CN112079390B - Polygonal layered manganous manganic oxide and preparation method thereof - Google Patents

Polygonal layered manganous manganic oxide and preparation method thereof Download PDF

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CN112079390B
CN112079390B CN201910504364.6A CN201910504364A CN112079390B CN 112079390 B CN112079390 B CN 112079390B CN 201910504364 A CN201910504364 A CN 201910504364A CN 112079390 B CN112079390 B CN 112079390B
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manganic oxide
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CN112079390A (en
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王福日
李娟�
朱孔磊
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BASF Shanshan Battery Materials Co Ltd
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Abstract

The invention discloses polygonal layered manganous-manganic oxide, which is in a polygonal layered accumulation shape, wherein the side length of a polygon is 5-50 mu m, and the thickness is 3-30 mu m; the preparation method comprises the following steps: (1) Injecting deionized water and ammonia water as base solution into a reaction kettle, starting a stirring paddle and a heater, introducing nitrogen as protective gas, and then introducing a manganese sulfate solution, a sodium hydroxide solution and ammonia water into the solution of the reaction kettle for reaction; (2) Stirring the material obtained after the reaction in the step (1) to ensure that the material is fully contacted with air until the material becomes brownish black; (3) And (3) standing the material obtained in the step (2), removing the supernatant, and performing blast drying on the material at the bottom layer to obtain the polygonal layered manganous-manganic oxide. The polygonal layered manganous-manganic oxide has wider particle size distribution, can be tightly connected together after being pressed, and effectively solves the problem of battery water-diving caused by easy rupture of manganous-manganic oxide with other shapes after being pressed.

Description

Polygonal layered manganous-manganic oxide and preparation method thereof
Technical Field
The invention belongs to the field of inorganic material preparation, and particularly relates to polygonal layered manganous-manganic oxide and a preparation method thereof.
Background
Trimanganese tetroxide is used as a stable oxide precursor, is a production raw material of lithium manganate as a positive material of a lithium ion battery, is generally prepared by a method of hydrolyzing and precipitating manganese ions in an ammonia medium by a manganese sulfate solution, and is researched and adopted by broad scholars due to the advantages of simple preparation process, high process controllability, low cost and the like. However, by a method of chemical coprecipitation of manganese ions in an ammonia medium by a manganese sulfate solution, the prepared manganous-manganic oxide particles are mostly spherical particles, and the spherical-structure lithium manganate is prepared after sintering, but the physical structure of the spherical-structure lithium manganate is different from that of the ternary spherical particles; the spherical lithium manganate structure is not resistant to compression, is easy to break when being compressed, generates microcracks and generates self-pulverization, and primary particles are electrically contacted, so that the full battery jumps; the compacted density of the flaky and ring-shaped manganous-manganic oxide is limited due to the geometric morphology problem, the energy density is reduced in different degrees after the flaky and ring-shaped manganous-manganic oxide is prepared into the lithium ion battery anode material, and if the flaky and ring-shaped manganous-manganic oxide is pressed into sheets by force, particles are broken, so that the full battery is subjected to water jumping. Therefore, how to improve the structure of the manganous-manganic oxide has certain improvement effect on solving the problem of the lithium manganate that is pressed to be broken.
Disclosure of Invention
The invention aims to solve the technical problem of overcoming the defects and shortcomings in the background technology and provides polygonal layered manganous-manganic oxide and a preparation method thereof.
In order to solve the technical problems, the technical scheme provided by the invention is as follows:
polygonal layered manganous-manganic oxide is in a polygonal layered accumulation shape, the side length of a polygon is 5-50 mu m, and the accumulation thickness is 3-30 mu m.
The polygonal layered manganomanganic oxide is preferably such that the particle size of the polygonal layered manganomanganic oxide agglomerated secondary particles is D10 > 1 μm, D50=5-25 μm, and D90 < 100 μm.
Preferably, the half-peak width of the 011 crystal plane of the polygonal layered manganous-manganic oxide is 0.1-0.3 deg.
