CN115321564B - Long rod-shaped lithium carbonate and preparation method thereof - Google Patents
Long rod-shaped lithium carbonate and preparation method thereof Download PDFInfo
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- CN115321564B CN115321564B CN202211054674.0A CN202211054674A CN115321564B CN 115321564 B CN115321564 B CN 115321564B CN 202211054674 A CN202211054674 A CN 202211054674A CN 115321564 B CN115321564 B CN 115321564B
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- XGZVUEUWXADBQD-UHFFFAOYSA-L lithium carbonate Chemical compound [Li+].[Li+].[O-]C([O-])=O XGZVUEUWXADBQD-UHFFFAOYSA-L 0.000 title claims abstract description 106
- 229910052808 lithium carbonate Inorganic materials 0.000 title claims abstract description 103
- 238000002360 preparation method Methods 0.000 title claims abstract description 9
- WHXSMMKQMYFTQS-UHFFFAOYSA-N Lithium Chemical compound [Li] WHXSMMKQMYFTQS-UHFFFAOYSA-N 0.000 claims abstract description 14
- 229910052744 lithium Inorganic materials 0.000 claims abstract description 14
- 239000007788 liquid Substances 0.000 claims description 58
- 238000006243 chemical reaction Methods 0.000 claims description 51
- 239000002002 slurry Substances 0.000 claims description 31
- 239000007787 solid Substances 0.000 claims description 26
- 238000003763 carbonization Methods 0.000 claims description 24
- 229920002125 Sokalan® Polymers 0.000 claims description 21
- 239000004584 polyacrylic acid Substances 0.000 claims description 21
- 238000001914 filtration Methods 0.000 claims description 20
- 150000003839 salts Chemical class 0.000 claims description 19
- 238000003756 stirring Methods 0.000 claims description 19
- 238000001035 drying Methods 0.000 claims description 16
- 238000002156 mixing Methods 0.000 claims description 14
- XLYOFNOQVPJJNP-UHFFFAOYSA-N water Substances O XLYOFNOQVPJJNP-UHFFFAOYSA-N 0.000 claims description 13
- 238000010438 heat treatment Methods 0.000 claims description 12
- 229920000058 polyacrylate Polymers 0.000 claims description 12
- 229910018068 Li 2 O Inorganic materials 0.000 claims description 6
- XAEFZNCEHLXOMS-UHFFFAOYSA-M potassium benzoate Chemical compound [K+].[O-]C(=O)C1=CC=CC=C1 XAEFZNCEHLXOMS-UHFFFAOYSA-M 0.000 claims description 6
- 238000000926 separation method Methods 0.000 claims description 6
- 159000000000 sodium salts Chemical class 0.000 claims description 6
- 239000002904 solvent Substances 0.000 claims description 6
- 238000004519 manufacturing process Methods 0.000 claims description 5
- 239000000463 material Substances 0.000 abstract description 2
- 239000000047 product Substances 0.000 description 37
- 239000002245 particle Substances 0.000 description 21
- 238000000034 method Methods 0.000 description 14
- 238000010298 pulverizing process Methods 0.000 description 11
- 230000000052 comparative effect Effects 0.000 description 9
- WMFOQBRAJBCJND-UHFFFAOYSA-M Lithium hydroxide Chemical compound [Li+].[OH-] WMFOQBRAJBCJND-UHFFFAOYSA-M 0.000 description 7
- 239000013078 crystal Substances 0.000 description 5
- 230000000694 effects Effects 0.000 description 5
- 229920001495 poly(sodium acrylate) polymer Polymers 0.000 description 4
- 239000002994 raw material Substances 0.000 description 4
- NNMHYFLPFNGQFZ-UHFFFAOYSA-M sodium polyacrylate Chemical compound [Na+].[O-]C(=O)C=C NNMHYFLPFNGQFZ-UHFFFAOYSA-M 0.000 description 4
- 239000002270 dispersing agent Substances 0.000 description 3
- 239000003792 electrolyte Substances 0.000 description 3
- 239000000243 solution Substances 0.000 description 3
- ATRRKUHOCOJYRX-UHFFFAOYSA-N Ammonium bicarbonate Chemical compound [NH4+].OC([O-])=O ATRRKUHOCOJYRX-UHFFFAOYSA-N 0.000 description 2
- 229910000013 Ammonium bicarbonate Inorganic materials 0.000 description 2
- CURLTUGMZLYLDI-UHFFFAOYSA-N Carbon dioxide Chemical compound O=C=O CURLTUGMZLYLDI-UHFFFAOYSA-N 0.000 description 2
- CDBYLPFSWZWCQE-UHFFFAOYSA-L Sodium Carbonate Chemical compound [Na+].[Na+].[O-]C([O-])=O CDBYLPFSWZWCQE-UHFFFAOYSA-L 0.000 description 2
