includes a mounting plate, a lifting cylinder, and a lifting plate. The lifting cylinder is mounted on a bracket via the mounting plate. One end of the lifting plate is connected to the output end of the lifting cylinder, and the other end is rotatably connected to the sleeve.

[0037] Preferably, the equipment for preparing the collector further includes multiple positioning structures, which are slidably mounted in a ring on the base.

[0038] Compared with related technologies, the lithium carbonate production method for battery materials provided by this invention has the following beneficial effects:

[0039] This invention provides a method for producing lithium carbonate, a battery material. Due to the good water solubility and surface activity of the quaternary ammonium cation structure, it can be stably adsorbed onto the negatively charged surface of minerals under acidic conditions, thereby enhancing the targeting effect and adsorption strength of the collector. β-hydroxyphosphonic acid serves as the coordination adsorption active center, endowing the collector with chelation adsorption function. The collector proposed in this invention integrates a hydrophobic alkyl chain, a quaternary ammonium cation center, and a β-hydroxyphosphonic acid functional group.

[0040] The collector proposed in this invention exhibits excellent enrichment performance and stable recovery effect, effectively improving the quality and yield of lepidolite concentrate. Compared with traditional aliphatic amine or sulfonic acid collectors, the product of this invention has a stronger molecular design space and controllability, especially showing higher selectivity and interference resistance in complex or low-grade lithium ores. The phosphonic acid groups in the structure possess excellent complexing and adsorption properties, enabling it to maintain good separation performance even in complex ionic environments, greatly improving the stability and adaptability of the process, thereby improving the quality of lepidolite concentrate and paving the way for the subsequent production of higher-quality lithium carbonate. Attached Figure Description

[0041] Figure 1 A flowchart illustrating the steps of a method for producing lithium carbonate, a battery material, provided by the present invention.

[0042] Figure 2 This is a flowchart illustrating the steps of the method for preparing the collector provided by the present invention;

[0043] Figure 3 This is a schematic diagram of the equipment for preparing the collector provided by the present invention;

[0044] Figure 4 for Figure 3 A schematic diagram of the equipment for preparing the collector from another perspective;

[0045] Figure 5 This is a partial structural schematic diagram of the equipment for preparing the collector provided by the present invention;

[0046] Figure 6This is a partial structural schematic diagram of the rotating device provided by the present invention;

[0047] Figure 7 A schematic diagram of the positioning structure provided by the present invention;

[0048] Figure 8 This is a schematic diagram of the working state of the equipment for preparing the collector provided by the present invention, wherein, Figure 8 (a) is a schematic diagram of the ultrasonic disperser in operation. Figure 8 (b) is a schematic diagram of the stirring device in operation;

[0049] Figure 9 This is a schematic diagram of the working state of the stirring device provided by the present invention, wherein... Figure 9 (a) is a schematic diagram showing the state in which the stirring blades are suspended above the material container. Figure 9 (b) is a schematic diagram of the state of the stirring blade descending into the container.

[0050] Numbering on the map:

[0051] 1. Base; 101. Bracket; 102. Slide; 103. Marking;

[0052] 2. Rotating device; 21. Motor; 22. Connecting shaft; 23. Right angle plate; 24. Main gear; 221. Square shaft; 222. Round shaft; 223. Sleeve; 231. Positioning hole;

[0053] 3. Ultrasonic disperser;

[0054] 4. Stirring device; 41. Drive component; 42. Stirring rod; 43. Stirring blade;

[0055] 5. Lifting device; 51. Mounting plate; 52. Lifting cylinder; 53. Lifting plate; 54. Slide rod;

[0056] 6. Positioning structure; 61. Slider; 62. Positioning frame; 63. Limiting component; 631. Bolt; 632. Stop plate;

[0057] 7. Container for holding materials. Detailed Implementation

[0058] 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.

[0059] This invention provides a method for producing lithium carbonate, a battery material.

