CN113582234A - Preparation method of battery-grade spheroidal manganese carbonate - Google Patents
Preparation method of battery-grade spheroidal manganese carbonate Download PDFInfo
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- CN113582234A CN113582234A CN202110920206.6A CN202110920206A CN113582234A CN 113582234 A CN113582234 A CN 113582234A CN 202110920206 A CN202110920206 A CN 202110920206A CN 113582234 A CN113582234 A CN 113582234A
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- 239000011656 manganese carbonate Substances 0.000 title claims abstract description 65
- 235000006748 manganese carbonate Nutrition 0.000 title claims abstract description 65
- 229940093474 manganese carbonate Drugs 0.000 title claims abstract description 65
- 229910000016 manganese(II) carbonate Inorganic materials 0.000 title claims abstract description 65
- XMWCXZJXESXBBY-UHFFFAOYSA-L manganese(ii) carbonate Chemical compound [Mn+2].[O-]C([O-])=O XMWCXZJXESXBBY-UHFFFAOYSA-L 0.000 title claims abstract description 65
- 238000002360 preparation method Methods 0.000 title claims abstract description 16
- 238000006243 chemical reaction Methods 0.000 claims abstract description 62
- PWHULOQIROXLJO-UHFFFAOYSA-N Manganese Chemical compound [Mn] PWHULOQIROXLJO-UHFFFAOYSA-N 0.000 claims abstract description 43
- 239000008367 deionised water Substances 0.000 claims abstract description 36
- 229910021641 deionized water Inorganic materials 0.000 claims abstract description 36
- XLYOFNOQVPJJNP-UHFFFAOYSA-N water Chemical compound O XLYOFNOQVPJJNP-UHFFFAOYSA-N 0.000 claims abstract description 36
- 229940099596 manganese sulfate Drugs 0.000 claims abstract description 35
- 239000011702 manganese sulphate Substances 0.000 claims abstract description 35
- 235000007079 manganese sulphate Nutrition 0.000 claims abstract description 35
- SQQMAOCOWKFBNP-UHFFFAOYSA-L manganese(II) sulfate Chemical compound [Mn+2].[O-]S([O-])(=O)=O SQQMAOCOWKFBNP-UHFFFAOYSA-L 0.000 claims abstract description 35
- 239000002245 particle Substances 0.000 claims abstract description 35
- 239000012535 impurity Substances 0.000 claims abstract description 26
- MHAJPDPJQMAIIY-UHFFFAOYSA-N Hydrogen peroxide Chemical compound OO MHAJPDPJQMAIIY-UHFFFAOYSA-N 0.000 claims abstract description 24
- 239000011572 manganese Substances 0.000 claims abstract description 22
- 239000008139 complexing agent Substances 0.000 claims abstract description 20
- 238000001914 filtration Methods 0.000 claims abstract description 20
- 238000000034 method Methods 0.000 claims abstract description 18
- 239000003513 alkali Substances 0.000 claims abstract description 17
- 229910052748 manganese Inorganic materials 0.000 claims abstract description 16
- 239000003795 chemical substances by application Substances 0.000 claims abstract description 12
- QAOWNCQODCNURD-UHFFFAOYSA-N sulfuric acid Substances OS(O)(=O)=O QAOWNCQODCNURD-UHFFFAOYSA-N 0.000 claims abstract description 12
- 230000032683 aging Effects 0.000 claims abstract description 11
- 150000002500 ions Chemical class 0.000 claims abstract description 9
- BVKZGUZCCUSVTD-UHFFFAOYSA-L Carbonate Chemical compound [O-]C([O-])=O BVKZGUZCCUSVTD-UHFFFAOYSA-L 0.000 claims abstract description 8
- 229910001385 heavy metal Inorganic materials 0.000 claims abstract description 8
- 239000012295 chemical reaction liquid Substances 0.000 claims abstract description 5
- 239000000706 filtrate Substances 0.000 claims abstract description 5
- 229910001437 manganese ion Inorganic materials 0.000 claims abstract description 5
- 238000001556 precipitation Methods 0.000 claims abstract description 5
- 230000035484 reaction time Effects 0.000 claims abstract description 5
- CWYNVVGOOAEACU-UHFFFAOYSA-N Fe2+ Chemical compound [Fe+2] CWYNVVGOOAEACU-UHFFFAOYSA-N 0.000 claims abstract description 4
- 229910001448 ferrous ion Inorganic materials 0.000 claims abstract description 4
- 239000000243 solution Substances 0.000 claims description 56
- 238000003756 stirring Methods 0.000 claims description 34
- ATRRKUHOCOJYRX-UHFFFAOYSA-N Ammonium bicarbonate Chemical compound [NH4+].OC([O-])=O ATRRKUHOCOJYRX-UHFFFAOYSA-N 0.000 claims description 12
- HEMHJVSKTPXQMS-UHFFFAOYSA-M Sodium hydroxide Chemical compound [OH-].[Na+] HEMHJVSKTPXQMS-UHFFFAOYSA-M 0.000 claims description 12
- 239000001099 ammonium carbonate Substances 0.000 claims description 12
- 238000001035 drying Methods 0.000 claims description 12
- 239000012670 alkaline solution Substances 0.000 claims description 9
- 239000002585 base Substances 0.000 claims description 9
- 239000012716 precipitator Substances 0.000 claims description 9
- CDBYLPFSWZWCQE-UHFFFAOYSA-L Sodium Carbonate Chemical compound [Na+].[Na+].[O-]C([O-])=O CDBYLPFSWZWCQE-UHFFFAOYSA-L 0.000 claims description 8
- 235000012501 ammonium carbonate Nutrition 0.000 claims description 8
- 239000011734 sodium Substances 0.000 claims description 8
- 238000005406 washing Methods 0.000 claims description 8
- VHUUQVKOLVNVRT-UHFFFAOYSA-N Ammonium hydroxide Chemical compound [NH4+].[OH-] VHUUQVKOLVNVRT-UHFFFAOYSA-N 0.000 claims description 7
- 235000011114 ammonium hydroxide Nutrition 0.000 claims description 7
- 239000007788 liquid Substances 0.000 claims description 7
- XEKOWRVHYACXOJ-UHFFFAOYSA-N Ethyl acetate Chemical compound CCOC(C)=O XEKOWRVHYACXOJ-UHFFFAOYSA-N 0.000 claims description 6
- KWYUFKZDYYNOTN-UHFFFAOYSA-M Potassium hydroxide Chemical compound [OH-].[K+] KWYUFKZDYYNOTN-UHFFFAOYSA-M 0.000 claims description 6
- UYJXRRSPUVSSMN-UHFFFAOYSA-P ammonium sulfide Chemical compound [NH4+].[NH4+].[S-2] UYJXRRSPUVSSMN-UHFFFAOYSA-P 0.000 claims description 6
