A continuous reactor and its application

Abstract

The present invention provides a continuous reactor and its application, wherein the continuous reactor comprises a reactor body, a reactor cover, a draft tube, a stirring mechanism, a first feed pipe for a main material, a second feed pipe for a main material, a first feed pipe for a precipitant solution, a second feed pipe for a precipitant solution and a feed pipe for a complexing agent solution; the first feed pipe for the main material extends into the interior of the draft tube, the second feed pipe for the main material extends into between the draft tube and the reactor body; the first feed pipe for the precipitant solution extends into the interior of the draft tube, the second feed pipe for the precipitant solution extends into between the draft tube and the reactor body; the feed pipe for the complexing agent solution extends into the interior of the draft tube; when the continuous reactor of the present invention is used to prepare a ternary precursor, the particle size distribution in the reactor can be controlled by adjusting the flow rates of different feed ports at different times, so as to realize continuous production of a single reactor and effectively control the product D 0.001 , D 99.999 Extreme value and suitable particle size distribution.

Description

Technical Field

[0001] The invention belongs to the technical field of lithium ion battery materials, and in particular relates to a continuous reactor and application thereof. Background Art

[0002] In recent years, lithium-ion batteries have rapidly developed into a research hotspot due to their advantages such as high specific energy, high voltage, long life, no memory effect and low pollution, and have been widely used in consumer electronics markets such as mobile phones, laptop batteries, digital cameras and the electric vehicle market.

[0003] At present, the cathode materials in the lithium-ion battery material market mainly include lithium cobalt oxide, lithium manganese oxide, ternary materials, and lithium iron phosphate. Among them, ternary materials have become the most promising cathode materials for lithium-ion batteries due to their outstanding safety and comprehensive performance.

[0004] As the demand for lithium-ion batteries increases, the use of ternary precursors also increases year by year, and stable continuous production has become a top priority. However, in the current continuous reaction, the particle size fluctuates greatly, D0.001 is small, and D99.999 is large. Therefore, solving the particle size fluctuation and distribution problem has become an urgent problem to be solved.

[0005] CN209237963U discloses a reactor for producing ternary precursors, comprising a reactor body, a stirring system, and a power transmission system. The reactor body comprises a reactor cover, a head, an inner cylinder and a jacketed cylinder. The stirring system extending into the cylinder body is composed of an upper stirring shaft, a lower stirring shaft, a coupling, and a stirring blade. The upper end of the upper stirring shaft is connected to the output shaft of the power transmission system, and the lower end of the upper stirring shaft is connected to the lower stirring shaft through a coupling. The stirring blade for stirring the material is connected to the lower stirring shaft. An internal guide tube is provided in the circumferential direction of the stirring blade. The upper end of the internal guide tube is connected to the reactor cover. A guide port is provided on the cylinder wall of the internal guide tube, and a material inlet pipe is provided on the reactor cover. The use of the reactor to prepare ternary precursors has the advantages of easy control of the reaction environment, short production cycle, high efficiency and high production capacity, but it cannot effectively control the fluctuation and distribution of particle size.

[0006] CN112678881A discloses a preparation of a nickel-cobalt-manganese precursor with controllable particle size distribution, comprising the following steps: adjusting the ammonia concentration and pH value in the reaction vessel 1 and the reaction vessel 2; adding a nickel-cobalt-manganese salt solution, an alkaline solution and ammonia water to the reaction vessel 1; overflowing the slurry in the reaction vessel 1 into the reaction vessel 2, adding a nickel-cobalt-manganese salt solution, an alkaline solution and ammonia water to the reaction vessel 2, and turning on ultrasound at the same time; when the solid content in the reaction vessel 2 reaches 450g / L-550g / L, taking the slurry at different heights of the reaction vessel 2 to test the particle size, popping out the slurry at the corresponding height that reaches the particle size target, washing, drying and screening, and obtaining nickel-cobalt-manganese precursors of different particle sizes. This preparation method requires the use of multiple kettles in series, which occupies a large area and has a high equipment cost.

[0007] In summary, it is of great significance to provide a device and method that can realize single-reactor continuous production and effectively control product particle size fluctuation and distribution. Summary of the invention

[0008] In view of the problems existing in the prior art, the purpose of the present invention is to provide a continuous reactor and its application. The continuous reactor optimizes the structure of the continuous reactor to solve the problem that the prior art cannot achieve single-reactor continuous production and control the product particle size. Through the distribution arrangement of the guide tube and each feed pipe, the raw material flow rate of different feed pipes can be controlled during the reaction, thereby regulating the particle size distribution of the reaction product to obtain a high-quality product.

[0009] To achieve this object, the present invention adopts the following technical solutions:

[0010] In a first aspect, the present invention provides a continuous reactor, comprising a reactor body, a reactor cover, a draft tube, a stirring mechanism, a first feed pipe for a main material, a second feed pipe for a main material, a first feed pipe for a precipitant solution, a second feed pipe for a precipitant solution, a feed pipe for a complexing agent solution, a pure water feed pipe, and a gas feed pipe;

[0011] The side wall of the kettle body is provided with an overflow port, and the bottom of the kettle body is provided with a reaction liquid outlet;

[0012] The guide tube has an opening at the upper end and an opening at the lower end, and is arranged inside the kettle body;

[0013] The first feed pipe for main material extends into the interior of the guide tube, and the second feed pipe for main material extends into between the guide tube and the kettle body;

[0014] The first feed pipe of the precipitant solution extends into the interior of the guide tube, and the second feed pipe of the precipitant solution extends between the guide tube and the kettle body;

[0015] The complexing agent solution feed pipe extends into the interior of the guide tube;

[0016] The pure water feed pipe and the gas feed pipe are independently passed through the kettle cover and are located above the upper end opening of the guide tube.

