CN115028213A - Wide-distribution lithium-rich manganese-based positive electrode precursor and preparation method thereof - Google Patents
Wide-distribution lithium-rich manganese-based positive electrode precursor and preparation method thereof Download PDFInfo
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- 239000002243 precursor Substances 0.000 title claims abstract description 49
- 239000011572 manganese Substances 0.000 title claims abstract description 42
- PWHULOQIROXLJO-UHFFFAOYSA-N Manganese Chemical compound [Mn] PWHULOQIROXLJO-UHFFFAOYSA-N 0.000 title claims abstract description 36
- 229910052748 manganese Inorganic materials 0.000 title claims abstract description 36
- WHXSMMKQMYFTQS-UHFFFAOYSA-N Lithium Chemical compound [Li] WHXSMMKQMYFTQS-UHFFFAOYSA-N 0.000 title claims abstract description 34
- 229910052744 lithium Inorganic materials 0.000 title claims abstract description 34
- 238000009826 distribution Methods 0.000 title claims abstract description 23
- 238000002360 preparation method Methods 0.000 title claims abstract description 13
- 238000006243 chemical reaction Methods 0.000 claims abstract description 70
- 239000002002 slurry Substances 0.000 claims abstract description 67
- 229910001453 nickel ion Inorganic materials 0.000 claims abstract description 22
- 238000000034 method Methods 0.000 claims abstract description 18
- 239000001488 sodium phosphate Substances 0.000 claims abstract description 18
- 229910000162 sodium phosphate Inorganic materials 0.000 claims abstract description 18
- RYFMWSXOAZQYPI-UHFFFAOYSA-K trisodium phosphate Chemical compound [Na+].[Na+].[Na+].[O-]P([O-])([O-])=O RYFMWSXOAZQYPI-UHFFFAOYSA-K 0.000 claims abstract description 18
- ZAUUZASCMSWKGX-UHFFFAOYSA-N manganese nickel Chemical compound [Mn].[Ni] ZAUUZASCMSWKGX-UHFFFAOYSA-N 0.000 claims abstract description 17
- 239000002245 particle Substances 0.000 claims abstract description 11
- PXHVJJICTQNCMI-UHFFFAOYSA-N nickel Substances [Ni] PXHVJJICTQNCMI-UHFFFAOYSA-N 0.000 claims description 44
- 239000000243 solution Substances 0.000 claims description 44
- CDBYLPFSWZWCQE-UHFFFAOYSA-L Sodium Carbonate Chemical compound [Na+].[Na+].[O-]C([O-])=O CDBYLPFSWZWCQE-UHFFFAOYSA-L 0.000 claims description 30
- HEMHJVSKTPXQMS-UHFFFAOYSA-M Sodium hydroxide Chemical compound [OH-].[Na+] HEMHJVSKTPXQMS-UHFFFAOYSA-M 0.000 claims description 30
- VEXZGXHMUGYJMC-UHFFFAOYSA-N Hydrochloric acid Chemical compound Cl VEXZGXHMUGYJMC-UHFFFAOYSA-N 0.000 claims description 16
- 238000005086 pumping Methods 0.000 claims description 16
- 239000012266 salt solution Substances 0.000 claims description 16
- 229910001437 manganese ion Inorganic materials 0.000 claims description 15
- 229910000029 sodium carbonate Inorganic materials 0.000 claims description 15
- 238000003756 stirring Methods 0.000 claims description 10
- XEEYBQQBJWHFJM-UHFFFAOYSA-N Iron Chemical compound [Fe] XEEYBQQBJWHFJM-UHFFFAOYSA-N 0.000 claims description 8
- 229910052759 nickel Inorganic materials 0.000 claims description 8
- 238000001035 drying Methods 0.000 claims description 7
- XLYOFNOQVPJJNP-UHFFFAOYSA-N water Substances O XLYOFNOQVPJJNP-UHFFFAOYSA-N 0.000 claims description 6
- 238000002156 mixing Methods 0.000 claims description 5
- 238000007873 sieving Methods 0.000 claims description 5
- 239000000126 substance Substances 0.000 claims description 5
- 238000005406 washing Methods 0.000 claims description 5
- 229910052742 iron Inorganic materials 0.000 claims description 4
- 150000001805 chlorine compounds Chemical group 0.000 claims description 2
- 150000003839 salts Chemical class 0.000 claims description 2
- 239000000463 material Substances 0.000 abstract description 18
- VEQPNABPJHWNSG-UHFFFAOYSA-N Nickel(2+) Chemical compound [Ni+2] VEQPNABPJHWNSG-UHFFFAOYSA-N 0.000 abstract description 10
- 230000015572 biosynthetic process Effects 0.000 abstract description 4
- 238000003786 synthesis reaction Methods 0.000 abstract description 4
- 238000000975 co-precipitation Methods 0.000 abstract description 3
- 239000012716 precipitator Substances 0.000 abstract description 3
- BVKZGUZCCUSVTD-UHFFFAOYSA-L Carbonate Chemical compound [O-]C([O-])=O BVKZGUZCCUSVTD-UHFFFAOYSA-L 0.000 abstract description 2
- 239000013078 crystal Substances 0.000 abstract description 2
