CN116443945B - Lithium-rich manganese-based mesoporous cathode material and preparation method and application thereof - Google Patents
Lithium-rich manganese-based mesoporous cathode material and preparation method and application thereof Download PDFInfo
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- 239000011572 manganese Substances 0.000 title claims abstract description 75
- PWHULOQIROXLJO-UHFFFAOYSA-N Manganese Chemical compound [Mn] PWHULOQIROXLJO-UHFFFAOYSA-N 0.000 title claims abstract description 70
- 229910052748 manganese Inorganic materials 0.000 title claims abstract description 70
- 229910052744 lithium Inorganic materials 0.000 title claims abstract description 65
- WHXSMMKQMYFTQS-UHFFFAOYSA-N Lithium Chemical compound [Li] WHXSMMKQMYFTQS-UHFFFAOYSA-N 0.000 title claims abstract description 61
- 239000010406 cathode material Substances 0.000 title claims abstract description 34
- 238000002360 preparation method Methods 0.000 title claims abstract description 24
- 239000011148 porous material Substances 0.000 claims abstract description 72
- HBBGRARXTFLTSG-UHFFFAOYSA-N Lithium ion Chemical compound [Li+] HBBGRARXTFLTSG-UHFFFAOYSA-N 0.000 claims abstract description 18
- 229910001416 lithium ion Inorganic materials 0.000 claims abstract description 18
- 238000000034 method Methods 0.000 claims abstract description 16
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- 239000000377 silicon dioxide Substances 0.000 claims description 29
- 150000003839 salts Chemical class 0.000 claims description 26
- 229910052751 metal Inorganic materials 0.000 claims description 22
- 239000002184 metal Substances 0.000 claims description 22
- 239000010405 anode material Substances 0.000 claims description 20
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- MIVBAHRSNUNMPP-UHFFFAOYSA-N manganese(2+);dinitrate Chemical compound [Mn+2].[O-][N+]([O-])=O.[O-][N+]([O-])=O MIVBAHRSNUNMPP-UHFFFAOYSA-N 0.000 description 5
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- QAHREYKOYSIQPH-UHFFFAOYSA-L cobalt(II) acetate Chemical group [Co+2].CC([O-])=O.CC([O-])=O QAHREYKOYSIQPH-UHFFFAOYSA-L 0.000 description 1
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- GELKBWJHTRAYNV-UHFFFAOYSA-K lithium iron phosphate Chemical compound [Li+].[Fe+2].[O-]P([O-])([O-])=O GELKBWJHTRAYNV-UHFFFAOYSA-K 0.000 description 1
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- UOGMEBQRZBEZQT-UHFFFAOYSA-L manganese(2+);diacetate Chemical group [Mn+2].CC([O-])=O.CC([O-])=O UOGMEBQRZBEZQT-UHFFFAOYSA-L 0.000 description 1
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Abstract
The invention provides a lithium-rich manganese-based mesoporous cathode material, and a preparation method and application thereof, and belongs to the technical field of lithium ion batteries. The lithium-rich manganese-based mesoporous cathode material is prepared by a template method, a mesoporous template with specific aperture and wall thickness is used as a container for preparing the lithium-rich manganese-based mesoporous cathode material, the morphology and the size of the lithium-rich manganese-based mesoporous cathode material are precisely controlled, and the prepared lithium-rich manganese-based mesoporous cathode material has smaller granularity, proper porosity and specific surface area, higher density and higher pore channel utilization rate, and is applied to a lithium ion battery, and has good cycling stability, high energy density, high discharge specific capacity and excellent electrochemical performance.
Description
Technical Field
The invention relates to the technical field of lithium ion batteries, in particular to a lithium-rich manganese-based mesoporous cathode material, and a preparation method and application thereof.
