Ternary precursor material preparation system

Abstract

The present disclosure relates to a ternary precursor material preparation system, which comprises a reaction device having a reaction device slurry inlet and a reaction device slurry outlet; a filtering device having a filtering device slurry inlet and a filtering device slurry outlet, the filtering device slurry inlet being connected with the reaction device slurry outlet, and the filtering device slurry outlet being connected with the reaction device slurry inlet; the filtering device comprises a cylindrical shell and a plurality of filtering tubes arranged in the shell, the filtering tubes extending in the axial direction, and the inner diameter of the filtering tubes being 20-200 mm. The system can realize large-flow circulation filtering of the reaction slurry, meet the solid extraction operation in the ternary precursor reaction, and the prepared ternary precursor material has better quality.

Description

TECHNICAL FIELD

[0001] The present disclosure relates to a ternary precursor material preparation system. BACKGROUND

[0002] With the rapid development of battery material field, ternary material has become one of the most widely used positive electrode materials due to its good cycle performance, large specific capacity and large energy density. The mainstream method for preparing ternary precursor in the industry is co-precipitation method, that is, using nickel salt, cobalt salt and manganese salt solution as raw material, sodium hydroxide as precipitator and ammonia water as complexing agent, the three are introduced into the reaction kettle for reaction, and the temperature, time, pH, stirring rate and solid content are adjusted to control the morphology and particle size of the product. When the particle size reaches the predetermined value, the reaction slurry is filtered, washed and dried to obtain the ternary precursor.

[0003] In the process of precursor synthesis, the solid content of the precursor slurry is mainly concentrated in 5-10%, and appropriately increasing the solid content can improve the product morphology, the product morphology is more regular, the surface of the secondary particles is more dense, the impurity content is significantly reduced, and the tap density is improved, so that the sintered positive electrode material has higher energy density. At present, the mainstream method for increasing the solid content is to use a stirring thickener or a hopper thickener. The stirring thickener has the disadvantages of high cost, high daily operation and maintenance cost, and large space occupation. At the same time, the thickener often needs a certain liquid level to ensure the thickening effect, thereby prolonging the residence time of the precursor particles in the thickener, but it cannot guarantee the synchronous growth of the particles, and the product particle size distribution is wide. The hopper thickener relies on gravity sedimentation for solid-liquid separation, but the solid content of the slurry is limited, and the equipment pipeline is easy to be blocked. SUMMARY

[0004] The purpose of the present disclosure is to provide a ternary precursor material preparation system to improve the product quality of the target product ternary material precursor.

[0005] In order to achieve the above purpose, the present disclosure provides a ternary precursor material preparation system, which comprises:

[0006] a reaction device having a reaction device slurry inlet and a reaction device slurry outlet;

[0007] a filtering device having a filtering device slurry inlet and a filtering device slurry outlet, the filtering device slurry inlet being connected with the reaction device slurry outlet, and the filtering device slurry outlet being connected with the reaction device slurry inlet; the filtering device comprises a cylindrical shell and a plurality of filtering pipes arranged in the shell, the filtering pipes extending in the axial direction, and the inner diameter of the filtering pipes being 20-200mm.

[0008] Optionally, the filter device slurry inlet is arranged at the upper portion of the filter device, the filter device slurry outlet is arranged at the lower portion of the filter device, the reaction device slurry inlet is arranged at the lower portion of the reaction device, and the reaction device slurry outlet is arranged at the upper portion of the reaction device.

[0009] Optionally, the filter device slurry inlet is arranged at the lower portion of the filter device, and the filter device slurry outlet is arranged at the upper portion of the filter device.

[0010] A circulating pump is arranged on the pipeline between the filter device slurry inlet and the reaction device slurry outlet.

[0011] Optionally, a pipeline vibrator is arranged on the pipeline between the filter device slurry outlet and the reaction device slurry inlet.

[0012] Optionally, the filter pipe is made of at least one of a metal sintered material, a ceramic material, a polymer material, and a composite material.

[0013] Optionally, the filter precision of the filter pipe is 0.01-20 μm, and the filter precisions of the plurality of filter pipes are arranged in a gradient manner.

[0014] Optionally, the shell is externally provided with a heat insulation layer.

[0015] Optionally, the reaction device is in a cylindrical shape, and a plurality of pH detection elements are arranged in the reaction device in an axial uniform interval and are respectively used for detecting the pH of the reaction slurry at different liquid levels.

[0016] Optionally, the system further comprises a backwashing assembly, the filter device is provided with a clear liquid discharge outlet, and the clear liquid discharge outlet is connected with the backwashing assembly.