- 239000002244 precipitate Substances 0.000 abstract description 2
- 238000004064 recycling Methods 0.000 abstract description 2
- 238000004519 manufacturing process Methods 0.000 abstract 1
- VEXZGXHMUGYJMC-UHFFFAOYSA-M Chloride anion Chemical compound [Cl-] VEXZGXHMUGYJMC-UHFFFAOYSA-M 0.000 description 3
- 239000011164 primary particle Substances 0.000 description 3
- 238000001878 scanning electron micrograph Methods 0.000 description 3
- 239000010405 anode material Substances 0.000 description 2
- 239000010406 cathode material Substances 0.000 description 2
- 229910000159 nickel phosphate Inorganic materials 0.000 description 2
- JOCJYBPHESYFOK-UHFFFAOYSA-K nickel(3+);phosphate Chemical compound [Ni+3].[O-]P([O-])([O-])=O JOCJYBPHESYFOK-UHFFFAOYSA-K 0.000 description 2
- 238000001556 precipitation Methods 0.000 description 2
- 230000002194 synthesizing effect Effects 0.000 description 2
- HBBGRARXTFLTSG-UHFFFAOYSA-N Lithium ion Chemical compound [Li+] HBBGRARXTFLTSG-UHFFFAOYSA-N 0.000 description 1
- 230000009286 beneficial effect Effects 0.000 description 1
- BVKZGUZCCUSVTD-UHFFFAOYSA-N carbonic acid Chemical compound OC(O)=O BVKZGUZCCUSVTD-UHFFFAOYSA-N 0.000 description 1
- 150000004649 carbonic acid derivatives Chemical class 0.000 description 1
- 239000002131 composite material Substances 0.000 description 1
- 238000009831 deintercalation Methods 0.000 description 1
- 238000003487 electrochemical reaction Methods 0.000 description 1
- 238000002474 experimental method Methods 0.000 description 1
- 230000005484 gravity Effects 0.000 description 1
- 150000004679 hydroxides Chemical class 0.000 description 1
- 238000009830 intercalation Methods 0.000 description 1
- 230000002687 intercalation Effects 0.000 description 1
- 230000002427 irreversible effect Effects 0.000 description 1
- 239000007788 liquid Substances 0.000 description 1
- 229910001416 lithium ion Inorganic materials 0.000 description 1
- GELKBWJHTRAYNV-UHFFFAOYSA-K lithium iron phosphate Chemical compound [Li+].[Fe+2].[O-]P([O-])([O-])=O GELKBWJHTRAYNV-UHFFFAOYSA-K 0.000 description 1
- 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 description 1
- 239000000178 monomer Substances 0.000 description 1
- 239000002114 nanocomposite Substances 0.000 description 1
- 239000002159 nanocrystal Substances 0.000 description 1
- 229910000008 nickel(II) carbonate Inorganic materials 0.000 description 1
- ZULUUIKRFGGGTL-UHFFFAOYSA-L nickel(ii) carbonate Chemical compound [Ni+2].[O-]C([O-])=O ZULUUIKRFGGGTL-UHFFFAOYSA-L 0.000 description 1
- 230000006911 nucleation Effects 0.000 description 1
- 238000010899 nucleation Methods 0.000 description 1
- 239000000047 product Substances 0.000 description 1
- 239000002153 silicon-carbon composite material Substances 0.000 description 1
- 239000007787 solid Substances 0.000 description 1
- 239000006104 solid solution Substances 0.000 description 1
- 239000002351 wastewater Substances 0.000 description 1
- 238000004065 wastewater treatment Methods 0.000 description 1
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- C01G53/00—Compounds of nickel
- C01G53/006—Compounds containing, besides nickel, two or more other elements, with the exception of oxygen or hydrogen
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- C01B—NON-METALLIC ELEMENTS; COMPOUNDS THEREOF; METALLOIDS OR COMPOUNDS THEREOF NOT COVERED BY SUBCLASS C01C
- C01B25/00—Phosphorus; Compounds thereof
- C01B25/16—Oxyacids of phosphorus; Salts thereof
- C01B25/26—Phosphates
- C01B25/37—Phosphates of heavy metals
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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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- H01M—PROCESSES OR MEANS, e.g. BATTERIES, FOR THE DIRECT CONVERSION OF CHEMICAL ENERGY INTO ELECTRICAL ENERGY
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- 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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Abstract