[0017] In the present invention, by optimizing the structure of the continuous reactor, the overall reactor can be divided into a nucleation zone, a growth zone and a stabilization zone. The guide tube area is the nucleation zone, the area below the guide tube is the growth zone, and the area above the guide tube is the stabilization zone, and the supersaturation of each area is: stabilization zone < growth zone < nucleation zone. The present invention adjusts the supersaturation of each area through each feed pipe, thereby controlling the nucleation and growth of the particle size.

[0018] The following are preferred technical solutions of the present invention, but are not intended to be limitations of the technical solutions provided by the present invention. Through the following technical solutions, the technical objectives and beneficial effects of the present invention can be better achieved and realized.

[0019] As a preferred technical solution of the present invention, a heating jacket is provided on the outer side of the kettle body.

[0020] Preferably, the kettle body is made of stainless steel or titanium.

[0021] As a preferred technical solution of the present invention, the stirring paddle includes an axial flow paddle or a radial flow paddle.

[0022] Preferably, the stirring paddle has no less than 2 layers of blades, such as 2 layers, 3 layers, 4 layers, 5 layers or 6 layers, but is not limited to the listed values. Other unlisted values ​​within the numerical range are also applicable, preferably 2 to 3 layers.

[0023] Preferably, when the stirring paddle has two layers of blades, the upper layer of blades is located in the middle of the guide tube, and the lower layer of blades is close to the bottom of the guide tube.

[0024] Preferably, when the stirring paddle has three layers of blades, the upper blades are located at the upper part of the guide tube, the middle blades are located in the middle of the guide tube, and the lower blades are close to the bottom of the guide tube.

[0025] As a preferred technical solution of the present invention, the pipe opening of the first feed pipe for the main material is located in the middle position of the guide tube.

[0026] Preferably, the orifice of the second main material feed pipe is close to the bottom of the guide tube.

[0027] Preferably, the orifice of the first feed pipe for the precipitant solution is located in the middle of the guide tube.

[0028] Preferably, the orifice of the second feed pipe for the precipitant solution is close to the bottom of the guide tube.

[0029] Preferably, the orifice of the complexing agent solution feed pipe is located at the lower middle position of the guide tube.

[0030] As a preferred technical solution of the present invention, the first feed pipe for the main material and the first feed pipe for the precipitant solution are symmetrically arranged about the center of the guide tube.

[0031] Preferably, the second main material feed pipe and the second precipitant solution feed pipe are symmetrically arranged about the center of the guide tube.

[0032] Preferably, with the center of the guide tube as the center of the circle, the angle between the first main material feed pipe and the second main material feed pipe is 0 to 45°, such as 0°, 10°, 20°, 30° or 45°, etc., but is not limited to the listed values, and other unlisted values ​​within the numerical range are also applicable.

[0033] Preferably, with the center of the guide tube as the center of the circle, the angle between the first feed pipe of the precipitant solution and the second feed pipe of the precipitant solution is 0 to 45°, such as 0°, 10°, 20°, 30° or 45°, etc., but is not limited to the listed values, and other unlisted values ​​within the numerical range are also applicable.

[0034] In the present invention, if the first main material feed pipe is too far away from the second main material feed pipe, the second main material feed pipe will be close to the precipitant feed pipe, which will cause excessive local supersaturation and affect product quality.

[0035] In a second aspect, the present invention provides a method for preparing a ternary precursor, the preparation method being carried out using the continuous reactor as described in the first aspect, the preparation method comprising:

[0036] respectively preparing a metal salt solution, a precipitant solution and a complexing agent solution;

[0037] A bottom liquid is arranged in the continuous reactor to immerse the guide tube, and stirring is started, and protective gas is introduced at the same time; then, in the first reaction stage, the first feed pipe of the main material and / or the second feed pipe of the main material are selected to introduce the metal salt solution; at the same time, the first feed pipe of the precipitant solution and / or the second feed pipe of the precipitant solution are selected to introduce the precipitant solution; at the same time, the complexing agent solution is introduced from the complexing agent solution feed pipe;

[0038] In the second reaction stage, the feed flow rate of the main material in the first feed pipe is regulated to account for 15-85% of the total flow rate of the metal salt solution, such as 15%, 25%, 30%, 35%, 40%, 45%, 50%, 55%, 60%, 65%, 70%, 75%, 80% or 85%. However, it is not limited to the listed values, and other values ​​not listed in the numerical range are also applicable;

[0039] At the same time, the feed flow rate in the first feed pipe of the precipitant solution is regulated so that it accounts for 15-85% of the total flow rate of the precipitant solution, for example 15%, 25%, 30%, 35%, 40%, 45%, 50%, 55%, 60%, 65%, 70%, 75%, 80% or 85%, but is not limited to the listed values, and other unlisted values ​​within the numerical range are also applicable, thereby controlling the particle size of the reaction product to obtain a ternary precursor.