[0017] Optionally, the system further comprises:

[0018] A secondary filter device is connected with the filter device and is used for recovering the solid product obtained by the filter device.

[0019] Through the above technical solution, the ternary precursor material preparation system of the present disclosure can realize large-flow circulation filtration of the reaction slurry, meet the solid extraction operation in the ternary precursor reaction, obviously increase the slurry concentration in the reaction device, enable the solid particles to return to the reaction device in time to participate in the reaction and growth, reduce the filter device blocking phenomenon, be conducive to the continuous operation of the system, reduce product loss, and make the prepared ternary precursor material better in quality and the sintered positive electrode material better in performance.

[0020] Other features and advantages of the present disclosure will be described in detail in the following specific embodiment part. BRIEF DESCRIPTION OF DRAWINGS

[0021] The accompanying drawings are included to provide a further understanding of the present disclosure and are incorporated in and constitute a part of the specification. The drawings illustrate embodiments of the present disclosure and, together with the description, serve to explain the principles of the present disclosure. In the drawings:

[0022] Figure 1 is a structural schematic diagram of one embodiment of the ternary precursor material preparation system provided by the present disclosure.

[0023] Figure 2 is a structural schematic diagram of one embodiment of the ternary precursor material preparation system provided by the present disclosure.

[0024] Figure 3 is a structural schematic diagram of one embodiment of the ternary precursor material preparation system provided by the present disclosure.

[0025] Figure 4 is a structural schematic diagram of one embodiment of the ternary precursor material preparation system provided by the present disclosure.

[0026] Figure 5 is a SEM photograph of the ternary precursor material prepared in Example 1.

[0027] Figure 6 is an XRD graph of the ternary precursor material prepared in Example 1.

[0028] Figure 7 is a SEM photograph of the ternary precursor material prepared in Example 2.

[0029] Figure 8 is an XRD graph of the ternary precursor material prepared in Example 2.

[0030] Figure 9 is a SEM photograph of the ternary precursor material prepared in Comparative Example 1.

[0031] Figure 10 is a SEM photograph of the ternary precursor material prepared in Comparative Example 2.

[0032] REFERENCE SIGNS

[0033] 1 salt solution feed port 2 alkali solution feed port

[0034] 3 complexing agent feed port 4 stirring assembly

[0035] 5 pipe pump 6 filtering device

[0036] 7 backwashing assembly 8 secondary filtering device

[0037] 9 circulating pump 10 heat exchange member

[0038] 11 pH detection element 12 Reaction device

[0039] 13 Slurry inlet of the reaction unit 14 Slurry outlet of the reaction unit

[0040] 15 Slurry inlet of the filter unit 16 Slurry outlet of the filter unit

[0041] 17 Clear liquid outlet Detailed Implementation

[0042] The specific embodiments of this disclosure will be described in detail below with reference to the accompanying drawings. It should be understood that the specific embodiments described herein are for illustration and explanation only and are not intended to limit this disclosure.

[0043] This disclosure provides a ternary precursor material preparation system, with reference to... Figures 1 to 4 As shown, the system includes: a reaction device 12, which has a slurry inlet 13 and a slurry outlet 14; and a filtration device 6, which has a slurry inlet 15, a slurry outlet 16, and a clear liquid outlet 17. The slurry inlet 15 is connected to the slurry outlet 14, and the slurry outlet 16 is connected to the slurry inlet 13. The filtration device 6 includes a cylindrical shell and a plurality of filter tubes disposed within the shell. The filter tubes extend axially and have an inner diameter of 20–200 mm.

[0044] The ternary precursor material preparation system disclosed herein allows the slurry obtained from the reaction device 12 to be filtered and concentrated by an external filter device 6. The concentrated slurry is then returned to the reaction device 12, enabling high-flow-rate circulating filtration of the reaction slurry. This satisfies the consolidation operation in the ternary precursor reaction, significantly increasing the slurry concentration within the reaction device 12. The reaction mother liquor can be discharged from the reaction device 12, and the precursor particles can be promptly returned to the reaction device 12 to participate in the reaction and growth until they reach the required particle size, at which point the reaction stops. This makes it easier to obtain better microstructure and sphericity, and also ensures that the prepared precursor particles have uniform particle size and controllable dimensions. This improves operational flexibility, reduces clogging of the filter device 6, facilitates continuous system operation, and reduces product loss.

