CN114249338B - Preparation method of battery-level high-purity hollow lithium carbonate structure for lithium ion battery - Google Patents
Preparation method of battery-level high-purity hollow lithium carbonate structure for lithium ion battery Download PDFInfo
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Abstract
The invention relates to a microscopic size preparation method of a battery-level high-purity hollow lithium carbonate structure for a lithium ion battery, which takes lithium carbonate powder with the purity of 99.6% as a raw material, distilled water as a solvent and analytically pure sodium dodecyl benzene sulfonate SDBS as a surfactant; and (3) dissolving and recrystallizing the lithium carbonate by adopting a microwave radiation technology and a hydrothermal synthesis method to prepare the lithium carbonate powder with a specific hollow structure. Aiming at the defects of complex process, easy aggregation of particles, difficult control of granularity and the like in the traditional method for regulating and controlling the microstructure of lithium carbonate; the microwave radiation technology and the hydrothermal synthesis method are combined, so that the characteristics of a high-efficiency microwave radiation method and a convenient high-pressure hydrothermal method are combined, the reaction rate is high, the process is simple and convenient, the reaction is mild and easy to control, the energy is saved, the environment is protected, the problems that lithium carbonate particles are easy to gather, the particle size is difficult to control and the like are effectively solved by the added surfactant SDBS, and the microscopic morphology of the material is regulated and controlled; in addition, the SDBS auxiliary microwave radiation method can also construct novel morphology, and finally the hollow structure lithium carbonate powder with high purity, small granularity, uniform granularity and regular morphology is obtained.
Description
[ technical field ]: the target product of the invention is mainly applied to the field of energy storage materials, and particularly relates to a microscopic-size preparation method of a battery-level high-purity hollow lithium carbonate structure for a lithium ion battery.
[ PREPARATION METHOD ]: with the aggravation of the problems of serious global energy crisis, ecological environment deterioration and the like, the development and the utilization of new energy are one difficulty that sustainable development must overcome from the aspects of the world, the country and the individual. At present, although clean energy sources such as wind energy, solar energy and the like can be used for replacing traditional fossil energy sources, the periodicity and randomness of the clean energy sources are strong, so that the development of high-performance energy storage equipment plays a vital role in improving the energy utilization efficiency.
The lithium ion battery has great application potential in power transportation and power grid storage due to the advantages of high energy efficiency, high power density, environmental friendliness and the like. The lithium ion battery installed in 2018 accounts for more than 86% of the total electrochemical energy storage device, and the market demand of the lithium ion battery is about $500 billion in 2020, and the figure is expected to increase to $1000 billion in 2025. Taking the electric vehicle industry as an example, in 2018, the total electric vehicle (including battery vehicles and hybrid electric vehicles) maintenance amount and new increase respectively exceed 500 ten thousand and 200 ten thousand, and the number of the electric vehicles is increased by 63% and 68% compared with that in 2017. Wherein, the number of electric vehicles put into use in China exceeds 200 ten thousand. The number of global electric vehicles is expected to exceed 2 hundred million in 2030. (E Fan, L Li, Z Wang, et al, sustainable recycling technology for Li-ion batteries and beyond: challenges and future prospects [ J ]. Chemical review.2020, 120 (14): 7020-7063).
At present, battery grade lithium carbonate is an important basic raw material for preparing lithium ion battery anode materials such as lithium cobaltate, lithium manganate, lithium iron phosphate and the like, and lithium ion battery electrolytes such as lithium hexafluorophosphate, lithium bistrifluoromethane sulfonyl imide and the like. There are many methods for purifying lithium carbonate, such as electrolytic method, precipitation method, carbonization decomposition method, and the like. Although the electrolytic method can directly electrolyze lithium chloride to prepare lithium carbonate with high crystallinity and finer granularity, the chlorine gas generated by the high energy consumption in the electrolytic process is difficult to treat (X Pan, Z Dou, T Zhang, et al basic study on direct preparation of lithium carbonate powders by membrane electrolysis [ J)]Hydrodynamics.2020, 191:105 A) is provided; the precipitation method is to prepare lithium carbonate in a reaction kettle by chemical reaction, but the obtained particles have larger particle size and are easy to aggregate (PTmu, Y Zeng, and XD Yu.the research progress on preparation of battery-grade lithium carbonate from salt lake [ J)]Acta Geologica Sinica (engish Edition) 2014, 88: 359-360). Although the carbonization decomposition method has simple process flow, high purity of the produced lithium carbonate and no pollution to the environment due to the discharge of carbon dioxide, the purity of the lithium carbonate depends on the carbonization process, and sufficient stirring strength needs to be provided in the production process, a large amount of carbon dioxide and impurity ions which are difficult to remove are generated (WT Yi, CY Yan, PH Ma, et al, refining of crop Li 2 CO 3 via slurry phase dissolution using CO 2 [J]Separation and purification technology.2007, 56 (3): 241-248). Besides the above preparation methods, causticizing method, recrystallization method, sulfate method, etc., these methods are usedThe problems of complex process, difficult control of granularity and the like exist to a certain extent; therefore, it is necessary to explore a simple and economical method for preparing high-quality lithium carbonate materials.
