CN114156480A - Cathode material for lithium battery and preparation method thereof - Google Patents
Cathode material for lithium battery and preparation method thereof Download PDFInfo
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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
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- H01M4/628—Inhibitors, e.g. gassing inhibitors, corrosion inhibitors
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- H—ELECTRICITY
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- H01F—MAGNETS; INDUCTANCES; TRANSFORMERS; SELECTION OF MATERIALS FOR THEIR MAGNETIC PROPERTIES
- H01F41/00—Apparatus or processes specially adapted for manufacturing or assembling magnets, inductances or transformers; Apparatus or processes specially adapted for manufacturing materials characterised by their magnetic properties
- H01F41/02—Apparatus or processes specially adapted for manufacturing or assembling magnets, inductances or transformers; Apparatus or processes specially adapted for manufacturing materials characterised by their magnetic properties for manufacturing cores, coils, or magnets
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- H—ELECTRICITY
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- H01M—PROCESSES OR MEANS, e.g. BATTERIES, FOR THE DIRECT CONVERSION OF CHEMICAL ENERGY INTO ELECTRICAL ENERGY
- H01M10/00—Secondary cells; Manufacture thereof
- H01M10/05—Accumulators with non-aqueous electrolyte
- H01M10/052—Li-accumulators
- H01M10/0525—Rocking-chair batteries, i.e. batteries with lithium insertion or intercalation in both electrodes; Lithium-ion batteries
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- H—ELECTRICITY
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- H01M—PROCESSES OR MEANS, e.g. BATTERIES, FOR THE DIRECT CONVERSION OF CHEMICAL ENERGY INTO ELECTRICAL ENERGY
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- H01M4/02—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
- H01M4/523—Selection of substances as active materials, active masses, active liquids of inorganic oxides or hydroxides of nickel, cobalt or iron for non-aqueous cells
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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
- H01M2004/026—Electrodes composed of, or comprising, active material characterised by the polarity
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- 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 cathode material for a lithium battery and a preparation method thereof, and relates to the technical field of electrode materials. The invention is used for preparing the cathode material for the lithium battery, firstly ferric chloride, ferrous chloride and ammonia water react, then the magnetic particles are prepared by reacting with oleic acid, first magnetic suspension is carried out to ensure that the magnetic particles react with trimesic acid to prepare modified magnetic particles, second magnetic suspension ensures that the modified magnetic particles are uniformly dispersed and thiophene diester is polymerized and deposited to prepare a deposition film, and the deposition film is hydrolyzed, chlorinated and vulcanized to form disulfide bonds to prepare the cathode material for the lithium battery. The cathode material for the lithium battery prepared by the invention has excellent electricity storage effect and charge-discharge service life.
Description
Technical Field
The invention relates to the technical field of electrode materials, in particular to a cathode material for a lithium battery and a preparation method thereof.
Background
The lithium ion battery is a secondary battery system in which 2 different lithium intercalation compounds capable of reversibly intercalating and deintercalating lithium ions are used as a cathode and an anode of the battery, respectively. During charging, lithium ions are extracted from crystal lattices of the cathode material and inserted into crystal lattices of the anode material after passing through the electrolyte, so that the negative electrode is rich in lithium and the negative electrode is poor in lithium; during discharge, lithium ions are extracted from the crystal lattice of the anode material and inserted into the crystal lattice of the cathode material after passing through the electrolyte, so that the cathode is rich in lithium and the anode is poor in lithium. Thus, the difference of the potentials of the cathode and anode materials relative to the metallic lithium during the insertion and extraction of lithium ions is the working voltage of the battery.
The main constituent materials of the lithium ion battery include electrolyte, separator, cathode and anode materials, etc. The cathode material occupies a large proportion (the mass ratio of the cathode material to the anode material is 3: 1-4: 1), and the performance of the cathode material directly influences the performance of the lithium ion battery, so that the cost directly determines the cost of the battery. Along with the development and the demand of society, the requirements on the electricity storage effect and the charging and discharging times of the lithium battery are higher and higher, and the charging and discharging times are influenced mainly because the charging and discharging life is influenced by the adhesion of substances such as lithium peroxide and the like generated on the surface of a cathode. The invention makes the lithium peroxide not easy to adhere through electromagnetic vibration, and has good electricity storage effect and charging and discharging service life.
Disclosure of Invention
The invention aims to provide a cathode material for a lithium battery and a preparation method thereof, which aim to solve the problems in the prior art.
