CN114455648A - Preparation method of double-layer composite low-cost lithium-rich manganese-based precursor - Google Patents
Preparation method of double-layer composite low-cost lithium-rich manganese-based precursor Download PDFInfo
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- 239000011572 manganese Substances 0.000 title claims abstract description 51
- PWHULOQIROXLJO-UHFFFAOYSA-N Manganese Chemical compound [Mn] PWHULOQIROXLJO-UHFFFAOYSA-N 0.000 title claims abstract description 43
- 229910052748 manganese Inorganic materials 0.000 title claims abstract description 42
- 239000002243 precursor Substances 0.000 title claims abstract description 41
- WHXSMMKQMYFTQS-UHFFFAOYSA-N Lithium Chemical compound [Li] WHXSMMKQMYFTQS-UHFFFAOYSA-N 0.000 title claims abstract description 39
- 229910052744 lithium Inorganic materials 0.000 title claims abstract description 39
- 239000002131 composite material Substances 0.000 title claims abstract description 15
- 238000002360 preparation method Methods 0.000 title claims abstract description 12
- HEMHJVSKTPXQMS-UHFFFAOYSA-M Sodium hydroxide Chemical compound [OH-].[Na+] HEMHJVSKTPXQMS-UHFFFAOYSA-M 0.000 claims abstract description 117
- 238000006243 chemical reaction Methods 0.000 claims abstract description 55
- 239000000243 solution Substances 0.000 claims abstract description 55
- CDBYLPFSWZWCQE-UHFFFAOYSA-L sodium carbonate Substances [Na+].[Na+].[O-]C([O-])=O CDBYLPFSWZWCQE-UHFFFAOYSA-L 0.000 claims abstract description 24
- VHUUQVKOLVNVRT-UHFFFAOYSA-N Ammonium hydroxide Chemical compound [NH4+].[OH-] VHUUQVKOLVNVRT-UHFFFAOYSA-N 0.000 claims abstract description 22
- 235000011114 ammonium hydroxide Nutrition 0.000 claims abstract description 22
- 239000003513 alkali Substances 0.000 claims abstract description 17
- IJGRMHOSHXDMSA-UHFFFAOYSA-N Atomic nitrogen Chemical compound N#N IJGRMHOSHXDMSA-UHFFFAOYSA-N 0.000 claims abstract description 14
- 238000003756 stirring Methods 0.000 claims abstract description 13
- 239000008139 complexing agent Substances 0.000 claims abstract description 12
- 229910000029 sodium carbonate Inorganic materials 0.000 claims abstract description 12
- 239000007788 liquid Substances 0.000 claims abstract description 10
- 239000002585 base Substances 0.000 claims abstract description 9
- 239000007853 buffer solution Substances 0.000 claims abstract description 7
- 238000000975 co-precipitation Methods 0.000 claims abstract description 7
- 229910052757 nitrogen Inorganic materials 0.000 claims abstract description 7
- KRKNYBCHXYNGOX-UHFFFAOYSA-N citric acid Chemical compound OC(=O)CC(O)(C(O)=O)CC(O)=O KRKNYBCHXYNGOX-UHFFFAOYSA-N 0.000 claims description 18
- XLYOFNOQVPJJNP-UHFFFAOYSA-N water Substances O XLYOFNOQVPJJNP-UHFFFAOYSA-N 0.000 claims description 17
- 238000000034 method Methods 0.000 claims description 16
- 229910052751 metal Inorganic materials 0.000 claims description 15
- 239000002184 metal Substances 0.000 claims description 15
- 239000012266 salt solution Substances 0.000 claims description 15
- PXHVJJICTQNCMI-UHFFFAOYSA-N nickel Substances [Ni] PXHVJJICTQNCMI-UHFFFAOYSA-N 0.000 claims description 14
- CIWBSHSKHKDKBQ-JLAZNSOCSA-N Ascorbic acid Chemical compound OC[C@H](O)[C@H]1OC(=O)C(O)=C1O CIWBSHSKHKDKBQ-JLAZNSOCSA-N 0.000 claims description 12
- XEEYBQQBJWHFJM-UHFFFAOYSA-N Iron Chemical compound [Fe] XEEYBQQBJWHFJM-UHFFFAOYSA-N 0.000 claims description 12
- 239000002002 slurry Substances 0.000 claims description 8
- 230000032683 aging Effects 0.000 claims description 6
- 239000011668 ascorbic acid Substances 0.000 claims description 6
- 229960005070 ascorbic acid Drugs 0.000 claims description 6
- 235000010323 ascorbic acid Nutrition 0.000 claims description 6
- 229910052742 iron Inorganic materials 0.000 claims description 6
- 238000000926 separation method Methods 0.000 claims description 6