[0040] In the present invention, a continuous reactor with optimized structure is used to prepare the ternary precursor, and a metal salt solution, a precipitant solution and a complexing agent solution are continuously pumped into the reactor by a pump, and the particle size distribution in the reactor is controlled by adjusting the flow rates of different feed ports at different times, thereby controlling the particle size of the precursor material; the preparation method can not only realize the continuous production of a single reactor, but also effectively control the extreme values ​​of product D0.001 and D99.999 and the appropriate particle size distribution, and has good application prospects.

[0041] As a preferred technical solution of the present invention, the base liquid includes pure water, alkali solution and ammonia water.

[0042] Preferably, the alkali solution comprises sodium hydroxide solution and / or potassium hydroxide solution.

[0043] Preferably, the metal salt solution comprises a nickel-cobalt-manganese mixed salt solution, wherein the nickel content is 0.35-0.75 mol%, for example, 0.35 mol%, 0.45 mol%, 0.55 mol%, 0.65 mol% or 0.75 mol%, etc.; the cobalt content is 0.10-0.55 mol%, for example, 0.10 mol%, 0.25 mol%, 0.35 mol%, 0.45 mol% or 0.55 mol%, etc.; the manganese content is 0.15-0.55 mol%, for example, 0.15 mol%, 0.25 mol%, 0.35 mol%, 0.45 mol% or 0.55 mol%, etc. The selection of the above numerical values ​​is not limited to the listed values, and other unlisted values ​​within the respective numerical ranges are equally applicable.

[0044] Preferably, the precipitant solution comprises any one of sodium hydroxide solution, sodium carbonate solution, potassium hydroxide solution or potassium carbonate solution, or a combination of at least two thereof. Typical but non-limiting examples of the combination include: a combination of sodium hydroxide solution and sodium carbonate solution, a combination of potassium hydroxide solution and potassium carbonate solution, and the like.

[0045] Preferably, the complexing agent solution comprises any one of aqueous ammonia, ammonium sulfate solution or ammonium chloride solution, or a combination of at least two thereof. Typical but non-limiting examples of the combination include: a combination of aqueous ammonia and ammonium sulfate solution, a combination of ammonium sulfate solution and ammonium chloride solution, a combination of aqueous ammonia, ammonium sulfate solution and ammonium chloride solution, etc.

[0046] Preferably, during the reaction process, the continuous reactor controls the reaction temperature to be 40-75°C, for example, 40°C, 45°C, 50°C, 55°C, 60°C, 65°C, 70°C or 75°C, etc., but is not limited to the listed values, and other unlisted values ​​within the numerical range are also applicable.

[0047] Preferably, the stirring speed is 150-550 rpm, for example 150 rpm, 200 rpm, 250 rpm, 300 rpm, 350 rpm, 400 rpm, 450 rpm, 500 rpm or 550 rpm, but is not limited to the listed values, and other unlisted values ​​within the numerical range are also applicable.

[0048] Preferably, during the reaction in the continuous reactor, the pH of the reaction system is controlled at 9.0 to 12.5, for example, 9.0, 9.5, 10.0, 10.5, 11.0, 11.5 or 12.5, but is not limited to the listed values, and other unlisted values ​​within the numerical range are also applicable.

[0049] Preferably, during the reaction process of the continuous reactor, the ammonia concentration of the reaction system is 1.7 to 17 g / L, for example, 1.7 g / L, 2 g / L, 3 g / L, 4 g / L, 5 g / L, 6 g / L, 7 g / L, 8 g / L, 9 g / L, 10 g / L, 12 g / L, 14 g / L or 17 g / L, but is not limited to the listed values, and other unlisted values ​​within the numerical range are also applicable.

[0050] As a preferred technical solution of the present invention, the first reaction stage refers to a stage in which the reaction time is less than 12 hours.

[0051] Preferably, the second reaction stage refers to a stage in which the reaction time is greater than 12 hours and the particle size span value in the kettle is 0.55 to 1.55.

[0052] In the present invention, the first reaction stage is the initial stage of the reaction. At this time, the reaction is in the initial stage of nucleation growth, the solid content of the material in the reactor is low, and the span value will gradually narrow from the initial wide distribution. If the flow rate is adjusted too early in the first stage, it will affect the system balance, resulting in too wide span distribution, affecting product quality, making D0.001 too small and D99.999 too large.

[0053] As a preferred technical solution of the present invention, when the reaction time of the second reaction stage is greater than 12 hours and the span value of the particle size in the kettle is 0.65≤≤0.85 and the span value of the particle size in the kettle is 1.15≤≤1.35, the feed flow rate in the first feed pipe of the main material is regulated to account for 15-85% of the total flow rate of the metal salt solution; at the same time, the feed flow rate in the first feed pipe of the precipitant solution is regulated to account for 15-85% of the total flow rate of the precipitant solution;

[0054] Preferably, when the second reaction stage is a stage in which the reaction time is greater than 12 hours, and the span value of the particle size in the kettle is 0.65≤0.85 and the span value of the particle size in the kettle is 1.15≤1.35, the feed flow rate of the first feed pipe of the main material is determined according to Formula I:

