CN115332500A - Preparation method and application of high-capacity battery active material - Google Patents

Preparation method and application of high-capacity battery active material Download PDF

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Publication number
CN115332500A
CN115332500A CN202210898632.9A CN202210898632A CN115332500A CN 115332500 A CN115332500 A CN 115332500A CN 202210898632 A CN202210898632 A CN 202210898632A CN 115332500 A CN115332500 A CN 115332500A
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sintering
preparation
ferric
temperature
active material
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王雀乐
李长东
阮丁山
刘伟健
缪建麟
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Hunan Brunp Recycling Technology Co Ltd
Guangdong Brunp Recycling Technology Co Ltd
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Hunan Brunp Recycling Technology Co Ltd
Guangdong Brunp Recycling Technology Co Ltd
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Priority to CN202210898632.9A priority Critical patent/CN115332500A/en
Priority to PCT/CN2022/117480 priority patent/WO2024021231A1/en
Publication of CN115332500A publication Critical patent/CN115332500A/en
Priority to FR2308123A priority patent/FR3138575A1/en
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    • H—ELECTRICITY
    • H01—ELECTRIC ELEMENTS
    • H01M—PROCESSES OR MEANS, e.g. BATTERIES, FOR THE DIRECT CONVERSION OF CHEMICAL ENERGY INTO ELECTRICAL ENERGY
    • H01M4/00—Electrodes
    • H01M4/02—Electrodes composed of, or comprising, active material
    • H01M4/36—Selection of substances as active materials, active masses, active liquids
    • H01M4/362—Composites
    • H01M4/364—Composites as mixtures
    • H—ELECTRICITY
    • H01—ELECTRIC ELEMENTS
    • H01M—PROCESSES OR MEANS, e.g. BATTERIES, FOR THE DIRECT CONVERSION OF CHEMICAL ENERGY INTO ELECTRICAL ENERGY
    • H01M10/00—Secondary cells; Manufacture thereof
    • H01M10/05—Accumulators with non-aqueous electrolyte
    • H01M10/052—Li-accumulators
    • H01M10/0525—Rocking-chair batteries, i.e. batteries with lithium insertion or intercalation in both electrodes; Lithium-ion batteries
    • H—ELECTRICITY
    • H01—ELECTRIC ELEMENTS
    • H01M—PROCESSES OR MEANS, e.g. BATTERIES, FOR THE DIRECT CONVERSION OF CHEMICAL ENERGY INTO ELECTRICAL ENERGY
    • H01M4/00—Electrodes
    • H01M4/02—Electrodes composed of, or comprising, active material
    • H01M4/04—Processes of manufacture in general
    • H01M4/0471—Processes of manufacture in general involving thermal treatment, e.g. firing, sintering, backing particulate active material, thermal decomposition, pyrolysis
    • H—ELECTRICITY
    • H01—ELECTRIC ELEMENTS
    • H01M—PROCESSES OR MEANS, e.g. BATTERIES, FOR THE DIRECT CONVERSION OF CHEMICAL ENERGY INTO ELECTRICAL ENERGY
    • H01M4/00—Electrodes
    • H01M4/02—Electrodes composed of, or comprising, active material
    • H01M4/13—Electrodes for accumulators with non-aqueous electrolyte, e.g. for lithium-accumulators; Processes of manufacture thereof
    • H01M4/131—Electrodes based on mixed oxides or hydroxides, or on mixtures of oxides or hydroxides, e.g. LiCoOx
    • H—ELECTRICITY
    • H01—ELECTRIC ELEMENTS
    • H01M—PROCESSES OR MEANS, e.g. BATTERIES, FOR THE DIRECT CONVERSION OF CHEMICAL ENERGY INTO ELECTRICAL ENERGY
    • H01M4/00—Electrodes
    • H01M4/02—Electrodes composed of, or comprising, active material
    • H01M4/13—Electrodes for accumulators with non-aqueous electrolyte, e.g. for lithium-accumulators; Processes of manufacture thereof
    • H01M4/139—Processes of manufacture