- 230000002411 adverse Effects 0.000 description 2
- 150000001412 amines Chemical class 0.000 description 2
- 235000012538 ammonium bicarbonate Nutrition 0.000 description 2
- 239000001099 ammonium carbonate Substances 0.000 description 2
- 230000009286 beneficial effect Effects 0.000 description 2
- KWGKDLIKAYFUFQ-UHFFFAOYSA-M lithium chloride Chemical compound [Li+].[Cl-] KWGKDLIKAYFUFQ-UHFFFAOYSA-M 0.000 description 2
- IIPYXGDZVMZOAP-UHFFFAOYSA-N lithium nitrate Chemical compound [Li+].[O-][N+]([O-])=O IIPYXGDZVMZOAP-UHFFFAOYSA-N 0.000 description 2
- 229910003002 lithium salt Inorganic materials 0.000 description 2
- 159000000002 lithium salts Chemical class 0.000 description 2
- 238000002844 melting Methods 0.000 description 2
- 230000008018 melting Effects 0.000 description 2
- 239000007774 positive electrode material Substances 0.000 description 2
- BWHMMNNQKKPAPP-UHFFFAOYSA-L potassium carbonate Chemical compound [K+].[K+].[O-]C([O-])=O BWHMMNNQKKPAPP-UHFFFAOYSA-L 0.000 description 2
- 239000000843 powder Substances 0.000 description 2
- 230000035484 reaction time Effects 0.000 description 2
- 238000011144 upstream manufacturing Methods 0.000 description 2
- OKTJSMMVPCPJKN-UHFFFAOYSA-N Carbon Chemical compound [C] OKTJSMMVPCPJKN-UHFFFAOYSA-N 0.000 description 1
- BVKZGUZCCUSVTD-UHFFFAOYSA-L Carbonate Chemical compound [O-]C([O-])=O BVKZGUZCCUSVTD-UHFFFAOYSA-L 0.000 description 1
- HBBGRARXTFLTSG-UHFFFAOYSA-N Lithium ion Chemical compound [Li+] HBBGRARXTFLTSG-UHFFFAOYSA-N 0.000 description 1
- 238000001994 activation Methods 0.000 description 1
- 239000003513 alkali Substances 0.000 description 1
- CNLWCVNCHLKFHK-UHFFFAOYSA-N aluminum;lithium;dioxido(oxo)silane Chemical compound [Li+].[Al+3].[O-][Si]([O-])=O.[O-][Si]([O-])=O CNLWCVNCHLKFHK-UHFFFAOYSA-N 0.000 description 1
- 239000003945 anionic surfactant Substances 0.000 description 1
- 239000007864 aqueous solution Substances 0.000 description 1
- 230000015572 biosynthetic process Effects 0.000 description 1
- 229910052799 carbon Inorganic materials 0.000 description 1
- 239000001569 carbon dioxide Substances 0.000 description 1
- 229910002092 carbon dioxide Inorganic materials 0.000 description 1
- 150000007942 carboxylates Chemical group 0.000 description 1
- 230000007547 defect Effects 0.000 description 1
- 230000008021 deposition Effects 0.000 description 1
- 239000003814 drug Substances 0.000 description 1
- 229940079593 drug Drugs 0.000 description 1
- 150000002148 esters Chemical class 0.000 description 1
- 239000012467 final product Substances 0.000 description 1
- 239000010419 fine particle Substances 0.000 description 1
- 239000012535 impurity Substances 0.000 description 1
- 150000002500 ions Chemical class 0.000 description 1
- 230000001788 irregular Effects 0.000 description 1
- 229910001416 lithium ion Inorganic materials 0.000 description 1
- INHCSSUBVCNVSK-UHFFFAOYSA-L lithium sulfate Inorganic materials [Li+].[Li+].[O-]S([O-])(=O)=O INHCSSUBVCNVSK-UHFFFAOYSA-L 0.000 description 1
- 239000002105 nanoparticle Substances 0.000 description 1
- 238000006386 neutralization reaction Methods 0.000 description 1
- -1 particle size Chemical compound 0.000 description 1
- 229910000027 potassium carbonate Inorganic materials 0.000 description 1
- 238000001556 precipitation Methods 0.000 description 1
- 239000011164 primary particle Substances 0.000 description 1
- 238000000746 purification Methods 0.000 description 1
- 238000011160 research Methods 0.000 description 1
- 238000005245 sintering Methods 0.000 description 1
- 229910000029 sodium carbonate Inorganic materials 0.000 description 1
- 229910052642 spodumene Inorganic materials 0.000 description 1
- 239000000126 substance Substances 0.000 description 1
- 125000001273 sulfonato group Chemical group [O-]S(*)(=O)=O 0.000 description 1
- 238000001308 synthesis method Methods 0.000 description 1
- 238000003786 synthesis reaction Methods 0.000 description 1