[0055] V 1a =|1-span|×V 金属盐溶液釜总 Formula I

[0056] Among them, V 1a is the feed flow rate of the first feed pipe for the main material, span is the particle size span value in the second reaction stage, V 金属盐溶液釜总 is the total feed flow rate of the metal salt solution in the kettle;

[0057] The feed flow rate of the second feed pipe of the main material is determined according to formula II:

[0058] V 1b =span×V 金属盐溶液釜总 Formula II

[0059] Among them, V 1b is the feed flow rate of the second feed pipe for the main material, span is the particle size span value in the second reaction stage, V 金属盐溶液釜总 is the total feed flow rate of the metal salt solution in the kettle;

[0060] The feed flow rate of the first feed pipe of the precipitant solution is determined according to Formula III:

[0061] V 2a =|1-span|×V 沉淀剂溶液釜总 Formula III

[0062] Among them, V 2a is the feed flow rate of the first feed pipe of the precipitant solution, span is the particle size span value in the second reaction stage, V 沉淀剂溶液釜总 is the total feed flow rate of the precipitant solution in the kettle;

[0063] The feed flow rate of the second feed pipe of the precipitant solution is determined according to Formula IV:

[0064] V 2b =span×V 沉淀剂溶液釜总 Formula IV

[0065] Among them, V 2b is the feed flow rate of the second feed pipe of the precipitant solution, span is the particle size span value in the second reaction stage, V 沉淀剂溶液釜总 is the total feed flow rate of the precipitant solution in the kettle.

[0066] Preferably, when the reaction time of the second reaction stage is greater than 12 hours and the span value of the particle size in the kettle is 0.85<1.15, the feed flow rate in the first feed pipe of the main material is regulated to account for 40-60% of the total flow rate of the metal salt solution, for example, 40%, 45%, 50%, 55% or 60%, etc.; at the same time, the feed flow rate in the first feed pipe of the precipitant solution is regulated to account for 40-60% of the total flow rate of the precipitant solution, for example, 40%, 45%, 50%, 55% or 60%, etc. The selection of the above numerical values ​​is not limited to the listed numerical values, and other unlisted numerical values ​​within their respective numerical ranges are equally applicable.

[0067] In a third aspect, the present invention provides a ternary precursor, wherein the ternary precursor is prepared by the preparation method described in the second aspect, and the ternary precursor is Ni a Co b Mn (1-a-b) (OH)2, wherein 0.35≤a≤0.75, for example, 0.35, 0.45, 0.55, 0.65 or 0.75, etc.; 0.10≤b≤0.55, for example, 0.10, 0.25, 0.35, 0.45 or 0.55, etc. The selection of the above values ​​is not limited to the listed values, and other unlisted values ​​within the respective numerical ranges are also applicable.

[0068] Compared with the prior art, the present invention has the following beneficial effects:

[0069] The continuous reactor of the present invention optimizes the structure, and controls the flow ratio of each feed pipe at different positions at different reaction time stages, so that the supersaturation of each area is different, thereby controlling the nucleation and growth of the particle size, and effectively controlling D 0.001 and D 99.999 The extreme value makes the product particle size distribution moderate. BRIEF DESCRIPTION OF THE DRAWINGS

[0070] Figure 1 It is a structural schematic diagram of a continuous reactor provided by a specific embodiment of the present invention.

[0071] Among them, 1-kettle body, 2-kettle cover, 3-guide tube, 4-stirring mechanism, 1a-first feed pipe for main material, 1b-second feed pipe for main material, 2a-first feed pipe for precipitant solution, 2b-second feed pipe for precipitant solution, c-complexing agent solution feed pipe, d-pure water feed pipe, e-gas feed pipe, 5-overflow port, 6-reaction liquid outlet. DETAILED DESCRIPTION

[0072] In order to better illustrate the present invention and facilitate understanding of the technical solution of the present invention, the present invention is further described in detail below. However, the following embodiments are only simple examples of the present invention and do not represent or limit the scope of protection of the present invention. The scope of protection of the present invention shall be subject to the claims.

[0073] In a specific embodiment, the present invention provides a continuous reactor, the structural schematic diagram of the continuous reactor is as follows Figure 1 As shown, the continuous reactor comprises a reactor body 1, a reactor cover 2, a guide tube 3, a stirring mechanism 4, a first main material feed pipe 1a, a second main material feed pipe 1b, a first precipitant solution feed pipe 2a, a second precipitant solution feed pipe 2b, a complexing agent solution feed pipe c, a pure water feed pipe d and a gas feed pipe e;

[0074] The side wall of the kettle body 1 is provided with an overflow port 5, and the bottom of the kettle body 1 is provided with a reaction liquid outlet 6;

[0075] The guide tube 3 has an upper opening and a lower opening, and is disposed inside the kettle body 1;

[0076] The first main material feed pipe 1a extends into the interior of the guide tube 3, and the second main material feed pipe 1b extends between the guide tube 3 and the kettle body 1;

[0077] The first feed pipe 2a of the precipitant solution extends into the interior of the guide tube 3, and the second feed pipe 2b of the precipitant solution extends between the guide tube 3 and the kettle body 1;

[0078] The complexing agent solution feed pipe c extends into the interior of the guide tube 3;

[0079] The pure water feed pipe d and the gas feed pipe e are independently passed through the kettle cover 2 and are located above the upper end opening of the guide tube 3 .