    • H01M4/1391—Processes of manufacture of electrodes based on mixed oxides or hydroxides, or on mixtures of oxides or hydroxides, e.g. LiCoOx
    • H—ELECTRICITY
    • H01—ELECTRIC ELEMENTS
    • H01M—PROCESSES OR MEANS, e.g. BATTERIES, FOR THE DIRECT CONVERSION OF CHEMICAL ENERGY INTO ELECTRICAL ENERGY
    • H01M4/00—Electrodes
    • H01M4/02—Electrodes composed of, or comprising, active material
    • H01M4/36—Selection of substances as active materials, active masses, active liquids
    • H01M4/48—Selection of substances as active materials, active masses, active liquids of inorganic oxides or hydroxides
    • H01M4/52—Selection of substances as active materials, active masses, active liquids of inorganic oxides or hydroxides of nickel, cobalt or iron
    • H01M4/525—Selection of substances as active materials, active masses, active liquids of inorganic oxides or hydroxides of nickel, cobalt or iron of mixed oxides or hydroxides containing iron, cobalt or nickel for inserting or intercalating light metals, e.g. LiNiO2, LiCoO2 or LiCoOxFy
    • H—ELECTRICITY
    • H01—ELECTRIC ELEMENTS
    • H01M—PROCESSES OR MEANS, e.g. BATTERIES, FOR THE DIRECT CONVERSION OF CHEMICAL ENERGY INTO ELECTRICAL ENERGY
    • H01M4/00—Electrodes
    • H01M4/02—Electrodes composed of, or comprising, active material
    • H01M4/36—Selection of substances as active materials, active masses, active liquids
    • H01M4/58—Selection of substances as active materials, active masses, active liquids of inorganic compounds other than oxides or hydroxides, e.g. sulfides, selenides, tellurides, halogenides or LiCoFy; of polyanionic structures, e.g. phosphates, silicates or borates
    • H01M4/583—Carbonaceous material, e.g. graphite-intercalation compounds or CFx
    • H01M4/587—Carbonaceous material, e.g. graphite-intercalation compounds or CFx for inserting or intercalating light metals
    • H—ELECTRICITY
    • H01—ELECTRIC ELEMENTS
    • H01M—PROCESSES OR MEANS, e.g. BATTERIES, FOR THE DIRECT CONVERSION OF CHEMICAL ENERGY INTO ELECTRICAL ENERGY
    • H01M4/00—Electrodes
    • H01M4/02—Electrodes composed of, or comprising, active material
    • H01M4/62—Selection of inactive substances as ingredients for active masses, e.g. binders, fillers
    • H01M4/624—Electric conductive fillers
    • H01M4/625—Carbon or graphite
    • Y—GENERAL TAGGING OF NEW TECHNOLOGICAL DEVELOPMENTS; GENERAL TAGGING OF CROSS-SECTIONAL TECHNOLOGIES SPANNING OVER SEVERAL SECTIONS OF THE IPC; TECHNICAL SUBJECTS COVERED BY FORMER USPC CROSS-REFERENCE ART COLLECTIONS [XRACs] AND DIGESTS
    • Y02—TECHNOLOGIES OR APPLICATIONS FOR MITIGATION OR ADAPTATION AGAINST CLIMATE CHANGE
    • Y02E—REDUCTION OF GREENHOUSE GAS [GHG] EMISSIONS, RELATED TO ENERGY GENERATION, TRANSMISSION OR DISTRIBUTION
    • Y02E60/00—Enabling technologies; Technologies with a potential or indirect contribution to GHG emissions mitigation
    • Y02E60/10—Energy storage using batteries

Abstract

The invention discloses a preparation method and application of a high-capacity battery active material. The invention adopts ferric hydroxide colloid as an iron source, the colloid dispersibility is good, the prepared ferric oxide particles are small, and the subsequent preparation of small-particle Li is facilitated 5 FeO 4 Is introduced into ferric hydroxide colloidThe conductive carbon source can prevent the material from melting and growing up, so that the synthesized particles are smaller, and the conductivity of the material is improved; organic polymer is added in the sanding process, so that a relatively compact coating layer can be formed on the surface of the material, and the stability and the conductivity of the material are further improved.