Background
With the rise of electric vehicles, new challenges are presented to the yield of lithium ion batteries. The popularization of electric vehicles depends on the continuous reduction of the cost of lithium ion batteries and the continuous improvement of safety, and the key to achieve the above-mentioned aim is more economical and safe battery materials. The current electric automobile power battery is mainly composed of a ternary material and a lithium iron phosphate material as positive electrode materials, and graphite as negative electrode materials. The ternary material contains more than 20% of nickel. Nickel is a strategic metal that is primarily used in stainless steel, and if all vehicles worldwide are replaced with electric vehicles, the global reserves and market proportions of nickel are far from adequate according to current practice. Cobalt is a scarce strategic metal, and has critical applications in the aerospace, nuclear, and pharmaceutical fields; the price of the battery is high, and the battery is an important obstacle for further reducing the cost of the power battery. Meanwhile, once leakage occurs, the cobalt has great harm to the environment and ecology and is difficult to repair. Therefore, there is an urgent need to develop a cobalt-free cathode material.
While manganese metal has long been considered the most likely cell metal to replace cobalt. Manganese is first a group VIII transition metal, like cobalt, with multiple valence states. Manganese is 11 times more abundant in the crust than nickel, and correspondingly, the price of manganese metal is only 1/9-1/12 of that of nickel. Therefore, the development of manganese compounds as positive electrode materials for lithium ion batteries has been the target of efforts by researchers. And manganese dioxide has been widely used in electroplating and zinc-manganese batteries. The harm of the manganese metal to the environment and human bodies is much smaller than that of cobalt, nickel and other metals; manganese dioxide has stable properties and low toxicity.
Since the discovery of the first manganese-based cathode material LiMn 2O4, significant progress has been made in the research of manganese-based cathode materials. In particular to a manganese-based layered positive electrode material represented by a lithium-rich manganese-based material, the specific discharge capacity of the manganese-based layered positive electrode material can reach 300mAh/g, and the electrochemical platform, structure and chemical composition are similar to those of a ternary material. The lithium-rich manganese base takes manganese as a main transition metal element, has relatively less demand on rare metals such as cobalt, nickel and the like, has less environmental pollution in the production and recovery processes, has the advantages of high capacity, low cost, low toxicity, safety and the like, and has obvious advantages as a high-energy-density battery anode material. Can meet the continuous-lifting requirements of the new energy automobile on the endurance mileage, meanwhile, the method is also helpful to continuously reduce the unit energy cost of the lithium ion battery, and is considered to be a novel positive electrode material with great potential.
However, with intercalation of lithium ions, the crystal structure of the lithium-rich manganese-based material is irreversibly transformed, reducing its circulation capacity. Irreversible transformation of the structure also produces large volume changes that lead to pulverization of the material and detachment from the battery current collector. The main disadvantages of the lithium-rich manganese-based material caused by the structural change are poor cycling stability and relatively poor pole piece processability.
For the above-mentioned problem of lithium ion intercalation, it has been reported that the lithium intercalation specific capacity of the manganese-based nanomaterial represented by beta-MnO 2 is greatly improved compared with that of the conventional material, and the lithium intercalation ratio is nearly 100% and is greatly improved compared with that of the conventional material (< 10%). Meanwhile, during the intercalation/deintercalation cycle, the crystal structure of beta-MnO 2 is retained without being converted to the spinel type Li [ Mn 2]O4 structure.
However, there are some drawbacks in the application of manganese-based nanomaterials to lithium ion batteries. Firstly, the electrode side reaction is increased due to the excessively high specific surface area, the first irreversible capacity is large, and the proportion of dead lithium in the battery is increased. In addition, the density of the nanomaterial is much lower than that of the conventional material, so that the volume energy density is greatly reduced when the nanomaterial is used as a positive electrode. Meanwhile, due to the characteristics of high specific surface area and the like of the nano particles, more conductive agents and adhesives are needed to be added when the nano particles are used as electrodes, and the energy density of a battery is further reduced.
Therefore, there is a need to develop a lithium-rich manganese-based positive electrode material with high electrochemical performance.