Based on the above consideration, the invention provides a microscopic-sized preparation method of a battery-level high-purity hollow lithium carbonate structure for a lithium ion battery. Combines the advantages of a microwave radiation technology and a hydrothermal synthesis method, dynamically drives lithium carbonate particles to construct novel morphology, induces the material to grow along a specific dimension, prevents aggregation of the crystal grains and reduces the adsorption quantity of impurities, thereby obtaining lithium carbonate powder (X Li, B Yuan, M Yi, et al study on removal of trace sulfur impurities from lithium carbonate by hydrothermal method [ J ] with high purity, small granularity, uniform particles and regular morphology].Inorganic Chemials Industry.2019，51(11)：28；M Matsumoto，Y Morita，M Yoshinaga，et al.Reactive crystallization of lithium carbonate nanoparticles by microwave irradiation of aqueous solution containing CO 2 microbubbles[J]Journal of Chemical Engineering of japan 2009, 42: 242-248) can well meet the process requirements, and has novelty, innovation and practicability.
[ invention ] the following: in order to overcome the defects of the prior art, the invention provides a microscopic-sized preparation method of a battery-grade high-purity hollow lithium carbonate structure for a lithium ion battery; firstly, crushing a lithium carbonate raw material into 3000-mesh micro powder, then carrying out reaction in a microwave reactor, putting the material obtained after the microwave reaction into a hydrothermal reaction kettle for hydrothermal reaction, adding a surfactant SDBS (sodium dodecyl benzene sulfonate) to effectively inhibit agglomeration of lithium carbonate particles, and finally obtaining a target product with high purity, small granularity, uniform particles and regular morphology through dissolution and recrystallization; the whole synthesis process has the advantages of high reaction rate, simple and convenient process, mild and controllable reaction, energy conservation and environmental protection, effectively relieves the problems of easy aggregation of lithium carbonate particles and difficult control of particle size, and can induce the lithium carbonate particles to grow along a specific direction, thereby synthesizing the lithium carbonate powder with the target hollow structure.
[ solution ] according to the present invention: the invention relates to a microscopic size preparation method of a battery-level high-purity hollow lithium carbonate structure for a lithium ion battery, which takes lithium carbonate powder with the purity of 99.6% as a raw material, distilled water as a solvent and analytically pure sodium dodecyl benzene sulfonate SDBS as a surfactant; the lithium carbonate powder with the hollow structure is synthesized by adopting a microwave radiation technology and a hydrothermal synthesis method through dissolution and recrystallization, and the specific synthesis steps are as follows:
firstly, accurately weighing 20.0000-50.0000 g of lithium carbonate powder with the purity of 99.6% at the room temperature of 25 ℃, placing the lithium carbonate powder into a mechanical shearing force grinding pulverizer with the total volume of 1000mL, the model of DS-T200A, the rotating speed of 29000r/min and the power of 800-1500W, wherein a cylindrical tank body is made of 304 stainless steel, and 4 shearing force grinding blades which are symmetrically distributed are arranged at the central position of the bottom of the tank body; taking away the friction weight of the powder by using a cooling water circulation sleeve arranged outside the mechanical polishing tank, controlling the external temperature of the mechanical shearing force polishing tank to be 25 ℃, and polishing the lithium carbonate powder for 3-10 min to obtain lithium carbonate powder with 3000 meshes;
secondly, mixing 0.0010-25.0000 g of lithium carbonate powder with the granularity of 3000 meshes obtained in the first step with 10-250 mL of distilled water, stirring clockwise for 3-5 min at the room temperature of 25 ℃, adding 0.5000-5.0000 g of SDBS at the speed of 0.0500-8.0000 g/min, stirring clockwise for 3-5 min, transferring the uniformly mixed suspension into a 250mL quartz round bottom flask, and placing the quartz round bottom flask into a microwave reactor with the temperature of 80-100 ℃ for reaction for 2-14 h, wherein the microwave reactor is a modified American PJ21C-AU microwave oven with a cooling reflux device, the power of the microwave oven is 200-1400W, and the reaction frequency is 2450MHz;
thirdly, after the product obtained in the second step is cooled to room temperature, placing the product in a centrifuge with the rotation speed of 5000-10000 r/min for centrifugation for 1-3 min, then washing the lower sediment with distilled water for 3-5 times, placing the sediment in a forced air drying oven with the temperature rising rate of 5 ℃/min, and drying the sediment for 12-24 h at 50-80 ℃;
fourthly, taking 0.0100-10.0000 g of the product obtained in the third step, adding 10-150 mL of distilled water and 0.0500-5.0000 g of analytically pure SDBS, stirring clockwise for 10-40 min, transferring the uniformly stirred suspension into a stainless steel high-pressure reaction kettle with 25-1000 mL of polytetrafluoroethylene as a lining, and performing hydrothermal reaction for 5-30 h at the temperature of 100-250 ℃;
fifthly, after the product obtained in the fourth step is cooled to room temperature, placing the product in a centrifugal machine with the rotation speed of 5000-10000 r/min for centrifugation for 1-3 min, washing the obtained precipitate with distilled water for 3-5 times, aiming at removing the surface active agent and impurities adsorbed on the surface of the product, and finally placing the washed product in a blast drying oven with the temperature rising rate of 5 ℃/min, and drying for 12-24 h at 50-80 ℃ to obtain the target hollow lithium carbonate powder; the obtained hollow structure lithium carbonate has high purity, small size, uniform granularity and regular morphology through an X-ray diffraction pattern and a scanning electron microscope image of the product.