[0045] Unlike other filtering and purifying devices, the filtering device 6 of the system of the present disclosure can circulate and concentrate the reaction slurry in the pipe. The arrangement of the multiple filtering pipes and the special inner diameter specification of the filtering device 6 can achieve a high circulation flux, which is conducive to the timely return of the reaction slurry to the reactor, avoids the sedimentation of the precursor slurry, and thus ensures excellent filtering effect under a large circulation amount. The system of the present disclosure can concentrate the slurry during the reaction process, reduce the influence of the slurry on the quality of the final product during the transfer process, and reduce equipment investment and simplify production operation.

[0046] In one specific embodiment of the present disclosure, as shown in Figure 1 , the filtering device slurry inlet 15 is arranged at the upper portion of the filtering device 6, the filtering device slurry outlet 16 is arranged at the lower portion of the filtering device 6, the reaction device slurry inlet 13 is arranged at the lower portion of the reaction device 12, and the reaction device slurry outlet 14 is arranged at the upper portion of the reaction device 12. In this way, the reaction device 12 and the filtering device 6 are naturally connected, so that the gas pressure at the liquid surface of the two parts is the same, and the slurry circulation flow can be achieved only by the difference in liquid gravity; under normal circumstances, when the slurry in the reaction device 12 reaches a certain liquid level, it flows out from the reaction device slurry outlet 14 at the upper portion and enters the filtering device 6 from the filtering device slurry inlet 15 at the upper portion, and the flow direction in the filtering device 6 is gravity flow. As the clear liquid is continuously discharged, the solid content of the slurry in the filtering device 6 increases, and the density of the slurry increases. Under the action of the density difference, the concentrated slurry can flow out from the filtering device slurry outlet 16 at the lower portion and automatically return to the reaction device 12 from the reaction device slurry inlet 13 at the lower portion. In order to improve the circulation flow rate, a pipeline pump 5 and a circulation pump 9 can be arranged on the pipeline between the reaction device slurry outlet 14 and the filtering device slurry inlet 15, and on the pipeline between the filtering device slurry outlet 16 and the reaction device slurry inlet 13, respectively.

[0047] In another specific embodiment of the present disclosure, as shown in Figures 2 to 4 , the filtering device slurry inlet 15 is arranged at the lower portion of the filtering device 6, the filtering device slurry outlet 16 is arranged at the upper portion of the filtering device 6, the reaction device slurry inlet 13 can be arranged at the upper portion Figure 2 , the middle portion Figure 3 or the lower portion Figure 4 of the reaction device 12, and the reaction device slurry outlet 14 can be arranged at the lower portion Figure 2 or the upper portion Figure 3 , Figure 4)。At this time, a circulating pump 9 is arranged on the pipeline between the filter device slurry inlet 15 and the reaction device slurry outlet 14. In this way, the slurry in the reaction device 12 enters the filter device 6 from the lower filter device slurry inlet 15, and the flow direction in the filter device 6 is countercurrent gravity flow. The self-deposition of the reaction slurry promotes the concentration of the slurry, while the circulating push of the circulating pump 9 also avoids excessive deposition of the slurry. The high-speed flow of the slurry can limit the thickness of the filter cake layer on the surface of the filter tube in the filter device 6, effectively preventing the surface of the filter tube from being blocked. The concentrated slurry can flow out from the upper filter device slurry outlet 16 and return to the reaction device 12. In order to improve the circulating flow rate, a pipeline pump 5 can also be arranged on the pipeline between the filter device slurry outlet 16 and the reaction device slurry inlet 13.

[0048] According to the present disclosure, the pipeline pump 5 and the circulating pump 9 can adjust the circulating amount of the slurry. In order to further avoid the deposition and blockage of the precursor particles, in a preferred embodiment of the present disclosure, a pipeline vibrator (not shown in the figure) can also be arranged on the pipeline between the filter device slurry outlet 5 and the reaction device slurry inlet 13, which is used to provide mechanical vibration to accelerate the flow of the slurry in the pipeline. The vibration frequency can be, for example, 10-200 Hz.

[0049] According to the present disclosure, the inner diameter of the filter tube is preferably 40-150 mm. Using a filter tube with an inner diameter in this range is beneficial to improve the slurry circulation flux, thereby further improving the product quality of the ternary precursor material. In the filter device 6, a plurality of filter tubes are preferably uniformly spaced, for example, they can be arranged in a regular triangle, a square, etc. The number of filter tubes can be determined by the filtered liquid flow, the effective filtration area of the filter tube, the filtration flux per unit area of the filter tube, etc. Specifically, the number of filter tubes can be 1-1000.