[0080] Furthermore, a heating jacket is provided on the outer side of the kettle body 1; the material of the kettle body 1 includes stainless steel or titanium.

[0081] Furthermore, the stirring mechanism 4 includes a stirring paddle, and the stirring paddle includes an axial flow paddle or a radial flow paddle.

[0082] Furthermore, the stirring paddle has no less than 2 layers of blades, preferably 2 to 3 layers.

[0083] Furthermore, when the stirring paddle has two layers of blades, the upper layer of blades is located in the middle of the guide tube 3 , and the lower layer of blades is close to the bottom of the guide tube 3 .

[0084] Furthermore, when the stirring paddle has three layers of blades, the upper blades are located at the upper position of the guide tube 3 , the middle blades are located in the middle position of the guide tube 3 , and the lower blades are close to the bottom of the guide tube 3 .

[0085] Furthermore, the pipe opening of the first main material feeding pipe 1 a is located in the middle of the guide tube 3 .

[0086] Furthermore, the pipe opening of the second main material feeding pipe 1 b is close to the bottom of the guide tube 3 .

[0087] Furthermore, the orifice of the first precipitant solution feed pipe 2 a is located in the middle of the guide tube 3 .

[0088] Furthermore, the orifice of the second precipitant solution feeding pipe 2 b is close to the bottom of the guide tube 3 .

[0089] Furthermore, the pipe opening of the complexing agent solution feeding pipe c is located at the middle and lower position of the guide tube 3.

[0090] Furthermore, the first main material feed pipe 1 a and the first precipitant solution feed pipe 2 a are symmetrically arranged about the center of the guide tube 3 .

[0091] Furthermore, the second main material feed pipe 1 b and the second precipitant solution feed pipe 2 b are symmetrically arranged about the center of the guide tube 3 .

[0092] Furthermore, with the center of the guide tube 3 as the center of the circle, the angle between the first main material feed pipe 1a and the second main material feed pipe 1b is 0-45°.

[0093] Furthermore, with the center of the guide tube 3 as the center of the circle, the angle between the first precipitant solution feed pipe 2a and the second precipitant solution feed pipe 2b is 0-45°.

[0094] The following are typical but non-limiting embodiments of the present invention:

[0095] Embodiment 1:

[0096] This embodiment provides a continuous reactor, based on the continuous reactor in the specific implementation manner, wherein:

[0097] The stirring paddle is an axial flow paddle with three layers of blades;

[0098] With the center of the guide tube 3 as the center of the circle, the angle between the first main material feed pipe 1a and the second main material feed pipe 1b is 0°;

[0099] With the center of the guide tube 3 as the center of the circle, the angle between the first precipitant solution feeding pipe 2a and the second precipitant solution feeding pipe 2b is 0°.

[0100] Application Example 1:

[0101] This application example provides a method for preparing a ternary precursor, the preparation method is carried out using a continuous reactor as in Example 1, and the preparation method comprises the following steps:

[0102] Prepare 2mol / L nickel-cobalt-manganese salt solution, in which the molar ratio of nickel, cobalt and manganese is 40:20:40; prepare 10mol / L sodium hydroxide solution; prepare 8mol / L ammonia solution. The continuous reactor is made of stainless steel and has an effective volume of 10m3.

[0103] Pure water, sodium hydroxide solution and ammonia water were added to the continuous reactor to prepare the bottom liquid, and the guide tube 3 was immersed. The pH value was controlled to be 11.25, the ammonia concentration was 8.5 g / L, the stirring speed was set to 195 rpm, the reaction system temperature was 60°C, and nitrogen was introduced as the protective gas.

[0104] The total feed flow rate of the nickel-cobalt-manganese salt solution is set to 10 L / min, and the total feed flow rate of the sodium hydroxide solution is set to 4 L / min. The feed conditions of the raw materials in the first reaction stage and the second reaction stage are shown in Table 1, wherein according to the flow control rules of Formula I, Formula II, Formula III, Formula IV of the present invention and the reaction time is greater than 12 hours, and the particle size span value in the kettle is 0.85<1.15, in the second reaction stage, three flow control conditions at different times are adaptively listed.

[0105] Table 1

[0106]

[0107]

[0108] After the reaction was run for 40 hours, samples were taken three times from the reaction liquid outlet 6, which were product A, product B and product C respectively.

[0109] Application Example 2:

[0110] This application example provides a method for preparing a ternary precursor, the preparation method is carried out using a continuous reactor as in Example 1, and the preparation method comprises the following steps:

[0111] Prepare 2mol / L nickel-cobalt-manganese salt solution, in which the molar ratio of nickel, cobalt and manganese is 55:15:30; prepare 10mol / L sodium hydroxide solution; prepare 8mol / L ammonia solution. The continuous reactor is made of stainless steel and has an effective volume of 10m3.

[0112] Pure water, sodium hydroxide solution and ammonia water were added to the continuous reactor to prepare the bottom liquid, and the guide tube 3 was immersed. The pH value was controlled to be 11.30, the ammonia concentration was 7.5 g / L, the stirring speed was set to 185 rpm, the reaction system temperature was 60°C, and nitrogen was introduced as the protective gas.