A cathode material for a lithium battery is characterized by mainly comprising the following components in parts by weight: 10-12 parts of modified magnetic particles, 21-25 parts of thiophene diester, 300-400 parts of phosphoric acid trichloride solution and 30-40 parts of sodium hydrosulfide.
Preferably, the modified magnetic particles are prepared by reacting the magnetic particles with trimesic acid.
Preferably, the magnetic particles are prepared by reacting ferric chloride, ferrous chloride and ammonia water, and then reacting with oleic acid.
Preferably, the thiophene diester is prepared by reacting 3, 4-thiophenol hydroxyl with acetic acid.
As optimization, the preparation method of the cathode material for the lithium battery mainly comprises the following preparation steps:
(1) preparation of magnetic microparticles: mixing ferric chloride, ferrous chloride and pure water according to a mass ratio of 5: 2: 20-5: 2: 25, uniformly mixing, heating to 80-90 ℃ in a nitrogen atmosphere, stirring for 3-5 min at 1500-2000 r/min, adding ammonia water with the mass fraction of 50% 2-3 times that of iron chloride, continuously stirring for 15-20 min at 1500-2000 r/min, adding oleic acid with the mass of 0.8-1.2 times that of iron chloride, continuously stirring for 8-12 min at 1500-2000 r/min, collecting by using a magnet, washing for 3-5 times by using pure water, drying for 4-6 h at 60-70 ℃ in a nitrogen atmosphere to prepare magnetic particles;
(2) primary magnetic suspension: mixing trimesic acid, absolute ethyl alcohol and pure water according to a mass ratio of 1: 4: 4-1: 8: 8, uniformly mixing to prepare a trimesic acid solution, placing magnetic particles in the trimesic acid solution with the mass 15-20 times that of the magnetic particles, applying an alternating magnetic field to enable the magnetic particles to be suspended and dispersed, reacting for 3-4 hours under the condition of 30-40 kHz ultrasonic oscillation at 60-70 ℃, filtering, and washing for 3-5 times by using absolute ethyl alcohol and pure water in sequence to prepare modified magnetic particles;
(3) secondary magnetic suspension and polymerization deposition: mixing thiophene diester, acetone and absolute ethyl alcohol according to a mass ratio of 1: 3: 3-1: 5: 5, uniformly mixing to prepare a thiophene diester solution, placing modified magnetic particles in the thiophene diester solution with the mass 15-20 times that of the modified magnetic particles, applying an alternating magnetic field to enable the modified magnetic particles to be suspended and dispersed, irradiating the modified magnetic particles for 3-4 hours at the temperature of 20-30 ℃ by using ultraviolet light with the wavelength of 350-380 nm, taking out the modified magnetic particles, washing the modified magnetic particles for 3-5 times by using absolute ethyl alcohol and pure water respectively, and drying the modified magnetic particles for 6-8 hours at the temperature of 1-10 Pa and-10-1 ℃ to prepare a deposition film;
(4) and (3) vulcanization: hydrolyzing and chloridizing the deposited film, then placing the film into pure water with the mass 15-20 times of that of the deposited film, adding sodium hydrosulfide with the mass 1.1-1.3 times of that of the deposited film, reacting for 70-90 min under the nitrogen atmosphere at 80-90 ℃ and the ultrasonic oscillation condition of 30-40 kHz, cooling to 10-20 ℃, adding hydrogen peroxide with the mass fraction of 10-15% of that of 0.9-1.3 times of that of the deposited film, reacting for 20-30 min under the ultrasonic oscillation condition of 10-20 ℃ and 30-40 kHz, taking out, washing for 3-5 times by using pure water, and drying for 6-8 h under the conditions of 1-10 Pa, minus 10-minus 1 ℃ to obtain the cathode material for the lithium battery.
And (3) optimally, the alternating magnetic field in the steps (2) and (3) is parallel to the gravity field and is formed by leading alternating current into an iron core electromagnet, the coil has 50 turns, the voltage is 36V, and the frequency is 50 Hz.
As an optimization, the preparation method of the thiophene diester in the step (3) comprises the following steps: mixing 3, 4-dihydroxythiophene with 45-50% of sulfuric acid solution in a mass ratio of 1: 10-1: 15 are sequentially added into a flask and uniformly mixed, then acetic acid with the mass of 0.8-1.2 times that of 3, 4-dihydroxythiophene is added, the flask is heated until the solution in the flask boils, the temperature is regulated to 100 ℃, the solution is kept for 50-60 min, the solution is cooled to 1-10 ℃ and filtered, absolute ethyl alcohol and pure water are respectively used for washing for 3-5 times, and the product is dried for 6-8 hours under the conditions of 1-10 Pa, minus 10-minus 1 ℃ to prepare the product.
