CN113772697B - Nanometer lithium carbonate and preparation method thereof - Google Patents
Nanometer lithium carbonate and preparation method thereof Download PDFInfo
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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 151
- 229910052808 lithium carbonate Inorganic materials 0.000 title claims abstract description 151
- 238000002360 preparation method Methods 0.000 title claims abstract description 23
- IAZDPXIOMUYVGZ-UHFFFAOYSA-N Dimethylsulphoxide Chemical compound CS(C)=O IAZDPXIOMUYVGZ-UHFFFAOYSA-N 0.000 claims abstract description 66
- 238000006243 chemical reaction Methods 0.000 claims abstract description 61
- PEDCQBHIVMGVHV-UHFFFAOYSA-N Glycerine Chemical compound OCC(O)CO PEDCQBHIVMGVHV-UHFFFAOYSA-N 0.000 claims abstract description 30
- 238000001035 drying Methods 0.000 claims abstract description 30
- BVKZGUZCCUSVTD-UHFFFAOYSA-L Carbonate Chemical compound [O-]C([O-])=O BVKZGUZCCUSVTD-UHFFFAOYSA-L 0.000 claims abstract description 24
- LYCAIKOWRPUZTN-UHFFFAOYSA-N Ethylene glycol Chemical compound OCCO LYCAIKOWRPUZTN-UHFFFAOYSA-N 0.000 claims abstract description 24
- 229910003002 lithium salt Inorganic materials 0.000 claims abstract description 23
- 159000000002 lithium salts Chemical class 0.000 claims abstract description 23
- 238000005406 washing Methods 0.000 claims abstract description 20
- 239000003960 organic solvent Substances 0.000 claims abstract description 18
- 239000002244 precipitate Substances 0.000 claims abstract description 17
- CCAFPWNGIUBUSD-UHFFFAOYSA-N diethyl sulfoxide Chemical compound CCS(=O)CC CCAFPWNGIUBUSD-UHFFFAOYSA-N 0.000 claims abstract description 10
- HTMQZWFSTJVJEQ-UHFFFAOYSA-N benzylsulfinylmethylbenzene Chemical compound C=1C=CC=CC=1CS(=O)CC1=CC=CC=C1 HTMQZWFSTJVJEQ-UHFFFAOYSA-N 0.000 claims abstract description 8
- CDBYLPFSWZWCQE-UHFFFAOYSA-L Sodium Carbonate Chemical compound [Na+].[Na+].[O-]C([O-])=O CDBYLPFSWZWCQE-UHFFFAOYSA-L 0.000 claims description 74
- WMFOQBRAJBCJND-UHFFFAOYSA-M Lithium hydroxide Chemical compound [Li+].[OH-] WMFOQBRAJBCJND-UHFFFAOYSA-M 0.000 claims description 42
- INHCSSUBVCNVSK-UHFFFAOYSA-L lithium sulfate Inorganic materials [Li+].[Li+].[O-]S([O-])(=O)=O INHCSSUBVCNVSK-UHFFFAOYSA-L 0.000 claims description 37
- 229910000029 sodium carbonate Inorganic materials 0.000 claims description 37
- 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 claims description 37
- KWGKDLIKAYFUFQ-UHFFFAOYSA-M lithium chloride Chemical compound [Li+].[Cl-] KWGKDLIKAYFUFQ-UHFFFAOYSA-M 0.000 claims description 28
- BWHMMNNQKKPAPP-UHFFFAOYSA-L potassium carbonate Chemical compound [K+].[K+].[O-]C([O-])=O BWHMMNNQKKPAPP-UHFFFAOYSA-L 0.000 claims description 26
- 238000000034 method Methods 0.000 claims description 19
- UIIMBOGNXHQVGW-UHFFFAOYSA-M Sodium bicarbonate Chemical compound [Na+].OC([O-])=O UIIMBOGNXHQVGW-UHFFFAOYSA-M 0.000 claims description 16
- 229910000027 potassium carbonate Inorganic materials 0.000 claims description 13
- 229910000030 sodium bicarbonate Inorganic materials 0.000 claims description 8
- 235000017557 sodium bicarbonate Nutrition 0.000 claims description 8
- 239000012046 mixed solvent Substances 0.000 claims 2
- IXKVYKPPJAWZLH-UHFFFAOYSA-N 7-thiabicyclo[4.1.0]hepta-2,4-diene Chemical compound C1=CC=CC2SC21 IXKVYKPPJAWZLH-UHFFFAOYSA-N 0.000 claims 1
- BTVWZWFKMIUSGS-UHFFFAOYSA-N dimethylethyleneglycol Natural products CC(C)(O)CO BTVWZWFKMIUSGS-UHFFFAOYSA-N 0.000 claims 1
- 239000002245 particle Substances 0.000 abstract description 23
- DNIAPMSPPWPWGF-UHFFFAOYSA-N Propylene glycol Chemical compound CC(O)CO DNIAPMSPPWPWGF-UHFFFAOYSA-N 0.000 abstract description 6
- GTTSNKDQDACYLV-UHFFFAOYSA-N Trihydroxybutane Chemical compound CCCC(O)(O)O GTTSNKDQDACYLV-UHFFFAOYSA-N 0.000 abstract description 2
- 238000011084 recovery Methods 0.000 description 29
- LFQSCWFLJHTTHZ-UHFFFAOYSA-N Ethanol Chemical compound CCO LFQSCWFLJHTTHZ-UHFFFAOYSA-N 0.000 description 24
- 239000000243 solution Substances 0.000 description 22
- 238000005119 centrifugation Methods 0.000 description 20
- 239000003795 chemical substances by application Substances 0.000 description 20
- 239000013078 crystal Substances 0.000 description 12
- 239000000203 mixture Substances 0.000 description 12
- 230000000052 comparative effect Effects 0.000 description 11
- 239000000047 product Substances 0.000 description 11
- 239000002904 solvent Substances 0.000 description 11
- XLYOFNOQVPJJNP-UHFFFAOYSA-N water Substances O XLYOFNOQVPJJNP-UHFFFAOYSA-N 0.000 description 11
- 239000008367 deionised water Substances 0.000 description 10
- 229910021641 deionized water Inorganic materials 0.000 description 10
- 238000003756 stirring Methods 0.000 description 10
- 239000006228 supernatant Substances 0.000 description 9
- 238000002441 X-ray diffraction Methods 0.000 description 8
- 238000000746 purification Methods 0.000 description 8
- WHXSMMKQMYFTQS-UHFFFAOYSA-N Lithium Chemical compound [Li] WHXSMMKQMYFTQS-UHFFFAOYSA-N 0.000 description 7
- 238000002425 crystallisation Methods 0.000 description 7
- 230000008025 crystallization Effects 0.000 description 7
- 229910052744 lithium Inorganic materials 0.000 description 7
- 239000007864 aqueous solution Substances 0.000 description 6
