WO2024040909A1 - 掺铝碳酸钴颗粒及其制备方法与应用 - Google Patents

掺铝碳酸钴颗粒及其制备方法与应用 Download PDF

Info

Publication number
WO2024040909A1
WO2024040909A1 PCT/CN2023/079346 CN2023079346W WO2024040909A1 WO 2024040909 A1 WO2024040909 A1 WO 2024040909A1 CN 2023079346 W CN2023079346 W CN 2023079346W WO 2024040909 A1 WO2024040909 A1 WO 2024040909A1
Authority
WO
WIPO (PCT)
Prior art keywords
cobalt
aluminum
particles
cobalt carbonate
solution
Prior art date
Legal status (The legal status is an assumption and is not a legal conclusion. Google has not performed a legal analysis and makes no representation as to the accuracy of the status listed.)
Ceased
Application number
PCT/CN2023/079346
Other languages
English (en)
French (fr)
Inventor
周思源
李长东
阮丁山
刘更好
卢星华
胡海涵
Current Assignee (The listed assignees may be inaccurate. Google has not performed a legal analysis and makes no representation or warranty as to the accuracy of the list.)
Hunan Brunp Recycling Technology Co Ltd
Guangdong Brunp Recycling Technology Co Ltd
Original Assignee
Hunan Brunp Recycling Technology Co Ltd
Guangdong Brunp Recycling Technology Co Ltd
Priority date (The priority date is an assumption and is not a legal conclusion. Google has not performed a legal analysis and makes no representation as to the accuracy of the date listed.)
Filing date
Publication date
Application filed by Hunan Brunp Recycling Technology Co Ltd, Guangdong Brunp Recycling Technology Co Ltd filed Critical Hunan Brunp Recycling Technology Co Ltd
Priority to GB2309728.0A priority Critical patent/GB2626389A/en
Publication of WO2024040909A1 publication Critical patent/WO2024040909A1/zh
Anticipated expiration legal-status Critical
Ceased legal-status Critical Current

Links

Classifications

    • C—CHEMISTRY; METALLURGY
    • C01—INORGANIC CHEMISTRY
    • C01G—COMPOUNDS CONTAINING METALS NOT COVERED BY SUBCLASSES C01D OR C01F
    • C01G51/00—Compounds of cobalt
    • C01G51/06—Carbonates
    • C—CHEMISTRY; METALLURGY
    • C01—INORGANIC CHEMISTRY
    • C01G—COMPOUNDS CONTAINING METALS NOT COVERED BY SUBCLASSES C01D OR C01F
    • C01G51/00—Compounds of cobalt
    • C01G51/04—Oxides
    • C—CHEMISTRY; METALLURGY
    • C01—INORGANIC CHEMISTRY
    • C01G—COMPOUNDS CONTAINING METALS NOT COVERED BY SUBCLASSES C01D OR C01F
    • C01G51/00—Compounds of cobalt
    • C01G51/40—Complex oxides containing cobalt and at least one other metal element
    • C01G51/42—Complex oxides containing cobalt and at least one other metal element containing alkali metals, e.g. LiCoO2
    • H—ELECTRICITY
    • H01—ELECTRIC ELEMENTS
    • H01M—PROCESSES OR MEANS, e.g. BATTERIES, FOR THE DIRECT CONVERSION OF CHEMICAL ENERGY INTO ELECTRICAL ENERGY
    • H01M4/00—Electrodes
    • H01M4/02—Electrodes composed of, or comprising, active material
    • H01M4/36—Selection of substances as active materials, active masses, active liquids
    • H01M4/48—Selection of substances as active materials, active masses, active liquids of inorganic oxides or hydroxides
    • H01M4/52—Selection of substances as active materials, active masses, active liquids of inorganic oxides or hydroxides of nickel, cobalt or iron
    • H01M4/525—Selection of substances as active materials, active masses, active liquids of inorganic oxides or hydroxides of nickel, cobalt or iron of mixed oxides or hydroxides containing iron, cobalt or nickel for inserting or intercalating light metals, e.g. LiNiO2, LiCoO2 or LiCoOxFy
    • C—CHEMISTRY; METALLURGY
    • C01—INORGANIC CHEMISTRY
    • C01P—INDEXING SCHEME RELATING TO STRUCTURAL AND PHYSICAL ASPECTS OF SOLID INORGANIC COMPOUNDS
    • C01P2002/00—Crystal-structural characteristics
    • C01P2002/50—Solid solutions
    • C01P2002/52—Solid solutions containing elements as dopants
    • C01P2002/54—Solid solutions containing elements as dopants one element only
    • C—CHEMISTRY; METALLURGY
    • C01—INORGANIC CHEMISTRY
    • C01P—INDEXING SCHEME RELATING TO STRUCTURAL AND PHYSICAL ASPECTS OF SOLID INORGANIC COMPOUNDS
    • C01P2004/00—Particle morphology
    • C01P2004/01—Particle morphology depicted by an image
    • C01P2004/03—Particle morphology depicted by an image obtained by SEM
    • C—CHEMISTRY; METALLURGY
    • C01—INORGANIC CHEMISTRY
    • C01P—INDEXING SCHEME RELATING TO STRUCTURAL AND PHYSICAL ASPECTS OF SOLID INORGANIC COMPOUNDS
    • C01P2004/00—Particle morphology
    • C01P2004/60—Particles characterised by their size
    • C01P2004/61—Micrometer sized, i.e. from 1-100 micrometer
    • C—CHEMISTRY; METALLURGY
    • C01—INORGANIC CHEMISTRY
    • C01P—INDEXING SCHEME RELATING TO STRUCTURAL AND PHYSICAL ASPECTS OF SOLID INORGANIC COMPOUNDS
    • C01P2004/00—Particle morphology
    • C01P2004/80—Particles consisting of a mixture of two or more inorganic phases
    • C01P2004/82—Particles consisting of a mixture of two or more inorganic phases two phases having the same anion, e.g. both oxidic phases
    • C01P2004/84—Particles consisting of a mixture of two or more inorganic phases two phases having the same anion, e.g. both oxidic phases one phase coated with the other
    • C—CHEMISTRY; METALLURGY
    • C01—INORGANIC CHEMISTRY
    • C01P—INDEXING SCHEME RELATING TO STRUCTURAL AND PHYSICAL ASPECTS OF SOLID INORGANIC COMPOUNDS
    • C01P2006/00—Physical properties of inorganic compounds
    • C01P2006/14—Pore volume
    • C—CHEMISTRY; METALLURGY
    • C01—INORGANIC CHEMISTRY
    • C01P—INDEXING SCHEME RELATING TO STRUCTURAL AND PHYSICAL ASPECTS OF SOLID INORGANIC COMPOUNDS
    • C01P2006/00—Physical properties of inorganic compounds
    • C01P2006/40—Electric properties
    • Y—GENERAL TAGGING OF NEW TECHNOLOGICAL DEVELOPMENTS; GENERAL TAGGING OF CROSS-SECTIONAL TECHNOLOGIES SPANNING OVER SEVERAL SECTIONS OF THE IPC; TECHNICAL SUBJECTS COVERED BY FORMER USPC CROSS-REFERENCE ART COLLECTIONS [XRACs] AND DIGESTS
    • Y02—TECHNOLOGIES OR APPLICATIONS FOR MITIGATION OR ADAPTATION AGAINST CLIMATE CHANGE
    • Y02E—REDUCTION OF GREENHOUSE GAS [GHG] EMISSIONS, RELATED TO ENERGY GENERATION, TRANSMISSION OR DISTRIBUTION
    • Y02E60/00—Enabling technologies; Technologies with a potential or indirect contribution to GHG emissions mitigation
    • Y02E60/10—Energy storage using batteries