- 239000012716 precipitator Substances 0.000 claims description 5
- 238000012216 screening Methods 0.000 claims description 5
- 229910052759 nickel Inorganic materials 0.000 claims description 3
- NWZSZGALRFJKBT-KNIFDHDWSA-N (2s)-2,6-diaminohexanoic acid;(2s)-2-hydroxybutanedioic acid Chemical compound OC(=O)[C@@H](O)CC(O)=O.NCCCC[C@H](N)C(O)=O NWZSZGALRFJKBT-KNIFDHDWSA-N 0.000 claims description 2
- LXAHHHIGZXPRKQ-UHFFFAOYSA-N 5-fluoro-2-methylpyridine Chemical compound CC1=CC=C(F)C=N1 LXAHHHIGZXPRKQ-UHFFFAOYSA-N 0.000 claims description 2
- ATRRKUHOCOJYRX-UHFFFAOYSA-N Ammonium bicarbonate Chemical compound [NH4+].OC([O-])=O ATRRKUHOCOJYRX-UHFFFAOYSA-N 0.000 claims description 2
- 229910000013 Ammonium bicarbonate Inorganic materials 0.000 claims description 2
- KCXVZYZYPLLWCC-UHFFFAOYSA-N EDTA Chemical compound OC(=O)CN(CC(O)=O)CCN(CC(O)=O)CC(O)=O KCXVZYZYPLLWCC-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
- 238000007605 air drying Methods 0.000 claims description 2
- 235000012538 ammonium bicarbonate Nutrition 0.000 claims description 2
- 239000001099 ammonium carbonate Substances 0.000 claims description 2
- 239000003638 chemical reducing agent Substances 0.000 claims description 2
- IKDUDTNKRLTJSI-UHFFFAOYSA-N hydrazine monohydrate Substances O.NN IKDUDTNKRLTJSI-UHFFFAOYSA-N 0.000 claims description 2
- 150000002696 manganese Chemical class 0.000 claims description 2
- 150000002815 nickel Chemical class 0.000 claims description 2
- 235000017550 sodium carbonate Nutrition 0.000 claims description 2
- 235000011121 sodium hydroxide Nutrition 0.000 claims description 2
- 239000002245 particle Substances 0.000 abstract description 12
- 239000011259 mixed solution Substances 0.000 abstract description 10
- 239000000463 material Substances 0.000 abstract description 7
- 230000003647 oxidation Effects 0.000 abstract description 5
- 238000007254 oxidation reaction Methods 0.000 abstract description 5
- 238000009826 distribution Methods 0.000 abstract description 4
- ZAUUZASCMSWKGX-UHFFFAOYSA-N manganese nickel Chemical compound [Mn].[Ni] ZAUUZASCMSWKGX-UHFFFAOYSA-N 0.000 abstract 2
- PMSHDIDZIMFTLH-UHFFFAOYSA-J S(=O)(=O)([O-])[O-].[Mn+2].S(=O)(=O)([O-])[O-].[Ni+2] Chemical compound S(=O)(=O)([O-])[O-].[Mn+2].S(=O)(=O)([O-])[O-].[Ni+2] PMSHDIDZIMFTLH-UHFFFAOYSA-J 0.000 description 4
- 239000010406 cathode material Substances 0.000 description 4
- 238000001035 drying Methods 0.000 description 4
- 238000010438 heat treatment Methods 0.000 description 4
- 239000000203 mixture Substances 0.000 description 4
- 239000013078 crystal Substances 0.000 description 3
- 238000004519 manufacturing process Methods 0.000 description 3
- BVKZGUZCCUSVTD-UHFFFAOYSA-L Carbonate Chemical compound [O-]C([O-])=O BVKZGUZCCUSVTD-UHFFFAOYSA-L 0.000 description 2
- HBBGRARXTFLTSG-UHFFFAOYSA-N Lithium ion Chemical compound [Li+] HBBGRARXTFLTSG-UHFFFAOYSA-N 0.000 description 2
- 239000003963 antioxidant agent Substances 0.000 description 2
- 230000003078 antioxidant effect Effects 0.000 description 2
- 235000006708 antioxidants Nutrition 0.000 description 2
- 229910001416 lithium ion Inorganic materials 0.000 description 2
- 230000002441 reversible effect Effects 0.000 description 2
- DGAQECJNVWCQMB-PUAWFVPOSA-M Ilexoside XXIX Chemical compound C[C@@H]1CC[C@@]2(CC[C@@]3(C(=CC[C@H]4[C@]3(CC[C@@H]5[C@@]4(CC[C@@H](C5(C)C)OS(=O)(=O)[O-])C)C)[C@@H]2[C@]1(C)O)C)C(=O)O[C@H]6[C@@H]([C@H]([C@@H]([C@H](O6)CO)O)O)O.[Na+] DGAQECJNVWCQMB-PUAWFVPOSA-M 0.000 description 1
- 229910012820 LiCoO Inorganic materials 0.000 description 1
- 229910032387 LiCoO2 Inorganic materials 0.000 description 1
- 238000002441 X-ray diffraction Methods 0.000 description 1
- 238000005054 agglomeration Methods 0.000 description 1
- 230000002776 aggregation Effects 0.000 description 1
- 238000004458 analytical method Methods 0.000 description 1