- UIIMBOGNXHQVGW-DEQYMQKBSA-M Sodium bicarbonate-14C Chemical compound [Na+].O[14C]([O-])=O UIIMBOGNXHQVGW-DEQYMQKBSA-M 0.000 description 5
- 230000000694 effects Effects 0.000 description 5
- 239000011259 mixed solution Substances 0.000 description 5
- HBBGRARXTFLTSG-UHFFFAOYSA-N Lithium ion Chemical compound [Li+] HBBGRARXTFLTSG-UHFFFAOYSA-N 0.000 description 4
- 239000003153 chemical reaction reagent Substances 0.000 description 4
- 238000010828 elution Methods 0.000 description 4
- 229910001416 lithium ion Inorganic materials 0.000 description 4
- OKKJLVBELUTLKV-UHFFFAOYSA-N Methanol Chemical compound OC OKKJLVBELUTLKV-UHFFFAOYSA-N 0.000 description 3
- HEMHJVSKTPXQMS-UHFFFAOYSA-M Sodium hydroxide Chemical compound [OH-].[Na+] HEMHJVSKTPXQMS-UHFFFAOYSA-M 0.000 description 3
- 230000006378 damage Effects 0.000 description 3
- 239000000945 filler Substances 0.000 description 3
- GELKBWJHTRAYNV-UHFFFAOYSA-K lithium iron phosphate Chemical compound [Li+].[Fe+2].[O-]P([O-])([O-])=O GELKBWJHTRAYNV-UHFFFAOYSA-K 0.000 description 3
- 239000000463 material Substances 0.000 description 3
- 239000002105 nanoparticle Substances 0.000 description 3
- 238000001556 precipitation Methods 0.000 description 3
- 239000002994 raw material Substances 0.000 description 3
- 238000004064 recycling Methods 0.000 description 3
- 238000000926 separation method Methods 0.000 description 3
- 238000012876 topography Methods 0.000 description 3
- CSCPPACGZOOCGX-UHFFFAOYSA-N Acetone Chemical compound CC(C)=O CSCPPACGZOOCGX-UHFFFAOYSA-N 0.000 description 2
- CURLTUGMZLYLDI-UHFFFAOYSA-N Carbon dioxide Chemical compound O=C=O CURLTUGMZLYLDI-UHFFFAOYSA-N 0.000 description 2
- LRHPLDYGYMQRHN-UHFFFAOYSA-N N-Butanol Chemical compound CCCCO LRHPLDYGYMQRHN-UHFFFAOYSA-N 0.000 description 2
- PMZURENOXWZQFD-UHFFFAOYSA-L Sodium Sulfate Chemical compound [Na+].[Na+].[O-]S([O-])(=O)=O PMZURENOXWZQFD-UHFFFAOYSA-L 0.000 description 2
- 238000009835 boiling Methods 0.000 description 2
- 239000003054 catalyst Substances 0.000 description 2
- 239000008139 complexing agent Substances 0.000 description 2
- 238000011161 development Methods 0.000 description 2
- 239000003792 electrolyte Substances 0.000 description 2
- 239000003480 eluent Substances 0.000 description 2
- 238000001914 filtration Methods 0.000 description 2
- 125000000524 functional group Chemical group 0.000 description 2
- WGCNASOHLSPBMP-UHFFFAOYSA-N hydroxyacetaldehyde Natural products OCC=O WGCNASOHLSPBMP-UHFFFAOYSA-N 0.000 description 2
- 239000012535 impurity Substances 0.000 description 2
- AMXOYNBUYSYVKV-UHFFFAOYSA-M lithium bromide Chemical compound [Li+].[Br-] AMXOYNBUYSYVKV-UHFFFAOYSA-M 0.000 description 2
- HQRPHMAXFVUBJX-UHFFFAOYSA-M lithium;hydrogen carbonate Chemical compound [Li+].OC([O-])=O HQRPHMAXFVUBJX-UHFFFAOYSA-M 0.000 description 2
- 238000004519 manufacturing process Methods 0.000 description 2
- 238000002156 mixing Methods 0.000 description 2
- 229920006395 saturated elastomer Polymers 0.000 description 2
- 229910052938 sodium sulfate Inorganic materials 0.000 description 2
- 235000011152 sodium sulphate Nutrition 0.000 description 2
- 238000001228 spectrum Methods 0.000 description 2
- 150000003462 sulfoxides Chemical class 0.000 description 2
- YLZOPXRUQYQQID-UHFFFAOYSA-N 3-(2,4,6,7-tetrahydrotriazolo[4,5-c]pyridin-5-yl)-1-[4-[2-[[3-(trifluoromethoxy)phenyl]methylamino]pyrimidin-5-yl]piperazin-1-yl]propan-1-one Chemical compound N1N=NC=2CN(CCC=21)CCC(=O)N1CCN(CC1)C=1C=NC(=NC=1)NCC1=CC(=CC=C1)OC(F)(F)F YLZOPXRUQYQQID-UHFFFAOYSA-N 0.000 description 1
- OKTJSMMVPCPJKN-UHFFFAOYSA-N Carbon Chemical compound [C] OKTJSMMVPCPJKN-UHFFFAOYSA-N 0.000 description 1
- 239000005955 Ferric phosphate Substances 0.000 description 1
- 206010026749 Mania Diseases 0.000 description 1
- XSTXAVWGXDQKEL-UHFFFAOYSA-N Trichloroethylene Chemical compound ClC=C(Cl)Cl XSTXAVWGXDQKEL-UHFFFAOYSA-N 0.000 description 1
- -1 and as a result Chemical compound 0.000 description 1
- 239000010405 anode material Substances 0.000 description 1
- 238000000498 ball milling Methods 0.000 description 1
- 230000009286 beneficial effect 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
- 239000000919 ceramic Substances 0.000 description 1
- 229910010293 ceramic material Inorganic materials 0.000 description 1
- 238000007796 conventional method Methods 0.000 description 1
- 230000007547 defect Effects 0.000 description 1
- 210000003298 dental enamel Anatomy 0.000 description 1
- 238000009792 diffusion process Methods 0.000 description 1
- 238000009826 distribution Methods 0.000 description 1
- 239000007772 electrode material Substances 0.000 description 1
- 238000005516 engineering process Methods 0.000 description 1
- 230000007613 environmental effect Effects 0.000 description 1
- 238000003912 environmental pollution Methods 0.000 description 1
- 238000002474 experimental method Methods 0.000 description 1
- 229940032958 ferric phosphate Drugs 0.000 description 1
- 239000011521 glass Substances 0.000 description 1
- WBJZTOZJJYAKHQ-UHFFFAOYSA-K iron(3+) phosphate Chemical compound [Fe+3].[O-]P([O-])([O-])=O WBJZTOZJJYAKHQ-UHFFFAOYSA-K 0.000 description 1
- 229910000399 iron(III) phosphate Inorganic materials 0.000 description 1
- 150000002576 ketones Chemical class 0.000 description 1