[ advantages and achievements of the invention ]: the invention relates to a microscopic-size preparation method of a battery-level high-purity hollow lithium carbonate structure for a lithium ion battery, which has the following advantages: (1) The microwave radiation technology and the hydrothermal synthesis method are combined, so that the reaction rate is high, the process is simple and convenient, the reaction is mild and easy to control, the energy is saved, the environment is protected, and the synthesized product has high purity, small size, uniform granularity and regular morphology; (2) The surfactant SDBS added by the method can effectively inhibit the agglomeration of the lithium carbonate particles and induce the lithium carbonate particles to grow along a specific direction, so that the hollow structure lithium carbonate powder with small size, high purity and good particle dispersion degree is synthesized; (3) The phase and morphology of the target product can be regulated and controlled by changing the amounts of the lithium carbonate raw material and the surfactant SDBS, the operation is simple and convenient, and the preparation of the lithium carbonate with specific morphology and performance is facilitated.
[ description of the drawings ]:
FIG. 1 is an X-ray diffraction (XRD) pattern of a hollow structure lithium carbonate powder sample
FIG. 2 is a 6 k-time Scanning Electron Microscope (SEM) image of a hollow structure lithium carbonate powder sample
FIG. 3 is a 12 k-time Scanning Electron Microscope (SEM) image of a hollow structure lithium carbonate powder sample
[ detailed description ] A method for manufacturing a semiconductor device includes:
the embodiments and effects of the present invention will be further described with reference to the following examples:
example 1: preparation of lithium carbonate Material sample 1
Accurately weighing 25.0000g of lithium carbonate powder with the purity of 99.6% at the room temperature of 25 ℃, placing the powder into a mechanical shearing force polishing pulverizer with the total volume of 1000mL, the model of DS-T200A, the rotating speed of 29000r/min and the power of 1000W, wherein a cylindrical tank body is made of 304 stainless steel, and 4 symmetrically distributed shearing force polishing pulverizing paddles are arranged at the central position of the bottom of the tank body; taking away the friction weight of the powder by using a cooling water circulation sleeve arranged outside the mechanical polishing tank, controlling the external temperature of the mechanical shearing force polishing tank to be 25 ℃, and polishing the lithium carbonate powder for 10min to obtain the lithium carbonate powder with the particle size of 3000 meshes; secondly, mixing 6.0710g of lithium carbonate powder with the granularity of 3000 meshes with 30mL of distilled water, stirring clockwise for 5min at the room temperature of 25 ℃, adding 1.0000g of SDBS at the rate of 3.5280g/min, stirring clockwise for 5min, transferring the uniformly mixed suspension into a 250mL quartz round bottom flask, and placing the quartz round bottom flask into a 100 ℃ microwave reactor for reaction for 8h, wherein the microwave reactor is a modified American PJ21C-AU microwave oven with a cooling reflux device, the power is 1000W, and the reaction frequency is 2450MHz; after the product is cooled to room temperature, placing the product in a centrifugal machine with the rotating speed of 8000r/min for centrifugation for 2min, washing the lower layer sediment with distilled water for 4 times, placing the sediment in a forced air drying oven with the heating rate of 5 ℃/min, and drying the sediment at 60 ℃ for 15h; after the dried product is cooled to room temperature, adding 50mL of distilled water and 1.5000g of analytically pure SDBS into 3.7620g of the product, stirring clockwise for 30min, transferring the uniformly stirred suspension into a stainless steel high-pressure reaction kettle with 100mL of polytetrafluoroethylene as a lining, and carrying out hydrothermal reaction for 10h at the temperature of 100 ℃; after the product is cooled to room temperature, placing the product in a centrifugal machine with the rotating speed of 8000r/min for centrifugation for 2min, washing the obtained precipitate with distilled water for 4 times, removing the surface active agent and impurities adsorbed on the surface of the product, and finally placing the washed product in a blast drying oven with the heating rate of 5 ℃/min, and drying for 15h at 60 ℃ to obtain the target hollow lithium carbonate powder; the X-ray diffraction pattern (figure 1) and the scanning electron microscope (figures 2 and 3) of the sample show that the obtained target lithium carbonate sample is a high-purity hollow structure lithium carbonate material with the particle size of 2.5 mu m, the length of 25 mu m and the shape of the material is regular.