Definitions

  • the present invention relates to the technical field of cobalt carbonate, and specifically to aluminum-doped cobalt carbonate particles and preparation methods and applications thereof.
  • Lithium cobalt oxide batteries have dominated consumer electronics since their commercialization. People's requirements for the standby time and volume and weight of consumer electronics are constantly increasing, which requires lithium cobalt oxide to be charged and discharged at high voltage to increase battery energy density.
  • Cobalt tetroxide is an important raw material for the synthesis of lithium cobalt oxide, and cobalt carbonate is one of the precursors for preparing cobalt tetroxide. Therefore, the precursor cobalt carbonate affects the performance of lithium cobalt oxide to a great extent.
  • One of the objects of the present invention is to provide aluminum-doped cobalt carbonate particles to solve the above technical problems.
  • the second object of the present invention is to provide a method for preparing the above-mentioned aluminum-doped cobalt carbonate particles.
  • the third object of the present invention is to provide a kind of cobalt tetroxide containing the above-mentioned aluminum-doped cobalt carbonate particles in the precursor.
  • the fourth object of the present invention is to provide a method for preparing lithium cobalt oxide containing the above-mentioned tricobalt tetroxide as a raw material.
  • the present application provides aluminum-doped cobalt carbonate particles, which have a core-shell structure, in which the primary cobalt carbonate particles forming the core are granular particles with evenly distributed aluminum, and the primary cobalt carbonate particles forming the shell are flake particles.
  • the length of the plate-shaped particles is 0.42-0.85 ⁇ m and the width is 0.083-0.249 ⁇ m.
  • the gaps between adjacent plate-like particles are 0.25-0.85 ⁇ m.
  • the aluminum-doped cobalt carbonate particles have a porosity of 20% to 30%.
  • the present application provides a method for preparing aluminum-doped cobalt carbonate particles according to the aforementioned embodiment, including the following steps:
  • a structural change agent is added to cause the metal salt solution and the precipitant solution to react, and some of the cobalt carbonate primary particles grow into flakes;
  • the metal salts include cobalt salts and soluble metal doped salts containing aluminum salts;
  • the structural change agent is a strong alkaline solution.
  • the structure change agent includes at least one of NaOH solution and KOH solution.
  • the flow rate of the metal salt solution is 5-30L/h, and the precipitant solution is fed at a mass concentration ratio of ammonium to cobalt in the metal salt solution of 0.61-0.92:1;
  • the concentration of cobalt in the metal salt solution is 0.5-3 mol/L
  • the mass concentration ratio of aluminum element to cobalt in the soluble metal doped salt is 0.0075-0.015:1
  • the concentration of the precipitant solution is 2-3 mol/L.
  • the cobalt salt includes at least one of cobalt chloride, cobalt sulfate, and cobalt nitrate.
  • the soluble metal doped salt includes aluminum sulfate octadecahydrate.
  • the precipitating agent includes at least one of ammonium bicarbonate and ammonium carbonate.
  • the concentration of the structural change agent is 0.5-1 mol/L, and the flow rate of the structural change agent is 3/10-5/10 of the cobalt salt flow rate.
  • the reaction is performed at 35-48°C and 12-28 Hz.
  • the bottom liquid is a precipitant solution with a concentration of 0.5-3 mol/L, and the volume of the bottom liquid is 3/10-6/10 of the total volume of the reaction vessel.
  • the flow rate of the metal salt solution is 3-15L/h, and the precipitant solution is fed at a mass concentration ratio of ammonium to cobalt in the metal salt solution of 0.61-0.92:1.
  • seed crystal synthesis and morphology control it also includes: a grain growth stage;
  • Grain growth includes: after obtaining the startup seed crystal, increasing the flow rate of the metal salt to 2-3 times the corresponding flow rate during the seed crystal synthesis process.
  • after morphology control it also includes: a secondary growth stage of grains;
  • the method further includes: centrifugally washing the cobalt carbonate product after secondary growth of crystal grains.
  • the present application also provides cobalt tetroxide, the precursor of which includes the aluminum-doped cobalt carbonate particles of the aforementioned embodiment.
  • the present application also provides a lithium cobalt oxide, the raw material of which includes cobalt tetraoxide of the aforementioned embodiment.
  • This application can obtain aluminum-doped cobalt carbonate particles with controllable morphology and core-shell structure through a specific preparation method, in which the primary cobalt carbonate particles forming the core are granular particles with evenly distributed aluminum, and the primary cobalt carbonate particles forming the shell are flakes. shaped particles.
  • the aluminum-doped cobalt carbonate particles have strong surface reactivity, and the doped aluminum elements are evenly distributed without segregation.
  • the aluminum-doped cobalt carbonate particles have short and narrow flaky primary particle morphology, large gaps between primary particles, and high porosity, which is beneficial to the removal of Cl, Na or K impurity elements during the washing process.
  • cobalt tetroxide It is used to sinter into cobalt tetroxide, which is beneficial to the release of carbon dioxide during the sintering process and prevents particle cracking; the cobalt tetroxide is used to mix with lithium salt, which is beneficial to lithium infiltration to synthesize lithium cobalt oxide.
  • the preparation method of the aluminum-doped cobalt carbonate particles is simple and can effectively control the morphology of the aluminum-doped cobalt carbonate particles.
  • Figure 1 is an SEM image of the finished product corresponding to Example 1 in the test example
  • Figures 2, 3 and 4 are SEM images of the morphology changes during the synthesis process of the finished product corresponding to Example 2 in the test examples;
  • Figure 5 is a cross-sectional SEM image of the finished product corresponding to Example 3 in the test example
  • Figure 6 is an SEM image of the finished product corresponding to Comparative Example 1 in the test example
  • Figure 7 is an SEM image of the finished product corresponding to Comparative Example 2 in the test example.
  • This application proposes aluminum-doped cobalt carbonate particles, which have a core-shell structure, in which the primary cobalt carbonate particles forming the core are granular particles with evenly distributed aluminum, and the primary cobalt carbonate particles forming the shell are flake particles.
  • flaky aluminum-doped cobalt carbonate currently has the problem of very uneven aluminum elements, and once aluminum segregation is formed in the center of the particles, it will continue to aggravate the degree of segregation.
  • This application uses primary particles with granular particles as cores. Compared with flakes, the distribution of aluminum elements is easier to control and uniform. Table of aluminum-doped cobalt carbonate particles having the structure provided in this application It has strong surface reactivity, controllable morphology, uniform distribution of aluminum elements and no segregation.
  • the aluminum-doped cobalt carbonate particles provided in this application have short and narrow flaky primary particles, and there are large gaps between the flaky primary particles, so that the aluminum-doped cobalt carbonate particles have higher porosity.
  • the length of the flaky particles formed above is about 0.42-0.85 ⁇ m, and the width is about 0.083-0.249 ⁇ m.
  • the gaps between adjacent plate-like particles are approximately 0.25-0.85 ⁇ m.
  • the porosity of aluminum-doped cobalt carbonate particles is approximately 20%-30%.
  • cobalt tetroxide Use it to sinter into cobalt tetroxide, which is beneficial to the release of carbon dioxide during the sintering process and prevents particle cracking; moreover, the produced cobalt tetroxide has inheritance of the physical and chemical indicators of cobalt carbonate.
  • the above-mentioned cobalt tetroxide is mixed with lithium salt to facilitate lithium infiltration to synthesize lithium cobalt oxide.
  • this application provides a method for preparing the above-mentioned aluminum-doped cobalt carbonate particles.
  • the key is to add a specific input amount and concentration of a structural transformation agent at a specific control node to effectively control the transformation of the morphology of the primary cobalt carbonate particles into flakes. In order to achieve controllable appearance.
  • the preparation method of the aluminum-doped cobalt carbonate particles includes: a morphology control stage.
  • the morphology is controlled in the following manner: during the feeding process of the metal salt solution and the precipitant solution, a structural change agent is added to make the metal salt solution and the precipitant When the solution reacts, some of the primary particles of cobalt carbonate grow into sheets.
  • the primary particles used to form the surface (shell) of the cobalt carbonate product can controllably grow from a granular structure to a sheet structure.
  • the reaction is at 35-48°C (such as 35°C, 38°C, 40°C, 42°C, 45°C or 48°C, etc.) and 12-28Hz (such as 12Hz, 15Hz, 18Hz, 20Hz, 22Hz , 25Hz or 28Hz, etc.
  • the corresponding stirring is preferably carried out under the conditions of single-layer propeller stirring paddle). After the reaction reaches the full pot, let it stand and drain.
  • Metal salts used in this application include cobalt salts and soluble metal doped salts containing aluminum salts.
  • the cobalt salt may include at least one of cobalt chloride, cobalt sulfate, and cobalt nitrate.
  • the soluble metal doped salt may include aluminum sulfate octahydrate, and may also be doped with other aluminum-containing substances or other soluble metal elements.
  • the precipitating agent may include at least one of ammonium bicarbonate and ammonium carbonate.
  • the structural change agent is a strong alkaline solution.
  • the structure change agent may include at least one of NaOH solution and KOH solution. It should be noted that in other embodiments, it is not excluded that other strong alkaline substances can be used as structural transformation agents.
  • the flow rate of the metal salt solution can be controlled to 5-30L/h (such as 5L/h, 10L/h, 15L/h, 20L/h, 25L/h or 30L/h, etc.), the precipitant solution can be based on the mass concentration ratio of ammonium to cobalt in the metal salt of 0.61-0.92:1 (such as 0.61:1, 0.65:1, 0.7:1, 0.75 :1, 0.8:1, 0.85:1, 0.9:1 or 0.92:1, etc.) feeding.
  • 5-30L/h such as 5L/h, 10L/h, 15L/h, 20L/h, 25L/h or 30L/h, etc.
  • the precipitant solution can be based on the mass concentration ratio of ammonium to cobalt in the metal salt of 0.61-0.92:1 (such as 0.61:1, 0.65:1, 0.7:1, 0.75 :1, 0.8:1, 0.85:1, 0.9:1 or 0.92:1, etc.) feeding.
  • the concentration of cobalt in the metal salt solution is 0.5-3mol/L (such as 0.5mol/L, 1mol/L, 1.5mol/L, 2mol/L, 2.5mol/L or 3mol/L, etc.), and soluble metal doping
  • the mass concentration ratio of aluminum element to cobalt in the salt is 0.0075-0.015:1 (such as 0.0075:1, 0.01:1, 0.0125:1 or 0.015:1, etc.); the concentration of the precipitant solution is 2-3mol/L (such as 2mol /L, 2.2mol/L, 2.5mol/L, 2.8mol/L or 3mol/L, etc.).
  • the concentration of the structural change agent is 0.5-1mol/L (such as 0.5mol/L, 0.6mol/L, 0.7mol/L, 0.8mol/L, 0.9mol/L or 1mol/L, etc.), and the flow rate of the structural change agent is 3/10-5/10 of the cobalt salt flow rate (such as 3/10, 3.5/10, 4/10, 4.5/10 or 5/10, etc.).
  • a seed crystal synthesis stage is also included.
  • the types of metal salt solutions and precipitant solutions used in this stage and the following stages are the same as in the above morphology control stage, and the relevant parts will not be repeated.