- 238000007664 blowing Methods 0.000 description 1
- 239000003795 chemical substances by application Substances 0.000 description 1
- 238000013461 design Methods 0.000 description 1
- 238000011161 development Methods 0.000 description 1
- 230000018109 developmental process Effects 0.000 description 1
- 238000010586 diagram Methods 0.000 description 1
- 230000000694 effects Effects 0.000 description 1
- 239000007772 electrode material Substances 0.000 description 1
- 238000005516 engineering process Methods 0.000 description 1
- XLYOFNOQVPJJNP-UHFFFAOYSA-M hydroxide Chemical compound [OH-] XLYOFNOQVPJJNP-UHFFFAOYSA-M 0.000 description 1
- 125000002887 hydroxy group Chemical group [H]O* 0.000 description 1
- 238000002156 mixing Methods 0.000 description 1
- 238000012986 modification Methods 0.000 description 1
- 230000004048 modification Effects 0.000 description 1
- 230000006911 nucleation Effects 0.000 description 1
- 238000010899 nucleation Methods 0.000 description 1
- 239000007774 positive electrode material Substances 0.000 description 1
- 230000001376 precipitating effect Effects 0.000 description 1
- 238000001556 precipitation Methods 0.000 description 1
- 238000011160 research Methods 0.000 description 1
- 238000001878 scanning electron micrograph Methods 0.000 description 1
- 238000007873 sieving Methods 0.000 description 1
- 229910052708 sodium Inorganic materials 0.000 description 1
- 239000011734 sodium Substances 0.000 description 1
- 238000003860 storage Methods 0.000 description 1
- 238000006467 substitution reaction Methods 0.000 description 1
- 230000002194 synthesizing effect Effects 0.000 description 1
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- C01G53/00—Compounds of nickel
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- 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
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- 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
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- 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
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- C01P2002/70—Crystal-structural characteristics defined by measured X-ray, neutron or electron diffraction data
- C01P2002/72—Crystal-structural characteristics defined by measured X-ray, neutron or electron diffraction data by d-values or two theta-values, e.g. as X-ray diagram
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Abstract
A preparation method of a double-layer composite low-cost lithium-rich manganese-based precursor belongs to the technical field of lithium battery material preparation. The general formula of the lithium-rich manganese-based precursor is (Ni)xMn（1‑x）)OH2@CO3X is more than or equal to 0.1 and less than or equal to 0.3. Preparing a nickel-manganese mixed solution and adding a complexing agent with a certain concentration; preparing a mixed alkali solution of sodium hydroxide and sodium carbonate; adding a buffer solution into the reaction kettle as a base solution; the first stage reaction: adding the nickel-manganese mixed solution, ammonia water and sodium hydroxide solution into a reaction kettle in a concurrent flow manner, and carrying out a coprecipitation reaction; and (3) second-stage reaction: when the granularity grows to 5 microns, replacing the sodium hydroxide solution with the mixed alkali solution prepared in the step (1), and closing ammonia water;continuing the reaction; controlling the temperature, the stirring speed and the feed liquid flow in the reaction process to be constant, and introducing nitrogen in the whole reaction process; the invention solves the problems of uncontrollable ph and easy oxidation in the reaction process, and the obtained lithium-rich manganese-based precursor has high sphericity, high tap density and narrow particle size distribution.