Disclosure of Invention
The invention aims to overcome the defect of poor electrochemical performance in the prior art and provide the lithium-rich manganese-based mesoporous anode material which has the advantages of proper specific surface area, good cycling stability, high energy density and high discharge specific capacity.
The invention also aims at providing a preparation method of the lithium-rich manganese-based mesoporous anode material.
The invention also aims to provide the application of the lithium-rich manganese-based mesoporous anode material as a lithium ion battery anode.
In order to achieve the above purpose, the invention adopts the following technical scheme:
The preparation method of the lithium-rich manganese-based mesoporous anode material comprises the following steps:
s1, mixing Li salt, ni salt, co salt and Mn salt, and adding a complexing agent to obtain a metal salt mixed solution;
S2, adding a mesoporous template into the metal salt mixed solution obtained in the step S1, and soaking to obtain a mixture; the ratio of the aperture of the mesoporous template to the thickness of the pore wall is 2-10: 1, a step of;
s3, drying and sintering the mixture obtained in the step S2, and removing the mesoporous template to obtain the lithium-rich manganese-based mesoporous anode material.
The lithium-rich manganese-based mesoporous anode material is prepared by a template method. The mesoporous template with higher pore diameter/pore wall thickness is used as a container for preparing the lithium-rich manganese-based mesoporous anode material, the shape and the size of the lithium-rich manganese-based mesoporous anode material are precisely controlled, and the prepared lithium-rich manganese-based mesoporous anode material has lower pore diameter/particle diameter ratio. The pore diameter of the lithium-manganese-based mesoporous positive electrode material corresponds to the pore wall thickness of the mesoporous template, and the particle diameter of the lithium-manganese-based mesoporous positive electrode material corresponds to the pore diameter of the mesoporous template. The lithium-rich manganese-based mesoporous anode material provided by the invention has a proper specific surface area, further has higher density and pore channel utilization rate, and has excellent electrochemical performance when being applied to a lithium ion battery.
The mesoporous templates used in the invention have high aperture/wall thickness ratio. The pore diameter of the mesoporous template inhibits overgrowth of lithium-rich manganese-based material grains at high temperature, so that the migration and diffusion distance of lithium ions in the positive electrode material is greatly shortened, and meanwhile, the capacity of the lithium-rich manganese-based mesoporous positive electrode material for the ginger-Taylor effect caused by volume expansion and Mn valence variation is greatly improved, and the multiplying power capacity and the cycling stability of the positive electrode material are remarkably improved.
The mesoporous template has a foam-like pore channel configuration, the internal gap is large and spherical, the pore size is proper, and the pore wall thickness is thin. Because the mesoporous template has stronger hydrophilicity, when the mesoporous template is immersed by the metal salt mixed solution, the metal salt solution can be adsorbed near the pore wall. And (3) drying and sintering the mixture in the step (S3), reacting the metal salt mixed solution to generate metal oxide, nucleating and growing the metal oxide on the pore walls, and finally filling the foam pore channels. The primary particles of the positive electrode material thus formed are spherical and the particle size corresponds to the shape and particle size of the cells of the foam-like template.
In the step S3, after the mesoporous template is removed, pore channels uniformly surrounding the particles are left around the lithium-rich manganese-based primary particles formed before, and the morphology of the pore channels corresponds to the pore wall of the mesoporous template. The pore canals are favorable for infiltration of electrolyte, and lithium ions can quickly reach the surface of primary particles of the positive electrode material, so that the performance and multiplying power capability of the material battery are improved.
Preferably, the pore diameter of the mesoporous template is 20-70 nm, and the pore wall thickness is 3-20 nm.
Optionally, the mesoporous template is a mesoporous silica template and/or a mesoporous carbon template. The mesoporous silica template and the mesoporous carbon template can realize the proper ratio of pore diameter to pore wall thickness.
The mesoporous silica template and the mesoporous carbon template can be obtained by purchasing commercial products, and can also be prepared by adopting a self-making method.