- NMHMDUCCVHOJQI-UHFFFAOYSA-N lithium molybdate Chemical compound [Li+].[Li+].[O-][Mo]([O-])(=O)=O NMHMDUCCVHOJQI-UHFFFAOYSA-N 0.000 description 1
- FUJCRWPEOMXPAD-UHFFFAOYSA-N lithium oxide Chemical compound [Li+].[Li+].[O-2] FUJCRWPEOMXPAD-UHFFFAOYSA-N 0.000 description 1
- 229910001947 lithium oxide Inorganic materials 0.000 description 1
- 239000000696 magnetic material Substances 0.000 description 1
- 238000013508 migration Methods 0.000 description 1
- 230000005012 migration Effects 0.000 description 1
- 238000010899 nucleation Methods 0.000 description 1
- 230000006911 nucleation Effects 0.000 description 1
- 230000003287 optical effect Effects 0.000 description 1
- 239000003495 polar organic solvent Substances 0.000 description 1
- 229910052573 porcelain Inorganic materials 0.000 description 1
- 239000000843 powder Substances 0.000 description 1
- 230000002035 prolonged effect Effects 0.000 description 1
- BDERNNFJNOPAEC-UHFFFAOYSA-N propan-1-ol Chemical compound CCCO BDERNNFJNOPAEC-UHFFFAOYSA-N 0.000 description 1
- 208000020016 psychiatric disease Diseases 0.000 description 1
- 238000010900 secondary nucleation Methods 0.000 description 1
- 238000005245 sintering Methods 0.000 description 1
- 239000002002 slurry Substances 0.000 description 1
- 239000007790 solid phase Substances 0.000 description 1
- 125000000475 sulfinyl group Chemical group [*:2]S([*:1])=O 0.000 description 1
- 238000012360 testing method Methods 0.000 description 1
- 238000005979 thermal decomposition reaction Methods 0.000 description 1
- 238000001291 vacuum drying Methods 0.000 description 1
- 239000010926 waste battery Substances 0.000 description 1
- 239000002699 waste material Substances 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
-
- B—PERFORMING OPERATIONS; TRANSPORTING
- B82—NANOTECHNOLOGY
- B82Y—SPECIFIC USES OR APPLICATIONS OF NANOSTRUCTURES; MEASUREMENT OR ANALYSIS OF NANOSTRUCTURES; MANUFACTURE OR TREATMENT OF NANOSTRUCTURES
- B82Y40/00—Manufacture or treatment of nanostructures
-
- 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
- C01P2004/62—Submicrometer sized, i.e. from 0.1-1 micrometer
-
- C—CHEMISTRY; METALLURGY
- C01—INORGANIC CHEMISTRY
- C01P—INDEXING SCHEME RELATING TO STRUCTURAL AND PHYSICAL ASPECTS OF SOLID INORGANIC COMPOUNDS
- C01P2004/00—Particle morphology
- C01P2004/60—Particles characterised by their size
- C01P2004/64—Nanometer sized, i.e. from 1-100 nanometer
-
- 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
- C01P2006/12—Surface area
-
- 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 discloses a nano carbonic acidThe preparation method of the nano lithium carbonate comprises the specific steps of introducing a high-polarity organic solvent into a reaction system of carbonate and lithium salt, reacting and crystallizing to obtain precipitate, washing, centrifuging and drying the precipitate to obtain the nano lithium carbonate, wherein the high-polarity organic solvent comprises at least one of ethylene glycol, propylene glycol, glycerol, butanetriol, dimethyl sulfoxide, diethyl sulfoxide and benzyl sulfoxide; the nanometer lithium carbonate has particle diameter of 50-500 nm and BET specific surface area of 13-30 m 2 /g。
Description
Technical Field
The invention belongs to the technical field of preparation of lithium carbonate, and particularly relates to nano lithium carbonate and a preparation method thereof.
Background
The industrial use of lithium carbonate is extremely wide, and is often used as a raw material for other lithium salts such as lithium chloride, lithium bromide, lithium molybdate, lithium hydroxide, lithium oxide, and the like; the ceramic material also has wide application in industries such as enamel, special glass, ceramic, porcelain glaze, electronic components, atomic energy industry and the like, and is a necessity for preparing optical materials, magnetic materials, electronic information materials and various fine lithium salts; in addition, lithium carbonate plays an important role in the treatment of mental diseases such as mania.
With the development of the age, 5G and new energy automobiles are popularized, the consumption of secondary batteries is increased day by day, and the consumption of lithium carbonate in the battery industry is greatly increased, so that the lithium carbonate can be used as a raw material for preparing electrode materials of lithium iron phosphate batteries and other lithium battery electrodes, and even the lithium carbonate is not involved in the preparation process of electrolyte, the film forming performance of the batteries can be improved by adding the lithium carbonate in the electrolyte, and the cycle performance and the low-temperature discharge performance of the batteries are improved. The most mature preparation process of the lithium iron phosphate as the battery anode material adopts a solid-phase sintering mode of ferric phosphate, lithium carbonate and an organic carbon source; and whether lithium carbonate, which is one of the raw materials, has low crystallinity and size uniformity, will affect the uniformity of the prepared lithium iron phosphate, the migration rate and diffusion rate of lithium ions, and thus the electrical properties.