Description
Technical Field
The invention relates to the technical field of lithium ion battery preparation, in particular to a preparation method of a double-layer composite low-cost lithium-rich manganese-based precursor.
Background
The development of novel electrode cathode materials with high performance and low cost is always the hot research direction of lithium ion batteries. Although LiCoO was early 19912The positive electrode material has been commercially used, but its reversible capacity is low and its price is expensive; therefore, researchers have focused on LiCoO2Alternative materials. Among the layered cathode materials, the lithium-rich manganese-based layered cathode material has received much attention due to its high reversible specific capacity, high operating voltage, and excellent storage performance at room temperature, is a key electrode material for lithium batteries with energy density exceeding 400 Wh/kg, and is considered as the most promising cathode material.
The coprecipitation method is the most common method for synthesizing the lithium-rich manganese-based precursor, and comprises the steps of enabling a metal salt solution, a precipitator and a complexing agent to flow into a reaction kettle containing a base solution in a parallel mode, and controlling process parameters in the reaction process to obtain a coprecipitation product; because the coprecipitation method is that after the liquids are uniformly mixed, a coprecipitation reaction occurs, and atomic-level mixing can be achieved; the selection of the reaction ph, the precipitating agent and the complexing agent is strictly controlled in the reaction process; the patent CN202010875186.0 introduces a method for mass production of a single crystal cobalt-free lithium-rich manganese-based binary material precursor, sodium hydroxide is used as a precipitator, ammonia water is used as a complexing agent, the obtained precursor has poor particle sphericity, and the tap density is indirectly low. And the lithium-rich manganese-based precursor is cobalt-free, and has lower cost compared with the existing low-cobalt lithium-rich manganese-based precursor.
Disclosure of Invention
The invention provides a preparation method of a double-layer composite low-cost lithium-rich manganese-based precursor. The method provided by the invention solves the problems of uncontrollable ph and easy oxidation in the reaction process, and the obtained lithium-rich manganese-based precursor has high sphericity, high tap density, narrow particle size distribution and general formula (Ni)xMn（1-x）)OH2@CO3（0.1≤x≤0.3)。
The preparation method comprises the following specific process steps:
a preparation method of a double-layer composite low-cost lithium-rich manganese-based precursor is disclosed, wherein the general formula of the lithium-rich manganese-based precursor is (Ni)xMn（1-x）)OH2@CO3And x is more than or equal to 0.1 and less than or equal to 0.3, and the specific preparation method comprises the following steps:
(1) preparing a mixed metal salt solution containing nickel salt and manganese salt according to the molar ratio of nickel to manganese in the molecular formula of the lithium-rich manganese-based precursor; adding a certain amount of complexing agent into the mixed metal salt solution; preparing a mixed alkali solution of sodium hydroxide and sodium carbonate;
(2) preparing a buffer solution containing a complexing agent, a precipitator and a reducing agent in a reaction kettle as a base solution;
(3) adding the metal salt solution, ammonia water and sodium hydroxide solution in the step (1) into the reaction kettle in the step (2) at the same time, carrying out coprecipitation reaction, adjusting ph, changing the sodium hydroxide solution into the mixed alkali solution prepared in the step (1) when the granularity grows to 5 micrometers, closing the ammonia water, adjusting ph, and continuing the reaction; controlling the temperature, the stirring speed and the feed liquid flow in the reaction process to be constant, and introducing nitrogen in the whole reaction process; and after the reaction is finished, performing post-treatment to obtain the lithium-rich manganese-based precursor.
The complexing agent added into the metal salt solution in the step (1) is one or more of EDTA, EDTA disodium and citric acid.