- 229910052749 magnesium Inorganic materials 0.000 claims description 6
- LRHPLDYGYMQRHN-UHFFFAOYSA-N N-Butanol Chemical compound CCCCO LRHPLDYGYMQRHN-UHFFFAOYSA-N 0.000 claims description 5
- 229910052791 calcium Inorganic materials 0.000 claims description 5
- 229910052751 metal Inorganic materials 0.000 claims description 5
- 239000002184 metal Substances 0.000 claims description 5
- 229910052700 potassium Inorganic materials 0.000 claims description 5
- 229910052708 sodium Inorganic materials 0.000 claims description 5
- 229910000013 Ammonium bicarbonate Inorganic materials 0.000 claims description 4
- 235000012538 ammonium bicarbonate Nutrition 0.000 claims description 4
- 229910052802 copper Inorganic materials 0.000 claims description 4
- 229910052742 iron Inorganic materials 0.000 claims description 4
- BWHMMNNQKKPAPP-UHFFFAOYSA-L potassium carbonate Chemical compound [K+].[K+].[O-]C([O-])=O BWHMMNNQKKPAPP-UHFFFAOYSA-L 0.000 claims description 4
- 229910000029 sodium carbonate Inorganic materials 0.000 claims description 4
- 235000017550 sodium carbonate Nutrition 0.000 claims description 4
- KEZYHIPQRGTUDU-UHFFFAOYSA-N 2-[dithiocarboxy(methyl)amino]acetic acid Chemical compound SC(=S)N(C)CC(O)=O KEZYHIPQRGTUDU-UHFFFAOYSA-N 0.000 claims description 3
- 229910052782 aluminium Inorganic materials 0.000 claims description 3
- 239000007864 aqueous solution Substances 0.000 claims description 3
- 229920001495 poly(sodium acrylate) polymer Polymers 0.000 claims description 3
- NNMHYFLPFNGQFZ-UHFFFAOYSA-M sodium polyacrylate Chemical compound [Na+].[O-]C(=O)C=C NNMHYFLPFNGQFZ-UHFFFAOYSA-M 0.000 claims description 3
- GSFSVEDCYBDIGW-UHFFFAOYSA-N 2-(1,3-benzothiazol-2-yl)-6-chlorophenol Chemical compound OC1=C(Cl)C=CC=C1C1=NC2=CC=CC=C2S1 GSFSVEDCYBDIGW-UHFFFAOYSA-N 0.000 claims description 2
- 229920002134 Carboxymethyl cellulose Polymers 0.000 claims description 2
- RWSOTUBLDIXVET-UHFFFAOYSA-N Dihydrogen sulfide Chemical compound S RWSOTUBLDIXVET-UHFFFAOYSA-N 0.000 claims description 2
- 239000003109 Disodium ethylene diamine tetraacetate Substances 0.000 claims description 2
- ZGTMUACCHSMWAC-UHFFFAOYSA-L EDTA disodium salt (anhydrous) Chemical compound [Na+].[Na+].OC(=O)CN(CC([O-])=O)CCN(CC(O)=O)CC([O-])=O ZGTMUACCHSMWAC-UHFFFAOYSA-L 0.000 claims description 2
- IGFHQQFPSIBGKE-UHFFFAOYSA-N Nonylphenol Natural products CCCCCCCCCC1=CC=C(O)C=C1 IGFHQQFPSIBGKE-UHFFFAOYSA-N 0.000 claims description 2
- UIIMBOGNXHQVGW-DEQYMQKBSA-M Sodium bicarbonate-14C Chemical compound [Na+].O[14C]([O-])=O UIIMBOGNXHQVGW-DEQYMQKBSA-M 0.000 claims description 2
- CJDPJFRMHVXWPT-UHFFFAOYSA-N barium sulfide Chemical compound [S-2].[Ba+2] CJDPJFRMHVXWPT-UHFFFAOYSA-N 0.000 claims description 2
- 229910052793 cadmium Inorganic materials 0.000 claims description 2
- 239000001768 carboxy methyl cellulose Substances 0.000 claims description 2
- 235000010948 carboxy methyl cellulose Nutrition 0.000 claims description 2
- 239000008112 carboxymethyl-cellulose Substances 0.000 claims description 2
- 229910052804 chromium Inorganic materials 0.000 claims description 2
- 229940028356 diethylene glycol monobutyl ether Drugs 0.000 claims description 2
- 235000019301 disodium ethylene diamine tetraacetate Nutrition 0.000 claims description 2
- SYELZBGXAIXKHU-UHFFFAOYSA-N dodecyldimethylamine N-oxide Chemical compound CCCCCCCCCCCC[N+](C)(C)[O-] SYELZBGXAIXKHU-UHFFFAOYSA-N 0.000 claims description 2
- 229910000037 hydrogen sulfide Inorganic materials 0.000 claims description 2
- 229910052745 lead Inorganic materials 0.000 claims description 2
- 229910052759 nickel Inorganic materials 0.000 claims description 2
- SNQQPOLDUKLAAF-UHFFFAOYSA-N nonylphenol Chemical compound CCCCCCCCCC1=CC=CC=C1O SNQQPOLDUKLAAF-UHFFFAOYSA-N 0.000 claims description 2
- JCGNDDUYTRNOFT-UHFFFAOYSA-N oxolane-2,4-dione Chemical compound O=C1COC(=O)C1 JCGNDDUYTRNOFT-UHFFFAOYSA-N 0.000 claims description 2
- 229940051841 polyoxyethylene ether Drugs 0.000 claims description 2
- 229920000056 polyoxyethylene ether Polymers 0.000 claims description 2
- 239000001267 polyvinylpyrrolidone Substances 0.000 claims description 2
- 229920000036 polyvinylpyrrolidone Polymers 0.000 claims description 2
- 235000013855 polyvinylpyrrolidone Nutrition 0.000 claims description 2
- 229910000027 potassium carbonate Inorganic materials 0.000 claims description 2
- 235000011181 potassium carbonates Nutrition 0.000 claims description 2
- BTURAGWYSMTVOW-UHFFFAOYSA-M sodium dodecanoate Chemical compound [Na+].CCCCCCCCCCCC([O-])=O BTURAGWYSMTVOW-UHFFFAOYSA-M 0.000 claims description 2
- 229940082004 sodium laurate Drugs 0.000 claims description 2
- 229910052979 sodium sulfide Inorganic materials 0.000 claims description 2
- GRVFOGOEDUUMBP-UHFFFAOYSA-N sodium sulfide (anhydrous) Chemical compound [Na+].[Na+].[S-2] GRVFOGOEDUUMBP-UHFFFAOYSA-N 0.000 claims description 2
- 229910052725 zinc Inorganic materials 0.000 claims description 2
- 238000004519 manufacturing process Methods 0.000 abstract description 8
- 230000001376 precipitating effect Effects 0.000 abstract description 2
- 239000000463 material Substances 0.000 description 15
- 239000000047 product Substances 0.000 description 10
- HBBGRARXTFLTSG-UHFFFAOYSA-N Lithium ion Chemical compound [Li+] HBBGRARXTFLTSG-UHFFFAOYSA-N 0.000 description 8
- XEEYBQQBJWHFJM-UHFFFAOYSA-N iron Substances [Fe] XEEYBQQBJWHFJM-UHFFFAOYSA-N 0.000 description 8
- 229910001416 lithium ion Inorganic materials 0.000 description 8
- 238000009826 distribution Methods 0.000 description 6
- 238000010438 heat treatment Methods 0.000 description 6
- 239000000956 alloy Substances 0.000 description 5