Example 2: preparation of lithium carbonate Material sample 2
Accurately weighing 30.0000g of lithium carbonate powder with the purity of 99.6% at the room temperature of 25 ℃, placing the powder into a mechanical shearing force polishing pulverizer with the total volume of 1000mL, the model of DS-T200A, the rotating speed of 29000r/min and the power of 1000W, wherein a cylindrical tank body is made of 304 stainless steel, and 4 symmetrically distributed shearing force polishing pulverizing paddles are arranged at the central position of the bottom of the tank body; taking away the friction weight of the powder by using a cooling water circulation sleeve arranged outside the mechanical polishing tank, controlling the external temperature of the mechanical shearing force polishing tank to be 25 ℃, and polishing the lithium carbonate powder for 10min to obtain the lithium carbonate powder with the particle size of 3000 meshes; secondly, mixing 8.0390g of lithium carbonate powder with the granularity of 3000 meshes with 50mL of distilled water, stirring clockwise for 5min at the room temperature of 25 ℃, adding 1.0000g of SDBS at the rate of 3.5280g/min, stirring clockwise for 5min, transferring the uniformly mixed suspension into a 250mL quartz round bottom flask, and placing the quartz round bottom flask into a 100 ℃ microwave reactor for reaction for 10h, wherein the microwave reactor is a modified American PJ21C-AU microwave oven with a cooling reflux device, the power is 1000W, and the reaction frequency is 2450MHz; after the product is cooled to room temperature, placing the product in a centrifugal machine with the rotating speed of 8000r/min for centrifugation for 2min, washing the lower layer sediment with distilled water for 4 times, placing the sediment in a forced air drying oven with the heating rate of 5 ℃/min, and drying the sediment at 60 ℃ for 15h; after the dried product is cooled to room temperature, adding 50mL of distilled water and 1.5000g of analytically pure SDBS into 4.23900g of the product, stirring clockwise for 30min, transferring the uniformly stirred suspension into a stainless steel high-pressure reaction kettle with 100mL of polytetrafluoroethylene as a lining, and carrying out hydrothermal reaction for 14h at the temperature of 100 ℃; after the product is cooled to room temperature, placing the product into a centrifugal machine with the rotating speed of 8000r/min for centrifugation for 2min, washing the obtained precipitate with distilled water for 4 times, removing the surface active agent and impurities adsorbed on the surface of the product, and finally placing the washed product into a blast drying oven with the heating rate of 5 ℃/min, and drying the product at the temperature of 60 ℃ for 15h to obtain the target hollow lithium carbonate powder.
Example 3: preparation of lithium carbonate Material sample 3
Accurately weighing 30.0000g of lithium carbonate powder with the purity of 99.6% at the room temperature of 25 ℃, placing the powder into a mechanical shearing force polishing pulverizer with the total volume of 1000mL, the model of DS-T200A, the rotating speed of 29000r/min and the power of 1000W, wherein a cylindrical tank body is made of 304 stainless steel, and 4 symmetrically distributed shearing force polishing pulverizing paddles are arranged at the central position of the bottom of the tank body; taking away the friction weight of the powder by using a cooling water circulation sleeve arranged outside the mechanical polishing tank, controlling the external temperature of the mechanical shearing force polishing tank to be 25 ℃, and polishing the lithium carbonate powder for 10min to obtain the lithium carbonate powder with the particle size of 3000 meshes; secondly, mixing 8.0239g of lithium carbonate powder with the granularity of 3000 meshes with 40mL of distilled water, stirring clockwise for 5min at the room temperature of 25 ℃, adding 1.0000g of SDBS at the rate of 3.5280g/min, stirring clockwise for 5min, transferring the uniformly mixed suspension into a 250mL quartz round bottom flask, and placing the quartz round bottom flask into a 100 ℃ microwave reactor for reaction for 7h, wherein the microwave reactor is a modified American PJ21C-AU microwave oven with a cooling reflux device, the power is 1000W, and the reaction frequency is 2450MHz; after the product is cooled to room temperature, placing the product in a centrifugal machine with the rotating speed of 8000r/min for centrifugation for 2min, washing the lower layer sediment with distilled water for 4 times, placing the sediment in a forced air drying oven with the heating rate of 5 ℃/min, and drying the sediment at 60 ℃ for 15h; after the dried product is cooled to room temperature, adding 40mL of distilled water and 1.5000g of analytically pure SDBS into 3.0000g of the product, stirring clockwise for 30min, transferring the uniformly stirred suspension into a stainless steel high-pressure reaction kettle with 100mL of polytetrafluoroethylene as a lining, and carrying out hydrothermal reaction for 10h at the temperature of 100 ℃; after the product is cooled to room temperature, placing the product into a centrifugal machine with the rotating speed of 8000r/min for centrifugation for 2min, washing the obtained precipitate with distilled water for 4 times, removing the surface active agent and impurities adsorbed on the surface of the product, and finally placing the washed product into a blast drying oven with the heating rate of 5 ℃/min, and drying the product at the temperature of 60 ℃ for 15h to obtain the target hollow lithium carbonate powder.
Comparative example 1: one method provided in publication number CN 108217699a (publication date 2018.06.29):
first, carbonic acid hydrogenation: adding industrial grade lithium carbonate and water and/or crystallization mother liquor into a reaction vessel, introducing carbon dioxide gas until the mixture is clear, and filtering to obtain lithium bicarbonate feed liquid; when the industrial grade lithium carbonate is mixed with water, the weight ratio of the industrial grade lithium carbonate to the water is 4-6:100; when the technical grade lithium carbonate is mixed with the crystallization mother liquor, the weight ratio of the technical grade lithium carbonate to the crystallization mother liquor is 2-4:100;
second step, purifying resin: respectively filling ion exchange and/or adsorption resin B in a resin column, regenerating the resin B, and enabling lithium bicarbonate feed liquid to flow through the regenerated resin B to obtain purified liquid; the resin is one or a combination of a plurality of styrene series macroporous adsorption resin, acrylic series macroporous adsorption resin, styrene series cation exchange resin, acrylic series cation exchange resin, phenolic series cation exchange resin, styrene series anion exchange resin, acrylic series anion exchange resin, epoxy series anion exchange resin, chelating resin and redox resin;
third step, pyrolysis crystallization: transferring the purified solution into a pyrolysis crystallization kettle, adding an auxiliary agent, stirring, heating, and carrying out pyrolysis crystallization; heating means that when the temperature is raised to above 60 ℃, the temperature is raised by a certain amplitude according to a gradient relation for a period of time, including but not limited to the following methods; heating to 65 ℃, and preserving heat for 30min at 65 ℃; heating to 75deg.C, and maintaining at 75deg.C for 30min; heating to 85deg.C, and maintaining at 85deg.C for 30min; heating to 95 ℃, and preserving heat for 30min at 95 ℃;
and fourthly, after crystallization, filtering while the solution is hot, and drying and crushing a filter cake to obtain a high-purity lithium carbonate product.