Description

Preparation method and application of high-capacity battery active material
Technical Field
The invention belongs to the technical field of lithium ion battery materials, and particularly relates to a preparation method and application of a high-capacity battery active material.
Background
At present, the new energy automobile has higher and higher requirements on the endurance mileage of a power battery, which puts higher requirements on the cycle capacity of a power battery material. As is known, in a lithium ion battery, due to the formation of an SEI film during the first charge and discharge, lithium ions cannot return to the positive electrode by 100%, but some lithium ions are lost, so that the first charge and discharge capacity and the cycle capacity of the lithium ion battery cannot be fully exerted.
Li 5 FeO 4 Has the advantage of ultrahigh theoretical capacity, and a certain amount of Li is added into the anode material 5 FeO 4 And the problem of lithium ion loss during first charging and discharging can be effectively solved. Currently synthesized Li 5 FeO 4 The method still has some problems, such as too large synthetic material particles, long lithium ion migration path, relatively low capacity, poor conductivity, poor stability and the like. In order to solve these problems, it is generally considered to reduce the size of the material by reducing the particle size of the iron oxide, but it is difficult to achieve the nano-scale iron oxide, and the nano-scale iron oxide on the market is expensive, has a small supply amount, and has no cost advantage. In addition, in the existing carbon coating technology, a method for carrying out gas phase coating on the surface of a material by adopting a gaseous low molecular weight organic matter is adopted, the conductivity and the stability of the material can be improved to a certain extent, but the gas phase coating has higher requirements on safe production and equipment and is not beneficial to the safety production and the equipmentAnd (4) industrialization.
Disclosure of Invention
The present invention has been made to solve at least one of the above-mentioned problems occurring in the prior art. Therefore, the invention provides a preparation method and application of a high-capacity battery active material.
According to one aspect of the invention, it is proposed that the method comprises the following steps:
s1: mixing ferric hydroxide colloid with a carbon source, and performing spray drying on the obtained mixed material to obtain carbon-doped nano ferric oxide;
s2: mixing the nano iron oxide with a lithium source, and sintering in an inert atmosphere to obtain a sintered material;
s3: mixing the sintering material, the organic polymer and the organic solvent, carrying out wet grinding in a protective atmosphere, and carrying out spray drying on the obtained grinding material in the protective atmosphere to obtain a dry material;
s4: and sintering the dried material in an inert atmosphere to obtain the battery active material.
In some embodiments of the present invention, in step S1, the method for preparing the iron hydroxide colloid comprises: and slowly adding the ferric salt solution into hot water while heating and stirring, and keeping the temperature for a period of time after the liquid adding is finished to obtain the ferric hydroxide colloid. Ferric salt solution is heated in water to generate hydrolysis reaction to prepare ferric hydroxide colloid. Further, the water is deionized water with the impurity content less than or equal to 1000 ppm; further, the concentration of the ferric salt solution is 0.1-12mol/L; further, the heating temperature is above 80 ℃; furthermore, the heat preservation time is more than 10min after the liquid adding is finished.
In some embodiments of the present invention, in step S1, the temperature of the hot water is 80 ℃ or higher.
In some embodiments of the invention, in step S1, the carbon source is at least one of carbon nanotubes, conductive carbon black, graphite powder, polyethyleneimine, glucose or polyvinyl alcohol. Further, the particle size Dv50 of the carbon source is 0.5 to 3 μm.
In some embodiments of the invention, the temperature of the spray drying in step S1 is 180 to 250 ℃.