As an optimization, the hydrolysis method in the step (4) comprises the following steps: placing the film in a sodium hydroxide solution with the mass fraction of 5-8% and the mass of 15-20 times that of the deposited film, reacting for 3-4 h at the temperature of 60-70 ℃ under the condition of 30-40 kHz ultrasonic oscillation, taking out the film, and washing for 3-5 times by using a hydrochloric acid solution with the mass fraction of 1%.
As an optimization, the chlorination method in the step (4) comprises the following steps: placing the film in a phosphorus trichloride solution 15-20 times of the mass of the deposited film, reacting for 40-50 min under the conditions of 60-70 ℃ and 30-40 kHz ultrasonic oscillation, taking out, and washing for 3-5 times by using pure water; the phosphorus trichloride solution is prepared from phosphorus trichloride and a hydrochloric acid solution with the mass fraction of 20% in a mass ratio of 1: 5-1: 8, mixing uniformly.
Compared with the prior art, the invention has the following beneficial effects:
the invention is used for preparing cathode materials of lithium batteries, and the cathode materials are prepared by preparing magnetic particles, performing primary magnetic suspension, performing secondary magnetic suspension, performing polymerization deposition and vulcanizing.
Firstly, ferric chloride, ferrous chloride and ammonia water are used to prepare magnetic ferroferric oxide, and then the magnetic ferroferric oxide reacts with oleic acid, carboxyl on the oleic acid can react with hydroxyl on the surface of the ferroferric oxide to form a long-chain surface, the dispersibility of magnetic particles is increased, the magnetic particles are not easy to agglomerate, so that the subsequent reaction is promoted, the inherent magnetic field of the magnetic particles can generate vibration by the interaction with the magnetic field generated by current during charging and discharging, the vibration is avoided, lithium peroxide and other non-conductive metal oxides attached to a cathode material are prevented from being generated during the use of a battery, and the charging and discharging life of the prepared cathode material is prolonged; the alternating magnetic field makes the magnetic particles suspended, and then trimesic acid is added for reaction to prepare modified magnetic particles, the magnetic suspension can make the magnetic particles suspended and dispersed, the surface can be fully exposed, and simultaneously, the trimesic acid is prevented from being simultaneously connected with different magnetic particles to form agglomeration, so that the lasting service life of the cathode material is improved, the trimesic acid can perform partial ion exchange on oleic acid grafted on the surface of the magnetic particles, and a metal organic framework network is formed on the surface of the magnetic particles by cooperating with trace hydrolyzed iron elements on the surface of ferroferric oxide, so that the magnetic center is protected and prevented from being lost, the charge and discharge life of the cathode material is prolonged, and in addition, the metal organic framework network has good conductivity and rich pore structure, and the electricity storage effect of the cathode material can be improved.
Secondly, reacting 3, 4-dihydroxythiophene with acetic acid to form thiophene diester, and performing polymerization deposition in a magnetic suspension solution of modified magnetic particles to uniformly disperse the modified magnetic particles in the polythiophene diester to prepare a deposition film, wherein oleic acid long chains on the surfaces of the magnetic particles can be wound on molecular chains of the polythiophene diester to form a winding center, so that the mechanical property of the material is improved, and meanwhile, the magnetic particles can increase gaps in the deposition layer and increase the electricity storage effect of the cathode material; and hydrolyzing ester groups on the deposited film to generate hydroxyl and acetic acid, converting the generated hydroxyl into sulfydryl and forming a disulfide bond to prepare the cathode material for the lithium battery, wherein the generated acetic acid overflows to form pores, so that the pores of the material are increased, the electricity storage effect of the cathode material is increased, and meanwhile, the formed disulfide bond can achieve the effect of charging and discharging through the mutual conversion of the disulfide bond and a sulfur-lithium bond.
Detailed Description
The technical solutions in the embodiments of the present invention will be clearly and completely described below with reference to the embodiments of the present invention, and it is obvious that the described embodiments are only a part of the embodiments of the present invention, and not all of the embodiments. All other embodiments, which can be derived by a person skilled in the art from the embodiments given herein without making any creative effort, shall fall within the protection scope of the present invention.
