CN113603144A - Preparation method of modified manganese hydroxide, product and application thereof - Google Patents
Preparation method of modified manganese hydroxide, product and application thereof Download PDFInfo
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- CN113603144A CN113603144A CN202110874733.8A CN202110874733A CN113603144A CN 113603144 A CN113603144 A CN 113603144A CN 202110874733 A CN202110874733 A CN 202110874733A CN 113603144 A CN113603144 A CN 113603144A
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- Prior art keywords
- manganese hydroxide
- manganese
- modified manganese
- hydroxide
- solution
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- IPJKJLXEVHOKSE-UHFFFAOYSA-L manganese dihydroxide Chemical class [OH-].[OH-].[Mn+2] IPJKJLXEVHOKSE-UHFFFAOYSA-L 0.000 title claims abstract description 92
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- 239000011572 manganese Substances 0.000 claims abstract description 55
- 239000002245 particle Substances 0.000 claims abstract description 22
- 239000013078 crystal Substances 0.000 claims abstract description 19
- 238000005406 washing Methods 0.000 claims abstract description 12
- 241000533950 Leucojum Species 0.000 claims abstract description 11
- 239000012266 salt solution Substances 0.000 claims abstract description 11
- WPBNNNQJVZRUHP-UHFFFAOYSA-L manganese(2+);methyl n-[[2-(methoxycarbonylcarbamothioylamino)phenyl]carbamothioyl]carbamate;n-[2-(sulfidocarbothioylamino)ethyl]carbamodithioate Chemical compound [Mn+2].[S-]C(=S)NCCNC([S-])=S.COC(=O)NC(=S)NC1=CC=CC=C1NC(=S)NC(=O)OC WPBNNNQJVZRUHP-UHFFFAOYSA-L 0.000 claims abstract description 7
- HEMHJVSKTPXQMS-UHFFFAOYSA-M Sodium hydroxide Chemical compound [OH-].[Na+] HEMHJVSKTPXQMS-UHFFFAOYSA-M 0.000 claims description 45
- PWHULOQIROXLJO-UHFFFAOYSA-N Manganese Chemical compound [Mn] PWHULOQIROXLJO-UHFFFAOYSA-N 0.000 claims description 39
- 239000000243 solution Substances 0.000 claims description 39
- 229910052748 manganese Inorganic materials 0.000 claims description 35
- 238000000034 method Methods 0.000 claims description 25
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- 239000004094 surface-active agent Substances 0.000 claims description 19
- 238000006243 chemical reaction Methods 0.000 claims description 18
- QHGJSLXSVXVKHZ-UHFFFAOYSA-N dilithium;dioxido(dioxo)manganese Chemical compound [Li+].[Li+].[O-][Mn]([O-])(=O)=O QHGJSLXSVXVKHZ-UHFFFAOYSA-N 0.000 claims description 18
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- 229910052758 niobium Inorganic materials 0.000 claims description 4
- GUCVJGMIXFAOAE-UHFFFAOYSA-N niobium atom Chemical compound [Nb] GUCVJGMIXFAOAE-UHFFFAOYSA-N 0.000 claims description 4
- 229910052719 titanium Inorganic materials 0.000 claims description 4
- 229910052727 yttrium Inorganic materials 0.000 claims description 4
- VWQVUPCCIRVNHF-UHFFFAOYSA-N yttrium atom Chemical compound [Y] VWQVUPCCIRVNHF-UHFFFAOYSA-N 0.000 claims description 4
- 239000004471 Glycine Substances 0.000 claims description 3
- 150000003841 chloride salts Chemical class 0.000 claims description 3
- 238000001914 filtration Methods 0.000 claims description 3
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- QNAYBMKLOCPYGJ-REOHCLBHSA-N L-alanine Chemical compound C[C@H](N)C(O)=O QNAYBMKLOCPYGJ-REOHCLBHSA-N 0.000 claims description 2
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- 235000004279 alanine Nutrition 0.000 claims description 2
- 229910001437 manganese ion Inorganic materials 0.000 claims description 2
- 239000002904 solvent Substances 0.000 claims description 2
- VEXZGXHMUGYJMC-UHFFFAOYSA-M Chloride anion Chemical compound [Cl-] VEXZGXHMUGYJMC-UHFFFAOYSA-M 0.000 claims 1
- QCWXUUIWCKQGHC-UHFFFAOYSA-N Zirconium Chemical compound [Zr] QCWXUUIWCKQGHC-UHFFFAOYSA-N 0.000 claims 1
- 239000000203 mixture Substances 0.000 claims 1
- 239000003002 pH adjusting agent Substances 0.000 claims 1
- 229910052726 zirconium Inorganic materials 0.000 claims 1
- 239000012535 impurity Substances 0.000 abstract description 14
- QVGXLLKOCUKJST-UHFFFAOYSA-N atomic oxygen Chemical compound [O] QVGXLLKOCUKJST-UHFFFAOYSA-N 0.000 abstract description 7
- 239000001301 oxygen Substances 0.000 abstract description 7
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- 230000004048 modification Effects 0.000 abstract description 6
- 238000012986 modification Methods 0.000 abstract description 6
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- 239000011259 mixed solution Substances 0.000 description 22
- 239000000047 product Substances 0.000 description 11
- -1 tin oxide compound Chemical class 0.000 description 11
- VHUUQVKOLVNVRT-UHFFFAOYSA-N Ammonium hydroxide Chemical compound [NH4+].[OH-] VHUUQVKOLVNVRT-UHFFFAOYSA-N 0.000 description 10
- 235000011114 ammonium hydroxide Nutrition 0.000 description 9