  • the bottom liquid is a precipitant solution with a concentration of 0.5-3 mol/L, and the volume of the bottom liquid is 3/10-6/10 of the total volume of the reaction vessel (such as 3/10, 4/10, 5/10 or 6/ 10 etc.).
  • the flow rate of the metal salt solution can be 3-15L/h (such as 3L/h, 5L/h, 8L/h, 10L/h, 12L/h or 15L/h, etc.), and the precipitant solution is
  • the mass concentration ratio of ammonium to cobalt in the metal salt solution is 0.61-0.92:1 (such as 0.61:1, 0.65:1, 0.7:1, 0.75:1, 0.8:1, 0.85:1, 0.9:1 or 0.92:1 etc.) feed.
  • grain growth includes: after obtaining the startup seed crystal, increasing the flow rate of the metal salt solution to 2-3 times the corresponding flow rate during the seed crystal synthesis process (such as 2 times, 2.2 times, 2.5 times, 2.8 times or 3 times, etc.), the precipitant solution is divided into ammonium and gold
  • morphology control it also includes: a secondary growth stage of grains.
  • the cobalt carbonate product after the secondary growth of crystal grains is centrifuged and washed.
  • a centrifuge is used for centrifugal washing.
  • pure water at 50-70°C is preferably used as the washing water.
  • this application also provides a kind of cobalt tetroxide, the precursor of which includes the above-mentioned aluminum-doped cobalt carbonate particles.
  • the present application also provides a lithium cobalt oxide, the raw materials for which are prepared include the above-mentioned tricobalt tetraoxide, and the lithium cobalt oxide has good cycle stability and rate performance.
  • This embodiment provides a method for preparing large particles of aluminum-doped cobalt carbonate with controllable morphology, including the following specific steps:
  • the cobalt salt is cobalt sulfate heptahydrate, and its cobalt concentration is 3mol/L.
  • the soluble metal doping salt is aluminum sulfate octadecahydrate.
  • the mass concentration ratio of aluminum to cobalt is 0.015:1.
  • the precipitating agent is ammonium bicarbonate solution, and its concentration is 3mol/L.
  • Seed crystal synthesis Add the metal salt solution and precipitant solution in the above (1) into the reaction kettle in the above (2) in parallel flow.
  • the flow rate of the mixed metal salt solution is 3L/h.
  • Morphology control The metal salt solution flow rate is maintained at 6L/h, ammonium bicarbonate is fed according to an ammonium-cobalt mass concentration ratio of 0.68:1, and NaOH solution is added to promote morphology transformation.
  • concentration of NaOH solution is 1mol/L, and the flow rate is 0.3 of the cobalt salt flow rate. times. Keep the temperature at 48°C, stir at 12Hz, react until the pot is full and let it stand to drain.
  • Post-processing Centrifuge and wash the finished cobalt carbonate product using a centrifuge, using pure water at 50°C as the washing water.
  • This embodiment provides a method for preparing large particles of aluminum-doped cobalt carbonate with controllable morphology, including the following specific steps:
  • the cobalt salt is cobalt chloride hexahydrate, and its cobalt concentration is 0.5 mol/L.
  • the soluble metal doping salt is aluminum sulfate octahydrate, and the mass concentration ratio of aluminum to cobalt is 0.0075:1.
  • the precipitating agent is ammonium bicarbonate solution, and its concentration is 2mol/L.
  • Seed crystal synthesis Add the metal salt solution and precipitant solution in the above (1) into the reaction kettle in the above (2) in parallel flow.
  • the flow rate of the mixed metal salt solution is 15L/h.
  • Morphology control The metal salt solution flow rate is maintained at 15L/h, ammonium bicarbonate is fed according to an ammonium-cobalt mass concentration ratio of 0.92:1, and NaOH solution is added to promote morphology transformation.
  • concentration of NaOH solution is 0.5 mol/L, and the flow rate is 0.5 times that of the cobalt salt. Keep the temperature at 35°C, stir at 28Hz, react until the pot is full and let it stand to drain.
  • Post-processing Centrifuge and wash the finished cobalt carbonate product using a centrifuge, using pure water at 70°C as washing water.
  • This embodiment provides a method for preparing large particles of aluminum-doped cobalt carbonate with controllable morphology, including the following specific steps:
  • the cobalt salt is cobalt nitrate hexahydrate, and its cobalt concentration is 2mol/L.
  • the soluble metal doping salt is aluminum sulfate octadecahydrate. Aluminum and Cobalt
  • the mass concentration ratio is 0.08:1.
  • the precipitating agent is ammonium carbonate solution, and its concentration is 2.5 mol/L.
  • Seed crystal synthesis Add the metal salt solution and precipitant solution in the above (1) into the reaction kettle in the above (2) in parallel flow.
  • the flow rate of the mixed metal salt solution is 10L/h.
  • Morphology control The flow rate of the metal salt solution is maintained at 20L/h, ammonium carbonate is fed according to the ammonium to cobalt mass concentration ratio of 0.61:1, and KOH solution is added to promote the morphology transformation.
  • concentration of the KOH solution is 0.6mol/L, and the flow rate is 0.4 times that of the cobalt salt. Keep the temperature at 40°C, stir at 20Hz, react until the pot is full and let it stand to drain.
  • Post-processing Centrifuge and wash the finished cobalt carbonate product using a centrifuge, using pure water at 60°C as the washing water.
  • This comparative example provides a method for preparing large particles of aluminum-doped cobalt carbonate, including the following specific steps:
  • the cobalt salt is cobalt sulfate heptahydrate, and its cobalt concentration is 3mol/L.
  • the soluble metal doping salt is aluminum sulfate octadecahydrate.
  • the mass concentration ratio of aluminum to cobalt is 0.015:1.
  • the precipitating agent is ammonium bicarbonate solution, and its concentration is 3mol/L.
  • Seed crystal synthesis Add the metal salt solution and precipitant solution in the above (1) into the reaction kettle in the above (2) in parallel flow.
  • the flow rate of the mixed metal salt solution is 3L/h.
  • the metal salt solution flow rate is maintained at 6L/h, and the ammonium bicarbonate mass concentration ratio is 0.68:1. Feed, keep the temperature at 48°C, and stir at 12Hz. When the cauldron is full, let it stand and drain. When D50 rises to 15 ⁇ m, divide the cauldron into half. After that, keep the flow rate and temperature of the above-mentioned metal salt solution and ammonium bicarbonate solution to continue the reaction, stir at 12 Hz, and let the pot stand until it is full to drain out, until the D50 rises to 20 ⁇ m to end the reaction.
  • Post-processing Centrifuge and wash the finished cobalt carbonate product using a centrifuge, using pure water at 50°C as the washing water.
  • this comparative example does not include step (5) in Example 1. In other words, this comparative example does not add a structural change agent for morphology control during the preparation process.
  • This comparative example provides a method for preparing large particles of aluminum-doped cobalt carbonate, including the following specific steps:
  • the cobalt salt is cobalt sulfate heptahydrate, and its cobalt concentration is 3mol/L.
  • the soluble metal doped salt is aluminum sulfate octadecahydrate.
  • the mass concentration ratio of aluminum to cobalt is 0.015:1.
  • the precipitating agent is ammonium bicarbonate solution, and its concentration is 3mol/L.
  • Seed crystal synthesis Add the metal salt solution and precipitant solution in the above (1) into the reaction kettle in the above (2) in parallel flow.
  • the flow rate of the mixed metal salt solution is 3L/h.
  • Post-processing Centrifuge and wash the finished cobalt carbonate product using a centrifuge, using pure water at 50°C as the washing water.
  • the structure change agent in this comparative example is added during the grain growth process.
  • the structure change agent is added after the grain D50 increases to 6.5 ⁇ m.
  • Electron microscopy scanning was performed on the large aluminum-doped cobalt carbonate particles prepared in Examples 1-3 and Comparative Examples 1-2. The results are shown in Figures 1 to 7.
  • Figure 1 is an SEM image of the finished product of aluminum-doped cobalt carbonate large particles prepared in Example 1. It can be seen from this figure: The primary particles on the surface of the aluminum-doped cobalt carbonate large particle finished product are short and narrow flakes, and the primary particles are uniform in size and have large gaps.
  • Figures 2, 3 and 4 respectively show the morphology changes during the synthesis process of the aluminum-doped cobalt carbonate large particle finished product prepared in Example 2.
  • Figure 2 shows the internal morphology of the core of the finished product of aluminum-doped cobalt carbonate large particles. It can be seen that the internal primary particles are in the shape of small blocks and there is no Al segregation.
  • Figure 3 shows the morphology of the sample after adding a structural change agent during the reaction process of the finished product. It can be seen that the primary particles on the surface gradually transform into flakes.
  • Figure 4 shows the morphology of the finished product. It can be seen that the primary particles on its surface are complete flakes.
  • Figure 5 is an SEM image (cross-sectional morphology) of the finished product of aluminum-doped cobalt carbonate large particles prepared in Example 3. It can be seen from the image that the cross-section of the sample is smooth and there is no Al segregation.
  • Figure 6 is an SEM image of the finished product of aluminum-doped cobalt carbonate large particles prepared in Comparative Example 1. It can be seen from this image that the primary particles on the surface of the sample are in the shape of fine rice grains. The reason may be that there is a lack of phase change in the reaction system. driving force.
  • Figure 7 is an SEM image of the finished product of aluminum-doped cobalt carbonate large particles prepared in Comparative Example 2. It can be seen from this figure that the addition of the structural change agent in the early stage of the reaction can easily cause the flaky primary particles of the sample to grow too large.
  • Example 1 the particle length, width, gap between primary particles and porosity of aluminum-doped cobalt carbonate particles are compared in sequence. The results are as shown in Table 1 shown.
  • Example 1-3 and Comparative Example 1-2 The cobalt carbonate prepared in Example 1-3 and Comparative Example 1-2 was respectively calcined at 700°C for 3 hours to obtain tricobalt tetroxide. Then, the obtained tricobalt tetroxide was evenly mixed with lithium carbonate according to the Li:Co molar ratio of 1.05, and placed in a push plate kiln for solid-phase sintering at 950°C for 12 hours to obtain lithium cobalt oxide cathode material, and each obtained Lithium cobalt oxide cathode material was tested for electrochemical performance.
  • the aluminum-doped cobalt carbonate particles provided by this application have strong surface reactivity, controllable morphology, uniform distribution of aluminum elements, and no segregation.
  • the aluminum-doped cobalt carbonate particles have short and narrow flaky primary particle morphology, large gaps between primary particles, and high porosity, which is beneficial to the removal of Cl, Na or K impurity elements during the washing process. It is used to sinter into cobalt tetroxide, which is beneficial to the release of carbon dioxide during the sintering process and prevents particle cracking; the cobalt tetroxide is used to mix with lithium salt, which is beneficial to lithium infiltration to synthesize lithium cobalt oxide.
  • the preparation method of the aluminum-doped cobalt carbonate particles is simple and can effectively control the morphology of the aluminum-doped cobalt carbonate particles.