- RBTVSNLYYIMMKS-UHFFFAOYSA-N tert-butyl 3-aminoazetidine-1-carboxylate;hydrochloride Chemical compound Cl.CC(C)(C)OC(=O)N1CC(N)C1 RBTVSNLYYIMMKS-UHFFFAOYSA-N 0.000 description 1
- 238000002076 thermal analysis method Methods 0.000 description 1
- 238000005406 washing Methods 0.000 description 1
Classifications
-
- C—CHEMISTRY; METALLURGY
- C01—INORGANIC CHEMISTRY
- C01D—COMPOUNDS OF ALKALI METALS, i.e. LITHIUM, SODIUM, POTASSIUM, RUBIDIUM, CAESIUM, OR FRANCIUM
- C01D15/00—Lithium compounds
- C01D15/08—Carbonates; Bicarbonates
-
- 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
- C01P2006/00—Physical properties of inorganic compounds
- C01P2006/11—Powder tap density
-
- 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
- C01P2006/80—Compositional purity
-
- 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
Abstract
The invention relates to long rod-shaped lithium carbonate and a preparation method thereof, and belongs to the technical field of lithium materials. The appearance of the long rod-shaped lithium carbonate is rod-shaped, D10 of the long rod-shaped lithium carbonate is less than or equal to 18 mu m and less than or equal to 20 mu m, D50 of the long rod-shaped lithium carbonate is less than or equal to 39 mu m and less than or equal to 46 mu m, D90 of the long rod-shaped lithium carbonate is less than or equal to 83 mu m and less than or equal to 96 mu m, and the purity of the lithium carbonate is more than or equal to 99.5%. The lithium carbonate product of the invention is in a rod shape, and the tap density of the product is low. The lithium carbonate product of the present invention is easily crushed. The purity of the lithium carbonate is more than or equal to 99.5 percent, and the purity is high.
Description
Technical Field
The invention relates to long rod-shaped lithium carbonate and a preparation method thereof, and belongs to the technical field of lithium materials.
Background
Under the background of carbon neutralization, the global new energy vehicle demand is continuously improved, and the ratio of renewable power sources inside and outside the sea is improved year by year. The rapid development of the new energy industry places more demands on upstream lithium raw materials, and the importance of upstream resources is also becoming increasingly prominent. At present, lithium resource supply mainly takes spodumene to extract lithium.
Different industries have different requirements for lithium carbonate. In recent years, the requirements on the purity and the properties of lithium carbonate in the fields of batteries, medicines, military industry, aerospace and the like are higher and higher, the development and evolution of high-purity lithium salt are continuously promoted, the preparation of high-purity lithium carbonate becomes one of hot spots in recent years, and the preparation methods of the high-purity lithium carbonate are mainly divided into a direct synthesis method and a crude lithium carbonate purification method. The preparation of the positive electrode material also puts higher demands on the properties of lithium carbonate, such as particle size, morphology, melting point, etc. The fine particle size, the spherical shape and the lower melting point can be beneficial to uniformity of lithium mixing, and further the positive electrode material with better performance is obtained through sintering.
In many prior arts, lithium sulfate, lithium nitrate, lithium chloride and the like are used as lithium sources, sodium carbonate and potassium carbonate are used as precipitants, the morphology of a precipitated lithium product is controlled, the morphology of the product is mainly in the form of blocks and sheets, and many researches are advanced. Because the traditional lithium deposition rate is faster, na, mg and SO 4 2- The ions are easily coated into the crystal particles, so that lithium carbonate cannot meet the battery level standard, and the lithium carbonate needs to be purified through washing or carbonization thermal analysis.