- NUJOXMJBOLGQSY-UHFFFAOYSA-N manganese dioxide Chemical compound O=[Mn]=O NUJOXMJBOLGQSY-UHFFFAOYSA-N 0.000 description 9
- 239000000463 material Substances 0.000 description 9
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- 230000002572 peristaltic effect Effects 0.000 description 7
- AMWRITDGCCNYAT-UHFFFAOYSA-L hydroxy(oxo)manganese;manganese Chemical compound [Mn].O[Mn]=O.O[Mn]=O AMWRITDGCCNYAT-UHFFFAOYSA-L 0.000 description 6
- WHXSMMKQMYFTQS-UHFFFAOYSA-N Lithium Chemical compound [Li] WHXSMMKQMYFTQS-UHFFFAOYSA-N 0.000 description 5
- 238000007259 addition reaction Methods 0.000 description 5
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- 238000003786 synthesis reaction Methods 0.000 description 5
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- XGZVUEUWXADBQD-UHFFFAOYSA-L lithium carbonate Chemical compound [Li+].[Li+].[O-]C([O-])=O XGZVUEUWXADBQD-UHFFFAOYSA-L 0.000 description 3
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Images
Classifications
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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
- C01G45/02—Oxides; Hydroxides
-
- H—ELECTRICITY
- H01—ELECTRIC ELEMENTS
- H01M—PROCESSES OR MEANS, e.g. BATTERIES, FOR THE DIRECT CONVERSION OF CHEMICAL ENERGY INTO ELECTRICAL ENERGY
- H01M10/00—Secondary cells; Manufacture thereof
- H01M10/05—Accumulators with non-aqueous electrolyte
- H01M10/052—Li-accumulators
- H01M10/0525—Rocking-chair batteries, i.e. batteries with lithium insertion or intercalation in both electrodes; Lithium-ion batteries
-
- H—ELECTRICITY
- H01—ELECTRIC ELEMENTS
- H01M—PROCESSES OR MEANS, e.g. BATTERIES, FOR THE DIRECT CONVERSION OF CHEMICAL ENERGY INTO ELECTRICAL ENERGY
- H01M4/00—Electrodes
- H01M4/02—Electrodes composed of, or comprising, active material
- H01M4/36—Selection of substances as active materials, active masses, active liquids
- H01M4/48—Selection of substances as active materials, active masses, active liquids of inorganic oxides or hydroxides
- H01M4/50—Selection of substances as active materials, active masses, active liquids of inorganic oxides or hydroxides of manganese
- H01M4/505—Selection of substances as active materials, active masses, active liquids of inorganic oxides or hydroxides of manganese of mixed oxides or hydroxides containing manganese for inserting or intercalating light metals, e.g. LiMn2O4 or LiMn2OxFy
-
- 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
- C01P2004/01—Particle morphology depicted by an image
- C01P2004/04—Particle morphology depicted by an image obtained by TEM, STEM, STM or AFM
-
- C—CHEMISTRY; METALLURGY
- C01—INORGANIC CHEMISTRY
- C01P—INDEXING SCHEME RELATING TO STRUCTURAL AND PHYSICAL ASPECTS OF SOLID INORGANIC COMPOUNDS
- C01P2006/00—Physical properties of inorganic compounds
- C01P2006/40—Electric properties
-
- Y—GENERAL TAGGING OF NEW TECHNOLOGICAL DEVELOPMENTS; GENERAL TAGGING OF CROSS-SECTIONAL TECHNOLOGIES SPANNING OVER SEVERAL SECTIONS OF THE IPC; TECHNICAL SUBJECTS COVERED BY FORMER USPC CROSS-REFERENCE ART COLLECTIONS [XRACs] AND DIGESTS
- Y02—TECHNOLOGIES OR APPLICATIONS FOR MITIGATION OR ADAPTATION AGAINST CLIMATE CHANGE
- Y02E—REDUCTION OF GREENHOUSE GAS [GHG] EMISSIONS, RELATED TO ENERGY GENERATION, TRANSMISSION OR DISTRIBUTION
- Y02E60/00—Enabling technologies; Technologies with a potential or indirect contribution to GHG emissions mitigation
- Y02E60/10—Energy storage using batteries
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- Chemical & Material Sciences (AREA)
- Inorganic Chemistry (AREA)
- Chemical Kinetics & Catalysis (AREA)
- Electrochemistry (AREA)
- General Chemical & Material Sciences (AREA)
- Organic Chemistry (AREA)
- Engineering & Computer Science (AREA)
- Materials Engineering (AREA)
- Manufacturing & Machinery (AREA)
- Inorganic Compounds Of Heavy Metals (AREA)
- Battery Electrode And Active Subsutance (AREA)
Abstract
The invention provides a preparation method of modified manganese hydroxide, a product and application thereof, wherein soluble salt solution containing an element A is doped in soluble salt solution of manganese, namely, the element A is doped on the basis of the manganese hydroxide for modification, the element A and Mn are uniformly precipitated, modified particles with snowflake lamellar structures are synthesized, and the modified particles have uniform crystal phase and low impurity content. The doped element A can form a compact coating layer on the surface of the manganese hydroxide particles, so that the manganese hydroxide is prevented from contacting oxygen in the air, the phase change caused by oxidation of the manganese hydroxide is avoided, and the crystal structure of the manganese hydroxide is protected. Therefore, the problems of high impurity content, low washing efficiency and damaged crystal structure in the existing preparation method are solved.