Landscapes

  • Chemical & Material Sciences (AREA)
  • Organic Chemistry (AREA)
  • Inorganic Chemistry (AREA)
  • Chemical Kinetics & Catalysis (AREA)
  • Electrochemistry (AREA)
  • General Chemical & Material Sciences (AREA)
  • Inorganic Compounds Of Heavy Metals (AREA)
  • Compounds Of Alkaline-Earth Elements, Aluminum Or Rare-Earth Metals (AREA)

Abstract

本发明公开了一种掺铝碳酸钴颗粒及其制备方法与应用，属于碳酸钴技术领域。该掺铝碳酸钴颗粒具有核壳结构，其中，形成核的碳酸钴一次颗粒为铝均匀分布的粒状颗粒，形成壳的碳酸钴一次颗粒为片状颗粒。该掺铝碳酸钴颗粒的表面反应活性强，且形貌可控，铝元素分布均匀，无偏析。此外，该掺铝碳酸钴颗粒具有短且窄的片状一次颗粒形貌，一次颗粒间具有较大的空隙，孔隙率高，有利于在洗涤环节中Cl、Na或K杂质元素的去除。将其用于烧结成四氧化三钴，有利于烧结过程中二氧化碳的释放，防止颗粒开裂；将该四氧化三钴用于与锂盐混合，利于渗锂合成钴酸锂。上述掺铝碳酸钴颗粒的制备方法简单，可有效控制掺铝碳酸钴颗粒的形貌。