The great consumption of lithium source directly brings a series of problems of lithium resource crisis, supply guarantee, environmental destruction and the like, and the development of efficient, green and low-cost waste battery recycling technology is an effective method for solving the serious problems. The traditional recovery process such as wet recovery process, dry recovery process, biological recovery process and the like cannot meet the requirement of recovering and extracting lithium, and secondary pollution and resource waste are often caused in the recovery process. Therefore, it is important to improve the conventional lithium resource recovery process, and to efficiently extract and recover the lithium resource, so that the lithium resource is converted into an industrial nano lithium carbonate source with low crystallinity and uniform size.
CN109942009a discloses a preparation method of battery grade lithium carbonate, which comprises crushing industrial lithium carbonate to 100 mesh, mixing with water to obtain lithium carbonate slurry, introducing into a filler tower, mixing with high purity CO 2 Countercurrent contact is carried out, then the mixture is uniformly mixed with sulfate radical complexing agent, and finally, lithium carbonate is obtained by thermal decomposition in a tower. The method for preparing the lithium carbonate starts from crushing industrial lithium carbonate, reacts in a filler tower to generate lithium bicarbonate, then decomposes the lithium bicarbonate to generate lithium carbonate, realizes a complex process flow for immediately recycling the lithium carbonate finished product in the tower, has high requirement on the filler tower, and the finally obtained lithium carbonate finished product is washed by sodium hydroxide solution with the pH value of 12-12.5 and deionized water for at least twice. The whole process is extremely complicated, the production cost is too high, and the purity of the lithium carbonate can be influenced by the added complexing agent.
CN102408119a discloses a method for preparing lithium carbonate ultrafine powder by adopting a solution reaction crystallization, which mainly comprises the steps of introducing one or more organic reagents of methanol, ethanol, propanol, butanol and acetone into a water-soluble lithium salt system as a reaction solution agent, and then adding a carbonate system or carbon dioxide, so as to crystallize and separate out lithium carbonate. The method is simple to operate, but the alcohol or ketone solvent such as ethanol has the characteristics of inflammability and volatility, and is extremely easy to bring about the problems of danger and environmental pollution. In addition, the secondary nucleation particle size of the lithium carbonate crystal prepared by using the organic solvent is still in the micron level, does not meet the actual requirement of the battery-level lithium carbonate particle size in the nanometer level, can meet the industrial application condition only by post-treatment such as ball milling, and is inconvenient for industrialization.
Therefore, how to further improve the recovery process of lithium carbonate to convert it into nano lithium carbonate with high purity, low crystallinity and uniform size remains a problem to be solved.
Disclosure of Invention
In order to solve the problems, the invention aims to provide nano lithium carbonate and a preparation method and application thereof.
In order to achieve the above purpose, the following technical scheme is provided:
a process for preparing nano lithium carbonate includes such steps as introducing high-polarity organic solvent to the reaction system of carbonate and lithium salt, reaction crystallizing to obtain deposit, washing, centrifugal separation and drying.
Further, the high-polarity organic solvent-out agent comprises at least one of dihydric alcohol containing a dihydroxyl functional group, trihydric alcohol containing a trihydric functional group and sulfoxide containing a sulfinyl functional group.
Further, the dihydric alcohol comprises at least one of ethylene glycol and propylene glycol; the triol comprises at least one of glycerol and butanetriol; the sulfoxide includes at least one of dimethyl sulfoxide, diethyl sulfoxide and benzyl sulfoxide.
Further, the concentration of the carbonate is 0.02-0.4 mol/L, and the concentration of the lithium salt is 0.02-0.4 mol/L.
Further, the carbonate comprises at least one of sodium carbonate, potassium carbonate and sodium bicarbonate; the lithium salt comprises at least one of lithium sulfate, lithium chloride and lithium hydroxide.
Further, the volume ratio of the high-polarity organic solvent to the reaction system of the carbonate and the lithium salt is (0.1-5): 1.
Further, the drying temperature is 20-40 ℃, the vacuum drying is carried out, the drying time is prolonged due to low temperature, the drying time is high, and the drying time is shortened.
The nano lithium carbonate prepared by the preparation method has the advantages of high purity, low crystallinity and uniform size.
Compared with the prior art, the invention has the beneficial effects that:
(1) According to the invention, the high-polarity organic solvent-out agent is introduced into a reaction system of carbonate and lithium salt, and as lithium carbonate is insoluble in the high-polarity organic solvent-out agent in the system, the solubility of lithium carbonate can be reduced by introducing the high-polarity organic solvent-out agent, and the supersaturation degree is increased, so that the nucleation rate of lithium carbonate crystals is increased, and the lithium carbonate crystals are rapidly separated out, so that nano lithium carbonate with high purity, low crystallinity and uniform size is obtained;
(2) The high-polarity organic solvent-out agent and the system aqueous solution have different proportions, and the different miscibility degrees of the high-polarity organic solvent-out agent and the system aqueous solution can lead to different precipitation speeds and crystallization qualities of lithium carbonate crystals, so that the crystallinity and the particle size are different; according to the invention, the supersaturation degree of lithium carbonate is increased by adjusting the ratio of the high-polarity organic solvent to the aqueous solution of the reaction system of carbonate and lithium salt, so that lithium carbonate precipitate with low crystallization degree and uniform size can be quickly nucleated and separated out;
(3) The particle size of the nano lithium carbonate provided by the invention is in the range of 50-500 nm; the specific surface area is large, and the BET specific surface area can reach 13-30 m 2 /g；
(4) The whole preparation process of the nano lithium carbonate provided by the invention has no scaling phenomenon, no damage to a reaction container, and the prepared lithium carbonate sample is easy to obtain and can be directly obtained through centrifugation or filtration separation; and the recovery yield is high, the process flow is simple, the reaction condition is mild (room temperature is 20 ℃), the implementation cost is low, and the industrial application is convenient.
Additional aspects and advantages of the invention will be set forth in part in the description which follows, and in part will be obvious from the description, or may be learned by practice of the invention.