In order to more clearly illustrate the method provided by the present invention, the following examples are given, and the method for testing each index of the cathode material for lithium battery manufactured in the following examples is as follows:
the electricity storage effect: the cathode material for lithium battery obtained in each example and the comparative example material were used as the cathode material of the battery, the same kind of cathode material, the same amount of electrolyte and the same amount of membrane were removed to form the lithium battery, and the lithium battery was charged and discharged at the same temperature and the same voltage to record the battery capacity.
Charge-discharge life: the cathode material for lithium batteries obtained in each example and the comparative example material are in the same mass shape as the battery cathode material, the same kind of cathode material and the same amount of electrolyte are removed, the lithium battery is formed by the membrane, the charging and discharging are carried out at the same temperature and the same voltage, the battery capacity after one hundred times of charging and discharging is recorded, and the calculated capacity retention ratio is the battery capacity after one hundred times of charging and discharging/initial battery capacity.
Example 1
A cathode material for a lithium battery mainly comprises the following components in parts by weight: 10 parts of modified magnetic particles, 21 parts of thiophene diester, 300 parts of phosphoric acid trichloride solution and 30 parts of sodium hydrosulfide.
A preparation method of a cathode material for a lithium battery mainly comprises the following preparation steps:
(1) preparation of magnetic microparticles: mixing ferric chloride, ferrous chloride and pure water according to a mass ratio of 5: 2: 20, uniformly mixing, heating to 80 ℃ in a nitrogen atmosphere, stirring for 5min at 1500r/min, adding ammonia water with the mass fraction of 50% 2 times that of the ferric chloride, continuously stirring for 20min at 1500r/min, adding oleic acid with the mass of 0.8 time that of the ferric chloride, continuously stirring for 8min at 1500r/min, collecting by using a magnet, washing for 3 times by using pure water, and drying for 4h at 60 ℃ in the nitrogen atmosphere to obtain magnetic particles;
(2) primary magnetic suspension: mixing trimesic acid, absolute ethyl alcohol and pure water according to a mass ratio of 1: 4: 4, uniformly mixing to prepare a trimesic acid solution, placing the magnetic particles in the trimesic acid solution with the mass 15 times that of the magnetic particles, applying an alternating magnetic field to make the magnetic particles suspended and dispersed, reacting for 4 hours under the condition of 30kHz ultrasonic oscillation at 60 ℃, filtering, and washing for 3 times by using absolute ethyl alcohol and pure water in sequence to prepare modified magnetic particles;
(3) secondary magnetic suspension and polymerization deposition: mixing 3, 4-dihydroxythiophene with 45 mass percent sulfuric acid solution according to the mass ratio of 1: 10, sequentially adding into a flask, uniformly mixing, adding acetic acid with the mass of 0.8 time of that of 3, 4-dihydroxythiophene, heating the flask until the solution in the flask boils, adjusting the temperature to 100 ℃, keeping the temperature for 50min, cooling to 1 ℃, filtering, washing for 3 times by using absolute ethyl alcohol and pure water respectively, drying for 8 hours at the temperature of 1Pa and-10 ℃ to prepare thiophene diester, and mixing the thiophene diester, acetone and the absolute ethyl alcohol according to the mass ratio of 1: 3: 3, uniformly mixing to prepare a thiophene diester solution, placing the modified magnetic particles in the thiophene diester solution 15 times the mass of the modified magnetic particles, applying an alternating magnetic field to make the modified magnetic particles suspended and dispersed, then irradiating the modified magnetic particles for 3 hours by using 300W and 350nm ultraviolet light at the temperature of 20 ℃, taking out the modified magnetic particles, washing the modified magnetic particles for 3 times by using absolute ethyl alcohol and pure water respectively, and drying the washed particles for 8 hours at the temperature of 1Pa and-10 ℃ to prepare a deposition film;
(4) and (3) vulcanization: placing the deposited film in a sodium hydroxide solution with the mass fraction of 5% and the mass fraction of 15 times of the deposited film, reacting for 4 hours at 60 ℃ under the condition of 30kHz ultrasonic oscillation, taking out, washing for 3 times by using a hydrochloric acid solution with the mass fraction of 1%, taking out, placing in a phosphorus trichloride solution with the mass fraction of 15% and the mass fraction of 20%, wherein the phosphorus trichloride solution is prepared by mixing phosphorus trichloride and the hydrochloric acid solution with the mass fraction of 20% according to the mass ratio of 1: 5, reacting for 50min under the ultrasonic oscillation condition of 30kHz at 60 ℃, taking out, washing for 3 times by pure water, taking out, placing in the pure water with 15 times of the mass of the deposition film, adding sodium hydrosulfide with 1.1 times of the mass of the deposition film, reacting for 90min under the nitrogen atmosphere at 80 ℃ and the ultrasonic oscillation condition of 30kHz, cooling to 10 ℃, adding hydrogen peroxide with 10 percent of mass fraction 0.9 times of the mass of the deposition film, reacting for 30min under the ultrasonic oscillation condition of 30kHz at 10 ℃, taking out, washing for 3 times by pure water, and drying for 8h under the conditions of 1Pa and-10 ℃ to prepare the cathode material for the lithium battery.