[0050] According to the present disclosure, the shape of the filter tube is not particularly limited, and it can be a filter tube with a circular, square, rectangular or other irregular cross section, or a combination of multiple shapes. The material of the filter tube can be at least one of a metal sintered material, a ceramic material, a high polymer polymeric material and a composite material. The filtration accuracy of the filter tube can be 0.01-20 μm, which can be tested according to the test method of GB / T 30176-2013 standard. When the filter tube is at the above-mentioned filtration accuracy, it has a good filtering effect.

[0051] According to the present disclosure, the outside of the shell of the filter device 6 can be provided with a heat preservation layer for heat preservation of the slurry in the filter device 6, so as to avoid the fluctuation of the reaction process parameters caused by the temperature reduction during the external circulation concentration of the slurry.

[0052] According to the present disclosure, the reaction device 12 is cylindrical, and a plurality of pH detection elements 11 are arranged in the reaction device 12 at uniform intervals along the axial direction, and are respectively used for detecting the pH of the reaction slurry at different liquid levels. Preferably, the number of the pH detection elements 11 is 2-20. Among them, the height of the uppermost pH detection element 11 can be 0.6-0.9 times the height of the cylinder of the reaction device 12; the lowermost pH detection element 11 can be installed at the bottom of the reaction device 12, and the height can be up to 0.3 times the height of the cylinder of the reaction device 12. During the reaction process, the measured values of the plurality of pH detection elements 11 can be obtained synchronously, and when the measured values of the plurality of pH detection elements 11 are not much different, it is proved that the mixing degree of the reaction slurry in the reaction device 12 is good. Maintaining the uniform and stable pH in the reaction device 12 is crucial to the product quality, and by arranging a plurality of pH detection elements 11 at different heights, the dispersion of the reaction raw materials in the reaction device 12 can be relatively accurately obtained through error analysis, and the parameters such as the rotation speed and the raw material input flow can be adjusted in time.

[0053] According to the present disclosure, the reaction device 12 can also be provided with a stirring assembly 4, which is arranged along the central axis of the reaction device 12. The stirring assembly 4 can include one or more groups of stirring paddles arranged at uniform intervals along the axial direction, and specifically, the stirring paddles can be 2-3 groups. The stirring paddles can be conventional in the art, for example, can be propeller stirring paddles, turbine stirring paddles or combinations thereof.

[0054] According to the present disclosure, the reaction device 12 can adopt a reactor common in the art, for example, a kettle-type reactor. The reaction device 12 can also be provided with a draft tube for guiding the reaction slurry. The outside of the reaction device 12 can also be provided with a heat exchange member, for example, a jacket or a coil.

[0055] The present disclosure is applicable to the preparation of various ternary material precursors, such as nickel-cobalt-manganese precursors, nickel-cobalt-aluminum precursors, etc., which are well known in the art. The raw material mixture is a mixture of common raw materials for preparing ternary material precursors, and the present disclosure is not particularly limited. For example, the raw material mixture can include a salt solution, a lye, and a complexing agent. In one specific embodiment of the present disclosure, the reaction device 12 further has a salt solution feed port 1, a lye feed port 2, and a complexing agent feed port 3 for adding the salt solution, the lye, and the complexing agent, respectively. The salt solution feed port 1, the lye feed port 2, and the complexing agent feed port 3 can further be provided with a rapid dispersion device or a distributor to improve the dispersion degree of the raw materials. The rapid dispersion device or the distributor can be of a branch pipe type, a pressure nozzle type, a shower type, a rotary atomizing wheel, etc., or a combination thereof. The types of the salt solution, the lye, and the complexing agent can be conventional in the art. For example, the salt solution can be a mixture of soluble nickel salt, soluble cobalt salt, soluble manganese salt, and water, or a combination of soluble nickel salt, soluble cobalt salt, and soluble aluminum salt solution, wherein the total molar concentration of metal ions can be 0.5-5.0 mol / L; the lye can be a sodium hydroxide aqueous solution, wherein the molar concentration of OH - may be 1.0-20.0 mol / L; and the complexing agent can be ammonia water, wherein the concentration of NH3 is 1-30 wt.%. Further, the reaction device 12 further has a slurry discharge port for collecting the ternary material precursor product.