Drawings
FIG. 1 is a Scanning Electron Microscope (SEM) topography of a lithium carbonate sample prepared in example 1 of the present invention;
FIG. 2 is an SEM topography of a lithium carbonate sample prepared according to example 2 of the present invention;
FIG. 3 is an SEM topography of a lithium carbonate sample prepared according to example 3 of the present invention;
FIG. 4 is an SEM morphology of a lithium carbonate sample prepared according to comparative example 2 using ethanol as a eluent;
fig. 5 is an X-ray diffraction pattern (XRD) of lithium carbonate samples prepared in examples 2 and 3 of the present invention and comparative example 2.
Detailed Description
The invention will be further described with reference to examples and figures of the accompanying drawings, to which the scope of protection of the invention is not limited.
The experimental methods in the following examples are conventional methods unless otherwise specified. The test materials used in the examples described below, unless otherwise specified, were purchased from conventional reagent stores.
Unless otherwise defined, technical or scientific terms used herein should be given the ordinary meaning as understood by one of ordinary skill in the art to which this invention belongs.
Example 1
The embodiment provides a preparation method of nano lithium carbonate, which comprises the following steps:
preparing a reaction system of sodium carbonate and lithium sulfate with the total volume of 100mL in a 250 mL reaction vessel, wherein the concentration of the sodium carbonate and the concentration of the lithium sulfate are both 0.1mol/L, and the pH value of the system is adjusted to 11;
adding 50 mL high-polarity organic solvent dimethyl sulfoxide into a reaction system of sodium carbonate and lithium sulfate at one time, stirring to uniformly mix the solution, rapidly transferring the solution into a centrifuge tube for centrifugal treatment (the rotation speed is 5000 r/min) after two minutes, pouring off supernatant obtained by centrifugation, collecting precipitate obtained by centrifugation, washing with a small amount of deionized water for three times, and finally drying in a vacuum oven at the drying temperature of 40 ℃ for the drying time of 24h to obtain the nano lithium carbonate.
Because sodium carbonate, lithium sulfate and lithium carbonate are insoluble in dimethyl sulfoxide and the solubility of the lithium carbonate is minimum, the lithium carbonate can be rapidly separated out after the dimethyl sulfoxide is introduced into a reaction system, and the dimethyl sulfoxide not only plays a role in dissolving out, but also plays a role in dispersing lithium carbonate crystals;
the experimental results show that: the specific surface area of the lithium carbonate prepared by the embodiment can reach 13m 2 And has a uniform particle size scale of about 500nm, as shown in FIG. 1. The method has the advantages of simple process flow, low implementation cost, mild reaction conditions and recovery yield of about 70.0 percent, and the purity of the product nano lithium carbonate after washing and purification can reach more than 99 percent.
Example 2
The embodiment provides a preparation method of nano lithium carbonate, which comprises the following steps:
preparing a reaction system of sodium carbonate and lithium sulfate with the total volume of 100mL in a 250 mL reaction vessel, wherein the concentration of the sodium carbonate and the concentration of the lithium sulfate are both 0.1mol/L, and the pH value of the system is adjusted to 11;
adding 100mL high-polarity organic solvent dimethyl sulfoxide into a reaction system of sodium carbonate and lithium sulfate at one time, stirring to uniformly mix the solution, rapidly transferring the solution into a centrifuge tube for centrifugal treatment (the rotation speed is 5000 r/min) after two minutes, pouring off supernatant obtained by centrifugation, collecting precipitate obtained by centrifugation, washing with a small amount of deionized water for three times, and finally drying in a vacuum oven at the drying temperature of 40 ℃ for the drying time of 24h to obtain the nano lithium carbonate.
Because sodium carbonate, lithium sulfate and lithium carbonate are insoluble in dimethyl sulfoxide and the solubility of the lithium carbonate is minimum, the lithium carbonate can be rapidly separated out after the dimethyl sulfoxide is introduced into a reaction system, and a solvent-out agent dimethyl sulfoxide not only plays a solvent-out role, but also plays a dispersing role on lithium carbonate crystals;
the experimental results show that: specific surface area of lithium carbonate prepared in this exampleCan reach 22.7m 2 The morphology of the composition is shown in FIG. 2, and the volume size of the lithium carbonate is not changed obviously after the addition amount of the dimethyl sulfoxide is increased in comparative example 1 and example 2, and the particle size is still kept uniform and is about 130 and nm. Meanwhile, the recovery yield is improved by about 93.2 percent, and the purity of the product can reach more than 99 percent after washing and purification.
In examples 1-2, the volume ratio of highly polar organic solvent and carbonate to lithium salt reaction system was 0.5:1 and 1:1.
The high-polarity organic solvent-out agent and the system aqueous solution have different proportions, and the different miscibility degrees of the high-polarity organic solvent-out agent and the system aqueous solution can lead to different precipitation speeds and crystallization qualities of lithium carbonate crystals, so that the crystallinity and the particle size are different; the supersaturation degree of lithium carbonate is increased by adjusting the ratio of the high-polarity organic solvent to the aqueous solution of the reaction system of carbonate and lithium salt, so that lithium carbonate precipitate with low crystallization degree and uniform size can be quickly nucleated and separated out.
Example 3
The embodiment provides a preparation method of nano lithium carbonate, which comprises the following steps:
preparing a reaction system of sodium carbonate and lithium sulfate with the total volume of 100mL in a 250 mL reaction vessel, wherein the concentration of the sodium carbonate and the concentration of the lithium sulfate are both 0.2mol/L, and the pH value of the system is adjusted to 11;
adding 100mL high-polarity organic solvent dimethyl sulfoxide into a reaction system of sodium carbonate and lithium sulfate at one time, stirring to uniformly mix the solution, rapidly transferring the solution into a centrifuge tube for centrifugal treatment (the rotation speed is 5000 r/min) after two minutes, pouring off supernatant obtained by centrifugation, collecting precipitate obtained by centrifugation, washing with a small amount of deionized water for three times, and finally drying in a vacuum oven at the drying temperature of 40 ℃ for the drying time of 24h to obtain the nano lithium carbonate.
Because sodium carbonate, lithium sulfate and lithium carbonate are insoluble in dimethyl sulfoxide and the solubility of the lithium carbonate is minimum, the lithium carbonate can be rapidly separated out after the dimethyl sulfoxide is introduced into a reaction system, and the dimethyl sulfoxide introduced into the system has a solvent-out effect and a dispersing effect;
experimental knotThe results show that: the specific surface area of the lithium carbonate prepared by the embodiment can reach 25 m 2 The morphology of the nano particles is shown in figure 3, in comparative example 2, the addition amount of dimethyl sulfoxide is kept unchanged, and after the concentration of sodium carbonate and lithium sulfate is increased, the particle size scale of the obtained nano particles of lithium carbonate is uniform and is about 100 nm; XRD spectrum shows that the nano crystallinity of lithium carbonate is basically kept unchanged (as shown in figure 5), and the recovery yield is further improved by 94.2%, and the purity of the product after washing and purification can reach more than 96%.