Description
Technical Field
The invention relates to the technical field of precursors of positive active materials, in particular to a preparation method of modified manganese hydroxide, a product and application thereof.
Background
Currently, lithium manganate sold in the market is mainly prepared by taking manganese dioxide (EMD) or manganous manganic oxide as a manganese source for electrolysis. The lithium manganate prepared by adopting electrolytic manganese dioxide as a raw material has poor high-temperature cycle performance and storage performance due to the uncontrollable impurities and morphology of EMD. While the problems of impurities and controllable appearance of manganese source materials are solved by using the trimanganese tetroxide as the raw material, the manganese element in the trimanganese tetroxide is in the valence states of +2 and +3, the valence state of the manganese element in the lithium manganate is +3, and the lithium element in the lithium carbonate can be embedded unevenly in the process of synthesizing the lithium manganate by using the trimanganese tetroxide as the raw material.
Based on the defects, the method for preparing the lithium manganate cathode material by using the manganese hydroxide as the raw material is also provided at present, and the problem of uneven valence state of the manganese element cannot exist in the preparation of the raw material. At present, the preparation method of manganese hydroxide is mainly prepared by reacting soluble manganese salt with sodium hydroxide, potassium hydroxide or ammonia water (ammonium monohydrate).
Chinese patent document (CN201110280431.4) mentions that spherical manganese hydroxide is continuously precipitated by ammonia water under the protection of nitrogen by using a manganese metal sheet and sulfuric acid to obtain a manganese sulfate solution, the precipitate is slurried by a stoichiometric lithium hydroxide solution and then is added into a high-pressure reaction kettle, the temperature and the oxygen partial pressure are controlled to react for a certain time so as to obtain pure-phase manganese dioxide, then carbon dioxide is introduced to react for a certain time so that lithium carbonate is uniformly precipitated on the surface of the manganese dioxide, the reaction is finished and then the lithium carbonate is filtered, and the precipitate is subjected to microwave drying, sintering and crushing classification to obtain the spherical lithium manganate positive electrode material with high tap density. However, the method is complex, the consistency of the product is low, and the method is not suitable for industrial production.
Chinese patent document (CN201110344396.8) proposes a preparation method of a spherical manganese hydroxide precursor of lithium manganate with good sphericity and strong oxidation resistance. The method is characterized in that the manganese hydroxide is prevented from being oxidized by atmosphere protection and adding a reducing agent in the synthesis process.
Chinese patent document (CN201810478501.9) mentions a new method for recovering manganese from titanium white waste acid, which extracts manganese from the waste acid by controlling the neutralization process of the waste acid and lime or carbide slag and by chemical oxidation and precipitation, so that the waste residue or waste water does not contain residual manganese, thereby achieving the purpose of protecting the environment.
However, the technical solutions involved in the above patents are based on the reaction of manganese sulfate solution with ammonia water or sodium hydroxide, and the hydrolysis into manganese hydroxide, all of which have the following problems: 1) in the synthesis process, inert gas atmosphere protection is required to be provided or a reducing agent is required to be added to prevent manganese hydroxide from being oxidized, so that the production cost is extremely high; 2) a large amount of sodium sulfate impurities are occluded in the synthesis process, the washing process is usually carried out in an inert atmosphere, the washing is difficult, and the performance of the lithium manganate anode material synthesized subsequently is easily influenced; 3) the obtained product is also easily oxidized by oxygen in the air when placed in the air, and phase change occurs, so that the defects of non-uniform crystal phase and disordered crystal structure of the product are caused.
In view of the above, it is necessary to provide a technical solution to the above problems.
Disclosure of Invention
One of the objects of the present invention is: provides a preparation method of modified manganese hydroxide, which solves the problems of high impurity content, low washing efficiency and damaged crystal structure in the existing preparation method.