[0056] According to the present disclosure, the system can further include a backwashing assembly 7, the clear liquid discharge port 17 of the filtering device 6 is connected to the backwashing assembly 7, and the backwashing assembly 7 is used to flush the filtering device 6 to avoid material accumulation. Further, the system can further include a secondary filtering device 8 connected to the filtering device 6 for recovering the solid product obtained by the filtering device 6, and a pressure control device (not shown in the figure) for controlling the pressure in the reaction device 12. Figure 1

[0057] ​The method for preparing the ternary precursor material by using the system provided by the present disclosure can be specifically as follows: the reaction raw material salt solution, the complexing agent, and the alkali solution are sent to the vicinity of the stirring assembly in the reaction device through the feeding pipe, and a co-precipitation reaction occurs under certain reaction conditions (for example, a reaction temperature of 20-100 ℃ and a reaction pressure of 0-3.0 MPa), the slurry obtained by the reaction is introduced into the filtering device for concentration, the concentrated slurry is returned to the reaction device for continuous growth, the material after the reaction is continuously or intermittently discharged from the bottom discharge port of the reaction device, and the ternary precursor material is separated and obtained, the filtrate filtered out of the filtering device is discharged after optional secondary filtration, the liquid level in the reaction device is kept stable during the filtration and concentration process, the total flow of the raw material liquid entering the reaction device is equal to the sum of the flow of the slurry after concentration and the flow of the filtrate after concentration, and the flow rate of the slurry in the filter tube in the filtering device can reach 1-10 m / s. The pressure on the pipe side of the filter tube in the filtering device is generally higher than the pressure on the shell side of the membrane assembly (for example, 0.01-0.5 MPa), the pressure in the reaction device can be appropriately increased to promote the discharge of the filtrate, or the shell side of the filtering device can be appropriately vacuumed to meet the above requirements, and the reaction kettle device is preferably pressurized to promote discharge. When the pressure difference between the pipe side and the shell side of the filter tube in the filtering device is too low, the filtering device 6 can be backwashed or regenerated, and a certain interval time (for example, 10-120 min) is preferably set for pulse backwashing of the filtering device 6, and the backwashing time can be 3-30 s each time.

[0058] The ternary precursor material preparation system provided by the present disclosure has the advantages of simple structure, convenient operation, low investment, quick effect, and the like, can be widely applied to the process of material concentration in a chemical reaction process, and is particularly suitable for the synchronous synthesis and concentration process of the ternary precursor material. The ternary material precursor prepared by using the system provided by the present disclosure has good micro-morphology and sphericity, and the particle size span value of the ternary precursor material is not greater than 1.

[0059] The present disclosure is further described through the following examples, but does not constitute a limitation on the present disclosure.

[0060] In the examples, the morphology of the ternary material precursor is detected by SEM, the particle size analysis is performed by using a laser particle size analyzer, and the crystal structure is detected by using an X-ray diffractometer.

[0061] Example 1

[0062] As shown in the above examples, the ternary material precursor prepared by using the system provided by the present disclosure has good micro-morphology and sphericity, and the particle size span value of the ternary precursor material is not greater than 1. Figure 1The system, the reaction device volume is 800L, the height is 1600mm, the reaction device slurry inlet is arranged at the lower part, the reaction device slurry outlet is arranged at the upper part, 2 pH detection elements are arranged in the inside, the heights are 50mm and 600mm on the tangent of the cylinder respectively, 2 groups of stirring paddles are arranged along the axis. The filter device volume is 800L, the total height is 1600mm, the metal powder isopressing sintering is selected as the filter tube, the filter tube filtering precision is 0.5μm, the inner diameter is 50mm, the length is 1000mm, 16 filter tubes are arranged in the form of equilateral triangle, the two ends are fixed on the shell tube plate, the filter device slurry inlet is arranged at the upper part, the filter device slurry outlet is arranged at the lower part, the clear liquid discharge port is connected with the backwashing assembly and the secondary filter device, the filter device shell is provided with a heat preservation layer. The pipeline between the filter device slurry outlet and the reaction device slurry inlet is provided with a pipeline shaker, and the vibration frequency is 50Hz.

[0063] Deionized water is used as the reaction pre-liquid and heated to 60℃, the pre-liquid ammonia concentration is adjusted to 4.0g / L, and the pre-liquid pH value is adjusted to 10.8. The prepared nickel sulfate solution, cobalt sulfate solution, manganese sulfate solution with a total metal ion concentration of 2.7mol / L, NaOH solution with a concentration of 20wt%, and ammonia water with a concentration of 18.2wt% are continuously added into the reaction kettle, the pH value is maintained at 10.85, the reaction is carried out at a temperature of 60℃ and a pressure of 0.08Mpa, when the reaction slurry is full, the slurry is drawn out from the upper paddle outlet of the reaction device and enters the filter device to concentrate the reaction slurry, and the filtered slurry returns from the lower slurry inlet of the reaction device. The slurry flow rate in the filter device is 4m / s, the pressure in the reaction device is maintained, the automatic backwashing is set, the filter device is pulse backwashed every 30min, and the backwashing time is 5s. When the cumulative reaction time is 48h, the reaction slurry is collected.