Example 4
The embodiment provides a preparation method of nano lithium carbonate, which comprises the following steps:
preparing a reaction system of sodium carbonate and lithium sulfate with the total volume of 100mL in a 250 mL reaction vessel, wherein the concentration of the sodium carbonate and the concentration of the lithium sulfate are both 0.4mol/L, and the pH value of the system is adjusted to 11;
adding 100mL of high-polarity organic solvent dimethyl sulfoxide into a reaction system of sodium carbonate and lithium sulfate at one time, stirring to uniformly mix the solution, rapidly transferring the solution into a centrifuge tube for centrifugal treatment (rotating speed is 5000 r/min) after two minutes, pouring off supernatant obtained by centrifugation, collecting precipitate obtained by centrifugation, washing with a small amount of deionized water for three times, and finally drying in a vacuum oven at a drying temperature of 40 ℃ for 24h to obtain the nano lithium carbonate.
Because sodium carbonate, lithium sulfate and lithium carbonate are insoluble in dimethyl sulfoxide and the solubility of the lithium carbonate is minimum, the lithium carbonate can be rapidly separated out after the dimethyl sulfoxide is introduced into a reaction system, and a solvent-out agent dimethyl sulfoxide not only plays a solvent-out role, but also plays a dispersing role on lithium carbonate crystals;
the experimental results show that: the morphology of the lithium carbonate prepared in the example still keeps smaller particle size, and the specific surface area of the lithium carbonate can reach 30 m after the concentration of the sodium carbonate and the lithium sulfate is increased in the comparative example 2 2 Per g, and the size is not changed obviously, the particle size is still kept uniform and is about 50nm, but the crystallinity of the lithium carbonate nano particles is greatly reduced, the recovery yield is greatly improved and is about 98.2%, and the product is washedThe purity after washing and purification can reach more than 95 percent.
In examples 2-4, the carbonate concentration was 0.1-0.4mol/L, i.e., 100-400 mM. The higher the concentration of carbonate, the higher the concentration of carbonate ions, and the higher the supersaturation degree of lithium carbonate after the addition of the solvent-out agent, so that the lithium carbonate is easier to crystallize and precipitate; thus, the concentration of carbonate affects the recovery yield, the greater the carbonate concentration, the higher the recovery yield. However, when the concentration of the carbonate exceeds 0.4mol/L, the addition of the elution reagent brings about impurities such as sodium sulfate, and the purity of the lithium carbonate produced is lowered. The embodiment of the invention adopts the carbonate with the concentration of 0.1-0.4mol/L, and is determined by comprehensively considering various factors such as recovery yield, purity and the like.
In examples 2 to 4, the concentration of the lithium salt was 0.1 to 0.4mol/L, i.e., 100 to 400. 400 mM. The higher the concentration of lithium salt, the higher the concentration of lithium ions, and the higher the supersaturation degree of lithium carbonate after the solvent is added, so that the lithium carbonate is easier to crystallize and precipitate; thus, the concentration of lithium salt affects the recovery yield, and the greater the concentration of lithium salt, the higher the recovery yield. However, if the concentration of the lithium salt exceeds 0.4mol/L, the addition of the elution reagent brings about impurities such as sodium sulfate, and the purity of the lithium carbonate obtained is lowered. The embodiment of the invention adopts the lithium salt with the concentration of 0.1-0.4mol/L, and is determined by comprehensively considering various factors such as recovery yield, purity and the like. After the concentration of sodium carbonate and lithium sulfate is improved, the recovery yield of lithium carbonate is effectively increased, and meanwhile, the simple process flow and mild reaction conditions are maintained, so that the method is convenient for direct industrialization.
Example 5
The embodiment provides a preparation method of nano lithium carbonate, which comprises the following steps:
preparing a reaction system of sodium carbonate, lithium chloride and lithium hydroxide with the total volume of 100mL in a 250 mL reaction vessel, wherein the concentration of sodium carbonate is 0.2mol/L, the lithium chloride, the lithium hydroxide and the like are added in an equal volume, the final concentration of lithium ions is 0.2mol/L, and the pH value of the system is adjusted to 11;
adding 100mL of high-polarity organic solvent dimethyl sulfoxide into a reaction system of sodium carbonate, lithium chloride and lithium hydroxide at one time, stirring to uniformly mix the solutions, rapidly transferring the solutions into a centrifuge tube for centrifugal treatment (the rotation speed is 5000 r/min) after two minutes, pouring out supernatant obtained by centrifugation, collecting precipitate obtained by centrifugation, washing with a small amount of deionized water for three times, and finally drying in a vacuum oven at the drying temperature of 40 ℃ for the drying time of 24h to obtain the nano lithium carbonate.
Because sodium carbonate, lithium chloride, lithium hydroxide and lithium carbonate are insoluble in dimethyl sulfoxide and the solubility of the lithium carbonate is minimum, the lithium carbonate can be rapidly separated out after the dimethyl sulfoxide is introduced into a reaction system, and a solvent-out agent dimethyl sulfoxide not only plays a solvent-out role, but also plays a dispersing role on lithium carbonate crystals;
the experimental results show that: the specific surface area of the nano lithium carbonate prepared by the reaction system of sodium carbonate, lithium chloride and lithium hydroxide can reach 20m 2 The volume size of the lithium carbonate is not obviously changed, the particle size is still kept uniform and is about 135nm, and meanwhile, the higher recovery yield can still be kept, namely, the recovery yield is about 91.7 percent, and the purity of the product can reach more than 99 percent after washing and purification.