The invention discloses a wide-distribution lithium-rich manganese-based positive electrode precursor and a preparation method thereof.A coprecipitation method is adopted to link two reaction kettles and concentration equipment, firstly, nickel-manganese binary carbonate is synthesized in a first reaction kettle, and slurry overflows to a second reaction kettle; and in the second reaction kettle, adopting precipitator sodium phosphate to completely precipitate nickel ions to form crystal nuclei, concentrating, recycling the concentrated nickel ions into the first reaction kettle, and continuously reacting to reach the target particle size. The wide-distribution lithium-rich manganese-based positive electrode precursor prepared by the method has a large particle size span value which is as high as 1.1-1.5, and a high tap density which is as high as 1.8-2.0 g/cm 3 Solves the problem of high loss rate of nickel ions in the synthesis process of the lithium-rich manganese-based anode precursor,the production cost is reduced, and the electrochemical performance of the material is improved.
Description
Technical Field
The invention relates to the technical field of lithium ion batteries, in particular to a wide-distribution lithium-rich manganese-based positive electrode precursor and a preparation method of the precursor.
Background
The lithium-rich manganese-based material has higher specific discharge capacity which is almost twice that of lithium iron phosphate, and if the lithium-rich manganese-based material is matched with a silicon-carbon composite material, the energy density of a battery monomer can reach 350 Wh.kg -1 . In the lithium-rich manganese-based material, the existence of manganese ore reduces the cost and improves the stability and safety of the material, but the factors of high initial irreversible capacity, poor cycle and rate performance, particularly continuous reduction of discharge medium voltage in the charge-discharge cycle process and the like hinder the practical application of the material. In addition, the current knowledge of the structure of lithium-rich manganese-based materials is controversial, such as whether it is a solid solution structure or a two-phase nanocomposite structure. Controversy also exists about the lithium intercalation and deintercalation mechanism of the material, such as whether the O element and the Mn element in the material can participate in electrochemical reaction reversibly.
The lithium-rich cathode material has certain inheritance to the spherical structure of the precursor, so that the spherical structure characteristics of the precursor directly influence the spherical structure characteristics of the lithium-rich cathode material, thereby indirectly influencing the electrochemical performance of the material. Therefore, the lithium-rich material needs to regulate and control the primary particle and secondary sphere structure of the material in the synthesis process of the precursor. As one of the future anode materials, the lithium-rich manganese base has many anode and precursor manufacturers strive to open the layout field, and has good market prospect.
Most of the precursors are nickel-manganese binary element composite hydroxides or carbonates, and the physical indexes of primary particles and secondary balls of the precursors are directly influenced by the process conditions such as pH value, temperature, slurry density and the like in the synthesis process. In the carbonic acid system, the solubility product of nickel carbonate is relatively large, so that nickel ions can not be completely precipitated in the process of synthesizing a precursor by coprecipitation, and the direct yield is low. Under certain specific conditions, the loss rate of nickel even exceeds 30%, the wastewater treatment pressure is greatly increased, the processing cost of the material is increased, and the tap density and the electrochemical performance of the precursor material are seriously influenced.
Disclosure of Invention
The invention aims to provide a wide-distribution lithium-rich manganese-based positive electrode precursor capable of maintaining physical indexes of primary particles and secondary spheres required by the precursor.
The invention also aims to provide the preparation method of the precursor, which solves the problem of nickel ion loss in the existing preparation process, reduces the material processing cost, increases the tap density of the material and improves the electrochemical performance of the anode material.