[0064] The collected reaction slurry is separated to obtain a nickel-cobalt-manganese ternary precursor material, the SEM photo is as shown in Figure 5 , and the XRD diagram is shown in Figure 6 The sphericity is good, the primary grain arrangement is dense and the orientation degree is high, the crystal structure conforms to the structure of β-Ni(OH)2, there is no impurity peak, the peak type is sharp, the precursor crystal structure is complete, the particle uniformity is high, and basically no small particles exist, and the calculated particle size Span value is 0.89.

[0065] Example 2

[0066] The prepared nickel-cobalt-manganese ternary precursor material is used as the raw material, and the preparation process is as shown in Figure 2The system, the reaction device volume is 800L, the height is 1600mm, the reaction device slurry inlet is arranged at the upper portion, the reaction device slurry outlet is arranged at the lower portion, 2 pH detection elements are arranged in the reaction device, the heights are 50mm and 600mm respectively on the tangent line of the cylinder body, 2 groups of stirring paddles are arranged along the shaft. The filter device volume is 800L, the total height is 1600mm, the metal powder is selected as the filter tube, the filter tube filtering precision is 0.5μm, the inner diameter is 50mm, the length is 900mm, 16 filter tubes are arranged in a equilateral triangle, the two ends are fixed on the shell tube plate, the filter device slurry inlet is arranged at the lower portion, the filter device slurry outlet is arranged at the upper portion, the clear liquid outlet is connected with the backwashing assembly and the secondary filter device, the filter device shell is provided with a heat preservation layer. The pipeline between the filter device slurry inlet and the reaction device slurry outlet is provided with a circulating pump. The pipeline between the filter device slurry outlet and the reaction device slurry inlet is provided with a pipeline shaker, the vibration frequency is 50Hz.

[0067] The deionized water is used as the reaction pre-liquid and heated to 60℃, the pre-liquid ammonia concentration is adjusted to 4.0g / L, and the pre-liquid pH value is adjusted to 10.55. The prepared nickel sulfate solution, cobalt sulfate solution, manganese sulfate solution with the total metal ion concentration of 2.7mol / L, the NaOH solution with the concentration of 20wt% and the ammonia water with the concentration of 18.2wt% are continuously added into the reaction kettle, the pH value is maintained at 10.85, the reaction is carried out at the temperature of 60℃ and the pressure of 0.08Mpa, when the reaction slurry is full, the slurry is led out from the lower paddle outlet of the reaction device and enters the filter device to concentrate the reaction slurry, the filtered slurry returns from the upper slurry inlet of the reaction device. The slurry flow rate in the filter device is 4m / s, the pressure in the reaction device is maintained, the automatic backwashing is set, the filter device is pulse backwashed every 30min, the backwashing time is 5s. When the cumulative reaction time is 48h, the reaction slurry is collected.

[0068] The collected reaction slurry is separated to obtain the nickel-cobalt-manganese ternary precursor material, the SEM photo is as Figure 7 , and the XRD graph is as Figure 8 The spherical degree is good, the primary grain arrangement is dense and the orientation degree is high, the crystal structure is consistent with the structure of β-Ni(OH)2, there is no impurity peak, the peak type is sharp, the precursor crystal structure is complete, the particle uniformity is high, and there is basically no small particles, the calculated particle size Span value is 0.83.

[0069] Example 3

[0070] The prepared nickel-cobalt-manganese ternary precursor material is used as the raw material, and the preparation process is as Figure 3The system shown has a reaction unit with a volume of 800L and a height of 1600mm. The slurry inlet is located in the middle, and the slurry outlet is located at the top. It contains two pH detection elements at heights of 50mm and 600mm tangent to the cylinder, respectively, and two sets of agitators are arranged along the axis. The filtration unit also has a volume of 800L and a total height of 1600mm. It uses isostatically pressed metal powder as filter tubes, with a filtration accuracy of 0.5μm, an inner diameter of 50mm, and a length of 900mm. Sixteen filter tubes are arranged in an equilateral triangle, fixed at both ends to the outer shell tube sheet. The slurry inlet of the filtration unit is located at the bottom, and the slurry outlet is located at the top. The clear liquid outlet connects to the backwashing assembly and the secondary filtration unit. The outer shell of the filtration unit is insulated. A circulation pump is installed on the pipeline between the slurry inlet of the filtration unit and the slurry outlet of the reaction unit. A pipeline vibrator with a vibration frequency of 50Hz is installed on the pipeline between the slurry outlet of the filtration unit and the slurry inlet of the reaction unit.