In some embodiments of the present invention, in step S1, the mixture is stirred during the spray drying process, and the stirring speed is 100-500rpm.
In some embodiments of the invention, in step S1, the amount of the carbon source added is 5% to 30% of the mass of the generated nano iron oxide.
In some embodiments of the invention, in step S1, the nano-iron oxide has a BET of 28 to 58m 2 (iv) g, the particle diameter Dv50 is 100-700nm.
In some embodiments of the present invention, in step S2, the lithium source is at least one of lithium hydroxide monohydrate, anhydrous lithium hydroxide or lithium oxide, and a molar ratio of lithium element in the lithium source to iron element in the nano iron oxide is 5.0 to 5.8.
In some embodiments of the invention, in step S2, the sintering temperature is 600 to 900 ℃. Further, the sintering time is 8-36h.
In some embodiments of the present invention, in step S3, the organic polymer is at least one of polypyrrole, polythiophene, polyacetylene, polyphenylene, or polyphenylacetylene. Further, the addition amount of the organic polymer is 0.1-3% of the mass of the theoretically obtained battery active material.
In some embodiments of the invention, in step S3, the organic solvent is at least one of triethanolamine, N-methylpyrrolidone, 2-hydroxyethylamine, glycerol, or di-N-amyl ether. Compared with low-lightning organic solvents such as methanol, ethanol and the like, the organic solvent selected by the invention has a relatively higher flash point, and ensures that the spray drying is carried out smoothly.
In some embodiments of the present invention, in step S3, the wet grinding process is: adding the sintering material into the organic solvent, performing wet coarse crushing under a protective atmosphere, then performing sand grinding, and adding the organic polymer in the sand grinding process to obtain the grinding material. Furthermore, the rotating speed of the coarse crushing is 400-800rpm, and the particle size Dv50 of the coarsely crushed material is less than or equal to 20 mu m. Further, the rotation speed of the sand grinding is 2000-3000rpm.
In some embodiments of the invention, in step S3, the particle size Dv50 of the abrasive is 0.5 to 3 μm.
In some embodiments of the invention, the temperature of the spray drying in step S3 is 150 to 220 ℃.
In some embodiments of the invention, the sintering temperature in step S4 is 200 to 400 ℃. Furthermore, the sintering time is 2-10h.
In some embodiments of the present invention, in step S4, the material obtained after the sintering is sieved, and the particle size Dv50 of the battery active material obtained is 2 to 8 μm.
The invention also provides application of the preparation method in preparation of the lithium ion battery.
According to a preferred embodiment of the present invention, at least the following advantages are provided:
1. the invention adopts the ferric hydroxide colloid as the iron source, and compared with the ferric hydroxide synthesized by directly utilizing the iron source and the alkali liquor to precipitate, the colloid has better dispersity, the prepared ferric oxide particles are smaller, and the method is favorable for preparing small Li particles subsequently 5 FeO 4 And the materials synthesized by the iron source and the alkali liquor are easy to agglomerate, the particles are larger, and the platform voltage is higher. In addition, the invention also introduces a conductive carbon source into the ferric hydroxide colloid, which can prevent the material from melting and growing in the sintering process, so that the synthesized particles are smaller, and the conductive performance of the material is favorably improved.
2. The invention is sintered and combined into block Li 5 FeO 4 Then, wet grinding is carried out in an organic solvent and a protective atmosphere, so that the material is prevented from deteriorating in the air, the particle size of the material can be effectively reduced, the migration path of lithium ions can be reduced, and the capacity of the material can be improved; the organic polymer is added in the sanding process to form a nano-coated carbon layer on the surface of the material, compared with common low-molecular-weight organic matters, the organic polymer used in the invention has large molecular chains, can form a relatively compact coating layer on the surface of the material to ensure the coating effect, has controllable thickness and can further improveThe stability and the conductivity of the material are improved; compared with gas phase coating, the invention has low requirement on equipment and higher safety.