- 239000000203 mixture Substances 0.000 description 5
- PXHVJJICTQNCMI-UHFFFAOYSA-N nickel Substances [Ni] PXHVJJICTQNCMI-UHFFFAOYSA-N 0.000 description 5
- 229910045601 alloy Inorganic materials 0.000 description 4
- DVATZODUVBMYHN-UHFFFAOYSA-K lithium;iron(2+);manganese(2+);phosphate Chemical compound [Li+].[Mn+2].[Fe+2].[O-]P([O-])([O-])=O DVATZODUVBMYHN-UHFFFAOYSA-K 0.000 description 4
- OAYXUHPQHDHDDZ-UHFFFAOYSA-N 2-(2-butoxyethoxy)ethanol Chemical compound CCCCOCCOCCO OAYXUHPQHDHDDZ-UHFFFAOYSA-N 0.000 description 3
- 230000001788 irregular Effects 0.000 description 3
- GELKBWJHTRAYNV-UHFFFAOYSA-K lithium iron phosphate Chemical class [Li+].[Fe+2].[O-]P([O-])([O-])=O GELKBWJHTRAYNV-UHFFFAOYSA-K 0.000 description 3
- 238000003921 particle size analysis Methods 0.000 description 3
- 238000001878 scanning electron micrograph Methods 0.000 description 3
- WHXSMMKQMYFTQS-UHFFFAOYSA-N Lithium Chemical compound [Li] WHXSMMKQMYFTQS-UHFFFAOYSA-N 0.000 description 2
- 229910019142 PO4 Inorganic materials 0.000 description 2
- 230000009286 beneficial effect Effects 0.000 description 2
- 230000000052 comparative effect Effects 0.000 description 2
- QHGJSLXSVXVKHZ-UHFFFAOYSA-N dilithium;dioxido(dioxo)manganese Chemical compound [Li+].[Li+].[O-][Mn]([O-])(=O)=O QHGJSLXSVXVKHZ-UHFFFAOYSA-N 0.000 description 2
- AMWRITDGCCNYAT-UHFFFAOYSA-L hydroxy(oxo)manganese;manganese Chemical compound [Mn].O[Mn]=O.O[Mn]=O AMWRITDGCCNYAT-UHFFFAOYSA-L 0.000 description 2
- 229910052744 lithium Inorganic materials 0.000 description 2
- 238000012986 modification Methods 0.000 description 2
- 230000004048 modification Effects 0.000 description 2
- 239000010452 phosphate Substances 0.000 description 2
- NBIIXXVUZAFLBC-UHFFFAOYSA-K phosphate Chemical compound [O-]P([O-])([O-])=O NBIIXXVUZAFLBC-UHFFFAOYSA-K 0.000 description 2
- 239000002244 precipitate Substances 0.000 description 2
- 229910000831 Steel Inorganic materials 0.000 description 1
- KFDQGLPGKXUTMZ-UHFFFAOYSA-N [Mn].[Co].[Ni] Chemical compound [Mn].[Co].[Ni] KFDQGLPGKXUTMZ-UHFFFAOYSA-N 0.000 description 1
- 239000010405 anode material Substances 0.000 description 1
- 229910002056 binary alloy Inorganic materials 0.000 description 1
- 239000000919 ceramic Substances 0.000 description 1
- 239000003153 chemical reaction reagent Substances 0.000 description 1
- 239000011248 coating agent Substances 0.000 description 1
- 238000000576 coating method Methods 0.000 description 1
- 239000002131 composite material Substances 0.000 description 1
- 230000001351 cycling effect Effects 0.000 description 1
- 238000000354 decomposition reaction Methods 0.000 description 1
- 230000007547 defect Effects 0.000 description 1
- 238000001514 detection method Methods 0.000 description 1
- 239000003814 drug Substances 0.000 description 1
- 229940079593 drug Drugs 0.000 description 1
- 239000000975 dye Substances 0.000 description 1
- 230000007613 environmental effect Effects 0.000 description 1
- 238000011049 filling Methods 0.000 description 1
- CPSYWNLKRDURMG-UHFFFAOYSA-L hydron;manganese(2+);phosphate Chemical compound [Mn+2].OP([O-])([O-])=O CPSYWNLKRDURMG-UHFFFAOYSA-L 0.000 description 1
- -1 iron ions Chemical class 0.000 description 1
- 238000012423 maintenance Methods 0.000 description 1
- 150000002696 manganese Chemical class 0.000 description 1
- PPNAOCWZXJOHFK-UHFFFAOYSA-N manganese(2+);oxygen(2-) Chemical compound [O-2].[Mn+2] PPNAOCWZXJOHFK-UHFFFAOYSA-N 0.000 description 1
- VASIZKWUTCETSD-UHFFFAOYSA-N manganese(II) oxide Inorganic materials [Mn]=O VASIZKWUTCETSD-UHFFFAOYSA-N 0.000 description 1
- 239000007773 negative electrode material Substances 0.000 description 1
- 239000007774 positive electrode material Substances 0.000 description 1
- 239000002994 raw material Substances 0.000 description 1
- 239000006104 solid solution Substances 0.000 description 1
- 239000010959 steel Substances 0.000 description 1
- 238000009827 uniform distribution Methods 0.000 description 1
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- C—CHEMISTRY; METALLURGY
- C01—INORGANIC CHEMISTRY
- C01G—COMPOUNDS CONTAINING METALS NOT COVERED BY SUBCLASSES C01D OR C01F
- C01G45/00—Compounds of manganese
-
- C—CHEMISTRY; METALLURGY
- C01—INORGANIC CHEMISTRY
- C01P—INDEXING SCHEME RELATING TO STRUCTURAL AND PHYSICAL ASPECTS OF SOLID INORGANIC COMPOUNDS
- C01P2004/00—Particle morphology
- C01P2004/01—Particle morphology depicted by an image
- C01P2004/03—Particle morphology depicted by an image obtained by SEM
-
- C—CHEMISTRY; METALLURGY
- C01—INORGANIC CHEMISTRY
- C01P—INDEXING SCHEME RELATING TO STRUCTURAL AND PHYSICAL ASPECTS OF SOLID INORGANIC COMPOUNDS
- C01P2004/00—Particle morphology
- C01P2004/30—Particle morphology extending in three dimensions
- C01P2004/32—Spheres
-
- C—CHEMISTRY; METALLURGY
- C01—INORGANIC CHEMISTRY
- C01P—INDEXING SCHEME RELATING TO STRUCTURAL AND PHYSICAL ASPECTS OF SOLID INORGANIC COMPOUNDS
- C01P2004/00—Particle morphology
- C01P2004/51—Particles with a specific particle size distribution
-
- 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
Abstract