CN111422889a discloses a preparation method of high-activity lithium carbonate, the raw materials used are lithium solution, alkali solution and ammonium bicarbonate solution, and by controlling reaction parameters, the battery-grade lithium carbonate with high activity, small primary particle size and high sphericity can be obtained. However, the precipitation process uses ammonium bicarbonate, the drying and activation processes use carbon dioxide, and the production cost is increased in an intangible way.
Yang Xuejun Synthesis of rod-like fine lithium carbonate powder [ J ], zhang Chang, zhao Li]University of ethnic group, southwest newspaper: natural science edition, 2006 (4): 4. A method for preparing rod-like fine lithium carbonate powder has been studied, and the best synthetic process conditions are LiOH and CO 2 As raw material, liOH with mass percentage concentration of 9%, CO 2 Flow rate 1L.min -1 The reaction temperature is 30 ℃, the drying temperature is 200 ℃, and the drying time is 2 hours, thus obtaining the product with the length of about 5 mu m, the diameter of about 1 mu m and the apparent density of 2.9 g.ml -1 The rod-shaped fine lithium carbonate powder has extremely white color and good uniformity and fluidity. However, the method needs LiOH as a raw material, and has high cost.
CN101209846a discloses a method for preparing nano-sized lithium carbonate for batteries, which comprises the contact reaction of lithium ions and carbonate ions in an aqueous solution, wherein the contact reaction is carried out in the presence of a dispersing agent, and the dispersing agent is a water-soluble anionic surfactant and/or organic amine with carboxylate groups and/or sulfonate groups. The granularity of the lithium carbonate prepared by the method provided by the invention is very small, the D10 particle size can be as small as below 80 nanometers, and the final product lithium carbonate only contains trace impurities which do not adversely affect the battery performance, so that the lithium carbonate completely meets the requirements of the battery electrolyte on the purity and granularity of the lithium carbonate, and is very suitable for being used in the battery electrolyte. The lithium carbonate prepared by the method is used in the electrolyte, so that not only does not have adverse effect on the battery performance, but also various performances of the battery such as overcharge resistance, low-temperature discharge performance and battery capacity can be improved. However, it is necessary to use a water-soluble lithium salt or lithium hydroxide, the cost is still high, and it is necessary to use a dispersant which is an ester or amine substance.
Disclosure of Invention
A first object of the present invention is to provide a new long rod-shaped lithium carbonate.
In order to achieve the first object of the invention, the morphology of the long rod-shaped lithium carbonate is rod-shaped, D10 is less than or equal to 18 μm and less than or equal to 20 μm, D50 is less than or equal to 39 μm and less than or equal to 46 μm, D90 is less than or equal to 83 μm and less than or equal to 96 μm, and the purity of the lithium carbonate is more than or equal to 99.5%.
In one embodiment, the long rod-shaped lithium carbonate has cracks on the surface and is easy to crush. The term "easily pulverized" means that the lithium carbonate is easily pulverized into a powder having a small particle diameter under the same pulverizing conditions as those of conventional lithium carbonate.
In one embodiment, the method for preparing the long rod-shaped lithium carbonate comprises the following steps:
a. mixing lithium carbonate slurry with CO 2 Performing carbonization reaction on the gas, and filtering to obtain carbonized liquid, wherein the solvent of the lithium carbonate slurry is water;
b. adding at least one of polyacrylic acid and salts thereof into the carbonized liquid, heating at 40-60 ℃ for reaction for 1-2 h, heating to 85-95 ℃ for reaction for 1-2 h, carrying out solid-liquid separation to obtain solid, and drying the solid to obtain the long rod-shaped lithium carbonate.
In one embodiment, the concentration of the lithium carbonate slurry in step a is Li 2 O is 30-50 g/L.
In one embodiment, the carbonization reaction time in the step a is 180 to 240min.
In a specific embodiment, the polyacrylate in step b is at least one of sodium salt or potassium salt.
In a specific embodiment, the polyacrylic acid and its salts in step b have an average molecular weight of 3000-5000, preferably the polyacrylate has an average molecular weight of 5000.
In one embodiment, lithium in the carbonized liquid is in the form of Li 2 The addition amount of the polyacrylic acid and the salt thereof in the step b is 0.3 to 1.0 weight percent of M.