[0113] The total feed flow rate of the nickel-cobalt-manganese salt solution is set to 10 L / min, and the total feed flow rate of the sodium hydroxide solution is set to 4 L / min. The feed conditions of each raw material in the first reaction stage and the second reaction stage are shown in Table 2. According to the flow control rules of Formula I, Formula II, Formula III, Formula IV of the present invention and the reaction time is greater than 12 hours, and the particle size span value in the kettle is 0.85<1.15, in the second reaction stage, the flow control conditions at three moments are adaptively listed.

[0114] Table 2

[0115]

[0116]

[0117] After the reaction was run for 40 hours, samples were taken three times from the reaction liquid outlet 6, which were product D, product E and product F respectively.

[0118] Application Example 3:

[0119] This application example provides a method for preparing a ternary precursor, the preparation method is carried out using a continuous reactor as in Example 1, and the preparation method comprises the following steps:

[0120] Prepare 2mol / L nickel-cobalt-manganese salt solution, in which the molar ratio of nickel, cobalt and manganese is 60:10:30; prepare 10mol / L sodium hydroxide solution; prepare 8mol / L ammonia solution. The continuous reactor is made of stainless steel and has an effective volume of 18m 3 .

[0121] Pure water, sodium hydroxide solution and ammonia water were added to the continuous reactor to prepare the bottom liquid, and the guide tube 3 was immersed. The pH value was controlled to be 11.30, the ammonia concentration was 7.0 g / L, the stirring speed was set to 160 rpm, the reaction system temperature was 60°C, and nitrogen was introduced as the protective gas.

[0122] The total feed flow rate of the nickel-cobalt-manganese salt solution is set to 20 L / min, and the total feed flow rate of the sodium hydroxide solution is set to 8 L / min. The feed conditions of the raw materials in the first reaction stage and the second reaction stage are shown in Table 3. According to the flow control rules of Formula I, Formula II, Formula III, Formula IV of the present invention and the reaction time is greater than 12 hours, and the span value of the particle size in the kettle is 0.85<1.15, in the second reaction stage, the flow control conditions at three moments are adaptively listed.

[0123] Table 3

[0124]

[0125] After the reaction was run for 40 hours, samples were taken three times from the reaction liquid outlet 6, which were product G, product H and product I respectively.

[0126] Comparative application example 1:

[0127] This comparative application example provides a method for preparing a ternary precursor. The preparation method refers to the preparation method in Application Example 2. The feeding conditions of each raw material in the entire reaction stage are shown in Table 4.

[0128] Table 4

[0129]

[0130] After the reaction was run for 40 hours, samples were taken from the reaction liquid outlet 6 twice in succession, which were product D-1 and product E-1 respectively.

[0131] Comparative application example 2:

[0132] This comparative application example provides a method for preparing a ternary precursor. The preparation method refers to the preparation method in Application Example 3. The feeding conditions of each raw material in the entire reaction stage are shown in Table 5.

[0133] Table 5

[0134]

[0135]

[0136] After the reaction was run for 40 hours, samples were taken from the reaction liquid outlet 6 twice in succession, which were product G-1 and product H-1 respectively.

[0137] The particle size distribution of the products obtained in Application Examples 1-3 and Comparative Application Examples 1-2 was analyzed by laser diffraction using Malvern Laser Particle Sizer 3000. The results are shown in Table 6.

[0138] Table 6

[0139]

[0140]

[0141] By comparing Application Examples 2-3 with Comparative Application Examples 1-2, it can be seen that the particle size distribution of the ternary precursor obtained by the continuous reactor and the preparation method of the present invention is moderate. 0.001 and D 99.999 The limit values ​​are smaller than those in the comparative application examples, and the span value is below 1.22, achieving better technical effects.

[0142] Application example 4:

[0143] This application example provides a method for preparing a ternary precursor. The preparation method refers to the preparation method in Application Example 1, with the only difference being that in the second reaction stage, the flow distribution conditions of the first feed pipe 1a of the main material and the second feed pipe 1b of the main material are exchanged, and the flow distribution conditions of the first feed pipe 2a of the precipitant solution and the second feed pipe 2b of the precipitant solution are exchanged, as shown in Table 7.

[0144] Table 7

[0145]

[0146] After the reaction was run for 44 h, samples were taken from the reaction liquid outlet 6 twice in succession, which were product A-1 and product B-1 respectively.

[0147] Application Example 5:

[0148] This application example provides a method for preparing a ternary precursor. The preparation method refers to the preparation method in Application Example 1, with the only difference being that in the second reaction stage, the feed flow rates in the first feed pipe 1a of the main material and the first feed pipe 2a of the precipitant solution are reduced. To ensure that the total feed flow rate remains unchanged, the flow rates in the second feed pipe 1b of the main material and the second feed pipe 2b of the precipitant solution are correspondingly increased. The specific details are shown in Table 8.

[0149] Table 8

[0150]

[0151] After the reaction was run for 44 h, samples were taken from the reaction liquid outlet 6 twice in succession, which were product A-2 and product B-2 respectively.

[0152] The particle size distribution of the products obtained in Application Examples 4 and 5 was analyzed by laser diffraction using Malvern Laser Particle Sizer 3000. The results are shown in Table 9.