Example 2
A cathode material for a lithium battery mainly comprises the following components in parts by weight: 11 parts of modified magnetic particles, 22 parts of thiophene diester, 350 parts of phosphoric acid trichloride solution and 35 parts of sodium hydrosulfide.
A preparation method of a cathode material for a lithium battery mainly comprises the following preparation steps:
(1) preparation of magnetic microparticles: mixing ferric chloride, ferrous chloride and pure water according to a mass ratio of 5: 2: 22, uniformly mixing, heating to 85 ℃ in a nitrogen atmosphere, stirring for 4min at 1800r/min, adding ammonia water with the mass fraction of 50% and the mass of 2 times of that of the ferric chloride, continuously stirring for 18min at 1800r/min, adding oleic acid with the mass of 1 time of that of the ferric chloride, continuously stirring for 10min at 1800r/min, collecting by using a magnet, washing for 4 times by using pure water, and drying for 5h in a nitrogen atmosphere to obtain magnetic particles;
(2) primary magnetic suspension: mixing trimesic acid, absolute ethyl alcohol and pure water according to a mass ratio of 1: 6: 6, uniformly mixing to prepare a trimesic acid solution, placing the magnetic particles in the trimesic acid solution with the mass 18 times that of the magnetic particles, applying an alternating magnetic field to make the magnetic particles suspended and dispersed, reacting for 3 hours at 65 ℃ under the condition of 35kHz ultrasonic oscillation, filtering, and washing for 3 times by using absolute ethyl alcohol and pure water in sequence to prepare modified magnetic particles;
(3) secondary magnetic suspension and polymerization deposition: mixing 3, 4-dihydroxythiophene with a sulfuric acid solution with the mass fraction of 48% according to the mass ratio of 1: 12, sequentially adding into a flask, uniformly mixing, adding acetic acid with the mass of 1 time of that of the 3, 4-dihydroxythiophene, heating the flask until the solution in the flask boils, adjusting the temperature to 100 ℃, keeping the temperature for 55min, cooling to 5 ℃, filtering, washing for 4 times by using absolute ethyl alcohol and pure water respectively, drying for 7 hours at the temperature of 5Pa and-5 ℃ to prepare the thiophene diester, and mixing the thiophene diester, the acetone and the absolute ethyl alcohol according to the mass ratio of 1: 4: 4, uniformly mixing to prepare a thiophene diester solution, placing the modified magnetic particles in the thiophene diester solution with the mass being 18 times that of the modified magnetic particles, applying an alternating magnetic field to make the modified magnetic particles suspended and dispersed, irradiating the modified magnetic particles for 3 hours at 25 ℃ by using ultraviolet light with the wavelength of 350W and 360nm, taking out the modified magnetic particles, washing the modified magnetic particles for 4 times by using absolute ethyl alcohol and pure water respectively, and drying the modified magnetic particles for 7 hours at the temperature of 5Pa and-5 ℃ to prepare a deposition film;
(4) and (3) vulcanization: placing the deposited film in a sodium hydroxide solution with the mass fraction of 6% and the mass of 18 times of the deposited film, reacting for 3 hours at 65 ℃ under the condition of 35kHz ultrasonic oscillation, taking out, washing for 4 times by using a hydrochloric acid solution with the mass fraction of 1%, taking out, and placing in a phosphorus trichloride solution with the mass fraction of 18 times of the deposited film, wherein the phosphorus trichloride solution is prepared by mixing phosphorus trichloride and a hydrochloric acid solution with the mass fraction of 20% according to the mass ratio of 1: 6, reacting for 45min under the ultrasonic oscillation condition of 35kHz at 65 ℃, taking out, washing for 4 times by pure water, taking out, placing in pure water with 18 times of the mass of the deposition film, adding sodium hydrosulfide with 1.2 times of the mass of the deposition film, reacting for 80min under the nitrogen atmosphere at 85 ℃ and the ultrasonic oscillation condition of 35kHz, cooling to 15 ℃, adding hydrogen peroxide with 12 percent of mass fraction with 1.1 times of the mass of the deposition film, reacting for 25min under the ultrasonic oscillation condition of 35kHz at 15 ℃, washing for 4 times by pure water, and drying for 7h under the condition of 5Pa and-5 ℃ to prepare the cathode material for the lithium battery.