[0071] Deionized water was used as the initial solution before the reaction and heated to 60°C. The ammonia concentration of the initial solution was adjusted to 4.0 g / L, and the pH value was adjusted to 10.55. A prepared solution of nickel sulfate (2.7 mol / L total metal ion concentration), cobalt sulfate, manganese sulfate, 20% (w / w) NaOH solution, and 18.2% (w / w) ammonia solution were continuously added to the reactor, maintaining the pH value at 10.85. The reaction was carried out at 60°C and 0.08 MPa. When the reaction slurry filled the reactor, it was drawn from the slurry outlet at the bottom of the reactor and entered a filtration device for concentration. The 0.5 μm filter tube was opened first under program control, and after 24 hours of reaction, the 1 μm filter tube was opened. The filtered slurry returned from the slurry inlet at the top of the reactor. The slurry flow rate in the filtration device was 4 m / s. The pressure inside the reactor was maintained, and automatic backwashing was set up. The filtration device was pulsed backwashed every 30 minutes for 5 seconds. When the cumulative reaction time is 48 hours, the reaction slurry is collected.

[0072] The collected reaction slurry was separated to obtain a nickel-cobalt-manganese ternary precursor material with good sphericity, dense primary grain arrangement and high orientation, high particle uniformity, and basically no small particles. The calculated particle size Span value was 0.85.

[0073] Example 4

[0074] Adopting such Figure 4The system is shown, the reaction device volume is 800L, the height is 1600mm, the reaction device slurry inlet is arranged at the lower part, the reaction device slurry outlet is arranged at the upper part, 2 pH detection elements are arranged inside, the heights are 50mm and 600mm on the tangent of the cylinder respectively, 2 groups of stirring paddles are arranged along the axis. The filter device volume is 800L, the total height is 1600mm, the metal powder isopressing sintering is selected as the filter tube, the filter tube filtering precision is 0.5μm, the inner diameter is 50mm, the length is 900mm, 16 filter tubes are arranged in a regular triangle, the two ends are fixed on the shell tube plate, the filter device slurry inlet is arranged at the lower part, the filter device slurry outlet is arranged at the upper part, the clear liquid outlet is connected with the backwashing assembly and the secondary filter device, the filter device shell is provided with a heat preservation layer. The pipeline between the filter device slurry inlet and the reaction device slurry outlet is provided with a circulating pump. The pipeline between the filter device slurry outlet and the reaction device slurry inlet is provided with a pipeline shaker, and the vibration frequency is 50Hz.

[0075] Deionized water is used as the reaction pre-liquid and heated to 60℃, the pre-liquid ammonia concentration is adjusted to 4.0g / L, and the pre-liquid pH value is adjusted to 10.55. The prepared nickel sulfate solution, cobalt sulfate solution, manganese sulfate solution with a total metal ion concentration of 2.7mol / L, NaOH solution with a concentration of 20wt%, and ammonia water with a concentration of 18.2wt% are continuously added into the reaction kettle, the pH value is maintained at 10.85, the reaction is carried out at a temperature of 60℃ and a pressure of 0.08Mpa, when the reaction slurry is full, the slurry is drawn out from the lower paddle outlet of the reaction device and enters the filter device to concentrate the reaction slurry, and the filtered slurry returns from the upper slurry inlet of the reaction device. The slurry flow rate in the filter device is 4m / s, the pressure in the reaction device is maintained, automatic backwashing is set, pulse backwashing is carried out on the filter device every 30min, and the backwashing time is 5s. When the cumulative reaction time is 48h, the reaction slurry is collected.

[0076] The collected reaction slurry is separated to obtain a nickel-cobalt-manganese ternary precursor material, which has good sphericity, dense primary grain arrangement and high orientation degree, high particle uniformity, and basically no small particles exist, and the calculated particle size Span value is 0.78.

[0077] Example 5

[0078] The nickel-cobalt-manganese ternary precursor material is prepared according to the method of example 1, and the difference is that the filter device volume is 800L, the total height is 1600mm, the filter tube filtering precision is 0.5μm, the inner diameter is 25mm, the length is 1000mm, and 32 filter tubes are arranged in a regular triangle.

[0079] The collected reaction slurry is separated to obtain the nickel-cobalt-manganese ternary precursor material, which has good sphericity, dense primary crystal grain arrangement and high orientation degree, high particle uniformity, and basically no small particles, and the calculated particle size Span value is 0.92.

[0080] Example 6

[0081] The nickel-cobalt-manganese ternary precursor material is prepared according to the method of Example 1, except that the filter device has a volume of 800 L, a total height of 1600 mm, and the filter tube has a filtering precision of 0.5 μm, an inner diameter of 200 mm, and a length of 1000 mm, and four filter tubes are arranged in a regular triangle.