Description

掺铝碳酸钴颗粒及其制备方法与应用 技术领域
本发明涉及碳酸钴技术领域，具体而言，涉及一种掺铝碳酸钴颗粒及其制备方法与应用。
背景技术
钴酸锂离子电池自商业化以来，一直在消费类电子产品领域占据主导地位。人们对消费类电子产品的待机时间和体积重量的要求不断提高，这需要钴酸锂在高电压下充放电以提高电池能量密度。四氧化三钴是合成钴酸锂的重要原料，而碳酸钴是制备四氧化三钴的前驱体之一，因此前驱体碳酸钴在很大程度上影响着钴酸锂的性能。
虽片状形貌的掺铝碳酸钴表面反应活性强，但目前制备片状形貌掺铝碳酸钴的工艺仍存在一些问题，如：
(1)碳酸钴片状形貌转变前存在孕育期，仅靠参数上的调整不易对孕育期时间进行控制，易导致形貌转变失败，不利于在烧结过程二氧化碳的释放，导致四氧化三钴开裂；
(2)利于碳酸钴片状制备的条件会加快铝的沉降速度，导致钴和铝共沉淀差异加大，从而表现出铝分布不均匀的现象，削弱掺铝对钴酸锂电化学性能提升的作用。
鉴于此，特提出本发明。
发明内容
本发明的目的之一在于提供一种掺铝碳酸钴颗粒，以解决上述技术问题。
本发明的目的之二在于提供一种上述掺铝碳酸钴颗粒的制备方法。
本发明的目的之三在于提供一种前驱体中含有上述掺铝碳酸钴颗粒的四氧化三钴。
本发明的目的之四在于提供一种制备原料中含有上述四氧化三钴的钴酸锂。
本申请可这样实现：
第一方面，本申请提供一种掺铝碳酸钴颗粒，其具有核壳结构，其中，形成核的碳酸钴一次颗粒为铝均匀分布的粒状颗粒，形成壳的碳酸钴一次颗粒为片状颗粒。
在可选的实施方式中，片状颗粒的长度为0.42-0.85μm，宽度为0.083-0.249μm。
在可选的实施方式中，相邻的片状颗粒之间的空隙为0.25-0.85μm。
在可选的实施方式中，掺铝碳酸钴颗粒的孔隙率为20％-30％。
第二方面，本申请提供如前述实施方式的掺铝碳酸钴颗粒的制备方法，包括以下步骤：
待碳酸钴晶粒长至D50＝9-10μm，按以下方式进行形貌控制：
在金属盐溶液和沉淀剂溶液的进料过程中，加入结构转变剂以使金属盐溶液与沉淀剂溶液反应时，部分碳酸钴一次颗粒向片状生长；
其中，金属盐包括钴盐和含有铝盐的可溶性金属掺杂盐；
结构转变剂为强碱溶液。
在可选的实施方式中，结构转变剂包括NaOH溶液和KOH溶液中的至少一种。
在可选的实施方式中，形貌控制过程中，金属盐溶液的流量为5-30L/h，沉淀剂溶液按铵与金属盐溶液中钴的质量浓度比为0.61-0.92:1进料；
其中，金属盐溶液中钴的浓度为0.5-3mol/L，可溶性金属掺杂盐中铝元素与钴的质量浓度比为0.0075-0.015:1；沉淀剂溶液的浓度为2-3mol/L。
在可选的实施方式中，钴盐包括氯化钴、硫酸钴和硝酸钴中的至少一种。
在可选的实施方式中，可溶性金属掺杂盐包括十八水硫酸铝。
在可选的实施方式中，沉淀剂包括碳酸氢铵和碳酸铵中的至少一种。
在可选的实施方式中，结构转变剂的浓度为0.5-1mol/L，结构转变剂的流量为钴盐流量的3/10-5/10。
在可选的实施方式中，形貌控制过程中，反应于35-48℃以及12-28Hz的条件下进行。
在可选的实施方式中，在碳酸钴晶粒长至D50＝9-10μm之前，还包括：晶种合成阶段；
晶种合成包括：于反应容器内的底液中并流加入金属盐溶液和沉淀剂溶液，于35-48℃以及12-28Hz的条件下反应，得到D50＝4.5-6.5μm的开机晶种。
在可选的实施方式中，底液为浓度为0.5-3mol/L的沉淀剂溶液，底液的体积为反应容器总体积的3/10-6/10。
在可选的实施方式中，晶种合成阶段，金属盐溶液的流量为3-15L/h，沉淀剂溶液按铵与金属盐溶液中钴的质量浓度比为0.61-0.92:1进料。
在可选的实施方式中，在晶种合成与形貌控制之间，还包括：晶粒长大阶段；
晶粒长大包括：在得到开机晶种后，将金属盐的流量提高至晶种合成过程中相应流量的2-3倍，沉淀剂溶液按铵与金属盐中钴的质量浓度比为0.61-0.92:1进料；随后于35-48℃以及12-28Hz的条件下反应，得到D50＝9-10μm的晶粒。
在可选的实施方式中，形貌控制后，还包括：晶粒二次生长阶段；
晶粒二次生长阶段包括：按形貌控制过程中金属盐溶液及沉淀剂溶液的流量进料，并以形貌控制过程中的反应温度和搅拌频率继续反应，直至晶粒长至D50＝18-20μm。
在可选的实施方式中，还包括：将晶粒二次生长后的碳酸钴产品进行离心洗涤。
第三方面，本申请还提供一种四氧化三钴，其前驱体包括前述实施方式的掺铝碳酸钴颗粒。
第四方面，本申请还提供一种钴酸锂，其制备原料包括前述实施方式的四氧化三钴。
本申请的有益效果包括：
本申请通过特定的制备方法可获得形貌可控的具有核壳结构的掺铝碳酸钴颗粒，其中形成核的碳酸钴一次颗粒为铝均匀分布的粒状颗粒，形成壳的碳酸钴一次颗粒为片状颗粒。该掺铝碳酸钴颗粒具有较强的表面反应活性，所掺杂的铝元素分布均匀，无偏析。此外，该掺铝碳酸钴颗粒具有短且窄的片状一次颗粒形貌，一次颗粒间具有较大的空隙，孔隙率高，有利于在洗涤环节中Cl、Na或K杂质元素的去除。将其用于烧结成四氧化三钴，有利于烧结过程中二氧化碳的释放，防止颗粒开裂；将该四氧化三钴用于与锂盐混合，利于渗锂合成钴酸锂。上述掺铝碳酸钴颗粒的制备方法简单，可有效控制掺铝碳酸钴颗粒的形貌。
附图说明
为了更清楚地说明本发明实施例的技术方案，下面将对实施例中所需要使用的附图作简单地介绍，应当理解，以下附图仅示出了本发明的某些实施例，因此不应被看作是对范围的限定，对于本领域普通技术人员来讲，在不付出创造性劳动的前提下，还可以根据这些附图获得其他相关的附图。
图1为试验例中实施例1对应的成品的SEM图；
图2、图3和图4为试验例中实施例2对应的成品在合成过程中的形貌变化SEM图；
图5为试验例中实施例3对应的成品的截面SEM图；
图6为试验例中对比例1对应的成品的SEM图；
图7为试验例中对比例2对应的成品的SEM图。
具体实施方式
为使本发明实施例的目的、技术方案和优点更加清楚，下面将对本发明实施例中的技术方案进行清楚、完整地描述。实施例中未注明具体条件者，按照常规条件或制造商建议的条件进行。所用试剂或仪器未注明生产厂商者，均为可以通过市售购买获得的常规产品。
下面对本申请提供的掺铝碳酸钴颗粒及其制备方法与应用进行具体说明。
本申请提出一种掺铝碳酸钴颗粒，其具有核壳结构，其中，形成核的碳酸钴一次颗粒为铝均匀分布的粒状颗粒，形成壳的碳酸钴一次颗粒为片状颗粒。
需说明的是，片状掺铝碳酸钴目前存在铝元素非常不均匀的问题，而且颗粒中心铝偏析一旦形成则会继续加重偏析程度。本申请通过以粒状颗粒作为核的一次颗粒，相比于片状而言，在铝元素分布上更易调控均匀。具有本申请所提供的结构的掺铝碳酸钴颗粒的表 面反应活性强，且形貌可控，铝元素分布均匀，无偏析。
可参考地，本申请提供的掺铝碳酸钴颗粒具有短且窄的片状一次颗粒，片状一次颗粒间具有较大的空隙，使得掺铝碳酸钴颗粒具有较高的孔隙率。
在一些实施方式中，上述形成的片状颗粒的长度约为0.42-0.85μm，宽度约为0.083-0.249μm。相邻的片状颗粒之间的空隙约为0.25-0.85μm。掺铝碳酸钴颗粒的孔隙率约为20％-30％。
上述形貌至少具有以下优势：
a、有利于在洗涤环节中Cl、Na或K杂质元素的去除。
b、将其用于烧结成四氧化三钴，有利于烧结过程中二氧化碳的释放，防止颗粒开裂；并且，所制得的四氧化三钴对碳酸钴的理化指标具有继承性。
c、将上述四氧化三钴用于与锂盐混合，利于渗锂合成钴酸锂。
相应地，本申请提供了上述掺铝碳酸钴颗粒的制备方法，其关键在于在特定的控制节点加入特定投入量和浓度的结构转变剂，以有效控制碳酸钴一次颗粒形貌向片状转变，进而实现相貌上的可控。
可参考地，该掺铝碳酸钴颗粒的制备方法包括：形貌控制阶段。
具体的，待碳酸钴晶粒长至D50＝9-10μm，按以下方式进行形貌控制：在金属盐溶液和沉淀剂溶液的进料过程中，加入结构转变剂以使金属盐溶液与沉淀剂溶液反应时，部分碳酸钴一次颗粒向片状生长。
也即，在加入结构转变剂后，用于形成碳酸钴产品表面(壳)的一次颗粒能够可控地由粒状结构生长成片状结构。
上述形貌控制过程中，反应是于35-48℃(如35℃、38℃、40℃、42℃、45℃或48℃等)以及12-28Hz(如12Hz、15Hz、18Hz、20Hz、22Hz、25Hz或28Hz等，对应的搅拌优选采用单层推进式搅拌桨搅拌)的条件下进行。反应至满釜后，静置抽清。
本申请所用的金属盐包括钴盐和含有铝盐的可溶性金属掺杂盐。
在一些示例性地实施方式中，钴盐可包括氯化钴、硫酸钴和硝酸钴中的至少一种。可溶性金属掺杂盐可包括十八水硫酸铝，也可掺杂其它含铝物质或其它可溶性金属元素。沉淀剂可包括碳酸氢铵和碳酸铵中的至少一种。
结构转变剂为强碱溶液。
在一些优选地实施方式中，结构转变剂可包括NaOH溶液和KOH溶液中的至少一种。需说明的是，在其它实施方式中，也不排除可以其它强碱类物质作为结构转变剂。
较佳地，形貌控制过程中，金属盐溶液的流量可控制为5-30L/h(如5L/h、10L/h、15L/h、 20L/h、25L/h或30L/h等)，沉淀剂溶液可按铵与金属盐中钴的质量浓度比为0.61-0.92:1(如0.61:1、0.65:1、0.7:1、0.75:1、0.8:1、0.85:1、0.9:1或0.92:1等)进料。
其中，金属盐溶液中钴的浓度为0.5-3mol/L(如0.5mol/L、1mol/L、1.5mol/L、2mol/L、2.5mol/L或3mol/L等)，可溶性金属掺杂盐中铝元素与钴的质量浓度比为0.0075-0.015:1(如0.0075:1、0.01:1、0.0125:1或0.015:1等)；沉淀剂溶液的浓度为2-3mol/L(如2mol/L、2.2mol/L、2.5mol/L、2.8mol/L或3mol/L等)。
结构转变剂的浓度为0.5-1mol/L(如0.5mol/L、0.6mol/L、0.7mol/L、0.8mol/L、0.9mol/L或1mol/L等)，结构转变剂的流量为钴盐流量的3/10-5/10(如3/10、3.5/10、4/10、4.5/10或5/10等)。
需说明的是，在pH较高的条件下有利于生成碱式碳酸钴，而碳酸氢铵和/或碳酸铵的碱性较弱，若单纯通过控制碳酸氢铵和/或碳酸铵的投入量以控制一次颗粒形貌转变无法确保成功率，也即无法实现可控转变。本申请通过在反应过程中加入强碱类物质(优选NaOH和/或KOH)的溶液作为结构转变剂对合成形貌进行诱导，使得反应pH突增，从而促进碳酸钴的一次颗粒向片状生长。再结合特定的投入量和浓度，避免了结构转变剂加入不当导致小核的生成和过多的Na或K杂质，影响成品质量和增加洗涤环节压力。
此外，还需强调的是，本申请中结构转变剂的加入时机只能在碳酸钴晶粒长至D50＝9-10μm后加入才能确保形貌可控，若在晶粒长至D50＝9-10μm过程中即加入结构转变剂，会导致片状一次颗粒生长过大，无法有效控制形貌。
本申请中，在碳酸钴晶粒长至D50＝9-10μm之前，还包括：晶种合成阶段。该阶段以及下述各阶段所用的金属盐溶液以及沉淀剂溶液的种类均同上述形貌控制阶段，相关部分不再赘述。
可参考地，晶种合成包括：于反应容器内的底液中并流加入金属盐溶液和沉淀剂溶液，于35-48℃以及12-28Hz的条件下反应，得到D50＝4.5-6.5μm的开机晶种。
其中，底液为浓度为0.5-3mol/L的沉淀剂溶液，底液的体积为反应容器总体积的3/10-6/10(如3/10、4/10、5/10或6/10等)。
该晶种合成阶段，金属盐溶液的流量可以为3-15L/h(如3L/h、5L/h、8L/h、10L/h、12L/h或15L/h等)，沉淀剂溶液按铵与金属盐溶液中钴的质量浓度比为0.61-0.92:1(如0.61:1、0.65:1、0.7:1、0.75:1、0.8:1、0.85:1、0.9:1或0.92:1等)进料。
进一步地，在晶种合成与形貌控制之间，还包括：晶粒长大阶段。
可参考地，晶粒长大包括：在得到开机晶种后，将金属盐溶液的流量提高至晶种合成过程中相应流量的2-3倍(如2倍、2.2倍、2.5倍、2.8倍或3倍等)，沉淀剂溶液按铵与金 属盐溶液中钴的质量浓度比为0.61-0.92:1(具体的质量浓度比同晶种合成阶段)进料；随后于35-48℃以及12-28Hz的条件下反应，得到D50＝9-10μm的晶粒。反应至满釜后，静置抽清，至D50＝9-10μm后分釜一半。
进一步地，在形貌控制后，还包括：晶粒二次生长阶段。
可参考地，晶粒二次生长阶段包括：按形貌控制过程中金属盐溶液及沉淀剂溶液的流量进料，并以形貌控制过程中的反应温度和搅拌频率继续反应，同理地，反应至满釜后，静置抽清。待晶粒长至D50＝14-15μm，分釜一半，随后再按上述相同的条件继续反应，直至晶粒长至D50＝18-20μm。