Example 3
A cathode material for a lithium battery mainly comprises the following components in parts by weight: 12 parts of modified magnetic particles, 25 parts of thiophene diester, 400 parts of phosphoric acid trichloride solution and 40 parts of sodium hydrosulfide.
A preparation method of a cathode material for a lithium battery mainly comprises the following preparation steps:
(1) preparation of magnetic microparticles: mixing ferric chloride, ferrous chloride and pure water according to a mass ratio of 5: 2: 25, uniformly mixing, heating to 90 ℃ in a nitrogen atmosphere, stirring for 5min at 2000r/min, adding ammonia water with the mass fraction of 50% and the mass of 3 times of that of the ferric chloride, continuing to stir for 15min at 2000r/min, adding oleic acid with the mass of 1.2 times of that of the ferric chloride, continuing to stir for 8min at 2000r/min, collecting by using a magnet, washing for 5 times by using pure water, and drying for 4h in a nitrogen atmosphere to obtain magnetic particles;
(2) primary magnetic suspension: mixing trimesic acid, absolute ethyl alcohol and pure water according to a mass ratio of 1: 8: 8, uniformly mixing to prepare a trimesic acid solution, placing the magnetic particles in the trimesic acid solution with the mass 20 times that of the magnetic particles, applying an alternating magnetic field to make the magnetic particles suspended and dispersed, reacting for 3 hours under the condition of 70 ℃ and 40kHz ultrasonic oscillation, filtering, and washing for 5 times by using absolute ethyl alcohol and pure water in sequence to prepare modified magnetic particles;
(3) secondary magnetic suspension and polymerization deposition: mixing 3, 4-dihydroxythiophene with 50% of sulfuric acid solution according to the mass ratio of 1: 15, adding the mixture into a flask in sequence, uniformly mixing, adding acetic acid with the mass of 1.2 times that of 3, 4-dihydroxythiophene, heating the flask until the solution in the flask boils, adjusting the temperature to 100 ℃, keeping the temperature for 50min, cooling to 10 ℃, filtering, washing for 5 times by using absolute ethyl alcohol and pure water respectively, drying for 6 hours at the temperature of 10Pa and-1 ℃ to prepare thiophene diester, and mixing the thiophene diester, acetone and the absolute ethyl alcohol according to the mass ratio of 1: 5: 5, uniformly mixing to prepare a thiophene diester solution, placing the modified magnetic particles in the thiophene diester solution with the mass of 20 times that of the modified magnetic particles, applying an alternating magnetic field to make the modified magnetic particles suspended and dispersed, irradiating the modified magnetic particles for 3 hours at 30 ℃ by using ultraviolet light of 400W and 380nm, taking out the modified magnetic particles, washing the modified magnetic particles for 5 times by using absolute ethyl alcohol and pure water respectively, and drying the washed particles for 6 hours at the temperature of 10Pa and-1 ℃ to prepare a deposition film;
(4) and (3) vulcanization: placing the deposited film in a sodium hydroxide solution with the mass fraction of 8% and the mass fraction of 20 times of the deposited film, reacting for 3 hours at 70 ℃ under the condition of 40kHz ultrasonic oscillation, taking out, washing for 5 times by using a hydrochloric acid solution with the mass fraction of 1%, taking out, placing in a phosphorus trichloride solution with the mass fraction of 20% and the mass fraction of the hydrochloric acid solution of 20 times of the deposited film, wherein the phosphorus trichloride solution is prepared by mixing phosphorus trichloride and the hydrochloric acid solution with the mass fraction of 20% according to the mass ratio of 1: 8, reacting for 40min under the condition of ultrasonic oscillation at 70 ℃ and 40kHz, then taking out, washing for 5 times by pure water, taking out, then placing in pure water with the mass 20 times of that of the deposition film, adding sodium hydrosulfide with the mass 1.3 times of that of the deposition film, reacting for 70min under the condition of ultrasonic oscillation at 40kHz and nitrogen atmosphere at 90 ℃, cooling to 20 ℃, adding hydrogen peroxide with the mass fraction of 15% of that of the deposition film being 1.3 times of that of the deposition film, reacting for 20min under the condition of ultrasonic oscillation at 20 ℃ and 40kHz, taking out, washing for 5 times by pure water, and drying for 6h under the condition of 10Pa and minus 1 ℃ to obtain the cathode material for the lithium battery.