[0060] Please refer to the following: Figure 1 In one embodiment of the present invention, the method for producing lithium carbonate battery material includes the following steps:

[0061] S1. Roughing: After ball milling, the lepidolite is added to the flotation cell. After settling and desliming, the modifier, collector, and MIBC frother are added in sequence with stirring.

[0062] The general chemical formula of the collector is: The general structural formula is:

[0063] ;

[0064] Where R is Straight-chain or branched alkyl or benzyl groups; It is a quaternary ammonium group;

[0065] S2. Fine treatment: After roughing, rough concentrate and rough tailings are obtained. Three fine treatments and two scavengings are performed to obtain lithium concentrate and lithium tailings.

[0066] S3. Calcination: The lithium concentrate is fed into a rotary kiln and calcined at 500-800℃ for 2-3 hours.

[0067] S4. Leaching and filtration: After cooling the calcined solid product, it is added to a sulfuric acid solution with a mass fraction of 5% - 25% for leaching. Then, after filtration, lithium-containing leachate and leaching residue are obtained.

[0068] S5. Purification and impurity removal: Add a preset amount of hydrogen peroxide to the lithium-containing leachate, then adjust the pH of the solution to 5-13, filter the precipitate, and finally use the ion exchange resin method to remove the residual impurity ions in the solution to obtain the purified lithium-containing solution.

[0069] S6. Preparation of lithium carbonate: Add sodium carbonate or ammonium carbonate solution to the purified lithium-containing solution, control the reaction pH value at 8-11, and generate lithium carbonate precipitate. Then, after filtration, washing and drying, lithium carbonate is obtained.

[0070] The modifier is at least one of water glass, oxalic acid, sodium hexametaphosphate, starch, and calcium lignosulfonate, and the dosage is 500-1000 g / t.

[0071] The amount of the collector is 100-500 g / t, and the amount of the foaming agent is 10-50 g / t.

[0072] Due to the excellent water solubility and surface activity of the quaternary ammonium cation structure, it can be stably adsorbed onto the negatively charged surface of minerals under acidic conditions, thereby enhancing the targeting effect and adsorption strength of the collector. β-hydroxyphosphonic acid serves as the coordination adsorption active center, endowing the collector with chelation adsorption function. The collector proposed in this invention integrates a hydrophobic alkyl chain, a quaternary ammonium cation center, and a β-hydroxyphosphonic acid functional group.

[0073] In flotation applications, the collector proposed in this invention exhibits excellent enrichment performance and stable recovery effect, effectively improving the quality and yield of lepidolite concentrate. Compared with traditional aliphatic amine or sulfonic acid collectors, the product of this invention has a stronger molecular design space and controllability, especially showing higher selectivity and interference resistance in complex or low-grade lithium ores. The phosphonic acid groups in the structure possess excellent complexing and adsorption properties, enabling it to maintain good separation performance even in complex ionic environments, greatly improving the stability and adaptability of the process, thereby improving the quality of lepidolite concentrate and paving the way for the subsequent production of higher-quality lithium carbonate.

[0074] Furthermore, the collector of this invention has a simple synthesis route, readily available raw materials, and high yield, providing a good foundation for industrial scale-up. The product can be applied under a wide range of temperature and pulp conditions, and possesses green and environmentally friendly characteristics such as low foaming, low toxicity, and easy degradation. In summary, this type of collector combines multiple advantages such as high selectivity, high adaptability, and green and low-carbon properties, and can be widely used in the efficient flotation process of lithium resources such as lepidolite and spodumene, demonstrating significant prospects for widespread application and economic value.

[0075] In S3, lithium concentrate is preferably mixed with sulfuric acid (or sulfates, such as sodium sulfate or potassium sulfate) in a certain proportion. Sulfuric acid can be used directly as a leaching agent, while sulfates can lower the roasting temperature and promote the activation of lithium.