[0153] Table 9

[0154]

[0155]

[0156] It can be seen from Application Examples 1 and 4-5 that if the flow control rules of Formula I, Formula II, Formula III, Formula IV of the present invention are violated and the reaction time is greater than 12 hours, and 0.85 < the particle size span value in the kettle < 1.15, the reaction stability system time will be prolonged and the product particle size distribution span value will become wider. At the same time, D0.001 and D99.999 are significantly different from those in Application Example 1.

[0157] Embodiment 2:

[0158] This embodiment provides a continuous reactor, which refers to the continuous reactor in Example 1, with the only difference that the orifice of the first main material feed pipe 1a is close to the bottom of the guide tube 3, and the orifice of the first precipitant solution feed pipe 2a is close to the bottom of the guide tube 3.

[0159] Application Example 6:

[0160] This application example provides a method for preparing a ternary precursor, which is carried out using a continuous reactor as in Example 2. The preparation method refers to the preparation method in Application Example 1, with the only difference being that the feeding conditions of the raw materials in the first reaction stage and the second reaction stage are changed, as shown in Table 10.

[0161] Table 10

[0162]

[0163]

[0164] After the reaction was run for 48 hours, samples were taken from the reaction liquid outlet 6 twice in succession, which were product A-3 and product B-3 respectively.

[0165] Embodiment 3:

[0166] This embodiment provides a continuous reactor, which is similar to the continuous reactor in Embodiment 1, except that: the center of the guide tube 3 is the center of the circle, and the angle between the first main material feed pipe 1a and the second main material feed pipe 1b is 180°;

[0167] With the center of the guide tube 3 as the center of the circle, the angle between the first precipitant solution feeding pipe 2a and the second precipitant solution feeding pipe 2b is 180°.

[0168] Application Example 7:

[0169] This application example provides a method for preparing a ternary precursor, which is carried out using a continuous reactor as in Example 3. The preparation method refers to the preparation method in Application Example 1, with the only difference being that the feeding conditions of the raw materials in the first reaction stage and the second reaction stage are changed, as shown in Table 11.

[0170] Table 11

[0171]

[0172] After the reaction was run for 48 h, samples were taken from the reaction liquid outlet 6 twice in succession, which were product A-4 and product B-4 respectively.

[0173] The particle size distribution of the products obtained in Application Examples 6 and 7 was analyzed by laser diffraction using Malvern Laser Particle Sizer 3000. The results are shown in Table 12.

[0174] Table 12

[0175]

[0176] It can be seen from Application Examples 1 and 6-7 that if the positions of the orifices of the first feed pipe 1a for the main material and the first feed pipe 2a for the precipitant solution in the guide tube are too low, the local supersaturation will become higher, the span value of the product particle size distribution will be larger, and the differences in D0.001 and D99.999 will be larger compared with those in Application Example 1; if the angle between the first feed pipe 1a for the main material and the second feed pipe 1b for the main material, as well as the angle between the first feed pipe 2a for the precipitant solution and the second feed pipe 2b for the precipitant solution are too large, that is, they are too far apart, the main feed and the precipitant will be too close, which will also lead to an increase in local supersaturation, and the product distribution span value, D0.001, and D99.999 will be larger than those in Application Example 1.

[0177] The present invention illustrates the device and detailed method of the present invention through the above embodiments, but the present invention is not limited to the above devices and detailed methods, that is, it does not mean that the present invention must rely on the above devices and detailed methods to be implemented. Those skilled in the art should understand that any improvement of the present invention, equivalent replacement of the operation of the present invention, addition of auxiliary operations, selection of specific methods, etc., all fall within the protection scope and disclosure scope of the present invention.

Claims

1. A continuous reactor, characterized in that: The continuous reactor comprises a reactor body, a reactor cover, a draft tube, a stirring mechanism, a first feed pipe for main material, a second feed pipe for main material, a first feed pipe for precipitant solution, a second feed pipe for precipitant solution, a feed pipe for complexing agent solution, a pure water feed pipe and a gas feed pipe; The side wall of the kettle body is provided with an overflow port, and the bottom of the kettle body is provided with a reaction liquid outlet; The guide tube has an opening at the upper end and an opening at the lower end, and is arranged inside the kettle body; The first feed pipe for main material extends into the interior of the guide tube, and the second feed pipe for main material extends into between the guide tube and the kettle body; The first feed pipe of the precipitant solution extends into the interior of the guide tube, and the second feed pipe of the precipitant solution extends between the guide tube and the kettle body; The complexing agent solution feed pipe extends into the interior of the guide tube; The orifice of the first main material feed pipe is located in the middle of the guide tube; the orifice of the second main material feed pipe is close to the bottom of the guide tube; The orifice of the first feed pipe of the precipitant solution is located in the middle of the guide tube; The orifice of the second feed pipe of the precipitant solution is close to the bottom of the guide tube; The orifice of the complexing agent solution feeding pipe is located in the middle and lower position of the guide tube; The first feed pipe for the main material and the first feed pipe for the precipitant solution are symmetrically arranged about the center of the guide tube; the second feed pipe for the main material and the second feed pipe for the precipitant solution are symmetrically arranged about the center of the guide tube; with the center of the guide tube as the center of the circle, the angle between the first feed pipe for the main material and the second feed pipe for the main material is 0-45°; the angle between the first feed pipe for the precipitant solution and the second feed pipe for the precipitant solution is 0-45°; The pure water feed pipe and the gas feed pipe are independently passed through the kettle cover and are located above the upper end opening of the guide tube.