Preferably, the mesoporous silica template is prepared by the following method:
mixing and stirring an oil phase reagent, a surfactant, a pore expanding agent and tetraethyl silicate (TEOS) with water to form a mixed solution, carrying out an aging reaction to obtain a precipitate, and washing, drying and sintering at 500-700 ℃ to obtain the mesoporous silica template.
Preferably, the surfactant is at least one of sodium hexadecyl sulfonate (SAS), stearic acid, P123 (polyethylene oxide-polypropylene oxide-polyethylene oxide triblock copolymer with a molecular formula of PEO-PPO-PEO) and SBA-15.
Preferably, the oil phase reagent is at least one of ethanol, 1,3,5 trimethylbenzene, xylene and phenol.
More preferably, the oil phase reagent is xylene.
Preferably, the pore-expanding agent is Tetramethylbenzidine (TMB) and/or NH 4 F.
In the preparation process of the mesoporous silica template, the selection of an oil phase reagent and a pore-expanding agent is a main factor influencing the pore diameter and pore wall size of the prepared mesoporous silica template. Mixing the oil phase reagent, the surfactant, the pore-expanding agent and water, and stirring vigorously to form a microemulsion with a spherical structure, adding TEOS, and stirring continuously to suspend the formed biphasic microsphere in the water. The oil phase agent and the pore expanding agent have proper lipophilicity, can form submicron-level microbeads in water, and can be connected into continuous microemulsion under the action of a proper surfactant. Through the preparation method, the mesoporous silica template with the aperture of 20-70 nm and the pore wall thickness of 3-20 nm can be prepared.
Preferably, the mesoporous silica template is prepared by the following method:
Mixing an oil phase reagent (dimethylbenzene), a surfactant and a pore-enlarging agent (TMB) with water, vigorously stirring at a constant temperature of 40 ℃ to form a microemulsion, adding tetraethyl silicate (TEOS), continuously stirring at a constant temperature of 40 ℃ for 20 hours to obtain a mixed solution, transferring the mixed solution into a high-pressure reaction kettle, reacting at a temperature of 110-120 ℃ for 24-144 hours to obtain a precipitate, washing the precipitate with water, drying in air, and sintering at a temperature of 500-700 ℃ to obtain the mesoporous silica template.
Preferably, the mesoporous carbon template is prepared by the following method:
Mixing porous biomass, an alkali source and a solvent, and drying to obtain a precursor; sintering the precursor at 500-700 ℃ under the protection of inert gas, and then burning at 400-450 ℃ in air atmosphere to obtain the carbon material; and (3) soaking the carbon material in a strong oxidant solution for reaction, taking out, washing and drying to obtain the mesoporous carbon template.
Preferably, the porous biomass is at least one of shaddock peel, leaf, coconut shell, shell and date pit.
Preferably, the strong oxidizer solution is at least one of H 2SO4、HNO3、KMnO4.
Preferably, the alkali source is NaOH.
Preferably, the carbon material is soaked in the strong oxidant solution for 10-15 hours.
Preferably, the mesoporous carbon template is prepared by the following method:
Drying porous biomass (shaddock peel), removing impurities, mixing with an alkali source (NaOH) and a solvent (NaClO 4), reacting for 12 hours, separating solid and liquid by adopting a centrifuge, washing a solid phase by using distilled water, and drying to obtain a precursor;
Under the protection of inert gas N 2, sintering the precursor under the following conditions: heating to 500 ℃ at a speed of 5 ℃/min for pre-carbonization for 1 hour, and then preserving heat at 700 ℃ for 10 hours;
then burning the mixture at 400-450 ℃ in air atmosphere to obtain a carbon material;
the carbon material is soaked in strong oxidant solution (85 wt.% concentrated sulfuric acid) for reaction for 12 hours, and is taken out, washed by distilled water, ultrasonically cleaned and dried to obtain the mesoporous carbon template.
Alternatively, in step S1, the Li salt, ni salt, co salt, mn salt may be Li, ni, co, mn sulfate, nitrate or acetate.