[0076] In step S4, a predetermined amount of hydrogen peroxide is added to the lithium-containing leachate to oxidize ferrous ions to ferric ions. The pH of the solution is then adjusted to 5-13, causing impurities such as ferric, aluminum, and magnesium ions to precipitate as hydroxides, which are then removed by filtration. Next, an ion exchange resin method is used to remove residual trace impurity ions such as calcium and magnesium from the solution, resulting in a purified lithium-containing solution.

[0077] The present invention also provides a method for preparing a collector.

[0078] Please see Figure 2 A method for preparing a collector, used in the production method of lithium carbonate battery material; comprising the following steps:

[0079] S11, Synthesis of Quaternary Ammonium Salts: This involves synthesizing amino compounds... With iodomethane A two-step nucleophilic substitution reaction is carried out to introduce two methyl groups, forming a stable [substance / form]. Type quaternary ammonium salt, namely ;

[0080] S12, Ring-opening addition of propylene oxide to construct a β-hydroxy intermediate: A nucleophilic addition reaction is performed between a quaternary ammonium cation and propylene oxide, introducing a β-hydroxypropyl substituent at the end of the quaternary ammonium structure, thus yielding... ;

[0081] S13, Mannich phosphonation reaction, introducing β-hydroxyphosphonic acid structure: Using the Mannich three-component condensation reaction, intermediate 2 is condensed with formaldehyde and phosphorous acid under acidic conditions to introduce the β-hydroxyphosphonic acid functional group, yielding the target product precursor, namely:

[0082] ;

[0083] S14. Ion exchange to prepare Cl⁻ type target product: The target product precursor was dissolved in an isopropanol-water mixed solution, 1.5 equivalents of NaCl were added, and the mixture was ultrasonically dispersed for 30 minutes and stirred at room temperature for 4 hours. After removing the generated NaI precipitate by filtration, the solution was concentrated under reduced pressure and vacuum dried at 50°C for 12 hours to obtain the final product.

[0084] .

[0085] In this embodiment, the specific method for preparing the collector includes:

[0086] Step 1: Synthesis of Quaternary Ammonium Salts

[0087] This step involves using amino compounds. With iodomethane A two-step nucleophilic substitution reaction is carried out to introduce two methyl groups, forming a stable [substance / form]. The quaternary ammonium salt significantly improves the hydrophilicity and surface activity of the product;

[0088] Add to a 500 mL three-necked flask 20 mmol of iodomethane was reacted with 100 mL of anhydrous acetonitrile, and 60 mmol of iodomethane was slowly added dropwise under stirring. The mixture was pre-reacted at room temperature for 30 minutes, then heated to 80 °C and refluxed for 6 hours. During the reaction, 10 mmol of sodium carbonate was added to maintain the pH of the solution at 8-9 to absorb the byproduct hydroiodic acid. After the reaction is complete and cooled, insoluble impurities and inorganic salts are removed by filtration, and acetonitrile solvent is removed by rotary evaporation to obtain intermediate 1, i.e. It is a pale yellow transparent liquid that can be used in the subsequent ring-opening reaction of propylene oxide.

[0089] ;

[0090] Step 2: Ring-opening addition of propylene oxide to construct the β-hydroxy intermediate;

[0091] This step involves a nucleophilic addition reaction between quaternary ammonium cations and propylene oxide, introducing a β-hydroxypropyl substituent at the end of the quaternary ammonium structure to enhance water solubility and subsequent phosphonate activity.

[0092] Under an inert atmosphere, intermediate 1 (20 mmol) was dissolved in 100 mL of anhydrous ethanol, and then... Molecular sieves adsorbed trace amounts of moisture, and after purging with nitrogen for 10 minutes, excess propylene oxide (25 mmol) was added dropwise. The reaction temperature was controlled at 55°C, and the reaction was carried out for 8 hours. The reaction progress was monitored by TLC during the reaction. After the reaction was completed, the solvent was removed to obtain intermediate 2, i.e. It is a pale yellow, transparent oily substance with good polarity and reactivity;

[0093] ;

[0094] Step 3: Mannich phosphonation reaction to introduce β-hydroxyphosphonic acid structure;

[0095] This step employs the Mannich three-component condensation reaction, in which intermediate 2 is condensed with formaldehyde and phosphorous acid under acidic conditions, introducing β-hydroxyphosphonic acid functional groups, thereby endowing the collector with chelation adsorption function.