[0082] The collected reaction slurry is separated to obtain the nickel-cobalt-manganese ternary precursor material, which has good sphericity, dense primary crystal grain arrangement and high orientation degree, high particle uniformity, and basically no small particles, and the calculated particle size Span value is 0.95.

[0083] Comparative Example 1

[0084] The nickel-cobalt-manganese ternary precursor material is prepared according to the method of Example 1, except that the filter device is replaced by a matching external thickener.

[0085] The collected reaction slurry is separated to obtain the nickel-cobalt-manganese ternary precursor material, and the SEM photograph is as shown in Figure 9 The particle size is not uniform, the primary crystal grains are needle-shaped, and the calculated particle size Span value is 1.02.

[0086] Comparative Example 2

[0087] The nickel-cobalt-manganese ternary precursor material is prepared according to the method of Example 1, except that no filter tube is arranged in the filter device, but a hollow fiber membrane (purchased from Shandong Jinhui Membrane Technology Co., Ltd., product number UF-8060, filtering precision 0.01 μm, membrane wire inner diameter 0.8 mm) is arranged instead.

[0088] The collected reaction slurry is separated to obtain the nickel-cobalt-manganese ternary precursor material, and the SEM photograph is as shown in Figure 10 Due to the small inner diameter of the membrane wire and the easy coalescence of the precursor slurry, the particle size of the product is not uniform, and the calculated particle size Span value is 2.32.

[0089] As can be seen from the comparison results of the examples and the comparative examples, the ternary precursor material prepared by the system of the present disclosure has good micro-morphology and sphericity, a lower particle size Span value, and higher particle uniformity. When the inner diameter of the filter tube is 40-150 mm, it is helpful to further reduce the particle size Span value of the ternary precursor material.

[0090] The preferred embodiments of the present disclosure are described in detail above with reference to the drawings, but the present disclosure is not limited to the specific details in the above-described embodiments. Various simple modifications can be made to the technical solutions of the present disclosure within the technical concept of the present disclosure, and these simple modifications all belong to the protection scope of the present disclosure.

[0091] In addition, it should be noted that each specific technical feature described in the above specific embodiments can be combined in any appropriate manner without contradiction. In order to avoid unnecessary repetition, various possible combinations are not described again in the present disclosure.

[0092] In addition, various different embodiments of the present disclosure can also be combined in any appropriate manner, as long as they do not deviate from the idea of the present disclosure, and they should also be considered as disclosed in the present disclosure.

Claims

1. A ternary precursor material preparation system, characterized by, The system comprises: a reaction device having a reaction device slurry inlet and a reaction device slurry outlet; a filtering device having a filtering device slurry inlet and a filtering device slurry outlet, the filtering device slurry inlet being connected to the reaction device slurry outlet, and the filtering device slurry outlet being connected to the reaction device slurry inlet; the filtering device comprises a cylindrical shell and a plurality of filtering tubes arranged in the shell, the filtering tubes extending in the axial direction, the inner diameter of the filtering tubes being 40-150 mm, and the filtering precision of the filtering tubes being 0.01-20 μm.

2. The system of claim 1, wherein, The filtering device slurry inlet is arranged at the upper part of the filtering device, the filtering device slurry outlet is arranged at the lower part of the filtering device, the reaction device slurry inlet is arranged at the lower part of the reaction device, and the reaction device slurry outlet is arranged at the upper part of the reaction device.

3. The system of claim 1, wherein, The filtering device slurry inlet is arranged at the lower part of the filtering device, and the filtering device slurry outlet is arranged at the upper part of the filtering device. A circulating pump is arranged on the pipeline between the filtering device slurry inlet and the reaction device slurry outlet.

4. The system of claim 1, wherein, A pipeline shaker is arranged on the pipeline between the filtering device slurry outlet and the reaction device slurry inlet.

5. The system of claim 1, wherein, The filtering tubes are made of at least one of metal sintered material, ceramic material, high polymer material and composite material.

6. The system of claim 1, wherein, The shell is externally provided with a heat insulation layer.

7. The system of claim 1, wherein, The reaction device is cylindrical, and a plurality of pH detecting elements are arranged in the reaction device at uniform intervals in the axial direction, and are used for detecting the pH of the reaction slurry at different liquid levels.

8. The system of claim 1, wherein, The system further comprises a backwashing assembly, and the filtering device is provided with a clear liquid outlet connected to the backwashing assembly.

9. The system of claim 1, wherein, The system further comprises: a secondary filtering device connected to the filtering device and used for recovering the solid product obtained by the filtering device.

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