In a specific embodiment, the reaction in step b is performed while stirring, and the linear speed of stirring is controlled to be 0.5-2 m/s.
The second object of the invention is to provide a method for preparing the long rod-shaped lithium carbonate.
To solve the second object of the present invention, the method for preparing long rod-shaped lithium carbonate comprises:
a. mixing lithium carbonate slurry with CO 2 Performing carbonization reaction on the gas, and filtering to obtain carbonized liquid, wherein the solvent of the lithium carbonate slurry is water;
b. adding at least one of polyacrylic acid and salts thereof into the carbonized liquid, heating at 40-60 ℃ for reaction for 1-2 h, heating to 85-95 ℃ for reaction for 1-2 h, carrying out solid-liquid separation to obtain solid, and drying the solid to obtain the long rod-shaped lithium carbonate.
In one embodiment, the concentration of the lithium carbonate slurry in step a is Li 2 O is 30-50 g/L; the time of the carbonization reaction in the step a is preferably 180-240 min.
In a specific embodiment, the polyacrylate of step b is at least one of sodium salt or potassium salt;
preferably, the average molecular weight of the polyacrylic acid and the salt thereof in the step b is 3000-5000, and more preferably the average molecular weight of the polyacrylate is 5000;
li in the carbonized liquid 2 The addition amount of the polyacrylic acid and the salt thereof in the step b is preferably 0.3 to 1.0wt.% M;
and b, stirring the reaction in the step, wherein the linear speed of stirring is controlled to be 0.5-2 m/s.
The beneficial effects are that:
1. the lithium carbonate product of the invention is in a rod shape, and the tap density of the product is low.
2. The surface of the crystal is observed by a microscope, a plurality of tiny cracks are formed on the rod-shaped particles, the crystal defects reduce the difficulty of later crystal crushing and are easy to crush, and the 1-min crushing effect of the product is equal to the 2-min crushing effect of the product without polyacrylic acid and salt thereof.
3. The purity of the lithium carbonate is more than or equal to 99.5 percent, and the purity is high.
Drawings
FIG. 1 is a microscopic view of the product of example 1.
Fig. 2 is a microscopic view of the product of example 2.
Fig. 3 is a microscopic view of the product of comparative example 1.
FIG. 4 is a microscopic image of the product of comparative example 2.
FIG. 5 is a microscopic image of the product of comparative example 3.
Detailed Description
In order to achieve the first object of the invention, the morphology of the long rod-shaped lithium carbonate is rod-shaped, D10 is less than or equal to 18 μm and less than or equal to 20 μm, D50 is less than or equal to 39 μm and less than or equal to 46 μm, D90 is less than or equal to 83 μm and less than or equal to 96 μm, and the purity of the lithium carbonate is more than or equal to 99.5%.
In one embodiment, the long rod-shaped lithium carbonate has cracks on the surface and is easy to crush. The term "easily pulverized" means that the lithium carbonate is easily pulverized into a powder having a small particle diameter under the same pulverizing conditions as those of conventional lithium carbonate.
In one embodiment, the method for preparing the long rod-shaped lithium carbonate comprises the following steps:
a. mixing lithium carbonate slurry with CO 2 Performing carbonization reaction on the gas, and filtering to obtain carbonized liquid, wherein the solvent of the lithium carbonate slurry is water;
b. adding at least one of polyacrylic acid and salts thereof into the carbonized liquid, heating at 40-60 ℃ for reaction for 1-2 h, heating to 85-95 ℃ for reaction for 1-2 h, carrying out solid-liquid separation to obtain solid, and drying the solid to obtain the long rod-shaped lithium carbonate.
In one embodiment, the concentration of the lithium carbonate slurry in step a is Li 2 O is 30-50 g/L.
In one embodiment, the carbonization reaction time in the step a is 180 to 240min.
In a specific embodiment, the polyacrylate in step b is at least one of sodium salt or potassium salt.
In a specific embodiment, the polyacrylic acid and its salts in step b have an average molecular weight of 3000-5000, preferably the polyacrylate has an average molecular weight of 5000.
In one embodiment, lithium in the carbonized liquid is in the form of Li 2 The addition amount of the polyacrylic acid and the salt thereof in the step b is 0.3 to 1.0 weight percent of M.
In a specific embodiment, the reaction in step b is performed while stirring, and the linear speed of stirring is controlled to be 0.5-2 m/s.
The second object of the invention is to provide a method for preparing the long rod-shaped lithium carbonate.