进一步地，将晶粒二次生长后的碳酸钴产品进行离心洗涤。
可参考地，采用离心机进行离心洗涤，该过程优选以50-70℃的纯水作为洗涤水。
此外，本申请还提供了一种四氧化三钴，其前驱体包括上述掺铝碳酸钴颗粒。
通过以上述掺铝碳酸钴颗粒作为前驱体中的一种，有利于碳酸钴烧结成四氧化三钴的过程中二氧化碳的释放，有效防止颗粒开裂。
进一步地，本申请还提供了一种钴酸锂，其制备原料包括上述四氧化三钴，该钴酸锂具有良好的循环稳定性和倍率性能。
以下结合实施例对本发明的特征和性能作进一步的详细描述。
实施例1
本实施例提供一种形貌可控的掺铝碳酸钴大颗粒制备方法，包括以下具体步骤：
(1)配制金属盐溶液和沉淀剂溶液：向金属配液罐里加入钴盐和可溶性金属掺杂盐。其中钴盐为七水硫酸钴，其钴浓度为3mol/L。可溶性金属掺杂盐为十八水硫酸铝。铝与钴的质量浓度比为0.015:1。沉淀剂为碳酸氢铵溶液，其浓度为3mol/L。
(2)底液制备：向反应釜中投入一定量的碳酸氢铵配制成3mol/L溶液为底液，溶液体积为反应釜总体积的0.6倍。
(3)晶种合成：将上述(1)中的金属盐溶液和沉淀剂溶液并流加入上述(2)中的反应釜中，混合金属盐溶液的流量为3L/h，碳酸氢铵按照铵钴质量浓度比为0.68:1进料，温度升到48℃，搅拌为12Hz(单层推进式搅拌桨搅拌，下同)，得到D50＝6.5μm的开机晶种。
(4)晶粒长大：晶种合成结束后，提高金属盐溶液的流量至6L/h，碳酸氢铵按照铵钴质量浓度比为0.68:1进料，温度保持48℃，搅拌为12Hz。满釜即静置抽清，至D50涨到10μm便分釜一半。
(5)形貌控制：金属盐溶液流量保持6L/h，碳酸氢铵按照铵钴质量浓度比为0.68:1进料，并加入NaOH溶液促进形貌转变。NaOH溶液的浓度为1mol/L，流量为钴盐流量的0.3 倍。温度保持48℃，搅拌为12Hz，反应至满釜并静置抽清。
(6)晶粒二次生长：金属盐溶液流量保持6L/h，碳酸氢铵按照铵钴质量浓度比为0.68:1进料，温度保持48℃，搅拌为12Hz。满釜即静置抽清，至D50涨到15μm便分釜一半。之后保持上述金属盐溶液、碳酸氢铵溶液的流量和温度继续反应，搅拌为12Hz，满釜即静置抽清，至D50涨到20μm结束反应。
(7)后处理：将碳酸钴成品使用离心机离心洗涤，以50℃的纯水为洗涤水。
实施例2
本实施例提供一种形貌可控的掺铝碳酸钴大颗粒制备方法，包括以下具体步骤：
(1)配制金属盐溶液和沉淀剂溶液：向金属配液罐里加入钴盐和可溶性金属掺杂盐。其中钴盐为六水氯化钴，其钴浓度为0.5mol/L。可溶性金属掺杂盐为十八水硫酸铝，铝与钴的质量浓度比为0.0075:1。沉淀剂为碳酸氢铵溶液，其浓度为2mol/L。
(2)底液制备：向反应釜中投入一定量的碳酸氢铵配制成0.5mol/L溶液为底液，溶液体积为反应釜总体积的0.3倍。
(3)晶种合成：将上述(1)中的金属盐溶液和沉淀剂溶液并流加入上述(2)中的反应釜中，混合金属盐溶液的流量为15L/h，碳酸氢铵按照铵钴质量浓度比为0.92:1进料，温度升到35℃，搅拌为30Hz(单层推进式搅拌桨搅拌，下同)，得到D50＝4.5μm的开机晶种。
(4)晶粒长大：晶种合成结束后，提高金属盐溶液的流量至30L/h，碳酸氢铵按照铵钴质量浓度比为0.92:1进料，温度保持35℃，搅拌为30Hz。满釜即静置抽清，至D50涨到9μm便分釜一半。
(5)形貌控制：金属盐溶液流量保持15L/h，碳酸氢铵按照铵钴质量浓度比为0.92:1进料，并加入NaOH溶液促进形貌转变。NaOH溶液的浓度为0.5mol/L，流量为钴盐流量的0.5倍。温度保持35℃，搅拌为28Hz，反应至满釜并静置抽清。
(6)晶粒二次生长：金属盐溶液的流量保持30L/h，碳酸氢铵按照铵钴质量浓度比为0.92:1进料，温度保持35℃，搅拌为28Hz。满釜即静置抽清，至D50涨到14μm便分釜一半。之后保持上述金属盐溶液、碳酸氢铵溶液的流量和温度继续反应，搅拌为26Hz，满釜即静置抽清，至D50涨到18μm结束反应。
(7)后处理：将碳酸钴成品使用离心机离心洗涤，以70℃的纯水为洗涤水。
实施例3
本实施例提供一种形貌可控的掺铝碳酸钴大颗粒制备方法，包括以下具体步骤：
(1)配制金属盐溶液和沉淀剂溶液：向金属配液罐里加入钴盐和可溶性金属掺杂盐。其中钴盐为六水硝酸钴，其钴浓度为2mol/L。可溶性金属掺杂盐为十八水硫酸铝。铝与钴 的质量浓度比为0.08:1。沉淀剂为碳酸铵溶液，其浓度为2.5mol/L。
(2)底液制备：向反应釜中投入一定量的碳酸铵配制成2.5mol/L溶液为底液，溶液体积为反应釜总体积的0.5倍。
(3)晶种合成：将上述(1)中的金属盐溶液和沉淀剂溶液并流加入上述(2)中的反应釜中，混合金属盐溶液的流量为10L/h，碳酸铵按照铵钴质量浓度比为0.61:1进料，温度升到40℃，搅拌为20Hz(单层推进式搅拌桨搅拌，下同)，得到D50＝5μm的开机晶种。
(4)晶粒长大：晶种合成结束后，提高金属盐溶液的流量至20/h，碳酸铵按照铵钴质量浓度比为0.61:1进料，温度保持40℃，搅拌为20Hz。满釜即静置抽清，至D50涨到9.5μm便分釜一半。
(5)形貌控制：金属盐溶液流量保持20L/h，碳酸铵按照铵钴质量浓度比为0.61:1进料，并加入KOH溶液促进形貌转变。KOH溶液的浓度为0.6mol/L，流量为钴盐流量的0.4倍。温度保持40℃，搅拌为20Hz，反应至满釜并静置抽清。
(6)晶粒二次生长：金属盐溶液的流量保持20L/h，碳酸铵按照铵钴质量浓度比为0.61:1进料，温度保持40℃，搅拌为20Hz。满釜即静置抽清，至D50涨到14.5μm便分釜一半。之后保持上述金属盐溶液、碳酸铵溶液和温度继续反应，搅拌为20Hz，满釜即静置抽清，至D50涨到19μm结束反应。
(7)后处理：将碳酸钴成品使用离心机离心洗涤，以60℃的纯水为洗涤水。
对比例1
本对比例提供一种掺铝碳酸钴大颗粒制备方法，包括以下具体步骤：
(1)配制金属盐溶液和沉淀剂溶液：向金属配液罐里加入钴盐和可溶性金属掺杂盐。其中钴盐为七水硫酸钴，其钴浓度为3mol/L。可溶性金属掺杂盐为十八水硫酸铝。铝与钴的质量浓度比为0.015:1。沉淀剂为碳酸氢铵溶液，其浓度为3mol/L。
(2)底液制备：向反应釜中投入一定量的碳酸氢铵配制成3mol/L溶液为底液，溶液体积为反应釜总体积的0.6倍。
(3)晶种合成：将上述(1)中的金属盐溶液和沉淀剂溶液并流加入上述(2)中的反应釜中，混合金属盐溶液的流量为3L/h，碳酸氢铵按照铵钴质量浓度比为0.68:1进料，温度升到48℃，搅拌为12Hz(单层推进式搅拌桨搅拌，下同)，得到D50＝6.5μm的开机晶种。
(4)晶粒长大：晶种合成结束后，提高金属盐溶液的流量至6L/h，碳酸氢铵按照铵钴质量浓度比为0.68:1进料，温度保持48℃，搅拌为12Hz。满釜即静置抽清，至D50涨到10μm便分釜一半。
(5)晶粒二次生长：金属盐溶液流量保持6L/h，碳酸氢铵按照铵钴质量浓度比为0.68:1 进料，温度保持48℃，搅拌为12Hz。满釜即静置抽清，至D50涨到15μm便分釜一半。之后保持上述金属盐溶液、碳酸氢铵溶液的流量和温度继续反应，搅拌为12Hz，满釜即静置抽清，至D50涨到20μm结束反应。
(6)后处理：将碳酸钴成品使用离心机离心洗涤，以50℃的纯水为洗涤水。
也即，与实施例1相比，本对比例中不含实施例1中的步骤(5)，换而言之，本对比例在制备过程中未添加结构转变剂进行形貌控制。
对比例2
本对比例提供一种掺铝碳酸钴大颗粒制备方法，包括以下具体步骤：
(1)配制金属盐溶液和沉淀剂溶液：向金属配液罐里加入钴盐和可溶性金属掺杂盐。其中钴盐为七水硫酸钴，其钴浓度为3mol/L。可溶性金属掺杂盐为十八水硫酸铝。铝与钴的质量浓度比为0.015:1。沉淀剂为碳酸氢铵溶液，其浓度为3mol/L。
(2)底液制备：向反应釜中投入一定量的碳酸氢铵配制成3mol/L溶液为底液，溶液体积为反应釜总体积的0.6倍。
(3)晶种合成：将上述(1)中的金属盐溶液和沉淀剂溶液并流加入上述(2)中的反应釜中，混合金属盐溶液的流量为3L/h，碳酸氢铵按照铵钴质量浓度比为0.68:1进料，温度升到48℃，搅拌为12Hz(单层推进式搅拌桨搅拌，下同)，得到D50＝6.5μm的开机晶种。
(4)晶粒长大和形貌控制：晶种合成结束后，提高金属盐溶液的流量至6L/h，碳酸氢铵按照铵钴质量浓度比为0.68:1进料。同时加入结构转变剂NaOH溶液，NaOH溶液的浓度为1mol/L，流量为钴盐流量的0.3倍。温度保持48℃，搅拌为12Hz。满釜即静置抽清，至D50涨到10μm便分釜一半。
(5)晶粒二次生长：金属盐溶液流量保持6L/h，碳酸氢铵按照铵钴质量浓度比为0.68:1进料，温度保持48℃，搅拌为12Hz。满釜即静置抽清，至D50涨到15μm便分釜一半。之后保持上述金属盐溶液、碳酸氢铵溶液的流量和温度继续反应，搅拌为12Hz，满釜即静置抽清，至D50涨到20μm结束反应。
(6)后处理：将碳酸钴成品使用离心机离心洗涤，以50℃的纯水为洗涤水。
也即，与实施例1相比，本对比例中结构转变剂在晶粒长大过程中加入，换而言之，本对比例中结构转变剂在晶粒D50涨至6.5μm后即加入。
试验例1
对实施例1-3以及对比例1-2制备得到的掺铝碳酸钴大颗粒进行电镜扫描。其结果如图1至图7所示。
其中，图1为实施例1制备所得掺铝碳酸钴大颗粒成品的SEM图，由该图可以看出： 掺铝碳酸钴大颗粒成品的表面的一次颗粒为短且窄的片状，一次颗粒尺寸均匀且存在较大的间隙。
图2、图3和图4依次为实施例2制备所得掺铝碳酸钴大颗粒成品在合成过程中的形貌变化图。图2为该掺铝碳酸钴大颗粒成品的核内部形貌，由此可以看出：内部的一次颗粒为细小块状，无Al偏析存在。图3为该成品反应过程中加入结构转变剂后样品的形貌，由此可以看出：表面的一次颗粒逐渐向片状转变。图4为该成品的形貌，由此可以看出：其表面的一次颗粒为完整片状。
图5为实施例3制备所得掺铝碳酸钴大颗粒成品的SEM图(截面形貌)，由该图可以看出：该样品的截面光滑且无Al偏析。
图6为对比例1制备所得掺铝碳酸钴大颗粒成品的SEM图，由该图可以看出：该样品表面的一次颗粒为细小的米粒状，其原因可能在于反应体系中缺少了相变的驱动力。
图7为对比例2制备所得掺铝碳酸钴大颗粒成品的SEM图，由该图可以看出：结构转变剂在反应前期加入，易导致样品的片状一次颗粒生长过大。
此外，就以实施例1、实施例2以及对比例2为例，对其所涉及的依次颗粒长、宽、一次颗粒间的间隙以及掺铝碳酸钴颗粒的孔隙率比较，其结果如表1所示。
表1结果
试验例2
将实施例1-3以及对比例1-2制备的碳酸钴分别于700℃煅烧3h得到四氧化三钴。再将所得的各四氧化三钴分别与碳酸锂进行按照Li：Co的摩尔比为1.05均匀混合，置于推板窑中进行于950℃高温固相烧结12h得到钴酸锂正极材料，并对所得的各钴酸锂正极材料进行电化学性能测试。
电化学性能测试具体步骤：按照质量比8:1:1称取一定量的钴酸锂正极材料、聚偏氟乙烯(PVDF)和乙炔黑，将三者置于玛瑙研钵中均匀混合后滴加N-甲基-2-吡咯烷酮(NMP)制成均匀浆料。将浆料均匀涂于铝箔表面，真空干燥，冲成圆形正极极片。之后，使用金属锂为负极，在手套箱中组成CR2025纽扣电池。在CT2001A型蓝电测试系统进行电性能测试，测试电压范围为3.0-4.6V，其结果如表2所示。
表2电化学性能测试结果(3.0-4.6V，1C＝150mAh/g)
由表2可以看出：实施例1-3的循环稳定性和倍率性能均优于对比例1-2，其原因主要在于实施例的样品中铝元素均匀分布，能更好稳定钴酸锂晶体结构，表现出优异的循环稳定性。钴酸锂可继承前驱体表面疏松形貌，有利于锂离子运输，拥有优异的倍率性能。
综上所述，本申请提供的掺铝碳酸钴颗粒的表面反应活性强，且形貌可控，铝元素分布均匀，无偏析。此外，该掺铝碳酸钴颗粒具有短且窄的片状一次颗粒形貌，一次颗粒间具有较大的空隙，孔隙率高，有利于在洗涤环节中Cl、Na或K杂质元素的去除。将其用于烧结成四氧化三钴，有利于烧结过程中二氧化碳的释放，防止颗粒开裂；将该四氧化三钴用于与锂盐混合，利于渗锂合成钴酸锂。上述掺铝碳酸钴颗粒的制备方法简单，可有效控制掺铝碳酸钴颗粒的形貌。
以上仅为本发明的优选实施例而已，并不用于限制本发明，对于本领域的技术人员来说，本发明可以有各种更改和变化。凡在本发明的精神和原则之内，所作的任何修改、等同替换、改进等，均应包含在本发明的保护范围之内。