In order to achieve the purpose, the invention adopts the following technical scheme:
a preparation method of modified manganese hydroxide comprises the following steps:
s1, adding soluble salt containing an element A into soluble salt of manganese, and mixing to obtain a mixed solution A, wherein the element A is at least one of yttrium (Y), nickel (Ni), cobalt (Co), magnesium (Mg), titanium (Ti), niobium (Nb), zirconium (Zr), bismuth (Bi), boron (B), antimony (Sb), cerium (Ce), aluminum (Al), molybdenum (Mo) and lanthanum (La); the molar ratio of the A element to Mn is x: (1-x), wherein x is more than 0 and less than or equal to 0.3;
s2, adding a surfactant solvent into the reaction kettle, stirring, and simultaneously adding the mixed solution A obtained in the step S1 and a precipitator for reaction to obtain slurry;
s3, adjusting the pH value of the slurry obtained in the step S2 to 8-13, aging, washing and filtering to obtain a primary product;
s4, drying the primary product obtained in the step S3 to obtain the snowflake lamellar modified manganese hydroxide.
Preferably, the particle structure of the modified manganese hydroxide is a snowflake lamellar single crystal structure.
Preferably, in the step S1, the concentration of manganese ions in the soluble salt solution of manganese is 1-4 mol/L.
Preferably, the soluble salt of manganese is at least one of chloride salt, sulfate, nitrate and acetate; the soluble salt solution containing the element A is at least one of chloride salt, sulfate, nitrate and acetate.
Preferably, in step S2, the surfactant solution is added into deionized water, stirred at a stirring speed of 200-1200 rpm for 30-100 min, and then the mixed manganese a solution and the precipitant are added at a feeding flow rate of 1-200 mL/min to react, so as to obtain a slurry. More preferably, the stirring speed is 500-1000 rpm, the stirring time is 40-80 min, and the feeding flow rate of the mixed manganese A solution is 5-100 mL/min. Preferably, the stirring speed is 500-800 rpm, the stirring time is 40-60 min, and the feeding flow rate of the mixed manganese A solution is 10-50 mL/min. More preferably, the feeding flow rate of the mixed manganese A solution is 10-20 mL/min.
Wherein, the stirring speed in the step S2 is controlled within the above range, the high molecular surfactant is more uniformly dispersible, and the manganese a mixed solution is added at the stirring speed, so that Mn and a element a can be more uniformly dispersed and precipitated, so that Mn can better react with the precipitant to generate manganese hydroxide, and the element a is doped, thereby forming a dense coating layer on the surface of manganese hydroxide particles, preventing the manganese hydroxide from contacting oxygen in the air, and further obtaining the modified manganese hydroxide doped with the element a with uniform crystal phase and low impurity content.
Preferably, the surfactant is at least one of glycine, alanine and leucine; the precipitant is at least one of sodium hydroxide, potassium hydroxide and lithium hydroxide.
Preferably, the concentration of the surfactant solution is 1-50 g/L; the concentration of the precipitant is 0.5-6 mol/L. More preferably, the concentration of the surfactant solution is 1-10 g/L; the concentration of the precipitant is 1-6 mol/L.
Preferably, in step S3, a pH regulator is added at a feed flow rate of 1-200 mL/min to regulate the pH value of the slurry to 8-13, and then the slurry is aged for 4-25 h, discharged, washed, and filtered to obtain a primary product. More preferably, the feeding flow rate of the pH regulator is 5-100 mL/min, the pH value is 9-11, and the aging time is 4-18 h. Preferably, the feeding flow rate of the pH regulator is 10-50 mL/min, the pH value is 9-11, and the aging time is 4-12 h. Further preferably, the feeding flow rate of the pH regulator is 10-20 mL/min, the pH value is 9-11, and the aging time is 6-8 h. Wherein the pH regulator can be at least one of sodium hydroxide, potassium hydroxide, ammonia water, sodium carbonate and sodium bicarbonate. Preferably, the pH regulator is ammonia water to avoid secondary pollution. Because the reaction of the manganese A mixed solution in the slurry and the precipitator is uniform and controllable, the generated manganese hydroxide has a complete crystal lattice structure, and impurities in the reaction process are basically blocked outside the manganese hydroxide crystal lattice structure by the coating of the element A, so that the washing difficulty is greatly reduced, and the washing efficiency and the washing effect are improved.
Preferably, in step S4, the drying temperature may be 60 to 70 ℃, 70 to 80 ℃, 80 to 90 ℃, 90 to 100 ℃, or 100 to 120 ℃, and the drying time may be 2 to 4 hours, 4 to 6 hours. More preferably, the drying temperature is 80-90 ℃, 90-100 ℃, or 100-120 ℃, and the drying time is 2-4 h. More preferably, the drying temperature is 100 ℃ and the drying time is 3 h.