To solve the second object of the present invention, the method for preparing long rod-shaped lithium carbonate comprises:
a. mixing lithium carbonate slurry with CO 2 Performing carbonization reaction on the gas, and filtering to obtain carbonized liquid, wherein the solvent of the lithium carbonate slurry is water;
b. adding at least one of polyacrylic acid and salts thereof into the carbonized liquid, heating at 40-60 ℃ for reaction for 1-2 h, heating to 85-95 ℃ for reaction for 1-2 h, carrying out solid-liquid separation to obtain solid, and drying the solid to obtain the long rod-shaped lithium carbonate.
In one embodiment, the concentration of the lithium carbonate slurry in step a is Li 2 O is 30-50 g/L; the time of the carbonization reaction in the step a is preferably 180-240 min.
In a specific embodiment, the polyacrylate of step b is at least one of sodium salt or potassium salt;
preferably, the average molecular weight of the polyacrylic acid and the salt thereof in the step b is 3000-5000, and more preferably the average molecular weight of the polyacrylate is 5000;
li in the carbonized liquid 2 The addition amount of the polyacrylic acid and the salt thereof in the step b is preferably 0.3 to 1.0wt.% M;
and b, stirring the reaction in the step, wherein the linear speed of stirring is controlled to be 0.5-2 m/s.
The following describes the invention in more detail with reference to examples, which are not intended to limit the invention thereto.
Example 1
Mixing the coarse lithium carbonate product with water to obtain Li 2 The O concentration of the lithium carbonate slurry is 50g/L. Placing the slurry into a reaction kettle, and introducing CO into the reaction kettle 2 And (3) carrying out carbonization reaction for 240min. Filtering the carbonized liquid, taking 10L of carbonized liquid after quantitative filtration. To the carbonized liquid was added 2.5g of sodium polyacrylate. The carbonized liquid is heated and reacted for 1h at 40 ℃, then heated to 95 ℃ and reacted for 1h, and the stirring linear velocity is 0.8m/s. Separating the hot solid from the hot liquid, and drying the solid. The main content of lithium carbonate in the product is 99.5%, and the tap density before crushing is 0.6g/cm 3 . The product morphology is more regular as shown in figure 1. 100g of the product was taken and put into an ore pulverizer to pulverize at a rotation speed of 15000rpm, and the particle size at each stage was as shown in Table 1 below.
Table 1 particle size of example 1
| D10 | D50 | D90 | |
| Before crushing | 18.94 | 39.26 | 83.05 |
| Pulverizing for 1min | 2.70 | 5.61 | 11.03 |
Example 2
Mixing the coarse lithium carbonate product with water to obtain Li 2 The O concentration of the lithium carbonate slurry is 30 g/L. Placing the slurry into a reaction kettle, and introducing CO into the reaction kettle 2 And (3) carrying out carbonization reaction for 180min. Filtering the carbonized liquid, taking 10L of carbonized liquid after quantitative filtration. To the carbonized liquid was added 3.0g of polyacrylic acid. The carbonized liquid is heated and reacted for 1h at 50 ℃, then heated to 95 ℃ and reacted for 1h, and the stirring linear velocity is 1.5m/s. Separating the hot solid from the hot liquid, and drying the solid. The main content of lithium carbonate in the product is 99.8%, and the tap density before crushing is 0.62g/cm 3 . The product morphology is more regular as shown in fig. 2. 100g of the product was taken and put into an ore pulverizer to pulverize at a rotation speed of 15000rpm, and the particle size at each stage was as shown in Table 2 below.
TABLE 2 particle size of example 2
| D10 | D50 | D90 | |
| Before crushing | 18.88 | 40.78 | 91.06 |
| Pulverizing for 1min | 2.65 | 5.60 | 11.19 |
Example 3
Mixing the coarse lithium carbonate product with water to obtain Li 2 The O concentration of the lithium carbonate slurry is 45 g/L. Placing the slurry into a reaction kettle, and introducing CO into the reaction kettle 2 And (3) carrying out carbonization reaction for 200min. Filtering the carbonized liquid, taking 10L of carbonized liquid after quantitative filtration. To the carbonized liquid was added 3.5g of polyacrylic acid. The carbonized liquid is heated at 60 ℃ to react for 1h, then heated to 95 ℃ to react for 1h, and the stirring linear velocity is 2.0m/s. Separating the hot solid from the hot liquid, and drying the solid. The main content of lithium carbonate in the product is 99.6%, and the tap density before crushing is 0.58g/cm 3 . 100g of the product was taken and put into an ore pulverizer for pulverization at a rotation speed of 15000rpm, and the particle sizes at each stage are shown in the following table. 100g of the product was taken and put into an ore pulverizer to pulverize at a rotation speed of 15000rpm, and the particle size at each stage was as shown in Table 3 below.