The concentration of the complexing agent added into the metal salt solution in the step (1) is 1-10 g/L.
The molar ratio of sodium hydroxide to sodium carbonate in the mixed alkali solution in the step (1) is 1: 20-1: 50.
the buffer solution in the step (2) contains one or more of ammonia water, sodium carbonate, sodium bicarbonate, ammonium bicarbonate, sodium hydroxide, hydrazine hydrate or ascorbic acid.
Step (3) maintaining ph11-12 when the grain size growth is less than 5 microns, and step (3) maintaining ph7-9 when the grain size growth is more than 5 microns.
And (4) stopping feeding when the grain size growth reaches 8 microns in the step (3).
The temperature of the reaction process in the step (3) is 50-60 ℃.
The post-treatment in the step (3) comprises the following steps: transferring the slurry in the reaction kettle to an aging kettle, adding a sodium hydroxide solution and hot water at 70 ℃, stirring for 1h, then carrying out solid-liquid separation, carrying out forced air drying at 105 ℃, and carrying out screening and iron removal.
The design principle and the effect of the invention are as follows:
1. because the manganese content in the precursor is more than 70 percent, the total specific surface area of the particles is large at the initial stage of reaction, oxidation slurry is oxidized, the particles grow slowly, and the production efficiency is reduced; according to the invention, by adding a proper amount of antioxidant into the base solution, the oxidation of the slurry in the earlier stage is effectively avoided, and the product quality and the production efficiency are improved.
2. The first stage of the reaction is carried out in a buffer solution, so that the initial nucleation speed is slowed down, and the generated hydroxide crystal nucleus has high dispersity and is more compact; in the second stage of the reaction, ammonia water is removed, and a mixed alkali solution with low ph and mainly containing sodium carbonate is used as a precipitator, so that the generated carbonate shell grows more uniformly, primary crystal grains are finer, and the sphericity is high;
the method provided by the technology of the invention not only solves the problems of poor sphericity of a carbonate system and low tap density of a hydroxyl system, but also can avoid oxidation and slow down the precipitation speed by preparing the buffer solution containing the antioxidant in the first stage, effectively avoid early-stage agglomeration, obtain the lithium-rich manganese-based precursor with high sphericity, high tap density and narrow particle size distribution, and the general formula is (Ni)xMn（1-x）)OH2@CO3。
Drawings
FIG. 1 is a scanning electron micrograph of a lithium-rich manganese-based precursor prepared in example 1;
fig. 2 is a particle size distribution diagram of the lithium-rich manganese-based precursor prepared in example 1.
Fig. 3 is an XRD pattern of the lithium-rich manganese-based precursor prepared in examples 1-4.
Detailed Description
In order to more clearly illustrate the invention, the invention is further described below in connection with preferred embodiments.
Example 1
Dissolving soluble nickel-manganese sulfate according to the weight ratio of 1:3 (the ratio of the nickel element to the manganese element is 1: 3) to prepare a mixed solution with the concentration of 1.6 mol/L; adding citric acid with the concentration of 1.5g/L into the mixed solution, and preparing a mixture with the molar ratio of sodium hydroxide to sodium carbonate being 1: 40 of mixed alkali solution; adding 35L of pure water into a 50L reaction kettle, and adding 3.5g of ascorbic acid, 2L of ammonia water and 400ml of sodium hydroxide solution to prepare a base solution; heating to 50 ℃, introducing nitrogen for 2h, and reacting in a first stage when the temperature and the rotating speed are constant: allowing a sodium hydroxide solution, ammonia water and a metal salt solution to flow into a reaction kettle; the particle size is stably increased to 5 microns by adjusting the flow of the sodium hydroxide solution and the ph to be about 11.8; and (3) a second reaction stage: stopping feeding ammonia water, replacing the sodium hydroxide solution with the mixed alkali solution, slowly reducing the ph to about 8.0, continuing the reaction, stopping feeding when the granularity reaches 8 micrometers, stirring for 30min to fully react the materials, transferring the slurry in the reaction kettle to an aging kettle, adding the sodium hydroxide solution and hot water at 70 ℃, stirring for 1h, then performing solid-liquid separation, performing blast drying at 105 ℃, screening and removing iron to obtain a lithium-rich manganese-based precursor (Ni is a lithium-rich manganese-based precursor)0.25Mn0.75)OH2@CO3。
Example 2