3. The high-capacity battery active material synthesized by the method has the advantages of simple synthesis process, low processing cost, high efficiency and easy realization of industrialization.
Drawings
The invention is further described with reference to the following figures and examples, in which:
FIG. 1 is a schematic diagram of the synthesis process of example 1 of the present invention;
FIG. 2 is an SEM photograph of iron oxide synthesized in example 1;
FIG. 3 shows Li synthesized in example 1 5 FeO 4 SEM picture of (1);
FIG. 4 shows Li synthesized in example 1 5 FeO 4 A TEM image of (B);
FIG. 5 shows Li synthesized in example 1 5 FeO 4 The charge-discharge curve of (1);
FIG. 6 shows Li synthesized in comparative example 1 5 FeO 4 SEM picture of (1);
FIG. 7 shows Li synthesized in comparative example 1 5 FeO 4 The charge-discharge curve of (1);
FIG. 8 shows Li synthesized in comparative example 2 5 FeO 4 SEM picture of (g);
FIG. 9 shows Li synthesized in comparative example 2 5 FeO 4 The charge and discharge curve of (1).
Detailed Description
The concept and technical effects of the present invention will be clearly and completely described below in conjunction with the embodiments to fully understand the objects, features and effects of the present invention. It is obvious that the described embodiments are only a part of the embodiments of the present invention, and not all embodiments, and those skilled in the art can obtain other embodiments without inventive effort based on the embodiments of the present invention, and all embodiments are within the protection scope of the present invention.
Example 1
This example synthesizes a high capacity battery active material Li 5 FeO 4 See FIG. 1 for a detailed processComprises the following steps:
(1) Slowly adding 3L ferric chloride solution with the concentration of 5mol/L into deionized water under the heating condition of 90 ℃, stirring the solution in the container with the stirring speed of 80rpm in the liquid adding process, keeping the temperature for 20min after the liquid adding is finished to form ferric hydroxide colloidal solution, adding graphite powder as a carbon source substance with the Dv50 of 1.5 mu m and the adding amount of 6.5 percent of the mass of the nano iron oxide theoretically formed after spray drying, continuously stirring with the stirring speed of 300rpm, performing spray drying with the spray drying temperature of 200 ℃, thus obtaining the carbon-doped nano iron oxide, wherein the morphology of the nano iron oxide is shown in figure 2, the measured particle size Dv50 of the nano iron oxide is 560nm, the BET is 42m 2 /g。
(2) Mixing nano iron oxide and lithium hydroxide at a high speed in a high-speed mixer, wherein the molar ratio of lithium element to iron element is 5.3, the mixing speed is 600rpm, and the mixing time is 40min to obtain a uniformly mixed material, placing the uniformly mixed material in a nitrogen atmosphere for high-temperature sintering at 680 ℃ for 25h to obtain a sintered block material;
(3) Carrying out double-roller rough crushing treatment on the sintered block-shaped material, wherein the gap between rollers is 1.5mm, adding the sintered block-shaped material into a 2-hydroxyethylamine solvent, carrying out wet rough crushing in a nitrogen atmosphere, wherein the rotating speed of a crusher is 650rpm, the particle size Dv50 of the roughly crushed material is 12 microns, then carrying out high-speed sanding at 2600rpm for 1.5h, the particle size of the sanded material is 0.9 microns, adding a certain amount of polythiophene in the sanding process, wherein the addition amount of polythiophene is 1% of the mass of the final theoretical synthetic material, carrying out spray drying in the nitrogen atmosphere after sanding is finished, and the drying temperature is 220 ℃ to obtain a dried material;
(4) Sintering the dried material at low temperature of 520 ℃ for 10h, and sieving the sintered material with a 400-mesh sieve to obtain the high-capacity battery active material Li 5 FeO 4 The particle diameter Dv50 was found to be 4 μm.