TABLE 3 particle size of example 3
| D10 | D50 | D90 | |
| Before crushing | 19.62 | 45.04 | 88.96 |
| Pulverizing for 1min | 2.61 | 5.49 | 11.02 |
Example 4
Mixing the coarse lithium carbonate product with water to obtain Li 2 The concentration of O is 35 g/L. Placing the slurry into a reaction kettle, and introducing CO into the reaction kettle 2 And (3) carrying out carbonization reaction for 220min. Filtering the carbonized liquid, taking 10L of carbonized liquid after quantitative filtration. To the carbonized liquid, 1.1g of sodium polyacrylate was added. The carbonized liquid is heated and reacted for 1h at 56 ℃, then heated to 95 ℃ and reacted for 1h, and the stirring linear velocity is 0.5m/s. Separating the hot solid from the hot liquid, and drying the solid. The main content of lithium carbonate in the product is 99.7%, and the tap density before crushing is 0.61g/cm 3 . 100g of the product was taken and crushed in an ore crusher at a rotation speed of 15000rpm, and the particle size at each stage was as shown in Table 4 below.
TABLE 4 particle size of example 4
| D10 | D50 | D90 | |
| Before crushing | 18.35 | 41.50 | 95.61 |
| Pulverizing for 1min | 2.55 | 5.43 | 11.19 |
Comparative example 1
Mixing the coarse lithium carbonate product with water to obtain Li 2 The O concentration of the lithium carbonate slurry is 50g/L. Placing the slurry into a reaction kettle, and introducing CO into the reaction kettle 2 And (3) carrying out carbonization reaction for 240min. Filtering the carbonized liquid, taking 10L of carbonized liquid after quantitative filtration. The carbonized liquid is heated and reacted for 1h at 40 ℃, then heated to 95 ℃ and reacted for 1h, and the stirring linear velocity is 0.8m/s. Separating the hot solid from the hot liquid, and drying the solid. The main content of lithium carbonate in the product is 99.6%, and the tap density before crushing is 0.82g/cm 3 . As shown in fig. 3, the crystals were dense and the morphology was irregular. 100g of the product was taken and crushed in an ore crusher at a rotation speed of 15000rpm, and the particle size at each stage was as shown in Table 5 below.
Table 5 particle size of comparative example 1
| D10 | D50 | D90 | |
| Before crushing | 9.52 | 27.91 | 68.10 |
| Pulverizing for 1min | 4.18 | 18.91 | 37.63 |
| Pulverizing for 2min | 3.52 | 6.82 | 14.25 |
Comparative example 2
Mixing the coarse lithium carbonate product with water to obtain Li 2 The O concentration of the lithium carbonate slurry is 50g/L. Placing the slurry into a reaction kettle, and introducing CO into the reaction kettle 2 And (3) carrying out carbonization reaction for 240min. Filtering the carbonized liquid, taking 10L of carbonized liquid after quantitative filtration. 10.0g of sodium polyacrylate was added to the carbonized liquid. The carbonized liquid is heated and reacted for 1h at 40 ℃, then heated to 95 ℃ and reacted for 1h, and the stirring linear velocity is 0.8m/s. Separating the hot solid from the hot liquid, and drying the solid. The main content of lithium carbonate in the product is 98.7%, and the tap density before crushing is 0.62g/cm 3 . As shown in fig. 4. 100g of the product was taken and crushed in an ore crusher at a rotation speed of 15000rpm, and the particle size at each stage was as shown in Table 6 below.