Dissolving soluble nickel-manganese sulfate according to the weight ratio of 1:3, preparing a mixed solution with the concentration of 1.8 mol/L; adding citric acid with the concentration of 2.0g/L into the mixed solution, and preparing a mixture with the molar ratio of sodium hydroxide to sodium carbonate being 1: 30 of mixed alkali solution; adding 35L of pure water into a 50L reaction kettle, and adding 3.5g of ascorbic acid, 2L of ammonia water and 400ml of sodium hydroxide solution to prepare a base solution; heating to 55 ℃, introducing nitrogen for 2h, and reacting in a first stage when the temperature and the rotating speed are constant: allowing a sodium hydroxide solution, ammonia water and a metal salt solution to flow into a reaction kettle; the particle size is stably increased to 5 microns by adjusting the flow of the sodium hydroxide solution and the ph to be about 11.6; and (3) a second reaction stage: stopping feeding ammonia water, replacing the sodium hydroxide solution with the mixed alkali solution, slowly reducing pH to about 8.5, continuing to react until the particle size reaches 8 microns, stopping feeding, stirring for 30min to fully react the materials, transferring the slurry in the reaction kettle to an aging kettle, adding the sodium hydroxide solution and 70 DEG CHot water, stirring for 1h, performing solid-liquid separation, drying by blowing at 105 ℃, sieving, and removing iron to obtain lithium-rich manganese-based precursor (Ni)0.25Mn0.75)OH2@CO3。
Example 3
Dissolving soluble nickel-manganese sulfate according to the weight ratio of 1:3, preparing a mixed solution with the concentration of 1.8 mol/L; adding citric acid with the concentration of 2.0g/L into the mixed solution, and preparing a mixture with the molar ratio of sodium hydroxide to sodium carbonate being 1: 20 of mixed alkali solution; adding 35L of pure water into a 50L reaction kettle, and adding 3.5g of ascorbic acid, 2L of ammonia water and 400ml of sodium hydroxide solution to prepare a base solution; heating to 55 ℃, introducing nitrogen for 2h, and reacting in a first stage when the temperature and the rotating speed are constant: allowing a sodium hydroxide solution, ammonia water and a metal salt solution to flow into a reaction kettle; the particle size is stably increased to 5 microns by adjusting the flow of the sodium hydroxide solution and the ph to be about 11.4; and (3) a second reaction stage: stopping feeding ammonia water, replacing the sodium hydroxide solution with the mixed alkali solution, slowly reducing the ph to about 9.0, continuing the reaction, stopping feeding when the granularity reaches 8 microns, stirring for 30min to fully react the materials, transferring the slurry in the reaction kettle to an aging kettle, adding the sodium hydroxide solution and hot water at 70 ℃, stirring for 1h, then performing solid-liquid separation, performing blast drying at 105 ℃, screening and removing iron to obtain a lithium-rich manganese-based precursor (Ni-rich manganese-based precursor)0.25Mn0.75)OH2@CO3。
Example 4
Dissolving soluble nickel-manganese sulfate according to the weight ratio of 1:3, preparing a mixed solution with the concentration of 1.8 mol/L; adding citric acid with the concentration of 2.0g/L into the mixed solution, and preparing a mixture with the molar ratio of sodium hydroxide to sodium carbonate being 1: 40 of mixed alkali solution; adding 35L of pure water into a 50L reaction kettle, and adding 3.5g of ascorbic acid, 2L of ammonia water and 400ml of sodium hydroxide solution to prepare a base solution; heating to 60 ℃, introducing nitrogen for 2h, and reacting in a first stage when the temperature and the rotating speed are constant: allowing a sodium hydroxide solution, ammonia water and a metal salt solution to flow into a reaction kettle; the particle size is stably increased to 5 microns by adjusting the flow of the sodium hydroxide solution and the ph to be about 11.6; and (3) a second reaction stage: stopping feeding ammonia water, and dissolving sodium hydroxideChanging the solution into the mixed alkali solution, slowly reducing the pH to about 8.3, continuing the reaction, stopping feeding when the granularity reaches 8 microns, stirring for 30min to fully react the materials, transferring the slurry in the reaction kettle to an aging kettle, adding a sodium hydroxide solution and hot water at 70 ℃, stirring for 1h, then performing solid-liquid separation, performing blast drying at 105 ℃, screening and removing iron to obtain a lithium-rich manganese-based precursor (Ni)0.25Mn0.75)OH2@CO3。
The precursors prepared in examples 1 to 4 were subjected to physicochemical analysis, and some indexes were as follows:
the invention has been described in detail with reference to specific embodiments and illustrative examples, but the description is not intended to be construed in a limiting sense. Those skilled in the art will appreciate that various equivalent substitutions, modifications or improvements may be made to the technical solution of the present invention and its embodiments without departing from the spirit and scope of the present invention, which fall within the scope of the present invention.