[0096] Intermediate 2 (20 mmol) was dissolved in an ethanol-water mixture (4:1, 100 mL) under ice bath conditions. 37% formaldehyde solution (20 mmol) and phosphorous acid (20 mmol) were added sequentially. The pH was adjusted to 3 with HCl, and the mixture was stirred continuously for 1 hour to ensure thorough mixing. The temperature was then raised to 80°C, and the reaction was carried out under nitrogen protection for 12 hours. After the reaction, ethanol was removed by rotary evaporation, and the product was diluted, filtered to remove impurities, and the concentrated aqueous phase yielded the target product precursor. It is a highly polar liquid with significant phosphonic acid adsorption function;

[0097] ;

[0098] Step 4: Ion exchange, preparation Target product;

[0099] To improve product stability and water solubility, iodide ions are converted into chloride ions through ion exchange, resulting in superior performance for industrial applications. Type of collector;

[0100] At room temperature, the product obtained in step three was dissolved in an isopropanol-water mixture (3:1, 50 mL), and 1.5 equivalents of NaCl (approximately 1.75 g) were added. After ultrasonic dispersion for 30 minutes, the mixture was stirred at room temperature for 4 hours. The resulting NaI precipitate was removed by filtration, and the solution was concentrated under reduced pressure and dried under vacuum at 50°C for 12 hours to obtain the final product. It is a light yellow viscous liquid that can be directly used in the lepidolite flotation system;

[0101] ;

[0102] In this embodiment, a lithium mica mine in Yichun, Jiangxi Province, was selected, with a lithium oxide grade of 0.75% and a grinding fineness of -200 mesh accounting for 60%. The flotation process consisted of one roughing stage, three cleaning stages, and two scavenging stages, with roughing taking 8 minutes, cleaning taking 3 minutes, and scavenging taking 5 minutes. The pulp concentration was 40%, and the stirring speed was 2500 r / min. The dosage of calcium lignosulfonate as a modifier was 600 g / t, and the dosage of MIBC as a frother was fixed at 20 g / t.

[0103] Comparison of five self-developed collectors:

[0104] 1. n-Decyl collector:

[0105] ;

[0106] 2. Isononyl collector:

[0107] ;

[0108] 3. Phenylethyl collector:

[0109] ;

[0110] 4. Cyclohexyl collector:

[0111] ;

[0112] 5. Thiophene ethyl collector:

[0113] ;

[0114] Each collector is used at a rate of 200 g / t in the roughing stage and an additional 20 g / t in the scavenging stage.

[0115] To address the technical bottlenecks in lepidolite flotation, such as poor selectivity and difficulty in improving concentrate grade, this study designed and synthesized five novel organic collectors with tunable structures. By introducing different types of hydrophobic groups (including straight-chain alkyl, branched-chain alkyl, aromatic, cycloalkyl, and thiophene ethyl groups), synergistic regulation of molecular polarity and hydrophobicity was achieved. The lithium oxide grades in lepidolite concentrates obtained by the five collectors were 2.53%, 2.36%, 3.18%, 2.07%, and 1.86%, respectively, with lithium recoveries of 95.21%, 92.16%, 88.37%, 94.22%, and 92.3%. These collectors all possess an organic combination of hydrophilic functional groups and hydrophobic structures, enabling them to disperse rapidly and adsorb directionally onto the surface of lepidolite in the slurry system, thereby enhancing the collection ability and interfacial selectivity for target minerals. The design of different R-groups not only improves the adaptability to the lepidolite surface but also allows for flexible selection based on ore properties, achieving precise flotation.

[0116] The present invention also provides an apparatus for preparing a collector.