In order to realize the purpose, the invention adopts the following technical scheme:
a wide-distribution lithium-rich manganese-based positive electrode precursor with a chemical formula of Ni x Mn 1-x CO 3 + yNi 3 (PO 4 ) 2 Wherein x is more than or equal to 0.1 and less than or equal to 0.4, and y is more than or equal to 0.04 and less than or equal to 0.1 x; the average particle size D50 of the precursor is 6-14 mu m, the radial span of the precursor is 1.1-1.5, and the tap density TD of the precursor is 1.8-2.0 g/cm 3 。
The preparation method of the wide-distribution lithium-rich manganese-based positive electrode precursor comprises the following steps: linking the two reaction kettles and concentration equipment by adopting a coprecipitation method, firstly synthesizing nickel-manganese binary carbonate in a first reaction kettle, and overflowing slurry to a second reaction kettle; and in the second reaction kettle, adopting precipitator sodium phosphate to completely precipitate nickel ions to form crystal nuclei, concentrating, recycling the concentrated nickel ions into the first reaction kettle, and continuously reacting to reach the target particle size. The method specifically comprises the following steps:
step one, preparing a nickel-manganese-containing mixed salt solution, a sodium carbonate solution, a dilute hydrochloric acid solution, a sodium phosphate solution and a sodium hydroxide solution; the nickel-manganese mixed salt is chloride;
step two, pumping the nickel-manganese mixed salt solution, the sodium carbonate solution and the dilute hydrochloric acid solution into a first reaction kettle in a parallel flow manner under the condition of stirring, controlling the reaction temperature to be 45-55 ℃ and the pH value to be 6.5-7.5 to prepare No. 1 slurry, and overflowing the No. 1 slurry from the first reaction kettle to a second reaction kettle in the reaction process;
step three, under the condition of stirring, co-currently pumping a sodium phosphate solution and a sodium hydroxide solution into the second reaction kettle, controlling the reaction temperature to be 65-75 ℃ and the pH value to be 8-9, and preparing No. 2 slurry; overflowing the No. 2 slurry to a concentration device for concentration to prepare No. 3 slurry; and pumping the No. 3 slurry into a first reaction kettle, so that the first reaction kettle, a second reaction kettle and a concentration device form circulation, and stopping reaction when the granularity D50 of the No. 3 slurry reaches the target granularity of 6-14 mu m.
And step four, mixing the No. 1 slurry, the No. 2 slurry and the No. 3 slurry, washing with pure water, centrifuging, and then performing a drying, sieving and deironing process to obtain the wide-distribution lithium-rich manganese-based anode precursor.
Preferably, in the second step, the molar ratio of the total nickel and manganese ions in the mixed salt solution containing nickel and manganese to the total sodium carbonate is 1: 0.9-0.95.
Furthermore, in the mixed salt solution containing nickel and manganese, the molar ratio of nickel and manganese ions is 1: 3.
Further, the molar ratio of the total amount of nickel and manganese ions in the mixed salt solution containing nickel and manganese to the total amount of sodium phosphate in the third step is 1: 0.1-0.2.
Further, in the fourth step, the drying temperature is 80-120 ℃.
In the second step of the present invention, the first reaction kettle comprises a nucleation and growth process, and the slurry contains 10-30% of precipitated nickel ions under the reaction condition and still exists in the water solution of the slurry. When the liquid level of the first reaction kettle reaches the overflow port pipeline, the subsequent generated slurry overflows into the second reaction kettle under the action of gravity.
In the third step, the applicant finds that sodium phosphate as a precipitator can perform precipitation reaction on the nickel ions which are not precipitated in the No. 1 slurry to form nickel phosphate through multiple experiments; and under the conditions of relatively high temperature and pH value (65-75 ℃ and 8-9), the precipitation reaction rate is accelerated, and the formed nickel phosphate exists in a nano crystal nucleus form and cannot grow on secondary balls in No. 1 slurry. And (3) after the No. 2 slurry overflows to the concentration device, forming No. 3 slurry with higher solid content, and pumping the slurry back to the first reaction kettle to form circulation. In the circulation process, the density of the slurry of No. 1 slurry, No. 2 slurry and No. 3 slurry is continuously increased, which is beneficial to improving the tap density index of the precursor. In the circulation process, small particles are continuously generated in the No. 2 slurry, so that the particle size span value of the precursor is favorably improved. When the granularity D50 of the No. 3 slurry reaches the target granularity of 6-14 mu m, stopping the reaction.