The second object of the present invention is to provide a modified manganese hydroxide prepared by the method for preparing modified manganese hydroxide according to any one of the above formulas, wherein the modified manganese hydroxide has a chemical formula of [ AxMn(1-x)](OH)2，0<x is less than or equal to 0.3. Wherein, the value range of x can be 0<x≤0.1，0.1<x≤0.2，0.2<x is less than or equal to 0.3. The specific value of x is related to the molar ratio of A to Mn in the adopted raw materials, namely the ratio of the molar mass of the element A in the soluble salt containing the element A to the molar mass of Mn in the soluble salt of manganese is considered to be x/(1-x). The element A may be yttrium (Y), nickel (Ni), cobalt (Co), magnesium (Mg), titanium (Ti), niobium (Nb), zirconium (Zr), bismuth (Bi), boron (B), antimony (Sb), cerium (Ce), aluminum (Al), molybdenum (Mo) and lanthanum (La) in various combinations, and the molar amount of the element A is the total molar amount of the various combinations. When the element A is a combination of two elements, the element A has a better effect compared with single element doping modification under a proper quality, and the synergistic effect of the two elements doped together is stronger.
Preferably, the median particle diameter D50 of the manganese hydroxide can be 3-5 μm, 5-10 μm, 10-15 μm, 15-20 μm, 20-25 μm, 25-30 μm. More preferably, the manganese hydroxide has a median particle diameter D50 of 5-10 μm, 10-15 μm, 15-20 μm, 20-25 μm. The particle size of the modified manganese hydroxide particles obtained by the preparation method is small, and when the modified manganese hydroxide particles and a lithium source are prepared into the lithium manganate cathode material, the modified manganese hydroxide particles are more favorable for diffusion and migration of lithium elements, and can also reduce the sintering temperature, reduce the sintering time and improve the sintering efficiency. In addition, because the surface of the manganese hydroxide is also doped with the element A, the element A can promote the grain growth in the lithium manganate synthesis process and simultaneously inhibit the appearance of an octahedral spinel structure.
The invention also aims to provide a positive electrode material which comprises the lithium manganate prepared by taking the modified manganese hydroxide as a raw material. And sintering the modified manganese hydroxide and a lithium source together to prepare the lithium manganate cathode material.
The invention also provides a lithium ion battery, which comprises a positive pole piece, a negative pole piece and a separation film which is arranged between the positive pole piece and the negative pole piece, wherein the positive pole piece comprises the positive pole material.
The positive pole piece comprises a positive current collector and a positive active substance layer coated on at least one surface of the positive current collector, and the lithium manganate positive material is made into slurry and coated on the surface of the positive current collector to form the positive active substance layer. The positive electrode current collector is generally a structure or part that collects current, and may be any of various materials suitable for use as a positive electrode current collector of a lithium ion battery in the art, for example, the positive electrode current collector may include, but is not limited to, a metal foil, and the like, and more specifically, may include, but is not limited to, an aluminum foil, and the like.
The negative pole piece comprises a negative current collector and a negative active material layer coated on at least one surface of the negative current collector. The negative electrode active material layer may include, but is not limited to, one or more of graphite, soft carbon, hard carbon, carbon fiber, mesocarbon microbeads, silicon-based materials, tin-based materials, lithium titanate, or other metals capable of forming an alloy with lithium. Wherein, the graphite can be selected from one or more of artificial graphite, natural graphite and modified graphite; the silicon-based material can be one or more selected from simple substance silicon, silicon-oxygen compound, silicon-carbon compound and silicon alloy; the tin-based material can be one or more selected from simple substance tin, tin oxide compound and tin alloy. While the negative electrode current collector is generally a structure or part that collects current, the negative electrode current collector may be any material suitable for use as a negative electrode current collector of a lithium ion battery in the art, for example, the negative electrode current collector may include, but is not limited to, a metal foil, and the like, and more specifically, may include, but is not limited to, a copper foil, and the like.
And the separator may be any material suitable for a lithium ion battery separator in the art, and for example, may be one or a combination of more of polyethylene, polypropylene, polyvinylidene fluoride, aramid, polyethylene terephthalate, polytetrafluoroethylene, polyacrylonitrile, polyimide, polyamide, polyester, natural fiber, and the like.
Compared with the prior art, the invention has the beneficial effects that:
1) according to the preparation method provided by the invention, the soluble salt solution containing the element A is doped in the soluble salt solution of manganese, namely the element A is doped on the basis of manganese hydroxide for modification, the element A and Mn are uniformly precipitated, modified particles with snowflake lamellar structures are synthesized, and the modified particle products are uniform in crystalline phase and low in impurity content. The doped element A can form a compact coating layer on the surface of the manganese hydroxide particles, so that the manganese hydroxide is prevented from contacting oxygen in the air, the phase change caused by oxidation of the manganese hydroxide is avoided, and the crystal structure of the manganese hydroxide is protected. Therefore, the problems of high impurity content, low washing efficiency and damaged crystal structure in the existing preparation method are solved.
2) The preparation method provided by the invention has the advantages that the protection of inert atmosphere is not needed in the reaction process and the washing process, the addition of a reducing agent is not needed, the vacuum drying is not needed, the preparation process is simple, and the production cost is greatly reduced.