Comparative example 1
A cathode material for a lithium battery mainly comprises the following components in parts by weight: 11 parts of magnetic particles, 22 parts of thiophene diester, 350 parts of phosphoric acid trichloride solution and 35 parts of sodium hydrosulfide.
A preparation method of a cathode material for a lithium battery mainly comprises the following preparation steps:
(1) preparation of magnetic microparticles: mixing ferric chloride, ferrous chloride and pure water according to a mass ratio of 5: 2: 22, uniformly mixing, heating to 85 ℃ in a nitrogen atmosphere, stirring for 4min at 1800r/min, adding ammonia water with the mass fraction of 50% and the mass of 2 times of that of the ferric chloride, continuously stirring for 18min at 1800r/min, adding oleic acid with the mass of 1 time of that of the ferric chloride, continuously stirring for 10min at 1800r/min, collecting by using a magnet, washing for 4 times by using pure water, and drying for 5h in a nitrogen atmosphere to obtain magnetic particles;
(2) suspension and polymerization deposition: mixing 3, 4-dihydroxythiophene with a sulfuric acid solution with the mass fraction of 48% according to the mass ratio of 1: 12, sequentially adding into a flask, uniformly mixing, adding acetic acid with the mass of 1 time of that of the 3, 4-dihydroxythiophene, heating the flask until the solution in the flask boils, adjusting the temperature to 100 ℃, keeping the temperature for 55min, cooling to 5 ℃, filtering, washing for 4 times by using absolute ethyl alcohol and pure water respectively, drying for 7 hours at the temperature of 5Pa and-5 ℃ to prepare the thiophene diester, and mixing the thiophene diester, the acetone and the absolute ethyl alcohol according to the mass ratio of 1: 4: 4, uniformly mixing to prepare a thiophene diester solution, placing magnetic particles in the thiophene diester solution with the mass being 18 times that of the magnetic particles, applying an alternating magnetic field to enable the magnetic particles to be suspended and dispersed, irradiating the magnetic particles for 3 hours by ultraviolet light with the wavelength of 350W and 360nm at the temperature of 25 ℃, taking out the magnetic particles, washing the magnetic particles for 4 times by absolute ethyl alcohol and pure water respectively, and drying the magnetic particles for 7 hours at the temperature of 5Pa and-5 ℃ to prepare a deposition film;
(3) and (3) vulcanization: placing the deposited film in a sodium hydroxide solution with the mass fraction of 6% and the mass of 18 times of the deposited film, reacting for 3 hours at 65 ℃ under the condition of 35kHz ultrasonic oscillation, taking out, washing for 4 times by using a hydrochloric acid solution with the mass fraction of 1%, taking out, and placing in a phosphorus trichloride solution with the mass fraction of 18 times of the deposited film, wherein the phosphorus trichloride solution is prepared by mixing phosphorus trichloride and a hydrochloric acid solution with the mass fraction of 20% according to the mass ratio of 1: 6, reacting for 45min under the ultrasonic oscillation condition of 35kHz at 65 ℃, taking out, washing for 4 times by pure water, taking out, placing in pure water with 18 times of the mass of the deposition film, adding sodium hydrosulfide with 1.2 times of the mass of the deposition film, reacting for 80min under the nitrogen atmosphere at 85 ℃ and the ultrasonic oscillation condition of 35kHz, cooling to 15 ℃, adding hydrogen peroxide with 12 percent of mass fraction with 1.1 times of the mass of the deposition film, reacting for 25min under the ultrasonic oscillation condition of 35kHz at 15 ℃, washing for 4 times by pure water, and drying for 7h under the condition of 5Pa and-5 ℃ to prepare the cathode material for the lithium battery.
Comparative example 2
Comparative example 2 was formulated in the same manner as in example 2. The preparation method of the non-slip ceramic tile only differs from the embodiment 2 in the difference of the step (2), and the step (2) is modified as follows: stirring modification: mixing trimesic acid, absolute ethyl alcohol and pure water according to a mass ratio of 1: 6: 6, uniformly mixing to prepare a trimesic acid solution, placing the magnetic particles in the trimesic acid solution with the mass of 18 times that of the magnetic particles, carrying out ultrasonic oscillation at 65 ℃ and 35kHz, stirring at 800r/min for reaction for 3 hours, filtering, and washing for 3 times by using absolute ethyl alcohol and pure water in sequence to prepare the modified magnetic particles.