The invention relates to a preparation method of battery-grade spheroidal manganese carbonate, which comprises the steps of adding electrolytic manganese metal sheets and deionized water into a dissolving tank together when preparing reaction liquid, adding 98% concentrated sulfuric acid by mass for dissolving, adjusting the pH value of the reaction solution to 4.0-5.5 by using manganese powder, adding hydrogen peroxide to remove ferrous ions, adding an impurity removing agent to remove heavy metal ions, filtering, taking filtrate to obtain a battery-grade manganese sulfate solution with low impurity content, adding the battery-grade manganese sulfate solution, a precipitating agent and an alkali liquor containing a complexing agent into a reaction kettle in a parallel flow manner for reaction, in the precipitation process, the mole ratio of carbonate to manganese ions, the reaction temperature and the reaction time are controlled, after the feeding is finished, then aging and filtering are carried out, the prepared battery-grade sphere-like manganese carbonate particles are all sphere-like, the manganese content is high, the impurity content is low, and the particle size of the battery-grade spheroidal manganese carbonate is controllable and has better uniformity; the battery-grade spheroidal manganese carbonate provided by the invention has the advantages of simple process flow and low production cost, and is suitable for industrial mass production.
Description
Technical Field
The invention relates to the technical field of preparation of manganese carbonate, in particular to a preparation method of battery-grade spheroidal manganese carbonate.
Background
Manganese carbonate has wide application in high and new technical fields such as electronics, ceramics, dyes and medicines, along with the high importance of new energy electric vehicles in recent years, the lithium ion battery industry is rapidly developed, the demand of lithium ion batteries is more and more large, the application field of manganese carbonate is continuously expanded, and simultaneously higher requirements on quality are provided.
The research direction for lithium ion batteries is mainly for positive electrode materials and negative electrode materials. At present, lithium cobaltate, lithium manganate, nickel cobalt manganese ternary materials, phosphate materials and the like are mainly used as the anode materials of the lithium ion battery, wherein the phosphate materials have the advantages of high theoretical capacity, good stability, low price, environmental friendliness and the like and are widely applied. The battery-grade spheroidal manganese carbonate is used as a manganese source, and the novel positive material lithium iron manganese phosphate is obtained by introducing Mn ions to dope modified lithium iron phosphate, so that the energy density of the material is improved while the advantages of the lithium iron phosphate are achieved, and the battery-grade spheroidal manganese carbonate is widely concerned by researchers. The lithium manganese iron phosphate is a stable binary system solid solution, the theoretical specific capacity is 170mAh/g, the electrode potential relative to Li +/Li is 4.1V, which is much higher than 3.4V of the lithium iron phosphate, the potential high-energy density is realized, meanwhile, the lithium manganese iron phosphate has two voltage platforms, the high voltage platform can improve the voltage of the battery, and the low voltage platform can quickly judge the residual capacity of the battery. In addition, the small-particle lithium ferric manganese phosphate can be filled into the gaps of the large-particle ternary material for mixed use, so that the volume energy density and the thermal stability of the material are greatly improved. And the lithium manganese iron phosphate has excellent cycle performance, low-temperature performance and safety performance, and has low cost and wide market prospect. The battery-grade spherical manganese carbonate can be used for preparing battery-grade trimanganese tetroxide, high-quality lithium manganate materials and battery-grade manganous oxide materials, and the discharge specific capacity, the cycle performance and the rate capability of the lithium ion battery are improved; in addition, the battery-grade spherical manganese carbonate can also be used for preparing a manganese carbonate composite material, and has excellent conductivity, specific capacity and cycling stability.
The purity and morphology of the material affects the properties of the material. The lithium ion battery material has the problems of reduced specific capacity, poor cycle performance and the like due to overhigh impurity content, even causes self-discharge of the battery and causes safety problems; the particle spheroids have the advantages of small specific area under unit mass, good fluidity and the like, the spheroids are not easy to agglomerate, the gap filling utilization rate is high, the volume density is improved, and the performance of the lithium ion battery material is improved. Therefore, the preparation of the manganese carbonate material with low impurity content and spheroidal particles is the basis for preparing the high-quality lithium ion battery material. The method for preparing manganese carbonate mainly uses manganese salt and a precipitator as raw materials, performs double decomposition reaction at a certain temperature and under stirring to obtain manganese carbonate precipitate, and then washes and dries the precipitate to obtain the product. The manganese carbonate prepared by the prior process has the advantages of wide particle distribution range, large particle size, irregular appearance, easy coating of impurity ions on the product, low manganese content and dark surface color of the dried product.
Disclosure of Invention
Aiming at the defects of the prior art, the invention aims to provide a preparation method of battery grade sphericity-like manganese carbonate, which has the advantages of simple preparation process, low production and maintenance cost, small granularity, uniform distribution, good sphericity and low impurity content.