Preferably, in step S1, in the molten metal mixed solution, the mole percentage of Mn is greater than or equal to 50% based on the total mole number of Ni, co, and Mn.
Alternatively, the molar ratio of Ni, co, mn may be: 20:10:70, 14:6:80, 30:5:65.
Preferably, in the step S1, the ratio of the mole number of Li to the sum of the mole numbers of Ni, co and Mn in the molten metal mixture is 1 to 1.45:1.
Preferably, in step S1, the molar concentration of Li, ni, co, mn in the molten metal mixed solution is between 0.01 and 4 mol/L.
Preferably, in step S1, the complexing agent is at least one of citric acid, ammonia, oxalic acid and tartaric acid.
In step S2, the mesoporous template is immersed by the metal salt mixed solution, so that metal oxide is generated in the pore wall of the template, and in order to ensure the preparation efficiency and the morphology of the metal oxide, the mixing proportion of the metal salt mixed solution and the mesoporous template is controlled, so that the generated metal oxide accounts for less than or equal to 50% of the pore volume ratio of the mesoporous template.
Preferably, in step S3, the sintering temperature is 400 to 800 ℃.
Preferably, in step S3, the mesoporous templates are removed by alkaline washing. The alkaline washing may be stirring and washing with NaOH solution.
The invention also protects the lithium-rich manganese-based mesoporous anode material prepared by the preparation method.
The invention also protects application of the lithium-rich manganese-based mesoporous anode material in a lithium ion battery.
Compared with the prior art, the invention has the beneficial effects that:
The invention develops a lithium-rich manganese-based mesoporous anode material, which is prepared by a template method. According to the invention, the mesoporous template is used as a container for preparing the lithium-rich manganese-based mesoporous cathode material, the lithium-rich manganese-based mesoporous cathode material is synthesized at one time through the salt solution, the uniformity of metal components in the salt solution is high, the morphology of the material is well controlled, the nano particles which are spherical and have the particle size close to the pore diameter of the template can be obtained, meanwhile, the pores among the nano particles cannot be too high, the specific surface area is proper, and the pore diameter/particle diameter ratio of the lithium-rich manganese-based mesoporous cathode material can be kept low.
The lithium-rich manganese-based mesoporous anode material prepared by the invention has smaller granularity, proper porosity and specific surface area, and further has higher density and pore channel utilization rate, and is applied to a lithium ion battery, and has the advantages of good cycling stability, high energy density, high discharge specific capacity and excellent electrochemical performance.
Drawings
FIG. 1 is a TEM image of a mesoporous silica template-1;
FIG. 2 is a pore size distribution diagram of mesoporous silica template-1;
FIG. 3 is a TEM image of a mesoporous carbon template;
FIG. 4 is a TEM image of the lithium-rich manganese-based mesoporous cathode material of example 1;
fig. 5 is a pore size distribution diagram of the lithium-rich manganese-based mesoporous cathode material of example 1.
Detailed Description
For a better description of the objects, technical solutions and advantages of the present invention, the present invention will be further described with reference to the following specific examples, which are not intended to limit the present invention in any way.