Claims (9)
1. A preparation method of a double-layer composite low-cost lithium-rich manganese-based precursor is characterized by comprising the following steps: the general formula of the lithium-rich manganese-based precursor is (Ni)xMn（1-x）)OH2@CO3And x is more than or equal to 0.1 and less than or equal to 0.3, and the specific preparation method comprises the following steps:
(1) preparing a mixed metal salt solution containing nickel salt and manganese salt according to the molar ratio of nickel to manganese in the molecular formula of the lithium-rich manganese-based precursor; adding a certain amount of complexing agent into the mixed metal salt solution; preparing a mixed alkali solution of sodium hydroxide and sodium carbonate;
(2) preparing a buffer solution containing a complexing agent, a precipitator and a reducing agent in a reaction kettle as a base solution;
(3) simultaneously adding the metal salt solution, ammonia water and sodium hydroxide solution in the step (1) into the reaction kettle in the step (2), carrying out coprecipitation reaction, adjusting ph, changing the sodium hydroxide solution into the mixed alkali solution prepared in the step (1) when the granularity grows to 5 micrometers, closing the ammonia water, adjusting ph, and continuing the reaction; controlling the temperature, the stirring speed and the feed liquid flow in the reaction process to be constant, and introducing nitrogen in the whole reaction process; and after the reaction is finished, performing post-treatment to obtain the lithium-rich manganese-based precursor.
2. The method for preparing the double-layer composite low-cost lithium-rich manganese-based precursor according to claim 1, characterized in that: the complexing agent added into the metal salt solution in the step (1) is one or more of EDTA, EDTA disodium and citric acid.
3. The method for preparing the double-layer composite low-cost lithium-rich manganese-based precursor according to claim 1, characterized in that: the concentration of the complexing agent added into the metal salt solution in the step (1) is 1-10 g/L.
4. The method for preparing the double-layer composite low-cost lithium-rich manganese-based precursor according to claim 1, characterized in that: the molar ratio of sodium hydroxide to sodium carbonate in the mixed alkali solution in the step (1) is 1: 20-1: 50.
5. the method for preparing the double-layer composite low-cost lithium-rich manganese-based precursor according to claim 1, characterized in that: the buffer solution in the step (2) contains one or more of ammonia water, sodium carbonate, sodium bicarbonate, ammonium bicarbonate, sodium hydroxide, hydrazine hydrate or ascorbic acid.
6. The method for preparing the double-layer composite low-cost lithium-rich manganese-based precursor according to claim 1, characterized in that: step (3) maintaining ph11-12 when the grain size growth is less than 5 microns, and step (3) maintaining ph7-9 when the grain size growth is more than 5 microns.
7. The method for preparing the double-layer composite low-cost lithium-rich manganese-based precursor according to claim 1, characterized in that: and (4) stopping feeding when the grain size growth reaches 8 microns in the step (3).
8. The method for preparing the double-layer composite low-cost lithium-rich manganese-based precursor according to claim 1, characterized in that: the temperature of the reaction process in the step (3) is 50-60 ℃.
9. The method for preparing the double-layer composite low-cost lithium-rich manganese-based precursor according to claim 1, wherein the post-treatment of step (3) comprises the steps of: transferring the slurry in the reaction kettle to an aging kettle, adding a sodium hydroxide solution and hot water at 70 ℃, stirring for 1h, then carrying out solid-liquid separation, carrying out forced air drying at 105 ℃, and carrying out screening and iron removal.
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