Table 6 particle size of comparative example 2
| D10 | D50 | D90 | |
| Before crushing | 18.82 | 42.50 | 99.01 |
| Pulverizing for 1min | 2.71 | 5.63 | 10.96 |
Comparative example 3
Mixing the coarse lithium carbonate product with water to obtain Li 2 The O concentration of the lithium carbonate slurry is 50g/L. Placing the slurry into a reaction kettle, and introducing CO into the reaction kettle 2 And (3) carrying out carbonization reaction for 240min. Filtering the carbonized liquid, taking 10L of carbonized liquid after quantitative filtration. To the carbonized liquid was added 0.5g of sodium polyacrylate. The carbonized liquid is heated and reacted for 1h at 40 ℃, then heated to 95 ℃ and reacted for 1h, and the stirring linear velocity is 0.8m/s. Separating the hot solid from the hot liquid, and drying the solid. The main content of lithium carbonate in the product is 99.5%, and the tap density before crushing is 0.73g/cm 3 . As shown in fig. 5, the product has poor morphology regularity. 100g of the product was taken and crushed in an ore crusher at a rotation speed of 15000rpm, and the particle size at each stage was as shown in Table 7 below.
TABLE 7 particle size of comparative example 3
| D10 | D50 | D90 | |
| Before crushing | 10.47 | 30.70 | 74.91 |
| Pulverizing for 1min | 4.03 | 20.18 | 36.52 |
Claims (8)
1. The long rod-shaped lithium carbonate is characterized in that the shape of the long rod-shaped lithium carbonate is rod-shaped, D10 is more than or equal to 18 mu m and less than or equal to 20 mu m, D50 is more than or equal to 39 mu m and less than or equal to 46 mu m, D90 is more than or equal to 83 mu m and less than or equal to 96 mu m, and the purity of the lithium carbonate is more than or equal to 99.5%;
the surface of the long rod-shaped lithium carbonate is cracked and is easy to crush;
the preparation method of the long rod-shaped lithium carbonate comprises the following steps:
a. mixing lithium carbonate slurry with CO 2 The gas is subjected to carbonization reaction, carbonization liquid is obtained by filtering after the carbonization reaction, the solvent of the lithium carbonate slurry is water, and the concentration of the lithium carbonate slurry in the step a is Li 2 O is 30-50 g/L;
b. adding at least one of polyacrylic acid and salt thereof into carbonized liquid, heating and reacting for 1-2 h at 40-60 ℃, then heating to 85-95 ℃ and reacting for 1-2 h, carrying out solid-liquid separation to obtain solid, drying the solid to obtain long rod-shaped lithium carbonate, b, wherein the polyacrylate is at least one of sodium salt or potassium salt, the polyacrylic acid and salt thereof have average molecular weight of 3000-5000, and lithium in the carbonized liquid is Li 2 The addition amount of the polyacrylic acid and the salt thereof in the step b is 0.3 to 1.0 weight percent of M.
2. The long rod-shaped lithium carbonate according to claim 1, wherein the carbonization reaction in the step a takes 180 to 240 minutes.
3. The lithium carbonate in long rod form according to claim 1, wherein the polyacrylate of step b has an average molecular weight of 5000.
4. The long rod-shaped lithium carbonate according to claim 1, wherein the reaction in the step b is performed while stirring, and the linear speed of the stirring is controlled to be 0.5-2 m/s.
5. The method for producing long-rod-shaped lithium carbonate according to any one of claims 1 to 4, comprising:
a. mixing lithium carbonate slurry with CO 2 The gas is subjected to carbonization reaction, carbonization liquid is obtained by filtering after the carbonization reaction, the solvent of the lithium carbonate slurry is water, and the concentration of the lithium carbonate slurry in the step a is Li 2 O is 30-50 g/L;
b. adding at least one of polyacrylic acid and salt thereof into carbonized liquid, heating and reacting for 1-2 h at 40-60 ℃, then heating to 85-95 ℃ and reacting for 1-2 h, carrying out solid-liquid separation to obtain solid, drying the solid to obtain long rod-shaped lithium carbonate, b, wherein the polyacrylate is at least one of sodium salt or potassium salt, the polyacrylic acid and salt thereof have average molecular weight of 3000-5000, and lithium in the carbonized liquid is Li 2 The addition amount of the polyacrylic acid and the salt thereof in the step b is 0.3 to 1.0 weight percent of M.
6. The method for producing long rod-shaped lithium carbonate according to claim 5, wherein the carbonization reaction in the step a is performed for 180 to 240 minutes.
7. The method for producing long rod-shaped lithium carbonate according to claim 5, wherein the reaction in step b is performed while stirring, and the linear velocity of stirring is controlled to be 0.5 to 2m/s.
8. The method for producing long rod-shaped lithium carbonate according to claim 5, wherein the polyacrylate has an average molecular weight of 5000.
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