3) In addition, the surface of the manganese hydroxide prepared by the method is doped with the element A, so that the element A can promote the growth of lithium manganate crystal grains in the process of synthesizing the lithium manganate positive active material, and simultaneously inhibit the occurrence of the lithium manganate with an octahedral spinel structure, thereby ensuring the electrochemical performance of the lithium manganate positive active material.
Drawings
FIG. 1 is an electron micrograph of a modified manganese hydroxide according to example 1 of the present invention.
FIG. 2 is an enlarged electron microscope image of the modified manganese hydroxide of FIG. 1.
Detailed Description
In order to make the technical solutions and advantages of the present invention clearer, the present invention and its advantages will be described in further detail below with reference to the following detailed description and the accompanying drawings, but the embodiments of the present invention are not limited thereto.
Example 1
A preparation method of modified manganese hydroxide comprises the following steps:
(1) preparing raw materials:
preparing a manganese A mixed solution: adding soluble salt containing an element A into soluble salt of manganese, and mixing to obtain a mixed solution A, wherein the element A is at least one of yttrium (Y), nickel (Ni), cobalt (Co), magnesium (Mg), titanium (Ti), niobium (Nb), zirconium (Zr), bismuth (Bi), boron (B), antimony (Sb), cerium (Ce), aluminum (Al), molybdenum (Mo) and lanthanum (La); the molar ratio of the A element to Mn is 2: 8. the preparation method comprises the following specific steps: 2543.5g of MnSO are weighed first4·H2O, dissolved in 4500g of deionized water at about 50 ℃, 28.91g of NiSO was weighed4·7H2O and 46.59g YSO4·8H2And adding O into the prepared manganese sulfate solution, and fixing the volume to 5L to obtain a manganese A mixed solution.
Preparing a high molecular surfactant solution: weighing 2g of high molecular surfactant glycine, and dissolving with 3L of deionized water to obtain a high molecular surfactant solution with the concentration of 0.7 g/L.
preparing a pH regulator: 700g of 25% ammonia water solution is weighed, and the volume is fixed to 2L, so that 10M ammonia water solution is obtained.
Preparing a precipitator: 1200g of sodium hydroxide solid is weighed and the volume is adjusted to 5L, thus obtaining 6M sodium hydroxide solution.
(2) Feeding and reacting: firstly, adding the prepared macromolecular surfactant solution into a reaction kettle, and stirring for 40min at the stirring speed of 800 rpm; then, the prepared manganese A mixed solution and the precipitant sodium hydroxide solution are added simultaneously by a peristaltic pump at a feeding rate of 10mL/min, and the materials are fed for 8.4 h.
(3) Aging and washing of slurry: after the feeding is finished, adding a prepared pH regulator ammonia water solution by using a peristaltic pump at a rate of 20mL/min, adjusting the pH to 10, keeping the stirring speed at 800rpm, aging for 6h, and then performing centrifugal filtration on the slurry by using a centrifugal machine with the model number of YLT-1200 to obtain a filter cake. Then, the slurry was washed 1 time with 6g/L sodium hydroxide solution at 35 ℃ and 1 time with pure water, followed by dehydration.
(4) Drying: and (3) putting the filter cake into an electric heating forced air drier (model 101-0ABS), drying at constant temperature of 100 ℃ for 3h, and taking out to obtain the snowflake lamellar modified manganese hydroxide.
The molecular formula of the snowflake lamellar modified manganese hydroxide prepared by the embodiment is [ Ni ]0.1Y0.1Mn0.8](OH)2The precursor particles of the modified manganese hydroxide consist of snowflake lamellar monocrystal structure particles. The median particle diameter D50 of the modified manganese hydroxide is 3-30 μm.
Example 2
Different from the example 1, the preparation of the manganese-aluminum mixed solution is carried out, and the mol (a) of the soluble salt containing the element a and the soluble salt of manganese: mol (mn) ═ 3: 7, the molecular formula of the modified manganese hydroxide prepared in this example is [ Ni ]0.1 Y0.2Mn0.7](OH)2。
The rest is the same as embodiment 1, and the description is omitted here.
Example 3
Different from the example 1, the preparation of the manganese-aluminum mixed solution is carried out, and the mol (a) of the soluble salt containing the element a and the soluble salt of manganese: mol (mn) ═ 2: 8, the molecular formula of the modified manganese hydroxide prepared in the example is [ Ni ]0.1 Al0.1Mn0.8](OH)2。
The rest is the same as embodiment 1, and the description is omitted here.
Example 4
Different from the example 1, the preparation of the manganese-aluminum mixed solution is carried out, and the mol (a) of the soluble salt containing the element a and the soluble salt of manganese: mol (mn) ═ 2: 8, the molecular formula of the modified manganese hydroxide prepared in the example is [ Ni ]0.2Mn0.8](OH)2。
The rest is the same as embodiment 1, and the description is omitted here.