In order to achieve the purpose, the technical scheme adopted by the invention is as follows: a preparation method of battery-grade spheroidal manganese carbonate comprises the following steps:
(1) adding the electrolytic manganese metal sheet and deionized water into a dissolving tank together, and controlling the solid-to-liquid ratio to be (1: 5) - (1: 20); adding 98% concentrated sulfuric acid by mass, and stirring for reaction for 10-60 min to obtain a reaction solution; the weight part ratio of the concentrated sulfuric acid with the mass fraction of 98% to the electrolytic manganese metal sheet is (1.7-2.1): 1;
(2) adjusting the pH value of the reaction solution to 4.0-5.5 by using manganese powder; adding hydrogen peroxide and stirring for 10-60 min to remove ferrous ions, wherein the amount of the hydrogen peroxide is 1-5% of the weight of the electrolytic manganese metal sheet in the step (1); adding an impurity removing agent, stirring for 10-60 min, and removing heavy metal ions, wherein the amount of the impurity removing agent is 0.2-1% of the weight of the metal manganese sheet in the step (1), so as to obtain an impurity removing solution;
(3) filtering the solution obtained in the step (2) after impurity removal, and taking filtrate to obtain a battery-grade manganese sulfate solution;
(4) adding a proper amount of deionized water into a full-automatic reaction kettle to serve as a base solution, wherein the addition amount of the base solution is 1/5-1/4 of the volume of the reaction kettle; opening a reaction kettle stirrer, wherein the stirring speed is 250-700 r/min; adding the battery-grade manganese sulfate solution and a precipitator into a reaction kettle respectively in a parallel flow mode, and adding an alkali liquor containing a complexing agent in a parallel flow mode to control the pH value of a reaction system to be 6.0-9.0; controlling the mole ratio n (CO) of carbonate to manganese ions during the precipitation process3 2-):n(Mn2+) = 1:1 to 2:1, the reaction temperature is 20-70 ℃, and the reaction time is 2-25 h; after the feeding is finished, continuously stirring and aging for 3-15 hours to obtain a reaction solution;
(5) filtering the reaction liquid obtained in the step (4), and taking filter residues; washing the filter residue with deionized water, and drying the filter residue in an oven at 60-100 ℃ for 6-15 h to obtain the battery-grade spheroidal manganese carbonate.
Further, the electrolytic manganese metal sheet in the step (1) is a common electrolytic manganese metal sheet, and the manganese content in the electrolytic manganese metal sheet is more than 99.5 wt%.
Further, the impurity removing agent in the step (2) is one or more of sodium dimethyl dithiocarbamate, ammonium sulfide, sodium sulfide, hydrogen sulfide and barium sulfide.
Further, the concentration of manganese sulfate in the battery-grade manganese sulfate solution in the step (3) is 0.1-4 mol/L, the content of Fe is lower than 0.001wt%, the content of Ca, Mg, K and Na is lower than 0.005wt%, and the content of heavy metal is lower than 0.001 wt%.
Further, the precipitant in step (4) is one or more of sodium carbonate, sodium bicarbonate, ammonium carbonate, ammonium bicarbonate and potassium carbonate.
Further, the complexing agent in the step (4) is one or more of carboxymethyl cellulose, sodium polyacrylate, polyvinylpyrrolidone, sodium metasilicate pentahydrate, sodium laurate, dodecyl dimethyl amine oxide, nonylphenol polyoxyethylene ether, diethylene glycol monobutyl ether, disodium ethylene diamine tetraacetate, ethyl acetate and n-butyl alcohol, wherein the concentration of the complexing agent in the alkaline liquor containing the complexing agent is 1-30 g/L.
Further, the alkaline solution containing the complexing agent in the step (4) refers to an alkaline solution added with the complexing agent, wherein the alkaline solution is one or more of aqueous solution of sodium hydroxide, ammonia water and potassium hydroxide, and the concentration of solute in the alkaline solution is 0.1-3 mol/L; specifically, when the alkali liquor is an aqueous solution of sodium hydroxide, the concentration of the sodium hydroxide in the alkali liquor is 0.1-3 mol/L.
Further, the feeding speed of the battery-grade manganese sulfate solution in the step (4) is 1-30 mL/min.
Furthermore, the battery-grade spherical-like manganese carbonate prepared by the preparation method has a spherical-like particle shape, a particle size index D50 of 5-20 mu m and a tap density of more than or equal to 2.0g/cm3,Mn≥45.0wt%,Al≤0.001wt%,Fe≤0.001wt%,Ca≤0.005wt%,Cr≤0.001wt%,Cd≤0.001wt%,Cu≤0.001wt%,Mg≤0.005wt%,K≤0.005wt%,Na≤0.005wt%,Pb≤0.001wt%,Ni≤0.001wt%,Ti≤0.001wt%,Zn≤0.001wt%,SO4 2-≤0.1wt%。
Further, the filter residue is washed by deionized water in the step (5) for 3-5 times.
The invention relates to a preparation method of battery-grade spheroidal manganese carbonate, which comprises the steps of adding an electrolytic metal manganese sheet and deionized water into a dissolving tank during reaction liquid preparation, adding 98% by mass of concentrated sulfuric acid for dissolving, adjusting the pH value of the reaction liquid to 4.0-5.5 by using manganese powder, adding hydrogen peroxide to remove divalent iron ions, adding an impurity removing agent to remove heavy metal ions, filtering, taking filtrate to obtain a battery-grade manganese sulfate solution with low impurity content, adding the battery-grade manganese sulfate solution, a precipitator and an alkali liquor containing a complexing agent into a reaction kettle in a parallel flow mode for reaction, controlling the molar ratio of the battery-grade manganese sulfate to the manganese ions, the reaction temperature and the reaction time during precipitation, aging and filtering after feeding is finished, and obtaining the battery-grade spheroidal manganese carbonate which has the following beneficial effects:
(1) the prepared manganese carbonate particles are all spherical-like;
(2) the prepared battery-grade spheroidal manganese carbonate is high in content and low in impurity content;
(3) the prepared battery-grade spheroidal manganese carbonate has controllable particle size and good uniformity;
(4) the battery-grade spheroidal manganese carbonate provided by the invention has the advantages of simple process flow and low production cost, and is suitable for industrial mass production.
Drawings
FIG. 1 is an SEM image of battery grade spheric manganese carbonate obtained in example 1 of the present invention.
FIG. 2 is a graph showing the particle size distribution of battery grade spheric manganese carbonate obtained in example 1 of the present invention.
FIG. 3 is an SEM image of battery grade spheric manganese carbonate obtained in example 2 of the present invention.
FIG. 4 is a graph showing the particle size distribution of battery grade spheric manganese carbonate obtained in example 2 of the present invention.