In conclusion, the lithium-rich manganese-based positive electrode precursor prepared by the method has a large particle size span value which is as high as 1.1-1.5, and a high tap density which is as high as 1.8-2.0 g/cm 3 The problem of high loss rate of nickel ions in the synthesis process of the precursor is solved, and the electrochemical performance of the material is improved; in addition, the preparation method is a closed cycle process, no wastewater is generated, and the processing cost of the material is further reduced.
Drawings
FIG. 1 is an SEM image of a broad distribution lithium-rich manganese-based positive electrode precursor of example 1 of the present invention;
FIG. 2 is an SEM image of a broad distribution lithium-rich manganese-based positive electrode precursor in example 2 of the present invention;
fig. 3 is an SEM image of a broad distribution lithium-rich manganese-based positive electrode precursor in example 3 of the present invention.
Detailed Description
The properties and preparation method of the wide-distribution lithium-rich manganese-based positive electrode precursor of the present invention are described in detail below with reference to the accompanying drawings and examples.
Example 1
Step one, preparing 2mol/L nickel-manganese mixed chloride solution (the molar ratio of nickel ions to manganese ions is 1: 2), 2mol/L sodium carbonate solution, 1mol/L hydrochloric acid solution, 0.5mol/L sodium phosphate solution and 2mol/L sodium hydroxide solution;
step two, under the condition of stirring, co-current flow pumping the nickel-manganese mixed salt solution, the sodium carbonate solution and the hydrochloric acid solution into a first reaction kettle, controlling the reaction temperature to be 48 ℃ and the pH value to be 6.8 to prepare No. 1 slurry, and overflowing the No. 1 slurry into a second reaction kettle in the reaction process; the molar ratio of the total amount of nickel and manganese ions to the total amount of sodium carbonate is 1: 0.9;
step three, under the condition of stirring, co-currently pumping a sodium phosphate solution and a sodium hydroxide solution into the second reaction kettle, controlling the reaction temperature to be 75 ℃ and the pH value to be 8.5, and preparing No. 2 slurry; the molar ratio of the total amount of nickel and manganese ions to the total amount of sodium phosphate in the mixed salt solution is 1: 0.2. Overflowing the No. 2 slurry to a concentration device for concentration to obtain No. 3 slurry; pumping the No. 3 slurry into a first reaction kettle, circulating the first reaction kettle, a second reaction kettle and a concentration device, and stopping reaction when the granularity D50 of the No. 3 slurry reaches the target granularity of 7 mu m;
step four, mixing the No. 1 slurry, the No. 2 slurry and the No. 3 slurry, washing with pure water, centrifuging, drying at 100 ℃, sieving to remove iron, and obtaining the wide-distribution lithium-rich manganese-based anode precursor with the chemical formula of Ni 0.28 Mn 0.72 CO 3 + 0.025Ni 3 (PO 4 ) 2 B, carrying out the following steps of; the average particle size D50 of the precursor was 7 μm, the span was 1.2, and the tap density TD was 1.8g/cm 3 And the tap density and the electrochemical performance are good.
Example 2
Step one, preparing 2mol/L nickel-manganese mixed chloride solution (the molar ratio of nickel-manganese ions is 1: 3), 2mol/L sodium carbonate solution, 1mol/L hydrochloric acid solution, 0.5mol/L sodium phosphate solution and 2mol/L sodium hydroxide solution;
step two, pumping the nickel-manganese mixed salt solution, the sodium carbonate solution and the hydrochloric acid solution into a first reaction kettle in a parallel flow manner under the condition of stirring, controlling the reaction temperature to be 48 ℃ and the pH value to be 6.8 to prepare No. 1 slurry, and overflowing the No. 1 slurry into a second reaction kettle in the reaction process; the molar ratio of the total amount of nickel and manganese ions to the total amount of sodium carbonate is 1: 0.9;
step three, under the condition of stirring, co-currently pumping a sodium phosphate solution and a sodium hydroxide solution into the second reaction kettle, controlling the reaction temperature to be 75 ℃ and the pH value to be 8.5, and preparing No. 2 slurry; the molar ratio of the total amount of nickel and manganese ions to the total amount of sodium phosphate in the mixed salt solution is 1: 0.2. Overflowing the No. 2 slurry to a concentration device for concentration to prepare No. 3 slurry; and pumping the No. 3 slurry into a first reaction kettle, circulating the first reaction kettle, a second reaction kettle and a concentration device until the granularity D50 of the No. 3 slurry reaches the target granularity of 14 mu m, and stopping reaction.