[0117] Please see Figure 3 A device for preparing a collector, used in the method for preparing the collector, includes: a base 1, on which a bracket 101 is mounted;

[0118] Rotating device 2, the rotating device 2 includes a motor 21 and a right-angle plate 23, the motor 21 is mounted on the bracket 101, the motor 21 is used to drive the right-angle plate 23 to rotate horizontally;

[0119] An ultrasonic disperser 3 and a stirring device 4 are respectively installed at both ends of the right-angle plate 23;

[0120] Lifting device 5, which is used to raise or lower the right-angle plate 23.

[0121] The rotating device 2 also includes a connecting shaft 22, which includes a square shaft 221 and a sleeve 223. The square shaft 221 is mounted on the output shaft of the motor 21, and the sleeve 223 is sleeved on the square shaft 221.

[0122] The right-angle plate 23 is mounted on the sleeve 223.

[0123] The inner cavity of the sleeve 223 is a square cavity that is adapted to the square shaft 221.

[0124] In this embodiment, the equipment for preparing the collector is specifically used in step S14 to dissolve the target product precursor in an isopropanol-water mixed solution, add 1.5 times the equivalent amount of NaCl, and then ultrasonically disperse the mixture for 30 minutes and stir at room temperature for 4 hours; and this equipment is mainly used in the laboratory.

[0125] Specifically, after dissolving the target product precursor in an isopropanol-water mixed solution and adding 1.5 times the equivalent amount of NaCl, the container 7 carrying the material is placed on the base 1 and located below the ultrasonic disperser 3. Then, the lifting device 5 lowers the right-angle plate 23, causing the ultrasonic disperser 3 to follow and descend, so that the ultrasonic probe of the ultrasonic disperser 3 enters the liquid surface 1-2 cm. The mixture is dispersed by the ultrasonic disperser 3. After the ultrasonic dispersion is completed;

[0126] The lifting device 5 raises the right-angle plate 23, causing the ultrasonic disperser 3 to move out of the material container 7. Then, the motor 21 drives the right-angle plate 23 to rotate 90 degrees via the square shaft 221 and the sleeve 223, suspending the stirring device 4 above the material container 7. Figure 8 (a) to Figure 8 In (b), the stirring device 4 is lowered by the lifting device 5 so that its stirring blades 43 enter the material container 7, and the mixture is mechanically stirred by the stirring device 4.

[0127] Thus, ultrasonic dispersion and mechanical mixing of materials can be completed with a single device, eliminating the need for multiple devices and material transfer, making the mixing operation more convenient.

[0128] The core function of ultrasonic dispersion of a mixture is to utilize the cavitation effect of ultrasound to disperse the cavitation waves. The solid is uniformly dispersed in the isopropanol-water mixed solution, which accelerates the subsequent dissolution and reaction process;

[0129] Mechanical stirring using stirring device 4 is used to maintain the homogeneity of the solution system and promote... The product solution reacts fully to ensure the reaction (genesis). (Precipitation) is complete;

[0130] In this embodiment, the ultrasonic disperser 3 uses a conventional ultrasonic analyzer, which typically includes a high-frequency signal generator, a transducer, and an ultrasonic probe.

[0131] In this embodiment, the ultrasonic disperser 3 and the stirring device 4 are set at a 90-degree angle. The stirring device 4 rotates the right-angle plate 23 90 degrees each time to switch the positions of the two.

[0132] The wiring connected to the ultrasonic disperser 3 is pre-set to a sufficient length to meet the length required when the ultrasonic disperser 3 rotates and moves.

[0133] Please see Figure 4In this embodiment, the stirring device 4 includes a driving member 41, a stirring rod 42, and a stirring blade 43. The stirring rod 42 passes through the right-angle plate 23 and is rotatably connected to the right-angle plate 23. The stirring blade 43 is installed at the bottom end of the stirring rod 42. The driving member 41 is used to drive the stirring rod 42 to rotate.

[0134] When mixing materials, after the stirring blade 43 enters below the surface of the solution, the driving component 41 drives the stirring rod 42 to rotate the stirring blade 43, thereby achieving stirring and mixing of the materials.