As a general inventive concept, the present invention also provides a method for preparing the polygonal layered trimanganese tetroxide, comprising the steps of:
(1) Injecting deionized water and ammonia water into a reaction kettle as base solution, starting a stirring paddle and a heater, introducing nitrogen as protective gas, controlling the temperature to be 55-65 ℃, controlling the ammonia value (the mass of ammonia in 1L of solution) in the reaction kettle to be 4.5-5.5g/L, and then introducing manganese sulfate solution, sodium hydroxide solution and ammonia water into the solution in the reaction kettle for reaction;
(2) Stirring the material obtained after the reaction in the step (1) to ensure that the material is fully contacted with air until the material becomes brownish black;
(3) And (3) standing the material obtained in the step (2), removing the supernatant, and performing forced air drying on the bottom material to obtain the polygonal layered manganous-manganic oxide.
The invention prepares polygonal layered trimanganese tetroxide by a method of manganese sulfate solution hydrolysis precipitation of manganese ions in an ammonia medium, and the reaction process is as follows: firstly, the manganese sulfate solution and ammonia water generate complexation effect to generate Mn 2+ The complex is then reacted with sodium hydroxide solution to precipitate the hydroxideDuring the reaction process, the shape, the granularity and the like of the crystallized particles can be controlled by controlling the concentrations and the feeding rates of a manganese sulfate solution, ammonia water and a sodium hydroxide solution.
Preferably, in the step (1), when the pH value of the system in the reaction kettle reaches 12-13, the introduction of the NaOH solution is stopped, the ammonia value of the solution is increased to 9.5-11g/L, and after the reaction is carried out for 10-15min, the NaOH solution is introduced again for reaction.
In the preparation method, preferably, in the step (1), the concentration of the manganese sulfate solution is 1.5-2.5mol/L, and the feeding rate is 30-40mL/min; the concentration of the sodium hydroxide solution is 9-11mol/L, and the feeding rate is 7-9mL/min; the concentration of ammonia water is 13-14mol/L, and the feeding speed is 3-15mL/min.
In the above preparation method, preferably, in the step (1), the stirring speed of the stirring blade is 650-1000rpm, and the reaction time is 5-7h.
In the above preparation method, preferably, in the step (2), the stirring speed is 200-400rpm.
In the preparation method, preferably, in the step (3), the drying temperature is 70-120 ℃, and the drying time is 12-24h.
In the preparation method, the reaction process is preferably a continuous method, all materials are injected from the bottom of the reaction kettle, and the materials flow out from an overflow port at the upper part; namely, after the materials are reacted in the reaction kettle for a period of time, the feed inlet and the discharge outlet are simultaneously opened, so that when the raw materials enter the reaction kettle, the precipitated manganese hydroxide crystals simultaneously overflow from the discharge outlet of the reaction kettle, and the overflowing materials are collected and oxidized to form polygonal layered trimanganese tetroxide particles. The continuous method can make the incompletely grown crystals which just enter the reaction kettle and the completely grown crystals which fully react overflow out of the reaction kettle simultaneously, so the particle size distribution of the obtained manganese hydroxide particles is wider, the particle size distribution of the prepared polygonal mangano-manganic oxide is also wider after oxidation, and the problem that the particles are easy to break when being pressed can be effectively solved due to the wider particle size distribution.
The invention prepares the precursor manganese salt by a liquid-phase coprecipitation method and controls the manganese sulfate solutionControlling the shape and granularity by the concentration and feeding rate of ammonia water and sodium hydroxide solution; meanwhile, the Mn in the reaction kettle is enabled to be added with the Mn by manufacturing a thin environmental phase, namely reducing the concentration of the solution-phase sodium hydroxide in the reaction kettle which is directly contacted with the crystalline particle phase (namely suddenly stopping the introduction of the sodium hydroxide solution and rapidly increasing the ammonia value concentration in the reaction process) 2+ Ammonia complex spiking) and reducing the precipitation reaction rate, the low order phase growth of crystal growth can be promoted, and a polygonal layered structure is formed; and then controlling the natural oxidation of the precursor in the air to finally obtain layered polygonal manganous-manganic oxide with a compact structure, and enhancing the structural stability of the precursor manganous-manganic oxide.
Compared with the prior art, the invention has the advantages that:
(1) According to the polygonal layered manganous-manganic oxide prepared by the invention, the particle size distribution of the manganous-manganic oxide particles is wider, the particles are layered polygons, the sheets are tightly combined and stacked to form layers, and the manganous-manganic oxide is sintered by doping lithium, so that the synthesized lithium manganate can completely inherit the structural characteristics of a precursor manganous-manganic oxide. And the lithium manganate material prepared by sintering the manganous-manganic oxide is used for assembling a button cell at room temperature, and tests show that the lithium manganate material has cycle performance and rate capability.