Step four, mixing the No. 1 slurry, the No. 2 slurry and the No. 3 slurry, washing with pure water, centrifuging, drying at 100 ℃, sieving to remove iron, and preparing the wide-distribution lithium-rich manganese-based anode precursor with the chemical formula of Ni 0.2 Mn 0.8 CO 3 + 0.017Ni 3 (PO 4 ) 2 B, carrying out the following steps of; the average particle size D50 of the precursor was 14 μm, the span was 1.3, and the tap density TD was 1.88g/cm 3 And the tap density and the electrochemical performance are good.
Example 3
Step one, preparing 2mol/L nickel-manganese mixed chloride solution (the molar ratio of nickel-manganese ions is 1: 3), 2mol/L sodium carbonate solution, 1mol/L hydrochloric acid solution, 0.5mol/L sodium phosphate solution and 2mol/L sodium hydroxide solution;
step two, under the condition of stirring, co-current flow pumping the nickel-manganese mixed salt solution, the sodium carbonate solution and the hydrochloric acid solution into a first reaction kettle, controlling the reaction temperature to be 55 ℃ and the pH value to be 7.5 to prepare No. 1 slurry, and overflowing the No. 1 slurry into a second reaction kettle in the reaction process; the molar ratio of the total amount of nickel and manganese ions to the total amount of sodium carbonate is 1: 0.95;
step three, under the condition of stirring, co-currently pumping a sodium phosphate solution and a sodium hydroxide solution into the second reaction kettle, controlling the reaction temperature to be 65 ℃ and the pH value to be 9, and preparing No. 2 slurry; the molar ratio of the total amount of nickel and manganese ions to the total amount of sodium phosphate in the mixed salt solution is 1: 0.1. Overflowing the No. 2 slurry to a concentration device for concentration to prepare No. 3 slurry; and pumping the No. 3 slurry into a first reaction kettle, circulating the first reaction kettle, a second reaction kettle and a concentration device until the granularity D50 of the No. 3 slurry reaches the target granularity of 14 mu m, and stopping reaction.
Step four, mixing the No. 1 slurry, the No. 2 slurry and the No. 3 slurry, washing with pure water, centrifuging, drying at 120 ℃, sieving to remove iron, and preparing the wide-distribution lithium-rich manganese-based anode precursor with the chemical formula of Ni 0.22 Mn 0.78 CO 3 + 0.01Ni 3 (PO 4 ) 2 (ii) a The average particle size D50 of the precursor was 14 μm, the span was 1.32, and the tap density TD was 1.93g/cm 3 And the tap density and the electrochemical performance are good.
Claims (6)
1. The wide-distribution lithium-rich manganese-based positive electrode precursor is characterized in that the chemical formula of the precursor is Ni x Mn 1-x CO 3 + yNi 3 (PO 4 ) 2 Wherein x is more than or equal to 0.1 and less than or equal to 0.4, and y is more than or equal to 0.04 and less than or equal to 0.1 x; the average particle size D50 of the precursor is 6-14 mu m, the radial span of the precursor is 1.1-1.5, and the tap density TD of the precursor is 1.8-2.0 g/cm 3 。
2. The preparation method of the wide-distribution lithium-rich manganese-based positive electrode precursor as claimed in claim 1, comprising the steps of:
step one, preparing a nickel-manganese-containing mixed salt solution, a sodium carbonate solution, a dilute hydrochloric acid solution, a sodium phosphate solution and a sodium hydroxide solution; the nickel-manganese mixed salt is chloride;
step two, pumping the nickel-manganese mixed salt solution, the sodium carbonate solution and the dilute hydrochloric acid solution into a first reaction kettle in a parallel flow manner under the condition of stirring, controlling the reaction temperature to be 45-55 ℃ and the pH value to be 6.5-7.5 to prepare No. 1 slurry, and overflowing the No. 1 slurry from the first reaction kettle to a second reaction kettle in the reaction process;
step three, under the condition of stirring, co-currently pumping a sodium phosphate solution and a sodium hydroxide solution into the second reaction kettle, controlling the reaction temperature to be 65-75 ℃ and the pH value to be 8-9, and preparing No. 2 slurry; overflowing the No. 2 slurry to a concentration device for concentration to prepare No. 3 slurry; pumping the No. 3 slurry into a first reaction kettle, so that the first reaction kettle, a second reaction kettle and a concentration device form circulation, and stopping reaction when the granularity D50 of the No. 3 slurry reaches the target granularity of 6-14 mu m;
and step four, mixing the No. 1 slurry, the No. 2 slurry and the No. 3 slurry, washing with pure water, centrifuging, and then drying, sieving and removing iron to obtain the wide-distribution lithium-rich manganese-based anode precursor.