FIG. 5 is an SEM image of battery grade spheric manganese carbonate obtained in example 3 of the present invention.
FIG. 6 is a graph showing the particle size distribution of battery grade spheric manganese carbonate obtained in example 3 of the present invention.
Detailed Description
The following examples may help one skilled in the art to more fully understand the present invention, but are not intended to limit the invention in any way.
The invention relates to a preparation method of battery-grade spheroidal manganese carbonate, wherein reagents such as hydrogen peroxide, an impurity removing agent and the like are all chemically pure.
Example 1:
(1) adding 1000g of electrolytic metal manganese sheet and 12L of deionized water into a beaker, adding 1000mL of 98% concentrated sulfuric acid for reaction, stirring for 30min, adjusting the pH value to 4.0-5.5 by using manganese powder, adding 45mL of hydrogen peroxide, stirring for 30min, adding 4.5g of ammonium sulfide, continuing stirring for 30min, and finally filtering to obtain a battery-grade manganese sulfate solution;
(2) preparing 12L of 1.5mol/L sodium carbonate solution from sodium carbonate and deionized water;
(3) preparing 12L of 0.5mol/L alkali liquor from ammonia water and deionized water, and adding 20g of sodium polyacrylate;
(4) adding 1/5 deionized water as a base solution into the reaction kettle, opening a reaction kettle stirrer, adjusting the stirring speed to 600r/min, opening the reaction kettle, and heating to 30 ℃; adding the prepared battery-grade manganese sulfate solution and a precipitator into a reaction kettle in a parallel flow mode, wherein the feeding speed of the manganese sulfate solution is 2mL/min, and then adding an alkali liquor containing a complexing agent in a parallel flow mode to control the pH value of a reaction system to be 6.0-7.0 and the mole ratio n (CO) of carbonate to manganese ions3 2-):n(Mn2+) = 1: 1; after the feeding is finished, continuously preserving heat, stirring and aging for 5 hours;
(5) and (4) filtering the solid-liquid mixture obtained by ageing in the step (4), washing with deionized water for 5 times, then putting into a drying oven, and drying for 14 hours at the temperature of 60 ℃ to obtain the battery-grade spheroidal manganese carbonate.
The battery grade spheroidal manganese carbonate prepared by the embodiment has the particle diameter D50 of 12.79 mu m and the tap density of 2.12g/cm3The alloy had a Mn content of 45.88%, an Al content of 0.0002wt%, an Fe content of 0.0005wt%, a Ca content of 0.0023wt%, a Cr content of 0.0001wt%, a Cd content of 0.0001wt%, a Cu content of 0.0001wt%, a Mg content of 0.0033wt%, a K content of 0.0008wt%, a Na content of 0.0029wt%, a Pb content of 0.0003wt%, a Ni content of 0.0002wt%, a Ti content of 0.0001wt%, a Zn content of 0.0004wt%, and an SO content of 0.0029wt%, a Pb content of 0.0003wt%, a Ni content of 0.0002wt%, a Ti content of 0.0001wt%, a Zn content of 0.0004wt%, and a SO content of 0.0005wt%, and the alloy was used for the production of the alloy4 2-The content was 0.072 wt%. The appearance of the particles is observed to be spheroidal particles by a Scanning Electron Microscope (SEM), and the result is shown in figure 1; the product was subjected to particle size analysis using a particle sizer, and the results are shown in the figure2, respectively.
Example 2:
(1) adding 2000g of electrolytic manganese metal sheet and 25L of deionized water into a beaker, adding 2000mL of 98% concentrated sulfuric acid for reaction, stirring for 30min, adjusting the pH value to 4.0-5.5 by using manganese powder, adding 90mL of hydrogen peroxide, stirring for 30min, adding 9.0g of ammonium sulfide, continuing stirring for 30min, and finally filtering to obtain a battery-grade manganese sulfate solution;
(2) preparing 25L of 2.5mol/L ammonium bicarbonate solution from ammonium bicarbonate and deionized water;
(3) preparing 25L of 0.5mol/L alkali liquor from ammonia water and deionized water, and adding 35g of sodium metasilicate pentahydrate;
(4) adding 1/5 deionized water as a base solution into the reaction kettle, opening a reaction kettle stirrer, adjusting the stirring speed to 500r/min, opening the reaction kettle, and heating to 50 ℃; adding the prepared battery-grade manganese sulfate solution and a precipitator into a reaction kettle in a parallel flow mode, wherein the feeding speed of the manganese sulfate solution is 10mL/min, and then adding an alkali liquor containing a complexing agent in a parallel flow mode to control the pH value of a reaction system to be 7.0-8.0 and the mole ratio n (CO) of carbonate to manganese ions3 2-):n(Mn2+) = 1.25: 1; after the feeding is finished, continuously preserving heat, stirring and aging for 5 hours;
(5) and (4) filtering the solid-liquid mixture obtained in the step (4), washing with deionized water for 5 times, then placing into a drying oven, and drying at 80 ℃ for 10 hours to obtain the battery grade spheroidal manganese carbonate.
The battery grade spheroidal manganese carbonate prepared by the embodiment has the particle diameter D50 of 18.70 mu m and the tap density of 2.28g/cm3The alloy had a Mn content of 45.76%, an Al content of 0.0002wt%, an Fe content of 0.0006wt%, a Ca content of 0.0026wt%, a Cr content of 0.0001wt%, a Cd content of 0.0002wt%, a Cu content of 0.0001wt%, an Mg content of 0.0036wt%, a K content of 0.0006wt%, a Na content of 0.0010wt%, a Pb content of 0.0004wt%, a Ni content of 0.0002wt%, a Ti content of 0.0001wt%, a Zn content of 0.0005wt%, and an SO content of 0.0005wt%, and was characterized by containing Al, Fe, Cu, Mg, and Cu, respectively4 2-The content was 0.081 wt%. The appearance of the particles is observed to be spheroidal particles by a Scanning Electron Microscope (SEM), and the result is shown in figure 3; the product was subjected to particle size analysis using a particle sizer, and the results are shown in FIG. 4.