Example 5
Different from the example 1, the preparation of the manganese-aluminum mixed solution is carried out, and the mol (a) of the soluble salt containing the element a and the soluble salt of manganese: mol (mn) ═ 2: 8 prepared in this exampleThe molecular formula of the modified manganese hydroxide is [ Al ]0.2Mn0.8](OH)2。
The rest is the same as embodiment 1, and the description is omitted here.
Example 6
Different from the example 1, the preparation of the manganese-aluminum mixed solution is carried out, and the mol (a) of the soluble salt containing the element a and the soluble salt of manganese: mol (mn) ═ 2: 8, the molecular formula of the modified manganese hydroxide prepared in this example is [ Y ]0.2Mn0.8](OH)2。
The rest is the same as embodiment 1, and the description is omitted here.
Example 7
Different from the example 1, the preparation of the manganese-aluminum mixed solution is carried out, and the mol (a) of the soluble salt containing the element a and the soluble salt of manganese: mol (mn) ═ 3: 7, the molecular formula of the modified manganese hydroxide prepared in this example is [ Y ]0.3Mn0.7](OH)2。
The rest is the same as embodiment 1, and the description is omitted here.
Example 8
The difference from example 1 is the addition reaction.
Firstly, adding the prepared macromolecular surfactant solution into a reaction kettle, and stirring for 40min at the stirring speed of 800 rpm; then, the prepared manganese A mixed solution and the precipitant sodium hydroxide solution are added simultaneously by a peristaltic pump at a feeding rate of 50mL/min, and fed for 8.4 h.
The rest is the same as embodiment 1, and the description is omitted here.
Example 9
The difference from example 1 is the addition reaction.
Firstly, adding the prepared macromolecular surfactant solution into a reaction kettle, and stirring for 40min at the stirring speed of 800 rpm; then, the prepared manganese A mixed solution and the precipitant sodium hydroxide solution are added simultaneously by a peristaltic pump at a feeding speed of 100mL/min, and the materials are fed for 8.4 h.
The rest is the same as embodiment 1, and the description is omitted here.
Example 10
The difference from example 1 is the addition reaction.
Firstly, adding the prepared macromolecular surfactant solution into a reaction kettle, and stirring for 40min at the stirring speed of 800 rpm; then, the prepared manganese A mixed solution and the precipitant sodium hydroxide solution are added simultaneously by a peristaltic pump at a feeding speed of 200mL/min, and the materials are fed for 8.4 h.
The rest is the same as embodiment 1, and the description is omitted here.
Example 11
The difference from example 1 is the addition reaction.
Firstly, adding the prepared macromolecular surfactant solution into a reaction kettle, and stirring for 40min at the stirring speed of 800 rpm; the prepared manganese A mixed solution was then added at a feed rate of 10mL/min using a peristaltic pump, while the precipitant sodium hydroxide solution was added at a feed rate of 50mL/min and fed for 8.4 h.
The rest is the same as embodiment 1, and the description is omitted here.
Example 12
The difference from example 1 is the addition reaction.
Firstly, adding the prepared macromolecular surfactant solution into a reaction kettle, and stirring for 40min at the stirring speed of 800 rpm; the prepared manganese A mixed solution was then added at a feed rate of 50mL/min using a peristaltic pump, while the precipitant sodium hydroxide solution was added at a feed rate of 10mL/min and fed for 8.4 h.
The rest is the same as embodiment 1, and the description is omitted here.
Comparative example 1
Different from example 1, the configuration of the manganese a mixed solution was not changed to the comparative example, and the soluble salt solution containing the a element was not added.
The rest is the same as embodiment 1, and the description is omitted here.
The performance of the manganese hydroxide obtained in the above examples 1 to 12 and comparative example 1 was tested. The measurements are shown in Table 1.
TABLE 1
The test results show that the modified manganese hydroxide prepared by the method effectively improves the content of Mn, reduces the content of impurities in the modified manganese hydroxide, and the obtained modified manganese hydroxide has complete crystal structure and high crystallinity. Correspondingly, as can be seen from the electron microscope images shown in fig. 1-2, the modified manganese hydroxide prepared by the invention is in a snowflake lamellar structure, and the crystal structure is complete. The preparation method is mainly characterized in that soluble salt solution containing the element A is doped in soluble salt solution of manganese, namely, the element A is doped on the basis of manganese hydroxide for modification, the element A and Mn are uniformly precipitated, modified particles with snowflake lamellar structures are synthesized, and the modified particle products have uniform crystalline phases and low impurity content. The doped element A can form a compact coating layer on the surface of the manganese hydroxide particles, so that the manganese hydroxide is prevented from contacting oxygen in the air, the phase change caused by oxidation of the manganese hydroxide is avoided, and the crystal structure of the manganese hydroxide is protected. Compared with the conventional hydrolysis reaction of the manganese sulfate solution and ammonia water or sodium hydroxide, the method provided by the invention has the advantages that inert gas is not required to be provided or a reducing agent is not required to be added in the preparation process to prevent the manganese hydroxide from being oxidized, the synthesis process is also not required to be carried out in an inert atmosphere, impurities are easily washed away, and the obtained product is placed in the air and is not easily oxidized by oxygen in the air, so that the crystal structure of the manganese hydroxide is ensured from multiple aspects.