In the embodiment and the comparative example of the invention, the mesoporous silica template is obtained by self-making, and the preparation method is as follows:
Mixing an oil phase reagent (dimethylbenzene), a surfactant (sodium hexadecyl sulfonate) and a pore-enlarging agent (TMB) with water, vigorously stirring at a constant temperature of 40 ℃ to form a microemulsion, adding tetraethyl silicate (TEOS), continuously stirring at a constant temperature of 40 ℃ for 20 hours to obtain a mixed solution, transferring the mixed solution into a high-pressure reaction kettle, reacting at a temperature of 110-120 ℃ for 24-144 hours to obtain a precipitate, washing the precipitate with water, centrifuging, separating solid from liquid, drying the solid in air, and sintering to obtain the mesoporous silica template;
mesoporous silica templates with different specifications can be prepared by adjusting the reaction time and temperature;
Wherein the average pore diameter of the mesoporous silica template-1 is 34nm, the average pore wall thickness is 5nm, and the ratio of pore diameter to pore wall thickness is 6.8:1, a step of;
wherein the pore diameter of the mesoporous silica template-2 is 40nm, the pore wall thickness is 20nm, and the ratio of the pore diameter to the pore wall thickness is 2:1, a step of;
wherein the pore diameter of the mesoporous silica template-3 is 40nm, the pore wall thickness is 10nm, and the ratio of the pore diameter to the pore wall thickness is 4:1, a step of;
wherein the pore diameter of the mesoporous silica template-4 is 60nm, the pore wall thickness is 6nm, and the ratio of the pore diameter to the pore wall thickness is 10:1, a step of;
In the examples and comparative examples of the present invention, mesoporous carbon templates were purchased from the mesoporous carbon spheres Macklin, M939262 of the microphone company, the pore diameter of the mesoporous carbon templates was 35nm, the pore wall thickness was 5nm, and the ratio of the pore diameter to the pore wall thickness was 7:1.
The TEM image of the mesoporous silica template-1 is shown in FIG. 1, the pore size distribution diagram is shown in FIG. 2, and the TEM image of the mesoporous carbon template is shown in FIG. 3. It can be seen that the mesoporous silica template and the mesoporous carbon template both have foam-like pore channel configurations, the internal voids are large and spherical, and the ratio of the pore diameter to the pore wall thickness is large.
Unless specifically stated otherwise, the reagents, methods and apparatus employed in the present invention are those conventional in the art. The reagents and materials used in the present invention are commercially available unless otherwise specified.
Example 1
The embodiment provides a lithium-rich manganese-based mesoporous cathode material, which is prepared by the following steps:
S1, mixing lithium nitrate, nickel nitrate, cobalt nitrate and manganese nitrate, and adding a complexing agent (oxalic acid) to obtain a metal salt mixed solution, wherein the molar concentration of the lithium nitrate is 1.45mol/L, the molar concentration of the nickel nitrate is 0.2mol/L, the molar concentration of the cobalt nitrate is 0.1mol/L, the molar concentration of the manganese nitrate is 0.7mol/L, and the molar concentration of the complexing agent oxalic acid is 0.2mol/L;
S2, taking the mesoporous silica template as a-1 mesoporous template, dropwise adding the metal salt mixed solution prepared in the step S1 for soaking until liquid redundancy appears on the surface of the mesoporous template, and obtaining a mixture;
S3, drying the mixture prepared in the step S2 at 60 ℃, then sintering at the constant temperature of 500 ℃ for 10 hours, washing the product by using a 1mol/L NaOH solution, stirring for 2 hours to remove the mesoporous template, centrifuging to separate a solid phase and a liquid phase, and washing the solid phase by using distilled water to obtain the lithium-rich manganese-based mesoporous anode material.
Example 2
The present embodiment provides a lithium-rich manganese-based mesoporous cathode material, and the preparation method is different from embodiment 1 in that: and step S2, a mesoporous silica template-2 is adopted as the mesoporous template.
Example 3
The present embodiment provides a lithium-rich manganese-based mesoporous cathode material, and the preparation method is different from embodiment 1 in that: and step S2, a mesoporous silica template-3 is adopted as the mesoporous template.
Example 4
The present embodiment provides a lithium-rich manganese-based mesoporous cathode material, and the preparation method is different from embodiment 1 in that: and step S2, a mesoporous silica template-4 is adopted as the mesoporous template.
Example 5
The present embodiment provides a lithium-rich manganese-based mesoporous cathode material, and the preparation method is different from embodiment 1 in that: and S2, adopting a mesoporous carbon template as the mesoporous template.
Example 6
The present embodiment provides a lithium-rich manganese-based mesoporous cathode material, and the preparation method is different from embodiment 1 in that: in the step S1, the molar concentration of lithium nitrate is 1.3mol/L, the molar concentration of nickel nitrate is 0.3mol/L, the molar concentration of cobalt nitrate is 0.05mol/L, the molar concentration of manganese nitrate is 0.65mol/L, and the molar concentration of complexing agent oxalic acid is 0.4mol/L.