(2) The polygonal layered manganous-manganic oxide has wider particle size distribution, can be tightly connected together after being pressed, cannot generate the problem of crushing after being pressed, and effectively solves the problem of battery water jumping caused by easy breakage of manganous-manganic oxide with other shapes after being pressed.
(3) The method for preparing the manganous-manganic oxide material is simple and easy to implement, convenient to operate and low in cost.
Drawings
In order to more clearly illustrate the embodiments of the present invention or the technical solutions in the prior art, the drawings needed to be used in the description of the embodiments will be briefly introduced below, and it is obvious that the drawings in the following description are some embodiments of the present invention, and it is obvious for those skilled in the art that other drawings can be obtained according to these drawings without creative efforts.
FIG. 1 shows Mn obtained in example 1 of the present invention 3 O 4 Particle size distribution diagram.
FIG. 2 shows Mn obtained in example 1 of the present invention 3 O 4 5000-fold FEI-SEM spectrum.
FIG. 3 shows Mn obtained in example 1 of the present invention 3 O 4 10000 times FEI-SEM spectrum.
FIG. 4 shows Mn obtained in example 1 of the present invention 3 O 4 XRD pattern of (a).
FIG. 5 shows Mn obtained in example 1 of the present invention 3 O 4 And sintering to obtain the discharge capacity diagram of lithium manganate.
FIG. 6 shows Mn obtained in comparative example 1 of the present invention 3 O 4 FEI-SEM of (g).
FIG. 7 shows Mn obtained in example 1 of the present invention 3 O 4 Sintering to obtain the lithium manganate with the discharge capacity of the lithium manganate and the conventional spherical Mn 3 O 4 And obtaining a comparative figure of the discharge capacity of lithium manganate after sintering.
FIG. 8 shows Mn obtained by the preparation of example 2 of the present invention 3 O 4 And sintering to obtain the discharge capacity diagram of lithium manganate.
FIG. 9 shows Mn obtained by the preparation of example 3 of the present invention 3 O 4 And sintering to obtain the discharge capacity diagram of lithium manganate.
FIG. 10 shows Mn obtained in example 1 of the present invention and comparative example 1 3 O 4 And obtaining a comparison graph of the discharge capacity of lithium manganate after sintering.
Detailed Description
In order to facilitate an understanding of the invention, the invention will be described more fully and in detail below with reference to the accompanying drawings and preferred embodiments, but the scope of the invention is not limited to the specific embodiments below.
Unless otherwise defined, all technical and scientific terms used herein have the same meaning as commonly understood by one of ordinary skill in the art to which this invention belongs. The terminology used herein is for the purpose of describing particular embodiments only and is not intended to limit the scope of the present invention.
Unless otherwise specifically stated, various raw materials, reagents, instruments, equipment and the like used in the present invention are commercially available or can be prepared by existing methods.
Example 1:
the invention relates to a preparation method of polygonal layered manganous-manganic oxide, which adopts a continuous method for preparation, namely raw materials are injected from the bottom of a reaction kettle and discharged from an overflow port at the upper part of the reaction kettle and then collected, and the preparation method comprises the following steps:
(1) Preparing manganese sulfate solution (the concentration is 1.98 mol/L), sodium hydroxide solution (the concentration is 10.86.mol/L) and ammonia water (the concentration is 13.3 mol/L) used for reaction;
(2) Injecting 4.5L of deionized water into a reaction kettle, introducing nitrogen, starting a stirring paddle, rotating at 800rpm, heating to 60 ℃, and adding ammonia water into the reaction kettle to ensure that the ammonia value concentration in the reaction kettle is 5g/L;
(3) Simultaneously introducing a manganese sulfate solution (36 mL/min), a sodium hydroxide solution (8 mL/min) and ammonia water (7.8 mL/min) into the reaction kettle, and keeping the ammonia concentration at 5g/L at the moment to continuously increase the pH value of the system;
(4) When the pH value of the system is 12.5, stopping introducing the NaOH solution, increasing the ammonia value to 9.8g/L, reacting for 11min, and then introducing the NaOH solution again for reaction, wherein the reaction time is 6.5h;
(5) And (3) placing the material obtained by the reaction in the step (4) into a plastic barrel, stirring at the stirring speed of 220rpm, stopping stirring after the material becomes brownish black, standing the material for 1h, removing the supernatant, taking out the material at the bottom layer from the barrel, and placing the material in an air-blast drying oven at 115 ℃ for drying for 15h to obtain the polygonal layered manganous manganic oxide.