Characterization test: li synthesized by the method 5 FeO 4 Referring to fig. 3, the material particle uniformity is better; referring to fig. 4, the synthesized material has better coating effect, and obvious coating is formedAnd (3) a layer.
Example 2
This example synthesizes a high capacity battery active material Li 5 FeO 4 The specific process is as follows:
(2) Slowly adding 3L ferric chloride solution with the concentration of 5mol/L into deionized water under the heating condition of 90 ℃, stirring the solution in the container at the stirring speed of 80rpm in the liquid adding process, preserving the temperature for 20min after the liquid adding is finished, adding carbon nano tubes as carbon source substances after the ferric hydroxide colloidal solution is formed, wherein the adding amount of the carbon nano tubes is 6.5% of the mass of the nano ferric oxide theoretically formed after spray drying, continuously stirring at the stirring speed of 300rpm, and performing spray drying at the spray drying temperature of 200 ℃, thus obtaining the carbon-doped nano ferric oxide.
(2) Mixing nano iron oxide and lithium hydroxide at a high speed in a high-speed mixer, wherein the molar ratio of lithium element to iron element is 5.3, the mixing speed is 600rpm, and the mixing time is 40min to obtain a uniformly mixed material, placing the uniformly mixed material in a nitrogen atmosphere for high-temperature sintering at 680 ℃ for 25h to obtain a sintered block material;
(3) Carrying out double-roller rough crushing treatment on the sintered block-shaped material, wherein the gap between rollers is 1.5mm, adding the sintered block-shaped material into an N-methylpyrrolidone solvent, carrying out wet rough crushing in a nitrogen atmosphere, wherein the rotating speed of a crusher is 650rpm, then carrying out high-speed sanding, the rotating speed of the sanding is 2600rpm, the sanding time is 1.5h, the granularity of the sanded material is 0.9 mu m, adding a certain amount of polyphenylene in the sanding process, the adding amount of the polyphenylene is 1% of the mass of the final theoretical synthetic material, carrying out spray drying in the nitrogen atmosphere after the sanding is finished, and obtaining a dried material, wherein the drying temperature is 220 ℃;
(4) Sintering the dried material at a low temperature of 550 ℃ for 10h, and sieving the sintered material with a 400-mesh sieve to obtain the high-capacity battery active material Li 5 FeO 4 。
Comparative example 1
This comparative example synthesizes a carbon-free coated Li 5 FeO 4 The difference from example 1 is that no carbon source is added andthe organic polymer comprises the following specific processes:
(1) Slowly adding 3L ferric chloride solution with concentration of 5mol/L into deionized water under heating condition of 90 deg.C, stirring the solution in the container at 80rpm during the liquid adding process, maintaining the temperature for 20min after the liquid adding process to form ferric hydroxide colloidal solution, spray drying at 200 deg.C to obtain nanometer ferric oxide with particle size Dv50 of 890nm and BET of 31m 2 /g。
(2) Mixing nano iron oxide and lithium hydroxide at a high speed in a high-speed mixer, wherein the molar ratio of lithium element to iron element is 5.3, the mixing speed is 600rpm, and the mixing time is 40min to obtain a uniformly mixed material, placing the uniformly mixed material in a nitrogen atmosphere for high-temperature sintering at 680 ℃ for 25h to obtain a sintered block material;
(3) Carrying out double-roller coarse crushing treatment on the sintered block-shaped material, wherein the gap between rollers is 1.5mm, adding the sintered block-shaped material into a 2-hydroxyethylamine solvent, carrying out wet coarse crushing in a nitrogen atmosphere, wherein the rotation speed of a crusher is 650rpm, the particle size Dv50 of the coarsely crushed material is 12 mu m, carrying out high-speed sanding at the rotation speed of 2600rpm for 1.5h and the particle size of the sanded material is 1.2 mu m, carrying out spray drying in the nitrogen atmosphere at the drying temperature of 220 ℃, obtaining a dried material, and sieving with a 400-mesh sieve to obtain the Li active material for the battery 5 FeO 4 The particle diameter Dv50 was found to be 5.2. Mu.m.