Example 6
The embodiment provides a preparation method of nano lithium carbonate, which comprises the following steps:
preparing a reaction system of potassium carbonate, sodium bicarbonate and lithium sulfate with the total volume of 100mL in a 250 mL reaction container, wherein the final concentration of carbonate ions added in the equal volume of the potassium carbonate and the sodium bicarbonate is 0.4mol/L, the concentration of lithium sulfate is 0.4mol/L, and the pH value of the system is adjusted to 11;
adding 10 mL high-polarity organic solvent-out agent glycol and benzyl sulfoxide (the volume ratio of the glycol to the benzyl sulfoxide is 1:1) into a reaction system of potassium carbonate, sodium bicarbonate and lithium sulfate at one time, stirring to uniformly mix the solutions, rapidly transferring the solutions into a centrifuge tube for centrifugal treatment (the rotating speed is 5000 r/min) after two minutes, pouring supernatant obtained by centrifugation, collecting precipitate obtained by centrifugation, washing three times with a small amount of deionized water, and finally drying in a vacuum oven at the drying temperature of 40 ℃ for 24 hours to obtain the nano lithium carbonate.
Because potassium carbonate, sodium bicarbonate, lithium sulfate and lithium carbonate are insoluble in ethylene glycol and benzyl sulfoxide and the solubility of the lithium carbonate is minimum, the lithium carbonate can be rapidly separated out after the ethylene glycol and the benzyl sulfoxide are introduced into a reaction system, and the solvent-out agent ethylene glycol and the benzyl sulfoxide not only play a role in solvent-out, but also play a role in dispersing lithium carbonate crystals;
the experimental results show that: the specific surface area of the nano lithium carbonate prepared by adopting the reaction system of potassium carbonate, sodium bicarbonate and lithium sulfate can reach 15 m 2 The bulk size of the lithium carbonate is not obviously changed, the particle size is still kept uniform and is about 200 and nm, and meanwhile, the higher recovery yield is still kept, and the purity of the product after washing and purification can reach more than 97 percent.
Example 7
The embodiment provides a preparation method of nano lithium carbonate, which comprises the following steps:
preparing a reaction system of potassium carbonate and sodium bicarbonate, lithium chloride and lithium hydroxide with the total volume of 100mL in a 250 mL reaction vessel, wherein the potassium carbonate and the sodium bicarbonate are added in equal volumes, the final concentration of carbonate ions is 0.1mol/L, the lithium chloride and the lithium hydroxide are added in equal volumes, the final concentration of lithium ions is 0.1mol/L, and the pH value of the system is adjusted to 11;
adding a mixed solution of 100mL high-polarity organic solvent of glycerol and diethyl sulfoxide (the volume ratio of glycerol to diethyl sulfoxide is 1:1) into a reaction system of potassium carbonate and sodium bicarbonate, lithium chloride and lithium hydroxide at one time, stirring to uniformly mix the solutions, rapidly transferring the solutions into a centrifuge tube for centrifugal treatment (the rotating speed is 5000 r/min) after two minutes, pouring out supernatant obtained by centrifugation, collecting precipitate obtained by centrifugation, washing three times with a small amount of deionized water, and finally drying in a vacuum oven at 40 ℃ for 24h to obtain the nano lithium carbonate.
Because potassium carbonate, sodium bicarbonate, lithium chloride and lithium hydroxide are insoluble in the mixed solution of glycerol and diethyl sulfoxide and the solubility of the lithium carbonate is minimum, the lithium carbonate can be rapidly separated out after the mixed solution of glycerol and diethyl sulfoxide is introduced into a reaction system, and the mixed solution of the eluent, namely glycerol and diethyl sulfoxide, has a dissolving out effect and also has a dispersing effect on lithium carbonate crystals;
the experimental results show that: the specific surface area of nano lithium carbonate prepared by adopting a reaction system of potassium carbonate and sodium bicarbonate, lithium chloride and lithium hydroxide can reach 19m 2 And when the mixed solution of the glycerol and the diethyl sulfoxide is used as a solvent, the volume size of the lithium carbonate is not obviously changed, the particle size is still kept uniform and is about 148nm, and meanwhile, the higher recovery yield can still be kept and is about 91.3 percent, and the purity of the product can reach more than 99 percent after washing and purification.
Example 8
The embodiment provides a preparation method of nano lithium carbonate, which comprises the following steps:
preparing a reaction system of sodium carbonate and lithium sulfate with the total volume of 100mL in a 250 mL reaction vessel, wherein the concentration of the sodium carbonate and the concentration of the lithium sulfate are both 0.02mol/L, and the pH value of the system is adjusted to 11;
adding 500 mL high-polarity organic solvent dimethyl sulfoxide into a reaction system of sodium carbonate and lithium sulfate at one time, stirring to uniformly mix the solution, rapidly transferring the solution into a centrifuge tube for centrifugal treatment (the rotation speed is 5000 r/min) after two minutes, pouring off supernatant obtained by centrifugation, collecting precipitate obtained by centrifugation, washing with a small amount of deionized water for three times, and finally drying in a vacuum oven at the drying temperature of 40 ℃ for the drying time of 24h to obtain the nano lithium carbonate.
Because sodium carbonate, lithium sulfate and lithium carbonate are insoluble in dimethyl sulfoxide and the solubility of the lithium carbonate is minimum, the lithium carbonate can be rapidly separated out after the dimethyl sulfoxide is introduced into a reaction system, and the dimethyl sulfoxide not only plays a role in dissolving out, but also plays a role in dispersing lithium carbonate crystals;
the experimental results show that: the specific surface area of the lithium carbonate prepared by the embodiment can reach 13.3m 2 And has a uniform particle size of about 450nm. The method has the advantages of simple process flow, low implementation cost, mild reaction condition and recovery yieldAbout 68.0%, and the purity of the product nano lithium carbonate can reach more than 99% after washing and purification.
In an embodiment, the carbonate comprises at least one of sodium carbonate, potassium carbonate, and sodium bicarbonate; the lithium salt includes at least one of lithium sulfate, lithium chloride, and lithium hydroxide.
According to the preparation method of the nano lithium carbonate, provided by the embodiment of the invention, no scaling phenomenon is generated in the whole preparation process, no damage is caused to a reaction container, and a prepared lithium carbonate sample is easy to obtain and can be directly obtained through centrifugation or filtration separation; and the recovery yield is high, the process flow is simple, the reaction condition is mild (room temperature is 20 ℃), the implementation cost is low, and the industrial application is convenient.
The nano lithium carbonate prepared by the embodiment of the invention has high recovery yield and large specific surface (BET specific surface area can reach 13-30 m) 2 High purity (more than 95%), low crystallinity, nano-level (particle size of 50-500 nm), uniform particle size, etc.