The manganomanganic oxide prepared in the embodiment has the advantages that D10=1.51 μm, D50=11.24 μm, D90=51.34 μm; the manganous-manganic oxide is in a polygonal layered accumulation shape, the side length of a polygon is 4-15 mu m, the layer thickness is 5-25 mu m, and the half-peak width of a 011 crystal plane is 0.18.
The particle size distribution, the FEI-SEM image and the XRD pattern of the polygonal layered trimanganese tetroxide prepared in this example are respectively shown in fig. 1 to 4, and fig. 1 shows that trimanganese tetroxide particles prepared by the continuous method have a wider particle size distribution, reducing the risk of easy breakage of the particles under pressure; FIGS. 2 and 3 prove that the morphology of the reaction particles can be effectively controlled by controlling the reaction conditions and the dilute environmental phase, and the manganous-manganic oxide with the polygonal layered structure is prepared; the characteristic peak of the XRD spectrum in figure 4 corresponds to the characteristic peak of the trimanganese tetroxide, which proves that the invention prepares the pure-phase trimanganese tetroxide.
The polygonal layered manganous-manganic oxide prepared in the embodiment is sintered to synthesize lithium manganate, then the lithium manganate is prepared into a button cell, the discharge capacity of the button cell is tested, the test temperature is 25 ℃, the test voltage range is 3-4.3V, and the test multiplying power is 1C, as shown in fig. 5. Tests prove that the first charging capacity of the charging is 109.5mAh/g, the first discharging capacity is 106.7mAh/g, the first coulombic efficiency is 97.45%, after 53 weeks of circulation, the discharging capacity at 54 weeks is 106.5mAh/g, the capacity retention rate at 54 weeks is 97.3%, and the circulation performance is good.
FIG. 7 shows Mn obtained by the preparation of example 1 of the present invention 3 O 4 Sintering to obtain the lithium manganate with the discharge capacity of the lithium manganate and the conventional spherical Mn 3 O 4 The discharge capacity of lithium manganate obtained after sintering is compared, and the testing temperature is 60 ℃; the test voltage range is 3-4.3V; the test multiplying power is 1C; in fig. 7, it can be seen that the cycle of the lithium manganate positive electrode material prepared from spherical manganous-manganic oxide begins to become unstable around 120-130 cycles under the same conditions; the lithium manganate positive electrode material prepared from the polygonal layered manganous-manganic oxide prepared by the invention is still stable after being circulated to 200 weeks, and the fact that the polygonal layered manganous-manganic oxide prepared by the invention can effectively resist pressure and improve the problem of battery water-jumping is proved.
Example 2:
a preparation method of polygonal layered manganous-manganic oxide adopts a continuous method for preparation, namely, solution is injected from the bottom of a reaction kettle and is discharged from an overflow port at the upper part of the reaction kettle and then is collected, and the preparation method comprises the following steps:
(1) Preparing manganese sulfate solution (the concentration is 2.07 mol/L), sodium hydroxide solution (the concentration is 9.87. Mol/L) and ammonia water (the concentration is 13.5 mol/L) for reaction;
(2) Injecting 4.5L of deionized water into a reaction kettle, introducing nitrogen, starting a stirring paddle, rotating at 850rpm, heating to 65 ℃, and adding ammonia water into the reaction kettle to ensure that the ammonia value concentration in the reaction kettle is 4.6g/L;
(3) Manganese sulfate solution (36 mL/min), sodium hydroxide solution (9 mL/min) and ammonia water (11 mL/min) are simultaneously introduced into the reaction kettle, and the pH value of the system is increased continuously;
(4) When the pH value is 12.2, stopping introducing the NaOH solution, increasing the ammonia value in the system to 10.8g/L, reacting for 13min, and then introducing the NaOH solution again for reaction, wherein the reaction time is 6.5h;
(5) And (5) taking the material obtained by the reaction in the step (4) out of the reaction kettle, placing the material in a plastic barrel for stirring at the stirring speed of 300rpm, stopping stirring after the material becomes brownish black, standing the material for 1h, then removing the supernatant, taking the material at the bottom layer out of the barrel, placing the material in a forced air drying oven, and drying the material at 115 ℃ for 18h to obtain the polygonal layered trimanganese tetroxide.