[0135] The number of stirring blades 43 is preferably multiple, and in this embodiment there are two.

[0136] As an optional embodiment, the drive unit 41 includes a drive motor and a mounting bracket. The mounting bracket is installed on the top of the right-angle plate 23, and the drive motor is mounted on the mounting bracket. The output end of the drive motor is connected to the stirring rod 42. The drive motor drives the stirring rod 42 to rotate the stirring blade 43, thereby achieving the mixing function.

[0137] Please see Figure 4 As another optional embodiment, the driving member 41 is a driven gear, which is installed at the top of the stirring rod 42. The rotating device 2 also includes a main gear 24, which is installed on the output shaft of the motor 21 and located above the square shaft 221. The driving member 41 is higher than the main gear 24.

[0138] The connecting shaft 22 also includes a round shaft 222, which is installed at the bottom end of the square shaft 221, and the sleeve 223 is sleeved on the round shaft 222 and the square shaft 221.

[0139] In the initial state, the driven gear is located above the master gear 24, and the teeth of the driven gear are aligned with the tooth grooves of the master gear 24.

[0140] After the mixture is ultrasonically dispersed, the motor 21 drives the right-angle plate 23 to rotate 90 degrees through the square shaft 221 and the sleeve 223 in sequence, thereby switching the position of the stirring device 4 and the ultrasonic disperser 3. During this process, the main gear 24 and the driving component 41 (driven gear) rotate synchronously and remain relatively stationary.

[0141] After the switching is completed, the lowering sleeve 223 of the lifting device 5 drives the right-angle plate 23 to descend, causing its stirring blade 43 to enter the material container 7. At the same time, the sleeve 223 separates from the square shaft 221 and is fitted onto the round shaft 222. Simultaneously, the stirring rod 42 drives the drive component 41 (driven gear) to descend and mesh with the main gear 24. Figure 9 (a) and Figure 9In (b), at this time, the motor 21 drives the main gear 24 to rotate, and the main gear 24 drives the stirring rod 42 to rotate through the driving component 41 (driven gear), thereby driving the stirring blade 43 to rotate to achieve the stirring and mixing function of the material. At the same time, since the sleeve 223 is sleeved on the round shaft 222, it will not drive the right angle plate 23 to rotate.

[0142] Thus, the rotating device 2 can switch the positions of the stirring device 4 and the lifting device 5 in one state, and drive the stirring device 4 to perform the stirring function in another state. The state switching of the rotating device 2 is achieved by raising and lowering the stirring device 4 through the lifting device 5 so that its output end enters or leaves the material container 7.

[0143] The circular shaft 222 is preferably the inscribed circle of the sleeve 223, that is, the circular shaft 222 is in contact with the four side walls of the sleeve 223.

[0144] The drive component 41 (driven gear) is thicker than the main gear 24, thus it can accommodate a certain depth of the bearing container 7.

[0145] When the motor 21 drives the stirring device 4 to rotate, it rotates an integer number of revolutions until the end of the operation, so that the square shaft 221 and the sleeve 223 can be directly aligned again. Alternatively, after the motor 21 is turned off, the direction of the square shaft 221 can be manually adjusted to align it with the sleeve 223.

[0146] Please see Figure 3 In this embodiment, the lifting device 5 includes a mounting plate 51, a lifting cylinder 52, and a lifting plate 53. The lifting cylinder 52 is mounted on the bracket 101 via the mounting plate 51. One end of the lifting plate 53 is connected to the output end of the lifting cylinder 52, and the other end is rotatably connected to the sleeve 223.

[0147] When it is necessary to raise or lower the right-angle plate 23, the lifting cylinder 52 raises or lowers the lifting plate 53. The lifting plate 53 drives the right-angle plate 23 to rise or fall through the sleeve 223, thereby realizing the raising and lowering of the ultrasonic disperser 3 and the stirring device 4.