Comparative example 1
In this comparative example, no elution agent was added to the reaction system of sodium carbonate and lithium sulfate, and as a result, lithium carbonate was not produced, and the procedure was as follows:
in a 250 mL reaction vessel, preparing a reaction system of sodium carbonate and lithium sulfate with the total volume of 100mL, wherein the concentration of the sodium carbonate and the concentration of the lithium sulfate are both 0.1mol/L, stirring to uniformly mix the solution, and adding no solvent for dissolving out, so that no precipitation of the lithium carbonate is seen.
This is because the critical saturated concentration of lithium carbonate at room temperature (20 ℃) is about 0.117mol/L, and under this condition, the actual concentration of lithium carbonate is 0.1mol/L lower than its critical saturated concentration, resulting in failure to precipitate. Therefore, the purpose of effectively recycling lithium carbonate can not be achieved under the condition of not introducing a solvent, and the high-activity nano lithium carbonate with low crystallinity and uniform size can not be prepared.
Comparative example 2
The comparative example provides a method for preparing lithium carbonate by adding ethanol which is a low-polarity solvent, comprising the following steps:
in a 250 mL reaction vessel, a reaction system of sodium carbonate and lithium sulfate with total volume of 100mL was prepared, wherein the concentration of sodium carbonate and lithium sulfate was 0.1 mol/L.
Adding 100mL solvent ethanol into a reaction system of sodium carbonate and lithium sulfate at one time, stirring to uniformly mix the solution, rapidly transferring the solution into a centrifuge tube for centrifugal treatment (the rotation speed is 5000 r/min) after two minutes, pouring out supernatant obtained by centrifugation, collecting precipitate obtained by centrifugation, washing three times with a small amount of deionized water, and finally drying in a vacuum oven at the drying temperature of 40 ℃ for 24h to obtain the nano lithium carbonate.
The experimental results show that: although the low-polarity ethanol is used as the solvent, the lithium carbonate can be separated out, the experimental result shows that the lithium carbonate product obtained by the method has poor uniformity of particle size scale, wide distribution range from hundreds of nanometers to micrometers, small specific surface area (6.0 m) 2 /g) (as shown in fig. 4), does not meet the requirement that battery-grade lithium carbonate is uniform in particle size and nano-grade particles; under the same condition, dimethyl sulfoxide with high polarity is adopted as an organic solvent, so that the catalyst can quickly obtain the catalyst with uniform particle size (about 130 nm) and large specific surface area (22.7 m) 2 And/g) and low crystallinity, completely meets the requirements of battery grade lithium carbonate, and the recovery yield is higher than 93 percent (see table 1). And, the crystallization rate of the lithium carbonate particles obtained by using ethanol as a solvent is slow, the crystallinity is obviously increased (see figure 5), and the recovery yield is obviously low (about 63.8%).
TABLE 1 comparison of lithium carbonate Properties under control with different solventout Agents
| Elution agent | Recovery yield | Particle size | Crystallinity degree | Specific surface area | Crystallization Rate |
| Ethanol | 63.8% | Several hundred nanometers to microns | High height | 6.0 m 2 /g | Slow down |
| Dimethyl sulfoxide | 93.2% | 130 nm | Low and low | 22.7 m 2 /g | Quick-acting toy |
In addition, the ethanol with low polarity is taken as a solvent, has obvious defects of easy volatilization, low boiling point, poor thermal stability and high risk, and is inconvenient for industrialization; and the dimethyl sulfoxide with high polarity is used as a solvent, so that the direct industrialization is facilitated due to the characteristics of low volatility, high boiling point, good thermal stability and high safety.
Fig. 5 of the present invention is an X-ray diffraction pattern (XRD) of lithium carbonate samples prepared in examples 2 and 3 and comparative example 2. The width of the peaks in the XRD pattern is related to the crystallinity of the sample, and the wider the spectrum peak is, the lower the crystallinity of the sample is. The XRD peak widths of the lithium carbonate samples prepared in example 2 and example 3 are different, so the crystallinity is different. Example 2 has a significantly wider XRD peak than comparative example 2, thus indicating that the nano lithium carbonate with low crystallinity cannot be prepared when ethanol is used as a solvent-out agent, and the nano lithium carbonate with low crystallinity can be prepared well when dimethyl sulfoxide is used as a solvent-out agent.
Claims (4)
1. The preparation method of the nano lithium carbonate is characterized by comprising the specific steps of introducing a high-polarity organic solvent into a reaction system of carbonate and lithium salt, reacting and crystallizing to obtain a precipitate, and washing, centrifuging and drying the precipitate to obtain the nano lithium carbonate;
the high-polarity organic solvent is a mixed solvent of dimethyl sulfoxide, ethylene glycol and benzyl sulfoxide or a mixed solvent of glycerol and diethyl sulfoxide;
the volume ratio of the ethylene glycol to the benzensulfide is 1:1, the volume ratio of glycerol to diethyl sulfoxide is 1:1, a step of;
the volume ratio of the high-polarity organic solvent to the reaction system of the carbonate and the lithium salt is 0.1-5: 1, a step of;
the temperature of the reaction is 20 ℃;
the concentration of the carbonate is 0.1-0.4mol/L, and the concentration of the lithium salt is 0.1-0.4 mol/L.
2. The method for preparing nano lithium carbonate according to claim 1, wherein the carbonate comprises at least one of sodium carbonate, potassium carbonate and sodium bicarbonate; the lithium salt comprises at least one of lithium sulfate, lithium chloride and lithium hydroxide.
3. The method for preparing nano lithium carbonate according to claim 1, wherein the drying temperature is 20-40 ℃.
4. A nano lithium carbonate prepared by the preparation method of any one of claims 1 to 3.
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| CN108821313A (en) * | 2018-09-25 | 2018-11-16 | 青海大学 | A method of Lithium hydroxide monohydrate is prepared using lithium carbonate |
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| CN102408119A (en) * | 2010-09-20 | 2012-04-11 | 华东理工大学 | Method for preparing lithium carbonate superfine powder through solvating-out and reaction crystallization |
| CN102583296A (en) * | 2011-01-06 | 2012-07-18 | 河南师范大学 | Method for preparing nanometer lithium iron phosphate in liquid phase |
| CN106654265A (en) * | 2017-03-14 | 2017-05-10 | 中国科学院青海盐湖研究所 | Method for preparing battery level micrometer lithium carbonate |
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