Trimanganese tetroxide prepared in this example, D10=1.25 μm, D50=10.58 μm, D90=50.62 μm; the manganous-manganic oxide is in a polygonal layered accumulation shape, and the side length of the polygon is 3-14 mu m; the layer thickness is 4-20 μm; the half-peak width of the 011 crystal plane is 0.24 deg.
FIG. 8 shows Mn produced in this example 3 O 4 The lithium manganate is sintered to obtain a discharge capacity diagram of lithium manganate, the test temperature is 60 ℃, the test voltage range is 3-4.3V, the test multiplying power is 1C, and the diagram shows that Mn obtained by the preparation of the embodiment 2 of the invention 3 O 4 The prepared lithium manganate cathode material has good cycling stability.
Example 3:
a preparation method of polygonal layered manganous-manganic oxide adopts a continuous method for preparation, namely, solution is injected from the bottom of a reaction kettle and discharged from an overflow port at the upper part of the reaction kettle and then collected, and the preparation method comprises the following steps:
(1) Preparing manganese sulfate solution (the concentration is 2.04 mol/L), sodium hydroxide solution (the concentration is 9.98 mol/L) and ammonia water (the concentration is 13.2 mol/L) for reaction;
(2) Injecting 4.5L of deionized water into a reaction kettle, introducing nitrogen, starting a stirring paddle, rotating at the speed of 830rpm, heating to 55 ℃, and adding ammonia water into the reaction kettle to ensure that the ammonia value concentration in the reaction kettle is 5.3g/L;
(3) Manganese sulfate solution (36 mL/min), sodium hydroxide solution (10 mL/min) and ammonia water (13 mL/min) are simultaneously introduced into the reaction kettle, and the pH value of the system is increased continuously;
(4) When the pH value is 12.8, stopping introducing the NaOH solution, increasing the ammonia value to 10.3g/L, reacting for 14min, and then introducing the NaOH solution again for reaction, wherein the reaction time is 6.5h;
(5) And (3) taking the material obtained by the reaction in the step (4) out of the reaction kettle, placing the material in a plastic barrel, stirring at the stirring speed of 350rpm, stopping stirring after the material becomes brownish black, standing the material for 1h, then removing supernatant, taking the bottom material out of the barrel, and placing the material in an air-blast drying oven for drying at 85 ℃ for 15h to obtain the polygonal layered trimanganese tetroxide.
The manganomanganic oxide prepared in the embodiment has the characteristics of D10=1.64 μm, D50=11.41 μm, D90=52.27 μm; the manganous-manganic oxide is in a polygonal stacked state, and the side length of a polygon is 3-18 mu m; the layer thickness is 3-25 μm; the half-width of the crystal plane 011 is 0.22 deg.
FIG. 9 shows Mn produced in example 3 3 O 4 The lithium manganate obtained after sintering has a discharge capacity diagram of the lithium manganate after being sintered, the test temperature is 60 ℃, the test voltage range is 3-4.3V, and the test multiplying power is 1C, and it can be seen from the diagram that Mn is obtained by the preparation of example 3 of the present invention 3 O 4 The prepared lithium manganate cathode material has good cycling stability.