Example 7
The present embodiment provides a lithium-rich manganese-based mesoporous cathode material, and the preparation method is different from embodiment 1 in that: in the step S1, the molar concentration of lithium nitrate is 1.3mol/L, the molar concentration of nickel nitrate is 0.14mol/L, the molar concentration of cobalt nitrate is 0.06mol/L, the molar concentration of manganese nitrate is 0.8mol/L, and the molar concentration of complexing agent oxalic acid is 0.4mol/L.
Example 8
The present embodiment provides a lithium-rich manganese-based mesoporous cathode material, and the preparation method is different from embodiment 1 in that: in the step S1, the complexing agent is replaced by tartaric acid; lithium nitrate, nickel nitrate, cobalt nitrate, and manganese nitrate are replaced with lithium acetate, nickel acetate, cobalt acetate, and manganese acetate, respectively.
Example 9
The present embodiment provides a lithium-rich manganese-based mesoporous cathode material, and the preparation method is different from embodiment 1 in that: in step S3, the sintering temperature is 800 ℃ and the sintering time is 8 hours.
Comparative example 1
The comparative example provides a lithium-rich manganese-based mesoporous cathode material, which is prepared by the following steps:
Nickel sulfate, cobalt sulfate and manganese sulfate are mixed according to a mole ratio of 2:1:7, mixing, adding NH 3·H2 O as a complexing agent to obtain a metal salt solution, continuously stirring the metal salt solution under the protection atmosphere of N 2, slowly adding NaOH to adjust the pH to 12, and obtaining a hydroxide precipitate; washing the obtained hydroxide precipitate with water and then drying to obtain a precursor; mixing the precursor and lithium carbonate according to a ratio of 1: and (3) mixing the materials according to the molar ratio of 1.2, loading the mixture into a sagger, keeping the temperature at 850 ℃ for 15 hours, taking out the materials, and crushing and sieving the materials to obtain the lithium-rich manganese-based anode material.
Comparative example 2
This comparative example provides a lithium-rich manganese-based mesoporous cathode material, the preparation method differs from example 1 in that: in the step S2, the mesoporous template is replaced by a commercially available gas phase method silicon dioxide template, the pore diameter of the template is 6.0nm, the pore wall thickness is 5.2nm, and the ratio of the pore diameter to the pore wall thickness is 1.15:1.
Performance testing
The performance of the positive electrode materials obtained in the above examples and comparative examples was characterized, and specific test items and test methods are as follows:
morphology and element content of the positive electrode material:
Particle size: is obtained by Jeol electronics TEM transmission electron microscope test;
specific surface area: the specific surface area meter is used for testing;
porosity: the porous ceramic material is obtained by testing Micromeritics porosity instrument;
tap density: is obtained by testing a tap density meter (AccuPycII; 1340);
elemental content: the weight ratio of Mn, ni, co, li was measured by ICP (inductively coupled plasma spectrometer).
(II) electrochemical properties:
The materials prepared in the examples and comparative examples of the invention are used as the positive electrode of a lithium ion battery, a lithium metal sheet is used as the negative electrode, 4.8V high-voltage electrolyte (code: LB 111) is charged at constant current and constant voltage in a charge-discharge cut-off voltage interval of 2.0-4.8V, and then discharged at constant current, and the first discharge specific capacity @1C, the first charge-discharge efficiency, the 1C cycle 100-week discharge capacity retention rate, the 2C discharge specific capacity and the 5C discharge specific capacity are detected.
A TEM image of the lithium-rich manganese-based mesoporous cathode material of example 1 is shown in fig. 4, and a pore size distribution diagram is shown in fig. 5. It can be seen that the lithium-rich manganese-based mesoporous anode material prepared by the invention has a spherical structure, the particle size is uniform, the main pore diameter peak values are distributed at 5nm and 34nm, wherein the peak value of 5nm corresponds to the pore wall thickness of the mesoporous template, and the peak value of 34nm corresponds to the pore diameter of the mesoporous template.