The patent of the invention discloses a microscopic-size preparation method of a battery-level high-purity hollow lithium carbonate structure for a lithium ion battery. As in example 1: accurately weighing 25.0000g of lithium carbonate powder with the purity of 99.6% at the room temperature of 25 ℃, placing the powder into a mechanical shearing force polishing pulverizer with the total volume of 1000mL, the model of DS-T200A, the rotating speed of 29000r/min and the power of 1000W, wherein a cylindrical tank body is made of 304 stainless steel, and 4 symmetrically distributed shearing force polishing pulverizing paddles are arranged at the central position of the bottom of the tank body; taking away the friction weight of the powder by using a cooling water circulation sleeve arranged outside the mechanical polishing tank, controlling the external temperature of the mechanical shearing force polishing tank to be 25 ℃, and polishing the lithium carbonate powder for 10min to obtain the lithium carbonate powder with the particle size of 3000 meshes; secondly, mixing 6.0710g of lithium carbonate powder with the granularity of 3000 meshes with 30mL of distilled water, stirring clockwise for 5min at the room temperature of 25 ℃, adding 1.0000g of SDBS at the rate of 3.5280g/min, stirring clockwise for 5min, transferring the uniformly mixed suspension into a 250mL quartz round bottom flask, and placing the quartz round bottom flask into a 100 ℃ microwave reactor for reaction for 8h, wherein the microwave reactor is a modified American PJ21C-AU microwave oven with a cooling reflux device, the power is 1000W, and the reaction frequency is 2450MHz; after the product is cooled to room temperature, placing the product in a centrifugal machine with the rotating speed of 8000r/min for centrifugation for 2min, washing the lower layer sediment with distilled water for 4 times, placing the sediment in a forced air drying oven with the heating rate of 5 ℃/min, and drying the sediment at 60 ℃ for 15h; after the dried product is cooled to room temperature, adding 50mL of distilled water and 1.5000g of analytically pure SDBS into 3.7620g of the product, stirring clockwise for 30min, transferring the uniformly stirred suspension into a stainless steel high-pressure reaction kettle with 100mL of polytetrafluoroethylene as a lining, and carrying out hydrothermal reaction for 10h at the temperature of 100 ℃; after the product is cooled to room temperature, placing the product in a centrifugal machine with the rotating speed of 8000r/min for centrifugation for 2min, washing the obtained precipitate with distilled water for 4 times, removing the surface active agent and impurities adsorbed on the surface of the product, and finally placing the washed product in a blast drying oven with the heating rate of 5 ℃/min, and drying for 15h at 60 ℃ to obtain the target hollow lithium carbonate powder; the X-ray diffraction pattern (figure 1) and the scanning electron microscope (figures 2 and 3) of the sample show that the obtained target lithium carbonate sample is a high-purity hollow structure lithium carbonate material with the particle size of 2.5 mu m, the length of 25 mu m and the shape of the material is regular.
The invention relates to a microscopic size preparation method of a battery-level high-purity hollow lithium carbonate structure for a lithium ion battery, which is based on the principle that a lithium carbonate material is dissolved and recrystallized, and a surfactant SDBS is added in the process to induce the growth of lithium carbonate, which is different from the method for preparing lithium carbonate in the patent with publication number CN 109942009A; compared with the material prepared by the method disclosed by the patent with the publication number CN 109942009A, the lithium carbonate powder prepared by combining the microwave radiation technology with the hydrothermal synthesis method has the advantages of better crystallinity, smaller particle size, higher product purity and simplicity in operation, and fully proves the novelty, innovation and practicability of the patent.