[0148] Please see Figures 3 to 5 The lifting device 5 also includes a slide bar 54, the bottom end of which is mounted on the base 1 and the top end of which passes through the lifting plate 53;

[0149] By setting a slide bar 54, the lifting plate 53 moves up and down along the slide bar 54, thereby improving the stability of the sliding of the lifting plate 53.

[0150] Preferably, the right-angle plate 23 has symmetrically arranged positioning holes 231. When the lifting cylinder 52 drives the right-angle plate 23 to descend through the lifting plate 53 and the sleeve 223, after the sleeve 223 separates from the square shaft 221, the corresponding positioning holes 231 on the right-angle plate 23 are fitted onto the slide rod 54, thereby axially limiting the right-angle plate 23 and ensuring the stability of the working of the stirring device 4 and the ultrasonic distributor 3.

[0151] Two positioning holes 231 are symmetrically opened on the right-angle plate 23. When the ultrasonic disperser 3 is working, one positioning hole 231 is aligned with the slide rod 54. When the right-angle plate 23 is rotated ninety degrees and the stirring device 4 is working, the other positioning hole 231 is aligned with the slide rod 54.

[0152] In other embodiments, the lifting device 5 may also adopt a screw lifting structure or a chain lifting structure, etc.

[0153] Please see Figure 3 and Figure 7 As a preferred embodiment of this example, the equipment for preparing the collector further includes a plurality of positioning structures 6, which are slidably mounted in a ring on the base 1.

[0154] Multiple positioning structures 6 can limit the movement of the material container 7, thereby preventing the material container 7 from moving due to vibration when it is working through the ultrasonic disperser or stirring device 4.

[0155] There are no fewer than two positioning mechanisms 6, and in this embodiment there are three, corresponding to three sliding grooves 102 provided on the base 1.

[0156] In one embodiment, the positioning structure includes a slider 61, a positioning frame 62, and a limiting member 63. The limiting member 63 includes a bolt 631 and a stop plate 632. The slider 61 is keyed to the slide groove 102, and there is a gap between the bottom of the slider 61 and the bottom of the slide groove 102. The bolt 631 passes through the slider 61 and is threadedly connected to the slider 61. The stop plate 632 is rotatably mounted on the bottom end of the bolt 631. One end of the positioning frame 62 is mounted on the slider 61, and the other end is horizontally suspended outside the slider 61.

[0157] By tightening the bolt 631, the stop plate 632 is pushed down and pressed against the bottom of the inner wall of the slide groove 102, thus limiting the entire limiting member 63. The positioning frame 62 among the multiple limiting members 63 contacts the material container 7, thereby limiting the material container 7.

[0158] By adjusting the position of the limiting component 63, it can accommodate material containers 7 of different diameters within a certain range.

[0159] Multiple markings 103 are provided on one side of the chute 102, and each marking 103 corresponds to a material container 7 of a different conventional size.

[0160] In another embodiment, the positioning structure 6 includes an inverted L-shaped rod and a stop head. Multiple limiting holes are arranged in a row on the base 1, and the number of limiting holes in a row corresponds to the number of positioning structures 6. The inverted L-shaped rod is inserted into the corresponding limiting hole, and the stop head is installed at the other end of the inverted L-shaped rod.

[0161] The working principle of the equipment for preparing the collector provided by this invention is as follows:

[0162] Specifically, after dissolving the target product precursor in an isopropanol-water mixed solution and adding 1.5 times the equivalent amount of NaCl, the container 7 carrying the material is placed on the base 1 and located below the ultrasonic disperser 3. Then, the lifting device 5 lowers the right-angle plate 23, causing the ultrasonic disperser 3 to follow and descend, so that the ultrasonic probe of the ultrasonic disperser 3 enters the liquid surface 1-2 cm. The mixture is dispersed by the ultrasonic disperser 3. After the ultrasonic dispersion is completed;

[0163] The lifting device 5 raises the right-angle plate 23, causing the ultrasonic disperser 3 to move out of the material container 7. Then, the motor 21 drives the right-angle plate 23 to rotate 90 degrees via the square shaft 221 and the sleeve 223, suspending the stirring device 4 above the material container 7. Figure 8 (a) to Figure 8 In (b), the stirring device 4 is lowered by the lifting device 5 so that its stirring blades 43 enter the material container 7, and the mixture is mechanically stirred by the stirring device 4.