Example 3:
(1) adding 1500g of electrolytic manganese metal sheet and 20L of deionized water into a beaker, adding 1500mL of 98% concentrated sulfuric acid for reaction, stirring for 30min, adjusting the pH value to 4.0-5.5 by using manganese powder, adding 65mL of hydrogen peroxide, stirring for 30min, adding 6.5g of ammonium sulfide, continuing stirring for 30min, and finally filtering to obtain a battery-grade manganese sulfate solution;
(2) preparing 20L of 2mol/L ammonium carbonate solution from ammonium carbonate and deionized water;
(3) preparing 20L of 0.5mol/L alkali liquor from ammonia water and deionized water, and adding 29g of diethylene glycol butyl ether;
(4) adding 1/5 deionized water as a base solution into the reaction kettle, opening a reaction kettle stirrer, adjusting the stirring speed to 600r/min, opening the reaction kettle, and heating to 40 ℃; adding the prepared battery-grade manganese sulfate solution and a precipitator into a reaction kettle in a parallel flow mode, wherein the feeding speed of the manganese sulfate solution is 5mL/min, and then adding an alkali liquor containing a complexing agent in a parallel flow mode to control the pH value of a reaction system to be 8.0-9.0 and the mole ratio n (CO) of carbonate to manganese ions3 2-):n(Mn2+) = 1.15: 1; after the feeding is finished, continuously preserving heat, stirring and aging for 8 hours;
(5) and (4) filtering the solid-liquid mixture obtained in the step (4), washing with deionized water for 5 times, then placing into a drying oven, and drying at 90 ℃ for 8 hours to obtain the battery grade spheroidal manganese carbonate.
The battery grade spheroidal manganese carbonate prepared in the example has the particle diameter D50 of 14.51 mu m and the tap density of 2.21g/cm3The alloy had an Mn content of 46.17%, an Al content of 0.0002wt%, an Fe content of 0.0004wt%, an Ca content of 0.0022wt%, an Cr content of 0.0001wt%, an Cd content of 0.0001wt%, an Cu content of 0.0002wt%, an Mg content of 0.0030wt%, an K content of 0.0009wt%, an Na content of 0.0016wt%, an Pb content of 0.0005wt%, an Ni content of 0.0001wt%, a Ti content of 0.0001wt%, an Zn content of 0.0005wt%, and an SO content of 0.0022wt%, and was subjected to heat treatment to prepare a steel sheet4 2-The content was 0.076 wt%. The appearance of the particles is observed to be spheroidal particles by a Scanning Electron Microscope (SEM), and the result is shown in figure 5; the product was subjected to particle size analysis using a particle sizer, and the results are shown in FIG. 6.
Comparative example 1:
(1) adding 1500g of electrolytic manganese metal sheet and 20L of deionized water into a beaker, adding 1500mL of 98% concentrated sulfuric acid for reaction, stirring for 30min, adjusting the pH value to 4.0-5.5 by using manganese powder, and finally filtering to obtain a battery-grade manganese sulfate solution; the content of Fe in the battery-grade manganese sulfate solution is higher than 0.001wt%, the content of Ca, Mg, K and Na in the battery-grade manganese sulfate solution is higher than 0.005wt%, and the content of heavy metal in the battery-grade manganese sulfate solution is higher than 0.001 wt%;
(2) preparing 20L of 2mol/L ammonium carbonate solution from ammonium carbonate and deionized water;
(3) preparing 20L of 0.5mol/L alkali liquor from ammonia water and deionized water, and adding 29g of diethylene glycol butyl ether;
(4) adding 1/5 deionized water as a base solution into the reaction kettle, opening a reaction kettle stirrer, adjusting the stirring speed to 600r/min, opening the reaction kettle, and heating to 40 ℃; adding the prepared battery-grade manganese sulfate solution and a precipitator into a reaction kettle in a parallel flow mode, wherein the feeding speed of the manganese sulfate solution is 5mL/min, and then adding an alkali liquor containing a complexing agent in a parallel flow mode to control the pH value of a reaction system to be 8.0-9.0 and the mole ratio n (CO) of carbonate to manganese ions3 2-):n(Mn2+) = 1.15: 1; after the feeding is finished, continuously preserving heat, stirring and aging for 8 hours;
(5) and (4) filtering the solid-liquid mixture obtained in the step (4), washing with deionized water for 5 times, then placing into a drying oven, and drying at 90 ℃ for 8 hours to obtain the battery grade spheroidal manganese carbonate.
The battery-grade spheroidal manganese carbonate particles prepared by the embodiment are wide in distribution range, large in particle size and irregular in shape, the product is easy to wrap impurity ions, the manganese content is low, and the surface color of the dried product is dark.
Comparative example 2:
(1) adding 1500g of electrolytic manganese metal sheet and 20L of deionized water into a beaker, adding 1500mL of 98% concentrated sulfuric acid for reaction, stirring for 30min, adjusting the pH value to 4.0-5.5 by using manganese powder, adding 65mL of hydrogen peroxide, stirring for 30min, adding 6.5g of ammonium sulfide, continuing stirring for 30min, and finally filtering to obtain a battery-grade manganese sulfate solution;
(2) preparing 20L of 2mol/L ammonium carbonate solution from ammonium carbonate and deionized water;
(3) preparing 20L of 0.5mol/L alkali liquor from ammonia water and deionized water, and adding 29g of diethylene glycol butyl ether;
(4) adding 1/5 deionized water as a base solution into the reaction kettle, opening a reaction kettle stirrer, adjusting the stirring speed to 600r/min, opening the reaction kettle, and heating to 40 ℃; sequentially adding the prepared battery-grade manganese sulfate solution and a precipitator into a reaction kettle, wherein the feeding speed of the manganese sulfate solution is 5mL/min, and adding an alkali liquor containing a complexing agent to control the pH value of a reaction system to be 8.0-9.0; after the feeding is finished, continuously preserving heat, stirring and aging for 8 hours;
(5) and (4) filtering the solid-liquid mixture obtained in the step (4), washing with deionized water for 5 times, then placing into a drying oven, and drying at 90 ℃ for 8 hours to obtain the battery grade spheroidal manganese carbonate.
The battery-grade spheroidal manganese carbonate particles prepared by the embodiment are wide in distribution range, large in particle size and irregular in shape, the product is easy to wrap impurity ions, the manganese content is low, and the surface color of the dried product is dark.