The dimensional morphology and element content of the positive electrode materials of examples 1 to 5 and comparative examples 1 to 2 are shown in Table 1.
TABLE 1
From the test results of table 1, it can be seen that the particle size ranges of the lithium-rich manganese-based mesoporous cathode materials prepared in examples 1 to 5 are far lower than that of comparative example 1, and the specific surface area and porosity are higher than those of comparative example 1. The comparative example 2 has a wide particle size distribution range and an excessively large specific surface area, resulting in a very low tap density of the cathode material.
The results of the electrochemical performance test of examples 1 to 9 and comparative examples 1 to 2 are shown in Table 2.
TABLE 2
From the test results of table 2, it can be seen that the electrochemical properties of the lithium-rich manganese-based mesoporous cathode materials prepared in examples 1 to 9 are far superior to those of the lithium-rich manganese-based cathode materials prepared by the conventional method of comparative example 1. While comparative example 2 is a lithium-rich manganese-based material obtained by using commercially available fumed silica as a template, although the specific capacity and rate capacity thereof are relatively high, the specific surface area of the material is too high, which results in low first charge and discharge efficiency, and in addition, the too high porosity and the too low tap density thereof result in too low volumetric energy density, so that practical application is severely limited.
Finally, it should be noted that the above embodiments are only for illustrating the technical solution of the present invention and not for limiting the scope of the present invention, and although the present invention has been described in detail with reference to the preferred embodiments, it should be understood by those skilled in the art that the technical solution of the present invention may be modified or substituted equally without departing from the spirit and scope of the technical solution of the present invention.
Claims (8)
1. The preparation method of the lithium-rich manganese-based mesoporous anode material is characterized by comprising the following steps of:
s1, mixing Li salt, ni salt, co salt and Mn salt, and adding a complexing agent to obtain a metal salt mixed solution;
s2, adding a mesoporous template into the metal salt mixed solution obtained in the step S1, and soaking to obtain a mixture; the ratio of the aperture of the mesoporous template to the thickness of the pore wall is 2-10:1;
S3, drying and sintering the mixture obtained in the step S2, and removing the mesoporous template to obtain the lithium-rich manganese-based mesoporous anode material;
The pore diameter of the mesoporous template is 20-70 nm, and the pore wall thickness is 3-20 nm;
The mesoporous template is a mesoporous silica template and/or a mesoporous carbon template.
2. The preparation method according to claim 1, wherein the mesoporous silica template is prepared by the following method:
Mixing and stirring the oil phase reagent, the surfactant, the pore-enlarging agent and the tetraethyl silicate with water to obtain a mixed solution, carrying out an aging reaction to obtain a precipitate, and washing, drying and sintering at 500-700 ℃ to obtain the mesoporous silica template.
3. The preparation method according to claim 1, wherein the mesoporous carbon template is prepared by the following method:
Mixing porous biomass, an alkali source and a solvent, and drying to obtain a precursor; sintering the precursor at 500-700 ℃ under the protection of inert gas, and then burning at 400-450 ℃ in air atmosphere to obtain the carbon material; and (3) soaking the carbon material in a strong oxidant solution for reaction, taking out, washing and drying to obtain the mesoporous carbon template.
4. The method according to claim 1, wherein in step S1, the Li salt, ni salt, co salt, mn salt is a sulfate, nitrate or acetate salt of Li, ni, co, mn.
5. The method according to claim 1, wherein in step S1, the complexing agent is at least one of citric acid, ammonia, oxalic acid, and tartaric acid.
6. The method according to claim 1, wherein in step S3, the mesoporous template is removed by alkali washing.
7. A lithium-rich manganese-based mesoporous cathode material, characterized by being prepared by the preparation method according to any one of claims 1 to 6.
8. The use of the lithium-rich manganese-based mesoporous cathode material according to claim 7 in lithium ion batteries.
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