Comparative example 1:
the preparation method of the manganous-manganic oxide of the comparative example also adopts a continuous method, namely, the solution is injected from the bottom of the reaction kettle and is discharged from an overflow port at the upper part of the reaction kettle and then collected, and the preparation method comprises the following steps:
(1) Preparing manganese sulfate solution (with the concentration of 1.98 mol/L), sodium hydroxide solution (with the concentration of 9.98. Mol/L) and ammonia water (with the concentration of 13.3 mol/L) for reaction;
(2) Injecting 4.5L of deionized water into a reaction kettle, introducing nitrogen, starting a stirring paddle, heating to 55 ℃ at the rotating speed of 650rpm, and adding ammonia water into the reaction kettle to ensure that the ammonia value concentration in the reaction kettle is 5g/L;
(3) Simultaneously introducing a manganese sulfate solution (36 mL/min), a sodium hydroxide solution (7 mL/min) and ammonia water (7 mL/min) into the reaction kettle to react for 12 hours;
(4) And (4) taking the material in the step (3) out of the reaction kettle, placing the material in a plastic barrel for stirring, stopping stirring after the material is brownish black, taking out supernatant after the material is kept stand for 1h, taking out the material at the bottom layer out of the barrel, and placing the material in an air-blast drying oven for drying at 85 ℃ for 15h to obtain the round flaky trimanganese tetroxide.
The FEI-SEM image of the trimanganese tetroxide prepared in this comparative example is shown in fig. 6, and it can be seen from comparison of fig. 6 with fig. 2 and 3 that trimanganese tetroxide prepared without the production of a dilute ambient phase is transformed from polygonal to circular.
The wafer-shaped manganomanganic oxide prepared by the comparative example has D10=2.05 μm, D50=9.57 μm and D90=47.52 μm. FIG. 10 shows Mn obtained in example 1 of the present invention and comparative example 1 3 O 4 A comparison graph of the discharge capacity of lithium manganate after sintering is obtained, the test temperature is 60 ℃, the test voltage range is 3-4.3V, the test multiplying power is 1C, and the graph shows that Mn obtained by the preparation of comparative example 1 3 O 4 Compared with Mn prepared in the embodiment 1 of the invention, the prepared lithium manganate cathode material has the cycle stability 3 O 4 The prepared lithium manganate cathode material has poor cycle performance.

Claims (8)

1. Polygonal layered manganous-manganic oxide is characterized in that the polygonal layered manganous-manganic oxide is in a polygonal layered accumulation shape, the side length of a polygon is 5-50 mu m, and the thickness of the polygon is 3-30 mu m; the half-peak width of 011 crystal face of the polygonal layered mangano-manganic oxide is 0.1-0.3 degrees.
2. The polygonal layered manganomanganic oxide of claim 1, wherein the polygonal layered manganomanganic oxide agglomerated secondary particles have a particle size D10 > 1 μ ι η, D50=5-25 μ ι η, D90 < 100 μ ι η.
3. A method for preparing polygonal layered trimanganese tetroxide according to any one of claims 1-2, comprising the steps of:
(1) Injecting deionized water and ammonia water into a reaction kettle as base solution, starting a stirring paddle and a heater, introducing nitrogen as protective gas, controlling the temperature to be 55-65 ℃, controlling the ammonia value concentration in the reaction kettle to be 4.5-5.5g/L, and then introducing manganese sulfate solution, sodium hydroxide solution and ammonia water into the reaction kettle solution for reaction; when the pH value of the system in the reaction kettle reaches 12-13, stopping introducing the NaOH solution, increasing the ammonia value of the solution to 9.5-11g/L, reacting for 10-15min, and then introducing the NaOH solution again for reaction;
(2) Stirring the material obtained after the reaction in the step (1) to ensure that the material is fully contacted with air until the material becomes brownish black;
(3) And (3) standing the material obtained in the step (2), removing the supernatant, and performing forced air drying on the bottom material to obtain the polygonal layered manganous-manganic oxide.
4. The method according to claim 3, wherein in the step (1), the concentration of the manganese sulfate solution is 1.5-2.5mol/L, and the feeding rate is 30-40mL/min; the concentration of the sodium hydroxide solution is 9-11mol/L, and the feeding rate is 7-9mL/min; the concentration of ammonia water is 13-14mol/L, and the feeding speed is 3-15mL/min.
5. The process according to any one of claims 3 to 4, wherein in the step (1), the stirring speed of the stirring blade is 650 to 1000rpm, and the reaction time is 5 to 7 hours.
6. The production method according to any one of claims 3 to 4, wherein in the step (2), the stirring rate is 200 to 400rpm.
7. The method according to any one of claims 3 to 4, wherein the drying temperature in the step (3) is 70 to 120 ℃ and the drying time is 12 to 24 hours.
8. The process according to any one of claims 3 to 4, wherein all the materials are injected from the bottom of the reaction vessel and the upper overflow port is discharged.
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