Comparative example 2: publication number CN 109942009A (publication date 2019.06.28) provides a method of preparation:
(1) Pulping lithium carbonate: crushing industrial lithium carbonate to 100 meshes, mixing the crushed industrial lithium carbonate with water and filtrate returned in the steps (3) and (4) according to a certain proportion, and stirring for standby;
(2) Lithium carbonate hydrogenation: adding the lithium carbonate slurry obtained in the step (1) from the top of the last filler tower, and introducing high-purity CO escaping from the top of the last tower into the bottom of the last filler tower 2 The gas is in countercurrent contact in a packed tower, and the slurry at the bottom of the tower and the CO escaping from the top of the tower are respectively collected 2 Adding gas and collected slurry into the top of the previous tower, and circulating until the effluent liquid of the tower bottom of the first tower is used as product liquid, and the CO escaping from the last tower 2 The gas is returned to the first column. Initial CO 2 The gas is introduced from the bottom of the first tower and is in countercurrent contact with the final-stage lithium carbonate slurry in the tower, and CO escapes from the top of the tower 2 The gas is introduced into a second tower and circulates in sequence; filtering the feed liquid collected at the bottom of the first tower, keeping filtrate for later use, and returning filter residues to the step (1) for preparing lithium carbonate slurry;
(3) Pyrolysis of lithium bicarbonate: adding sulfate radical complexing agent into the filtrate obtained in the step (2), stirring and mixing uniformly, heating to remove carbon dioxide, stirring while heating until no bubbles escape, and heating and stirring for 10min; filtering the slurry obtained after pyrolysis to obtain lithium carbonate and filtrate, partially returning part of the filtrate to the step (1) of pulping, and partially recycling lithium;
(4) Washing a lithium carbonate product: pulping and washing lithium carbonate obtained in the step (3) by adopting a sodium hydroxide solution with the pH value of 12-12.5, filtering, returning filtrate to the step (1) for pulping, and carrying out countercurrent pulping and washing on filter residues by adopting deionized water for at least 2 times; the washing water obtained by the primary washing is used for preparing sodium hydroxide solution, the new water is used for the secondary washing, the obtained washing water is used for the next primary washing, the secondary washing slag is used as a product for drying, and the impurity content is analyzed.
In the step (1), the mass ratio of the lithium carbonate to water to the filtrate returned in the step (3) and the step (4) is 1:20-30.
In the step (1), stirring into uniform slurry at room temperature for later use.
In the step (2), the filler is one of triangular spiral filler, theta-ring filler, calendaring hole ring filler and stepped ring filler.
In the step (2), the filling height of the filling material is not less than 1000mm, the single tower residence time of the slurry is not less than 5 minutes, and the CO is 2 The molar ratio of the gas to the lithium carbonate in the slurry is more than or equal to 1.1.
In the step (3), the sulfate complexing agent is any one of polyoxyethylene sorbitan fatty acid ester, cetyl trimethyl ammonium bromide, cetyl trimethyl ammonium chloride, cetyl trimethyl ammonium hydroxide, dodecyl trimethyl ammonium bromide, dodecyl trimethyl ammonium chloride, dodecyl trimethyl ammonium hydroxide and the like, sodium cetyl sulfonate, sodium dodecyl sulfonate and the like, and triethanolamine.
In the step (3), the dosage of the lithium solution is 0.05-0.5 g/L.
In the step (3), the temperature of the carbon dioxide for driving is more than or equal to 70 ℃, and the heating temperature raising process is not less than 30min.
In the step (4), the solid volume mass ratio of the washing liquid is 0.5-2, the temperature is more than or equal to 70 ℃, and the time is not less than 10min.
In the step (4), the volume-mass ratio (L/kg) of deionized water to lithium carbonate is 0.5-2, the washing temperature is more than or equal to 70 ℃, and the washing time is not less than 10min.
The patent of the invention discloses a microscopic-size preparation method of a battery-level high-purity hollow lithium carbonate structure for a lithium ion battery. As in example 1: accurately weighing 25.0000g of lithium carbonate powder with the purity of 99.6% at the room temperature of 25 ℃, placing the powder into a mechanical shearing force polishing pulverizer with the total volume of 1000mL, the model of DS-T200A, the rotating speed of 29000r/min and the power of 1000W, wherein a cylindrical tank body is made of 304 stainless steel, and 4 symmetrically distributed shearing force polishing pulverizing paddles are arranged at the central position of the bottom of the tank body; taking away the friction weight of the powder by using a cooling water circulation sleeve arranged outside the mechanical polishing tank, controlling the external temperature of the mechanical shearing force polishing tank to be 25 ℃, and polishing the lithium carbonate powder for 10min to obtain the lithium carbonate powder with the particle size of 3000 meshes; secondly, mixing 6.0710g of lithium carbonate powder with the granularity of 3000 meshes with 30mL of distilled water, stirring clockwise for 5min at the room temperature of 25 ℃, adding 1.0000g of SDBS at the rate of 3.5280g/min, stirring clockwise for 5min, transferring the uniformly mixed suspension into a 250mL quartz round bottom flask, and placing the quartz round bottom flask into a 100 ℃ microwave reactor for reaction for 8h, wherein the microwave reactor is a modified American PJ21C-AU microwave oven with a cooling reflux device, the power is 1000W, and the reaction frequency is 2450MHz; after the product is cooled to room temperature, placing the product in a centrifugal machine with the rotating speed of 8000r/min for centrifugation for 2min, washing the lower layer sediment with distilled water for 4 times, placing the sediment in a forced air drying oven with the heating rate of 5 ℃/min, and drying the sediment at 60 ℃ for 15h; after the dried product is cooled to room temperature, adding 50mL of distilled water and 1.5000g of analytically pure SDBS into 3.7620g of the product, stirring clockwise for 30min, transferring the uniformly stirred suspension into a stainless steel high-pressure reaction kettle with 100mL of polytetrafluoroethylene as a lining, and carrying out hydrothermal reaction for 10h at the temperature of 100 ℃; after the product is cooled to room temperature, placing the product in a centrifugal machine with the rotating speed of 8000r/min for centrifugation for 2min, washing the obtained precipitate with distilled water for 4 times, removing the surface active agent and impurities adsorbed on the surface of the product, and finally placing the washed product in a blast drying oven with the heating rate of 5 ℃/min, and drying for 15h at 60 ℃ to obtain the target hollow lithium carbonate powder; the X-ray diffraction pattern (figure 1) and the scanning electron microscope (figures 2 and 3) of the sample show that the obtained target lithium carbonate sample is a high-purity hollow structure lithium carbonate material with the particle size of 2.5 mu m, the length of 25 mu m and the shape of the material is regular.