According to the detection results of the battery-grade spheroidal manganese carbonate prepared by the embodiment, the method for preparing the battery-grade spheroidal manganese carbonate has the advantages that when the reaction solution is prepared, adding electrolytic metal manganese sheets and deionized water into a dissolving tank together, firstly adding 98% concentrated sulfuric acid by mass for dissolving, then adjusting the pH value of the reaction solution to 4.0-5.5 by using manganese powder, then adding hydrogen peroxide to remove ferrous ions, adding an impurity removing agent to remove heavy metal ions, filtering, taking filtrate to obtain a battery-grade manganese sulfate solution with low impurity content, adding the battery-grade manganese sulfate solution, a precipitating agent and an alkali liquor containing a complexing agent into a reaction kettle in a parallel flow mode for reaction, in the precipitation process, the mole ratio of carbonate to manganese ions, the reaction temperature and the reaction time are controlled, after the feeding is finished, and then aging and filtering are carried out, and the prepared battery-grade spheroidal manganese carbonate has the following beneficial effects: (1) the prepared manganese carbonate particles are all spherical-like; (2) the prepared battery-grade spheroidal manganese carbonate is high in content and low in impurity content; (3) the prepared battery-grade spheroidal manganese carbonate has controllable particle size and good uniformity; (4) the battery-grade spheroidal manganese carbonate provided by the invention has the advantages of simple process flow and low production cost, and is suitable for industrial mass production.
Although the invention has been described in detail hereinabove with respect to a general description and specific embodiments thereof, it will be apparent to those skilled in the art that modifications or improvements may be made thereto based on the invention. Accordingly, such modifications and improvements are intended to be within the scope of the invention as claimed.
Claims (10)
1. A preparation method of battery-grade spheroidal manganese carbonate is characterized by comprising the following steps:
(1) adding the electrolytic manganese metal sheet and deionized water into a dissolving tank together, and controlling the solid-to-liquid ratio to be (1: 5) - (1: 20); adding 98% concentrated sulfuric acid by mass, and stirring for reaction for 10-60 min to obtain a reaction solution; the weight part ratio of the concentrated sulfuric acid with the mass fraction of 98% to the electrolytic manganese metal sheet is (1.7-2.1): 1;
(2) adjusting the pH value of the reaction solution to 4.0-5.5 by using manganese powder; adding hydrogen peroxide and stirring for 10-60 min to remove ferrous ions, wherein the amount of the hydrogen peroxide is 1-5% of the weight of the electrolytic manganese metal sheet in the step (1); adding an impurity removing agent, stirring for 10-60 min, and removing heavy metal ions, wherein the amount of the impurity removing agent is 0.2-1% of the weight of the metal manganese sheet in the step (1), so as to obtain an impurity removing solution;
(3) filtering the solution obtained in the step (2) after impurity removal, and taking filtrate to obtain a battery-grade manganese sulfate solution;
(4) adding a proper amount of deionized water into a full-automatic reaction kettle to serve as a base solution, wherein the addition amount of the base solution is 1/5-1/4 of the volume of the reaction kettle; opening a reaction kettle stirrer, wherein the stirring speed is 250-700 r/min; adding the battery-grade manganese sulfate solution and a precipitator into a reaction kettle respectively in a parallel flow mode, and adding an alkali liquor containing a complexing agent in a parallel flow mode to control the pH value of a reaction system to be 6.0-9.0; controlling the mole ratio n (CO) of carbonate to manganese ions during the precipitation process3 2-):n(Mn2+) = 1:1 to 2:1, the reaction temperature is 20-70 ℃, and the reaction time is 2-25 h; after the feeding is finished, continuously stirring and aging for 3-15 hours to obtain a reaction solution;
(5) filtering the reaction liquid obtained in the step (4), and taking filter residues; washing the filter residue with deionized water, and drying the filter residue in an oven at 60-100 ℃ for 6-15 h to obtain the battery-grade spheroidal manganese carbonate.
2. The method for preparing battery grade manganese carbonate sphere as claimed in claim 1, wherein the electrolytic manganese metal sheet in step (1) is a common electrolytic manganese metal sheet, and the manganese content in the electrolytic manganese metal sheet is more than 99.5 wt%.
3. The method for preparing battery grade manganese carbonate of similar spherical shape according to claim 1, wherein the impurity removing agent in step (2) is one or more of sodium dimethyl dithiocarbamate, ammonium sulfide, sodium sulfide, hydrogen sulfide and barium sulfide.
4. The method for preparing battery-grade spheroidal manganese carbonate according to claim 1, wherein the concentration of manganese sulfate in the battery-grade manganese sulfate solution in the step (3) is 0.1-4 mol/L, the content of Fe is less than 0.001wt%, the content of Ca, Mg, K and Na is less than 0.005wt%, and the content of heavy metals is less than 0.001 wt%.
5. The method for preparing battery grade spheric manganese carbonate according to claim 1, wherein the precipitant in step (4) is one or more of sodium carbonate, sodium bicarbonate, ammonium carbonate, ammonium bicarbonate and potassium carbonate.
6. The method for preparing battery grade manganese carbonate spheres as claimed in claim 1, wherein the complexing agent in step (4) is one or more of carboxymethylcellulose, sodium polyacrylate, polyvinylpyrrolidone, sodium metasilicate pentahydrate, sodium laurate, dodecyl dimethyl amine oxide, nonylphenol polyoxyethylene ether, diethylene glycol monobutyl ether, disodium ethylenediamine tetraacetate, ethyl acetate and n-butanol, and the concentration of the complexing agent in the alkaline solution containing the complexing agent is 1-30 g/L.
7. The method for preparing battery-grade spheroidal manganese carbonate according to claim 1, wherein the alkaline solution containing the complexing agent in the step (4) is an alkaline solution added with the complexing agent, wherein the alkaline solution is an aqueous solution of one or more of sodium hydroxide, ammonia water and potassium hydroxide, and the concentration of solute in the alkaline solution is 0.1-3 mol/L.
8. The method for preparing battery-grade spheroidal manganese carbonate according to claim 1, wherein the feeding speed of the battery-grade manganese sulfate solution in the step (4) is 1-30 mL/min.
9. The preparation method of battery-grade spheroidal manganese carbonate according to claim 1, characterized in that the particle morphology of the battery-grade spheroidal manganese carbonate prepared by the preparation method is spheroidal, the particle size index D50 is 5-20 μm, and the tap density is not less than 2.0g/cm3,Mn≥45.0wt%,Al≤0.001wt%,Fe≤0.001wt%,Ca≤0.005wt%,Cr≤0.001wt%,Cd≤0.001wt%,Cu≤0.001wt%,Mg≤0.005wt%,K≤0.005wt%,Na≤0.005wt%,Pb≤0.001wt%,Ni≤0.001wt%,Ti≤0.001wt%,Zn≤0.001wt%,SO4 2-≤0.1wt%。
10. The method for preparing battery-grade spheroidal manganese carbonate according to claim 1, wherein the number of times of washing the filter residue with deionized water in the step (5) is 3-5 times.
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