2. The continuous reactor according to claim 1, characterized in that: The outer side of the kettle body is provided with a heating jacket.

3. The continuous reactor according to claim 1, characterized in that: The material of the kettle body includes stainless steel or titanium.

4. The continuous reactor according to claim 1, characterized in that: The stirring mechanism comprises a stirring paddle, and the stirring paddle comprises an axial flow paddle or a radial flow paddle.

5. The continuous reactor according to claim 4, characterized in that: The stirring paddle has no less than 2 layers of blades.

6. The continuous reactor according to claim 5, characterized in that: The stirring paddle has 2 to 3 layers of blades.

7. The continuous reactor according to claim 6, characterized in that: When the stirring paddle has two layers of blades, the upper blades are located in the middle of the guide tube, and the lower blades are close to the bottom of the guide tube.

8. The continuous reactor according to claim 6, characterized in that: When the stirring paddle has three layers of blades, the upper blades are located at the upper part of the guide tube, the middle blades are located in the middle of the guide tube, and the lower blades are close to the bottom of the guide tube.

9. A method for preparing a ternary precursor, characterized in that: The preparation method is carried out using a continuous reactor as described in any one of claims 1 to 8, and the preparation method comprises: A bottom liquid is arranged in the continuous reactor to immerse the guide tube, and stirring is started, and protective gas is introduced at the same time; then, in the first reaction stage, the first feed pipe of the main material and / or the second feed pipe of the main material are selected to introduce the metal salt solution; at the same time, the first feed pipe of the precipitant solution and / or the second feed pipe of the precipitant solution are selected to introduce the precipitant solution; at the same time, the complexing agent solution is introduced from the complexing agent solution feed pipe; In the second reaction stage, the feed flow rate in the first feed pipe of the main material is regulated to account for 15-85% of the total flow rate of the metal salt solution; at the same time, the feed flow rate in the first feed pipe of the precipitant solution is regulated to account for 15-85% of the total flow rate of the precipitant solution, thereby controlling the particle size of the reaction product and obtaining a ternary precursor.

10. The preparation method according to claim 9, characterized in that: The base liquid comprises pure water, alkali solution and ammonia water.

11. The preparation method according to claim 10, characterized in that: The alkali solution includes sodium hydroxide solution and / or potassium hydroxide solution.

12. The preparation method according to claim 9, characterized in that: The metal salt solution comprises a nickel-cobalt-manganese mixed salt solution, wherein the nickel content is 0.35-0.75 mol%, the cobalt content is 0.10-0.55 mol%, and the manganese content is 0.15-0.55 mol%.

13. The preparation method according to claim 9, characterized in that: The precipitant solution includes any one of sodium hydroxide solution, sodium carbonate solution, potassium hydroxide solution or potassium carbonate solution, or a combination of at least two of them.

14. The preparation method according to claim 9, characterized in that: The complexing agent solution includes any one of ammonia water, ammonium sulfate solution or ammonium chloride solution, or a combination of at least two of them.

15. The preparation method according to claim 9, characterized in that: During the reaction process, the reaction temperature of the continuous reactor is controlled to be 40-75°C.

16. The preparation method according to claim 9, characterized in that: The stirring speed is 150-550 rpm.

17. The preparation method according to claim 9, characterized in that: During the reaction process of the continuous reactor, the pH of the reaction system is controlled at 9.0-12.

5.

18. The preparation method according to claim 9, characterized in that: During the reaction process of the continuous reactor, the ammonia concentration of the reaction system is 1.7-17 g / L.

19. The preparation method according to claim 9, characterized in that: The first reaction stage refers to a stage in which the reaction time is less than 12 hours.

20. The preparation method according to claim 9, characterized in that: The second reaction stage refers to a stage in which the reaction time is greater than 12 hours and the particle size span value in the kettle is 0.55-1.

55.

21. The preparation method according to claim 9, characterized in that: In the second reaction stage, when the reaction time is greater than 12 hours and the particle size span value in the kettle is 0.65≤≤0.85 and the particle size span value in the kettle is 1.15≤≤1.35, the feed flow rate in the first feed pipe of the main material is regulated to account for 15-85% of the total flow rate of the metal salt solution; at the same time, the feed flow rate in the first feed pipe of the precipitant solution is regulated to account for 15-85% of the total flow rate of the precipitant solution.

22. The preparation method according to claim 9, characterized in that: In the second reaction stage, when the reaction time is greater than 12 hours and the particle size span value in the kettle is 0.85<1.15, the feed flow rate in the first feed pipe of the main material is regulated to account for 40-60% of the total flow rate of the metal salt solution; at the same time, the feed flow rate in the first feed pipe of the precipitant solution is regulated to account for 40-60% of the total flow rate of the precipitant solution.

23. A ternary precursor, characterized in that: The ternary precursor is prepared by the preparation method according to any one of claims 9 to 22, and the ternary precursor is Ni a Co b Mn (1-a-b) (OH)2, where 0.35≤a≤0.75, 0.10≤b≤0.55.

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