3. The method for preparing the wide-distribution lithium-rich manganese-based positive electrode precursor as claimed in claim 2, wherein in the second step, the molar ratio of the total amount of nickel and manganese ions to the total amount of sodium carbonate in the mixed salt solution containing nickel and manganese is 1: 0.9-0.95.
4. The preparation method of the wide-distribution lithium-rich manganese-based positive electrode precursor as claimed in claim 2 or 3, wherein the molar ratio of nickel to manganese ions in the mixed salt solution containing nickel and manganese is 1: 3.
5. The preparation method of the wide-distribution lithium-rich manganese-based positive electrode precursor as claimed in claim 2, wherein: the molar ratio of the total amount of nickel and manganese ions in the nickel and manganese-containing mixed salt solution to the total amount of sodium phosphate in the third step is 1: 0.1-0.2.
6. The preparation method of the wide-distribution lithium-rich manganese-based positive electrode precursor as claimed in claim 2, wherein: in the fourth step, the drying temperature is 80-120 ℃.
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Citations (6)
| Publication number | Priority date | Publication date | Assignee | Title |
|---|---|---|---|---|
| US20060275667A1 (en) * | 2005-05-27 | 2006-12-07 | Haruo Watanabe | Cathode active material, method of manufacturing it, cathode, and battery |
| CN107180959A (en) * | 2017-06-07 | 2017-09-19 | 北京当升材料科技股份有限公司 | It is a kind of to mix rich lithium manganese base solid solution positive electrode of sodium and preparation method thereof |
| CN109422297A (en) * | 2017-08-28 | 2019-03-05 | 湖南杉杉能源科技股份有限公司 | Regulate and control the method for nucleation in a kind of nickel cobalt manganese presoma crystallization process |
| CN110871094A (en) * | 2018-08-30 | 2020-03-10 | 荆门市格林美新材料有限公司 | Mn-doped sodium nickel phosphate photocatalytic material and preparation method thereof |
| CN111490241A (en) * | 2020-04-16 | 2020-08-04 | 南开大学 | Lithium phosphate in-situ coated lithium-rich manganese-based positive electrode material and preparation method thereof |
| CN113247971A (en) * | 2021-06-28 | 2021-08-13 | 金驰能源材料有限公司 | Carbonate precursor and preparation method thereof |
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Patent Citations (6)
| Publication number | Priority date | Publication date | Assignee | Title |
|---|---|---|---|---|
| US20060275667A1 (en) * | 2005-05-27 | 2006-12-07 | Haruo Watanabe | Cathode active material, method of manufacturing it, cathode, and battery |
| CN107180959A (en) * | 2017-06-07 | 2017-09-19 | 北京当升材料科技股份有限公司 | It is a kind of to mix rich lithium manganese base solid solution positive electrode of sodium and preparation method thereof |
| CN109422297A (en) * | 2017-08-28 | 2019-03-05 | 湖南杉杉能源科技股份有限公司 | Regulate and control the method for nucleation in a kind of nickel cobalt manganese presoma crystallization process |
| CN110871094A (en) * | 2018-08-30 | 2020-03-10 | 荆门市格林美新材料有限公司 | Mn-doped sodium nickel phosphate photocatalytic material and preparation method thereof |
| CN111490241A (en) * | 2020-04-16 | 2020-08-04 | 南开大学 | Lithium phosphate in-situ coated lithium-rich manganese-based positive electrode material and preparation method thereof |
| CN113247971A (en) * | 2021-06-28 | 2021-08-13 | 金驰能源材料有限公司 | Carbonate precursor and preparation method thereof |
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