Characterization test: li synthesized by the method 5 FeO 4 Referring to fig. 6, the material particles are better uniform.
The particle size of the nano iron oxide obtained in the comparative example is larger than that of the nano iron oxide obtained in the example 1, because the graphite powder is added into the iron hydroxide colloid in the example 1, the iron oxide can be prevented from melting and growing, the particle size of the nano iron oxide obtained in the example 1 is lower, and the particle size of the finally obtained finished product is also lower.
Comparative example 2
This comparative example synthesizes a battery active material Li 5 FeO 4 The method is different from the embodiment 1 in that dry crushing is adopted, and the specific process is as follows:
(1) Mixing the nano iron oxide and lithium hydroxide obtained in the example 1 at a high speed in a high-speed mixer, wherein the molar ratio of lithium element to iron element is 5.3, the mixing speed is 600rpm, the mixing time is 40min, so as to obtain a uniformly mixed material, placing the uniformly mixed material in a nitrogen atmosphere for high-temperature sintering, wherein the sintering temperature is 680 ℃ and the sintering time is 25h, so as to obtain a sintered block material;
(2) And carrying out double-roller coarse crushing treatment on the block material obtained by sintering, wherein the gap between rollers is 1.5mm, carrying out dry crushing by using jet milling, adding a certain amount of polythiophene after the jet milling for dry mixing, wherein the addition amount of the polythiophene is 1 percent of the mass of the final theoretical synthetic material, and sintering under the nitrogen atmosphere, and the sintering temperature is 520 ℃.
(3) Sieving the sintered material with a 400-mesh sieve to obtain the battery active material Li 5 FeO 4 The particle diameter Dv50 was found to be 8.2. Mu.m.
Characterization test: li obtained by the method 5 FeO 4 Referring to fig. 8, the resulting material particles are seen to be larger.
Comparative example 3
This comparative example synthesizes a battery active material Li 5 FeO 4 The difference from the embodiment 1 is that the low molecular organic substance is finally adopted to replace the high molecular polymer, and the specific process is as follows:
preparing a sintered block material according to the processes of the steps (1) and (2) in the embodiment 1, performing double-roller rough crushing treatment on the sintered block material, wherein the gap between rollers is 1.5mm, adding the rough crushed material into a 2-hydroxyethylamine solvent, performing wet rough crushing in a nitrogen atmosphere, the rotating speed of a crusher is 650rpm, the particle size Dv50 of the rough crushed material is 12 microns, performing high-speed sanding, the rotating speed of the sanding is 2600rpm, the sanding time is 1.5h, the particle size of the sanded material is 0.9 microns, adding a certain amount of glucose in the sanding process, the adding amount of the glucose is 1% of the mass of the final theoretical synthetic material, performing spray drying in the nitrogen atmosphere after the sanding is finished, and obtaining a dried material, wherein the drying temperature is 220 ℃;
sintering the dried material at 550 deg.C for a period of timeThe reaction time is 10 hours, and the lithium ion battery active material Li is obtained by sieving the sintered lithium ion battery active material with a 400-mesh sieve 5 FeO 4 。
Test examples
Li of example 1, example 2, comparative example 1, comparative example 2 and comparative example 3 5 FeO 4 The button cell is manufactured respectively, and the steps of slurry preparation, coating, drying, tabletting, assembly, cabinet loading test and the like are required: (1) preparing slurry, weighing 4g of material, mixing with a conductive agent and a binder, wherein the material: conductive agent: the mass ratio of the binder is 8; (2) coating, namely coating on the aluminum foil by using a scraper; (3) drying, namely drying the coated pole piece in a vacuum drying oven at the drying temperature of 120 ℃ for 2 hours; (4) tabletting, namely tabletting the dried pole piece by using a double-roller machine; (5) and assembling the battery parts such as the positive pole piece, the negative pole piece, the diaphragm, the electrolyte and the like into the button battery. The specific capacity was measured under the conditions of a charging voltage of 4.25V and a charging rate of 0.1C, and the results are shown in table 1.