Claims (10)

  1. 一种掺铝碳酸钴颗粒，其特征在于，所述掺铝碳酸钴颗粒具有核壳结构，其中，形成核的碳酸钴一次颗粒为铝均匀分布的粒状颗粒，形成壳的碳酸钴一次颗粒为片状颗粒。
  2. 如权利要求1所述的掺铝碳酸钴颗粒的制备方法，其特征在于，包括以下步骤：
    待碳酸钴晶粒长至D50＝9-10μm，按以下方式进行形貌控制：
    在金属盐溶液和沉淀剂溶液的进料过程中，加入结构转变剂以使所述金属盐溶液与所述沉淀剂溶液反应时，部分碳酸钴一次颗粒向片状生长；
    其中，金属盐包括钴盐和含有铝盐的可溶性金属掺杂盐；
    所述结构转变剂为强碱溶液；
    优选地，所述结构转变剂包括NaOH溶液和KOH溶液中的至少一种。
  3. 根据权利要求2所述的制备方法，其特征在于，形貌控制过程中，所述金属盐溶液的流量为5-30L/h，所述沉淀剂溶液按铵与所述金属盐中钴的质量浓度比为0.61-0.92:1进料；
    其中，所述金属盐溶液中钴的浓度为0.5-3mol/L，所述可溶性金属掺杂盐中铝元素与钴的质量浓度比为0.0075-0.015:1；所述沉淀剂溶液的浓度为2-3mol/L；
    优选地，所述钴盐包括氯化钴、硫酸钴和硝酸钴中的至少一种；
    优选地，所述可溶性金属掺杂盐包括十八水硫酸铝；
    优选地，沉淀剂包括碳酸氢铵和碳酸铵中的至少一种。
  4. 根据权利要求3所述的制备方法，其特征在于，所述结构转变剂的浓度为0.5-1mol/L，所述结构转变剂的流量为钴盐流量的3/10-5/10。
  5. 根据权利要求2-4任一项所述的制备方法，其特征在于，形貌控制过程中，所述反应于35-48℃以及12-28Hz的条件下进行。
  6. 根据权利要求2所述的制备方法，其特征在于，在碳酸钴晶粒长至D50＝9-10μm之前，还包括：晶种合成阶段；
    晶种合成包括：于反应容器内的底液中并流加入金属盐溶液和沉淀剂溶液，于35-48℃以及12-28Hz的条件下反应，得到D50＝4.5-6.5μm的开机晶种；
    优选地，所述底液为浓度为0.5-3mol/L的沉淀剂溶液，所述底液的体积为所述反应容器总体积的3/10-6/10；
    优选地，晶种合成阶段，所述金属盐溶液的流量为3-15L/h，所述沉淀剂溶液按铵与金属盐溶液中钴的质量浓度比为0.61-0.92:1进料。
  7. 根据权利要求6所述的制备方法，其特征在于，在晶种合成与形貌控制之间，还包 括：晶粒长大阶段；
    晶粒长大包括：在得到开机晶种后，将所述金属盐溶液的流量提高至晶种合成过程中相应流量的2-3倍，所述沉淀剂溶液按铵与所述金属盐中钴的质量浓度比为0.61-0.92:1进料；随后于35-48℃以及12-28Hz的条件下反应，得到D50＝9-10μm的晶粒。
  8. 根据权利要求2所述的制备方法，其特征在于，形貌控制后，还包括：晶粒二次生长阶段；
    晶粒二次生长阶段包括：按形貌控制过程中金属盐溶液及沉淀剂溶液的流量进料，并以形貌控制过程中的反应温度和搅拌频率继续反应，直至晶粒长至D50＝18-20μm；
    优选地，还包括：将晶粒二次生长后的碳酸钴产品进行离心洗涤。
  9. 一种四氧化三钴，其特征在于，所述四氧化三钴的前驱体包括权利要求1所述的掺铝碳酸钴颗粒。
  10. 一种钴酸锂，其特征在于，所述钴酸锂的制备原料包括权利要求9所述的四氧化三钴。
PCT/CN2023/079346 2022-08-26 2023-03-02 掺铝碳酸钴颗粒及其制备方法与应用 Ceased WO2024040909A1 (zh)

Priority Applications (1)

Application Number Priority Date Filing Date Title
GB2309728.0A GB2626389A (en) 2022-08-26 2023-03-02 Aluminum-doped cobalt carbonate particles, and preparation method therefor and use thereof

Applications Claiming Priority (2)

Application Number Priority Date Filing Date Title
CN202211035405.X 2022-08-26
CN202211035405.XA CN115321606B (zh) 2022-08-26 2022-08-26 掺铝碳酸钴颗粒及其制备方法与应用

Publications (1)