The method for preparing lithium carbonate related by the patent is basically different from the method for preparing lithium carbonate described in the patent with publication number CN 109942009A in preparation principle, and is characterized in that firstly, a microwave method is utilized to optimize a target lithium carbonate material, and then the lithium carbonate is further treated in a sealed high-temperature hydrothermal reaction kettle to obtain a target battery-grade lithium carbonate material, and compared with the lithium carbonate material obtained by the method described in the patent with publication number CN 109942009A, the granularity of the obtained target lithium carbonate product is smaller, the purity of the product is higher, the operation is simpler, and the method is more beneficial to the later commercial production.
Comparative example 3: publication number CN 100428524C (publication date 2008.10.22) provides a method of preparation:
1. a lithium ion battery anode material, which is characterized by comprising 69.48wt% of LiFePO4 and 30.52wt% of carbon, and comprises the following steps:
(1) Mixing lithium oxalate, ammonium dihydrogen phosphate and ferrous oxalate, ball milling, wherein the molar ratio of lithium to iron to phosphorus is 1:1:1, drying, and preheating for 6 hours at 400 ℃ under the protection of nitrogen;
(2) Adding active carbon into the mixture, wherein the weight ratio of the mixture to the active carbon is 5:1;
(3) Roasting the mixture obtained in the step (2) under the protection of inert gas, wherein the roasting temperature is 600 ℃, and the roasting time is 15 hours;
(4) Tabletting the roasted product, putting the product into a crucible containing 10g of active carbon, putting the crucible into a microwave oven, adjusting the microwave power to 600W, and controlling the time to be 5 minutes.
2. A method for preparing a positive electrode material of a lithium ion battery, which is characterized by comprising the following steps:
(1) Mixing lithium salt, phosphorus salt and ferrous oxalate, ball milling, wherein the molar ratio of lithium to iron to phosphorus element is 1:1:1, drying, and preheating for 5-8 hours at 300-400 ℃ under the protection of nitrogen;
(2) Adding an additive into the mixture, wherein the weight ratio of the mixture to the additive is 3-10:1;
(3) Roasting the mixture obtained in the step (2) under the protection of inert gas, wherein the roasting temperature is 500-800 ℃ and the roasting time is 10-24 hours;
(4) Tabletting the roasted product, putting the product into a crucible containing 10-40 g of active carbon, putting the crucible into a microwave oven, adjusting the microwave power to 140-700W, and controlling the time to 1-14 minutes; the additive in the step (2) is one of sucrose, citric acid, polypropylene or activated carbon.
3. The method of preparing a positive electrode material for a lithium ion battery according to claim 2, wherein the lithium salt is lithium oxalate or lithium carbonate.
4. The method for preparing a positive electrode material for a lithium ion battery according to claim 2, wherein the phosphorus salt is a hydrogen diamine phosphate or a dihydrogen amine phosphate.
5. The method of claim 2, wherein the inert gas is one of nitrogen, argon or a mixture of hydrogen and argon.
The patent of the invention discloses a microscopic-size preparation method of a battery-level high-purity hollow lithium carbonate structure for a lithium ion battery. As in example 1: accurately weighing 25.0000g of lithium carbonate powder with the purity of 99.6% at the room temperature of 25 ℃, placing the powder into a mechanical shearing force polishing pulverizer with the total volume of 1000mL, the model of DS-T200A, the rotating speed of 29000r/min and the power of 1000W, wherein a cylindrical tank body is made of 304 stainless steel, and 4 symmetrically distributed shearing force polishing pulverizing paddles are arranged at the central position of the bottom of the tank body; taking away the friction weight of the powder by using a cooling water circulation sleeve arranged outside the mechanical polishing tank, controlling the external temperature of the mechanical shearing force polishing tank to be 25 ℃, and polishing the lithium carbonate powder for 10min to obtain the lithium carbonate powder with the particle size of 3000 meshes; secondly, mixing 6.0710g of lithium carbonate powder with the granularity of 3000 meshes with 30mL of distilled water, stirring clockwise for 5min at the room temperature of 25 ℃, adding 1.0000g of SDBS at the rate of 3.5280g/min, stirring clockwise for 5min, transferring the uniformly mixed suspension into a 250mL quartz round bottom flask, and placing the quartz round bottom flask into a 100 ℃ microwave reactor for reaction for 8h, wherein the microwave reactor is a modified American PJ21C-AU microwave oven with a cooling reflux device, the power is 1000W, and the reaction frequency is 2450MHz; after the product is cooled to room temperature, placing the product in a centrifugal machine with the rotating speed of 8000r/min for centrifugation for 2min, washing the lower layer sediment with distilled water for 4 times, placing the sediment in a forced air drying oven with the heating rate of 5 ℃/min, and drying the sediment at 60 ℃ for 15h; after the dried product is cooled to room temperature, adding 50mL of distilled water and 1.5000g of analytically pure SDBS into 3.7620g of the product, stirring clockwise for 30min, transferring the uniformly stirred suspension into a stainless steel high-pressure reaction kettle with 100mL of polytetrafluoroethylene as a lining, and carrying out hydrothermal reaction for 10h at the temperature of 100 ℃; after the product is cooled to room temperature, placing the product in a centrifugal machine with the rotating speed of 8000r/min for centrifugation for 2min, washing the obtained precipitate with distilled water for 4 times, removing the surface active agent and impurities adsorbed on the surface of the product, and finally placing the washed product in a blast drying oven with the heating rate of 5 ℃/min, and drying for 15h at 60 ℃ to obtain the target hollow lithium carbonate powder; the X-ray diffraction pattern (figure 1) and the scanning electron microscope (figures 2 and 3) of the sample show that the obtained target lithium carbonate sample is a high-purity hollow structure lithium carbonate material with the particle size of 2.5 mu m, the length of 25 mu m and the shape of the material is regular.