TABLE 1
Sample numbering Charging capacity mAh/g
Example 1 705
Example 2 698
Comparative example 1 220
Comparative example 2 545
Comparative example 3 621
It can be seen from table 1 that the charge capacity of comparative example 3 is lower than that of example 1, because the carbon coating material of comparative example 3 is a low molecular organic substance and the formed carbon coating layer is not as dense as that of example 1, resulting in a decrease in capacity.
FIG. 5 shows Li synthesized in example 1 5 FeO 4 The capacity of the charge-discharge curve can reach 705mAh/g.
FIG. 7 shows Li synthesized in comparative example 1 5 FeO 4 The capacity of the charge-discharge curve is 220mAh/g, which is obviously lower than that of the material doped and coated by adding the carbon source in example 1, and the charge-discharge curve shows that the capacity of the material can be greatly improved by carbon doping and coating.
FIG. 9 shows Li synthesized in comparative example 2 5 FeO 4 The charge and discharge curves of (1) show that the capacity is 545mAh/g, and smaller particles of Li are synthesized by wet milling than in example 1 5 FeO 4 The capacity of (A) is about 160mAh/g lower. The wet grinding can effectively reduce the particle size of the material, thereby shortening the migration path of lithium ions and improving the capacity of the material.
The embodiments of the present invention have been described in detail with reference to the accompanying drawings, but the present invention is not limited to the above embodiments, and various changes can be made within the knowledge of those skilled in the art without departing from the gist of the present invention. Furthermore, the embodiments of the present invention and the features of the embodiments may be combined with each other without conflict.

Claims (10)

1. A method of preparing a battery active material, comprising the steps of:
s1: mixing ferric hydroxide colloid with a carbon source, and performing spray drying on the obtained mixed material to obtain carbon-doped nano ferric oxide;
s2: mixing the nano iron oxide with a lithium source, and sintering in an inert atmosphere to obtain a sintered material;
s3: mixing the sintering material, the organic polymer and the organic solvent, carrying out wet grinding in a protective atmosphere, and carrying out spray drying on the obtained grinding material in the protective atmosphere to obtain a dry material;
s4: and sintering the dried material in an inert atmosphere to obtain the battery active material.
2. The method according to claim 1, wherein in step S1, the iron hydroxide colloid is prepared by: and slowly adding the ferric salt solution into the water while heating and stirring, and keeping the temperature for a period of time after the liquid adding is finished to obtain the ferric hydroxide colloid.
3. The method according to claim 1, wherein in step S1, the carbon source is at least one of carbon nanotubes, conductive carbon black, graphite powder, polyethyleneimine, glucose, or polyvinyl alcohol.
4. The method according to claim 1, wherein the temperature of the spray-drying in step S1 is 180 to 250 ℃.
5. The preparation method according to claim 1, wherein in the step S1, the addition amount of the carbon source is 5-30% of the mass of the generated nano iron oxide.
6. The method according to claim 1, wherein the sintering temperature in step S2 is 600 to 900 ℃.
7. The method according to claim 1, wherein in step S3, the organic polymer is at least one of polypyrrole, polythiophene, polyacetylene, polyphenylene, or polyphenylacetylene.
8. The method according to claim 1, wherein in step S3, the particle size Dv50 of the abrasive is 0.5 to 3 μm.
9. The method according to claim 1, wherein the sintering temperature in step S4 is 400 to 600 ℃.
10. Use of the preparation process according to any one of claims 1 to 9 for the preparation of lithium ion batteries.
CN202210898632.9A 2022-07-28 2022-07-28 Preparation method and application of high-capacity battery active material Pending CN115332500A (en)

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