[0164] When the mixture is ultrasonically dispersed, the motor 21 drives the right-angle plate 23 to rotate 90 degrees through the square shaft 221 and the sleeve 223 in sequence, thereby switching the position of the stirring device 4 and the ultrasonic disperser 3. During this process, the main gear 24 and the driving component 41 (driven gear) rotate synchronously and remain relatively stationary.

[0165] After the switching is completed, the lifting device 5 lowers the sleeve 223, which drives the right-angle plate 23 to descend, so that its stirring blade 43 enters the material container 7. At the same time, the sleeve 223 separates from the square shaft 221 and is fitted onto the round shaft 222. Meanwhile, the stirring rod 42 drives the driving component 41 (driven gear) to descend and mesh with the main gear 24. At this time, the motor 21 drives the main gear 24 to rotate. The main gear 24 drives the stirring rod 42 to rotate through the driving component 41 (driven gear), thereby driving the stirring blade 43 to rotate to achieve the stirring and mixing function of the material. At the same time, since the sleeve 223 is fitted onto the round shaft 222, it will not drive the right-angle plate 23 to rotate.

[0166] Thus, the rotating device 2 can switch the positions of the stirring device 4 and the lifting device 5 in one state, and drive the stirring device 4 to perform the stirring function in another state. The state switching of the rotating device 2 is achieved by raising and lowering the stirring device 4 through the lifting device 5 so that its output end enters or leaves the material container 7.

[0167] The above description is merely an embodiment of the present invention and does not limit the patent scope of the present invention. Any equivalent structural or procedural transformations made based on the content of the present invention specification and drawings, or direct or indirect applications in other related technical fields, are similarly included within the patent protection scope of the present invention.

Claims

1. A method for producing lithium carbonate, a battery material, characterized in that, Includes the following steps: S1. Roughing: After ball milling, the lepidolite is added to the flotation cell. After settling and desliming, the modifier, collector, and MIBC frother are added in sequence with stirring. The general chemical formula of the collector is: The general structural formula is: ； Where R is Straight-chain or branched alkyl or benzyl groups; It is a quaternary ammonium group; S2. Fine treatment: After roughing, rough concentrate and rough tailings are obtained. Three fine treatments and two scavengings are performed to obtain lithium concentrate and lithium tailings. S3. Calcination: The lithium concentrate is fed into a rotary kiln and calcined at 500-800℃ for 2-3 hours. S4. Leaching and filtration: After cooling the calcined solid product, it is added to a sulfuric acid solution with a mass fraction of 5% - 25% for leaching. Then, after filtration, lithium-containing leachate and leaching residue are obtained. S5. Purification and impurity removal: Add a preset amount of hydrogen peroxide to the lithium-containing leachate, then adjust the pH of the solution to 5-13, filter the precipitate, and finally use the ion exchange resin method to remove the residual impurity ions in the solution to obtain the purified lithium-containing solution. S6. Preparation of lithium carbonate: Add sodium carbonate or ammonium carbonate solution to the purified lithium-containing solution, control the reaction pH value at 8-11, and generate lithium carbonate precipitate. Then, after filtration, washing and drying, lithium carbonate is obtained.

2. The method for producing lithium carbonate battery material according to claim 1, characterized in that, The modifier is at least one of water glass, oxalic acid, sodium hexametaphosphate, starch, and calcium lignosulfonate, and the dosage is 500-1000 g / t.

3. The method for producing lithium carbonate battery material according to claim 1, characterized in that, The amount of the collector is 100-500 g / t, and the amount of the foaming agent is 10-50 g / t.

Images