The process of the present invention differs from the process described in publication No. CN 100428524C essentially in that the principle of preparation and the target product are different. The method disclosed in the publication number CN 100428524C is to prepare a lithium iron phosphate material by a microwave solid-phase method, and the method is to optimize a target lithium carbonate material by a microwave method, and then to further treat a product obtained after microwave reaction in a sealed hydrothermal reaction kettle at high temperature to obtain the target battery-grade lithium carbonate material.
Claims (1)
1. A preparation method of a battery-grade high-purity hollow lithium carbonate structure for a lithium ion battery uses lithium carbonate powder with the purity of 99.6% as a raw material, distilled water as a solvent and analytically pure sodium dodecyl benzene sulfonate SDBS as a surfactant; the lithium carbonate powder with the hollow structure is synthesized by adopting a microwave radiation technology and a hydrothermal synthesis method through dissolution and recrystallization, and the specific synthesis steps are as follows:
firstly, accurately weighing 20.0000-50.0000 g of lithium carbonate powder with the purity of 99.6% at the room temperature of 25 ℃, placing the lithium carbonate powder into a mechanical shearing force grinding pulverizer with the total volume of 1000mL, the model of DS-T200A, the rotating speed of 29000r/min and the power of 800-1500W, wherein a cylindrical tank body is made of 304 stainless steel, and 4 shearing force grinding pulverizing paddles which are symmetrically distributed are arranged at the central position of the bottom of the tank body; taking away powder friction heat by using cooling water circulation sleeve arranged outside the mechanical polishing tank, controlling the external temperature of the mechanical shearing force polishing tank to be 25 ℃, and polishing lithium carbonate powder for 3-10 min to obtain lithium carbonate powder with 3000 meshes;
secondly, mixing 0.0010-25.0000 g of lithium carbonate powder with the granularity of 3000 meshes obtained in the first step with 10-250 mL of distilled water, stirring clockwise for 3-5 min at the room temperature of 25 ℃, adding 0.5000-5.0000 g of SDBS at the speed of 0.0500-8.0000 g/min, stirring clockwise for 3-5 min, transferring the uniformly mixed suspension into a 250mL quartz round bottom flask, and placing the quartz round bottom flask into a microwave reactor with the temperature of 80-100 ℃ for reaction for 2-14 h, wherein the microwave reactor is a modified American PJ21C-AU microwave oven with a cooling reflux device, the power of the microwave oven is 200-1400W, and the reaction frequency is 2450MHz;
thirdly, after the product obtained in the second step is cooled to room temperature, placing the product in a centrifuge with the rotation speed of 5000-10000 r/min for centrifugation for 1-3 min, then washing the lower sediment with distilled water for 3-5 times, placing the sediment in a forced air drying oven with the temperature rising rate of 5 ℃/min, and drying the sediment for 12-24 h at 50-80 ℃;
fourthly, taking 0.0100-10.0000 g of the product obtained in the third step, adding 10-150 mL of distilled water and 0.0500-5.0000 g of analytically pure SDBS, stirring clockwise for 10-40 min, transferring the uniformly stirred suspension into a stainless steel high-pressure reaction kettle with 25-1000 mL of polytetrafluoroethylene as a lining, and performing hydrothermal reaction for 5-30 h at the temperature of 100-250 ℃;
fifthly, after the product obtained in the fourth step is cooled to room temperature, placing the product in a centrifugal machine with the rotation speed of 5000-10000 r/min for centrifugation for 1-3 min, washing the obtained precipitate with distilled water for 3-5 times, aiming at removing the surface active agent and impurities adsorbed on the surface of the product, and finally placing the washed product in a blast drying oven with the temperature rising rate of 5 ℃/min, and drying for 12-24 h at 50-80 ℃ to obtain the target hollow lithium carbonate powder; the obtained hollow structure lithium carbonate has high purity, small size, uniform granularity and regular morphology through an X-ray diffraction pattern and a scanning electron microscope image of the product.
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