Publication Number Publication Date
WO2024040909A1 true WO2024040909A1 (zh) 2024-02-29

Family

ID=83927429

Family Applications (1)

Application Number Title Priority Date Filing Date
PCT/CN2023/079346 Ceased WO2024040909A1 (zh) 2022-08-26 2023-03-02 掺铝碳酸钴颗粒及其制备方法与应用

Country Status (3)

Country Link
CN (1) CN115321606B (zh)
FR (1) FR3139133A1 (zh)
WO (1) WO2024040909A1 (zh)

Cited By (2)

* Cited by examiner, † Cited by third party
Publication number Priority date Publication date Assignee Title
WO2026018099A1 (en) * 2024-07-16 2026-01-22 Dyson Technology Limited Method of manufacturing a particulate transition metal carbonate material
WO2026018098A1 (en) * 2024-07-16 2026-01-22 Dyson Technology Limited Method of manufacturing a particulate transition metal carbonate material

Families Citing this family (4)

* Cited by examiner, † Cited by third party
Publication number Priority date Publication date Assignee Title
CN115321606B (zh) * 2022-08-26 2023-06-13 广东邦普循环科技有限公司 掺铝碳酸钴颗粒及其制备方法与应用
GB2626389A (en) * 2022-08-26 2024-07-24 Guangdong Brunp Recycling Technology Co Ltd Aluminum-doped cobalt carbonate particles, and preparation method therefor and use thereof
CN115849458B (zh) * 2022-12-09 2024-11-19 广西中伟新能源科技有限公司 掺铝碳酸钴、掺铝四氧化三钴、制备方法、正极材料、锂离子电池
CN116282216A (zh) * 2023-02-24 2023-06-23 格林美股份有限公司 一种正极前驱体材料及其制备方法和应用

Citations (7)

* Cited by examiner, † Cited by third party
Publication number Priority date Publication date Assignee Title
CN110217832A (zh) * 2019-04-23 2019-09-10 金川集团股份有限公司 一种大颗粒窄分布掺铝四氧化三钴的制备方法
CN112125350A (zh) * 2019-06-24 2020-12-25 荆门市格林美新材料有限公司 一种多层核壳结构铝掺杂四氧化三钴及其制备方法
CN112723422A (zh) * 2020-12-30 2021-04-30 湖南杉杉能源科技股份有限公司 一种掺铝四氧化三钴核壳材料及其制备方法
CN113636604A (zh) * 2021-08-30 2021-11-12 衢州华友钴新材料有限公司 一种高掺铝小粒径碳酸钴颗粒的制备方法
CN113830839A (zh) * 2021-08-18 2021-12-24 广东邦普循环科技有限公司 片状形貌掺铝碳酸钴的制备方法及其应用
CN114180644A (zh) * 2021-12-21 2022-03-15 湖南中伟新能源科技有限公司 一种掺铝碳酸钴材料及其制备方法、掺铝四氧化三钴和钴酸锂正极材料
CN115321606A (zh) * 2022-08-26 2022-11-11 广东邦普循环科技有限公司 掺铝碳酸钴颗粒及其制备方法与应用

Family Cites Families (7)

* Cited by examiner, † Cited by third party
Publication number Priority date Publication date Assignee Title
KR100495865B1 (ko) * 2000-08-11 2005-06-16 에스케이씨 주식회사 리튬 니켈 복합 산화물, 그 제조방법 및 그를 캐소드활물질로서 채용하고 있는 리튬 2차전지
CN108373175B (zh) * 2018-01-23 2020-08-21 湖南雅城新材料有限公司 铝掺杂四氧化三钴及其制备方法和应用
CN111825125B (zh) * 2020-09-16 2020-12-22 金驰能源材料有限公司 一种掺杂型碱式碳酸钴/碳酸钴复合前驱体及其制备方法和应用
CN113307308B (zh) * 2021-06-25 2023-05-23 巴斯夫杉杉电池材料有限公司 一种掺杂型大颗粒碳酸钴及其制备方法
CN113697865B (zh) * 2021-08-27 2023-07-28 湖南中伟新能源科技有限公司 一种四氧化三钴及其制备方法和锂离子电池
CN113772746A (zh) * 2021-09-01 2021-12-10 荆门市格林美新材料有限公司 一种高振实掺铝小粒径四氧化三钴的制备方法
CN114751465B (zh) * 2022-05-24 2023-06-27 荆门市格林美新材料有限公司 一种分阶段元素替代实现制备高Al均匀四氧化三钴方法

Patent Citations (8)

* Cited by examiner, † Cited by third party
Publication number Priority date Publication date Assignee Title
CN110217832A (zh) * 2019-04-23 2019-09-10 金川集团股份有限公司 一种大颗粒窄分布掺铝四氧化三钴的制备方法
CN112125350A (zh) * 2019-06-24 2020-12-25 荆门市格林美新材料有限公司 一种多层核壳结构铝掺杂四氧化三钴及其制备方法
CN112723422A (zh) * 2020-12-30 2021-04-30 湖南杉杉能源科技股份有限公司 一种掺铝四氧化三钴核壳材料及其制备方法
WO2022142327A1 (zh) * 2020-12-30 2022-07-07 巴斯夫杉杉电池材料有限公司 一种掺铝四氧化三钴核壳材料及其制备方法
CN113830839A (zh) * 2021-08-18 2021-12-24 广东邦普循环科技有限公司 片状形貌掺铝碳酸钴的制备方法及其应用
CN113636604A (zh) * 2021-08-30 2021-11-12 衢州华友钴新材料有限公司 一种高掺铝小粒径碳酸钴颗粒的制备方法
CN114180644A (zh) * 2021-12-21 2022-03-15 湖南中伟新能源科技有限公司 一种掺铝碳酸钴材料及其制备方法、掺铝四氧化三钴和钴酸锂正极材料
CN115321606A (zh) * 2022-08-26 2022-11-11 广东邦普循环科技有限公司 掺铝碳酸钴颗粒及其制备方法与应用

Cited By (2)

* Cited by examiner, † Cited by third party
Publication number Priority date Publication date Assignee Title
WO2026018099A1 (en) * 2024-07-16 2026-01-22 Dyson Technology Limited Method of manufacturing a particulate transition metal carbonate material
WO2026018098A1 (en) * 2024-07-16 2026-01-22 Dyson Technology Limited Method of manufacturing a particulate transition metal carbonate material

Also Published As

Publication number Publication date
FR3139133A1 (fr) 2024-03-01
CN115321606B (zh) 2023-06-13
CN115321606A (zh) 2022-11-11

Similar Documents

Publication Publication Date Title
CN111180690B (zh) 改性镍钴铝酸锂正极材料及其制备方法与应用
CN108878818B (zh) 核壳结构镍钴锰三元正极材料前驱体及其制备方法
CN115321606A (zh) 掺铝碳酸钴颗粒及其制备方法与应用
CN101447566B (zh) 层状-尖晶石共生结构锂离子电池正极材料及制备方法
EP3719885A1 (en) Ternary precursor material and preparation method therefor
WO2024066892A1 (zh) 富锰氧化物前驱体及其制备方法和应用
CN108793268A (zh) 核壳结构梯度镍钴锰三元正极材料前驱体及其制备方法
WO2024040903A1 (zh) 共沉淀制备磷酸锰铁的方法及其应用
CN110127777A (zh) 一种湿法掺锆浓度梯度镍钴铝三元前驱体及其制备方法
CN114084914A (zh) 一种三元前驱体及其制备方法与应用
CN109244454B (zh) 一种具有分级结构的ncm三元正极材料
CN106058188A (zh) 一种具有核壳结构的锂离子电池复合正极材料LiNi1‑x‑yMxAlyO2及其制备方法
CN115477331B (zh) 一种掺铝碳酸钴及其制备方法
CN111732131A (zh) 一种核壳结构三元正极材料的制备方法
CN115745028B (zh) 一种二元材料前驱体及其制备方法和正极材料
CN117886296A (zh) 磷酸锰铁铵、磷酸锰铁锂及其制备方法和应用
CN111777103B (zh) 一种制备镍钴铝酸锂正极材料的方法
CN110697797A (zh) 一种空心碳酸盐前驱体的制备方法和应用
CN108987744A (zh) 热稳定性且安全性高的高镍系正极材料的制备方法
CN116588993A (zh) 三元前驱体及其制备方法、锂电正极材料和锂电池
CN116425210B (zh) 一种高镍前驱体、正极材料及其制备方法
WO2007000075A1 (en) Method for preparing spherical nickelous hydroxide which is dopped and multiple metal oxides, and lithium ion secondary battery
CN109755524B (zh) 改性LiNi0.6Co0.2Mn0.2O2三元正极材料的制备方法及产品和电池
CN114538534B (zh) 掺杂铝的正极材料前驱体及其制备方法和应用
CN113387401B (zh) 钪、钨掺杂的正极材料前驱体的制备方法

Legal Events

Date Code Title Description
ENP Entry into the national phase

Ref document number: 202309728

Country of ref document: GB

Kind code of ref document: A

Free format text: PCT FILING DATE = 20230302

WWE Wipo information: entry into national phase

Ref document number: 2309728.0

Country of ref document: GB

121 Ep: the epo has been informed by wipo that ep was designated in this application

Ref document number: 23856006

Country of ref document: EP

Kind code of ref document: A1

WWP Wipo information: published in national office

Ref document number: 2309728.0

Country of ref document: GB

NENP Non-entry into the national phase

Ref country code: DE

122 Ep: pct application non-entry in european phase

Ref document number: 23856006

Country of ref document: EP

Kind code of ref document: A1