In addition, as can be seen from the comparison of the test results of examples 1 to 12, the purity and crystallinity of the final modified manganese hydroxide are affected by the content of the doped element a, the feeding rate of the manganese a mixed solution, the feeding rate of the precipitant, and other factors. Through repeated experimental tests, the inventor finds that the purity, the lattice structure and the crystallinity of the modified manganese hydroxide are easier to ensure under the preparation conditions of the example 1. Under the condition, the uniform precipitability of the element A and the element Mn is better, the reaction of the precipitator and the manganese A mixed solution is more sufficient, the element A can be better coated on the surface of the manganese hydroxide while the manganese hydroxide is generated, so that the manganese hydroxide is prevented from being oxidized by contacting with air, the integrity of a crystal lattice structure of the manganese hydroxide is ensured, and the modified manganese hydroxide with lower impurity content and higher crystallinity is obtained.
Variations and modifications to the above-described embodiments may also occur to those skilled in the art, which fall within the scope of the invention as disclosed and taught herein. Therefore, the present invention is not limited to the above-mentioned embodiments, and any obvious improvement, replacement or modification made by those skilled in the art based on the present invention is within the protection scope of the present invention. Furthermore, although specific terms are employed herein, they are used in a generic and descriptive sense only and not for purposes of limitation.
Claims (13)
1. The preparation method of the modified manganese hydroxide is characterized by comprising the following steps:
s1, adding soluble salt containing an element A into soluble salt of manganese, and mixing to obtain a mixed manganese A solution, wherein the element A is at least one of yttrium, nickel, cobalt, magnesium, titanium, niobium, zirconium, bismuth, boron, antimony, cerium, aluminum, molybdenum and lanthanum; the molar ratio of the A element to Mn is x: (1-x), wherein x is more than 0 and less than or equal to 0.3;
s2, adding a surfactant solvent into the reaction kettle, stirring, and simultaneously adding the mixed manganese A solution obtained in the step S1 and a precipitator for reaction to obtain slurry;
s3, adjusting the pH value of the slurry obtained in the step S2 to 8-13, aging, washing and filtering to obtain a primary product;
s4, drying the primary product obtained in the step S3 to obtain the modified manganese hydroxide with the snowflake lamellar structure.
2. The method for preparing modified manganese hydroxide according to claim 1, wherein the particle structure of the modified manganese hydroxide is a snowflake lamellar single crystal structure.
3. The method for preparing modified manganese hydroxide according to claim 1, wherein in step S1, the concentration of manganese ions in the soluble salt solution of manganese is 1-4 mol/L.
4. The method for preparing modified manganese hydroxide according to claim 1 or 3, wherein said soluble salt of manganese is at least one of chloride, sulfate, nitrate, and acetate; the soluble salt solution containing the element A is at least one of chloride salt, sulfate, nitrate and acetate.
5. The method for preparing modified manganese hydroxide according to claim 1, wherein in step S2, the surfactant solution is added into deionized water, the mixture is stirred at a stirring speed of 200-1200 rpm for 30-100 min, and then the mixed manganese a solution and the precipitant are added at a feeding flow rate of 1-200 mL/min for reaction, so as to obtain slurry.
6. The method for preparing modified manganese hydroxide according to claim 1 or 5, wherein the surfactant is at least one of glycine, alanine, leucine; the precipitant is at least one of sodium hydroxide, potassium hydroxide and lithium hydroxide.
7. The method for preparing modified manganese hydroxide according to claim 6, wherein the concentration of the surfactant solution is 1-50 g/L; the concentration of the precipitant is 0.5-6 mol/L.
8. The method for preparing modified manganese hydroxide according to claim 1, wherein in step S3, a pH adjusting agent is added at a feed flow rate of 1-200 mL/min to adjust the pH of the slurry to 8-13, and then the slurry is aged for 4-25 h, discharged, washed, and filtered to obtain an initial product.
9. The method for preparing modified manganese hydroxide according to claim 1, wherein in step S4, the drying temperature is 60-120 ℃ and the drying time is 2-6 h.
10. The modified manganese hydroxide prepared by the preparation method of the modified manganese hydroxide according to any one of claims 1 to 9, wherein the chemical formula of the modified manganese hydroxide is [ A ]xMn(1-x)](OH)2，0<x≤0.3。
11. The modified manganese hydroxide according to claim 10, wherein the median particle diameter D50 of the manganese hydroxide is 3 to 30 μm.
12. A positive electrode material comprising the lithium manganate produced from the modified manganese hydroxide according to claim 10 or 11 as a raw material.
13. A lithium ion battery comprising a positive electrode sheet, a negative electrode sheet, and a separator spaced between the positive electrode sheet and the negative electrode sheet, wherein the positive electrode sheet comprises the positive electrode material of claim 12.
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