Comparative example 3
A cathode material for a lithium battery mainly comprises the following components in parts by weight: 11 parts of modified magnetic particles, 22 parts of 3, 4-dihydroxythiophene, 350 parts of phosphoric acid trichloride solution and 35 parts of sodium hydrosulfide.
A preparation method of a cathode material for a lithium battery mainly comprises the following preparation steps:
(1) preparation of magnetic microparticles: mixing ferric chloride, ferrous chloride and pure water according to a mass ratio of 5: 2: 22, uniformly mixing, heating to 85 ℃ in a nitrogen atmosphere, stirring for 4min at 1800r/min, adding ammonia water with the mass fraction of 50% and the mass of 2 times of that of the ferric chloride, continuously stirring for 18min at 1800r/min, adding oleic acid with the mass of 1 time of that of the ferric chloride, continuously stirring for 10min at 1800r/min, collecting by using a magnet, washing for 4 times by using pure water, and drying for 5h in a nitrogen atmosphere to obtain magnetic particles;
(2) primary magnetic suspension: mixing trimesic acid, absolute ethyl alcohol and pure water according to a mass ratio of 1: 6: 6, uniformly mixing to prepare a trimesic acid solution, placing the magnetic particles in the trimesic acid solution with the mass 18 times that of the magnetic particles, applying an alternating magnetic field to make the magnetic particles suspended and dispersed, reacting for 3 hours at 65 ℃ under the condition of 35kHz ultrasonic oscillation, filtering, and washing for 3 times by using absolute ethyl alcohol and pure water in sequence to prepare modified magnetic particles;
(3) secondary magnetic suspension and polymerization deposition: mixing 3, 4-dihydroxythiophene, acetone and absolute ethyl alcohol according to a mass ratio of 1: 4: 4, uniformly mixing to prepare a dihydroxythiophene solution, placing the modified magnetic particles in a thiophene diester solution with the mass being 18 times that of the modified magnetic particles, applying an alternating magnetic field to make the modified magnetic particles suspended and dispersed, irradiating the modified magnetic particles for 3 hours at 25 ℃ by using ultraviolet light with the wavelength of 350W and 360nm, taking out the modified magnetic particles, washing the modified magnetic particles for 4 times by using absolute ethyl alcohol and pure water respectively, and drying the modified magnetic particles for 7 hours at the temperature of 5Pa and-5 ℃ to prepare a deposition film;
(4) and (3) vulcanization: placing the deposited film in a sodium hydroxide solution with the mass fraction of 6% and the mass of 18 times of the deposited film, reacting for 3 hours at 65 ℃ under the condition of 35kHz ultrasonic oscillation, taking out, washing for 4 times by using a hydrochloric acid solution with the mass fraction of 1%, taking out, and placing in a phosphorus trichloride solution with the mass fraction of 18 times of the deposited film, wherein the phosphorus trichloride solution is prepared by mixing phosphorus trichloride and a hydrochloric acid solution with the mass fraction of 20% according to the mass ratio of 1: 6, reacting for 45min under the ultrasonic oscillation condition of 35kHz at 65 ℃, taking out, washing for 4 times by pure water, taking out, placing in pure water with 18 times of the mass of the deposition film, adding sodium hydrosulfide with 1.2 times of the mass of the deposition film, reacting for 80min under the nitrogen atmosphere at 85 ℃ and the ultrasonic oscillation condition of 35kHz, cooling to 15 ℃, adding hydrogen peroxide with 12 percent of mass fraction with 1.1 times of the mass of the deposition film, reacting for 25min under the ultrasonic oscillation condition of 35kHz at 15 ℃, washing for 4 times by pure water, and drying for 7h under the condition of 5Pa and-5 ℃ to prepare the cathode material for the lithium battery.
Comparative example 4
Comparative example 4 was formulated as in example 2. The preparation method of the non-slip ceramic tile only differs from the embodiment 2 in the difference of the step (3), and the step (3) is modified as follows: polymerization and deposition: mixing 3, 4-dihydroxythiophene with a sulfuric acid solution with the mass fraction of 48% according to the mass ratio of 1: 12, sequentially adding into a flask, uniformly mixing, adding acetic acid with the mass of 1 time of that of the 3, 4-dihydroxythiophene, heating the flask until the solution in the flask boils, adjusting the temperature to 100 ℃, keeping the temperature for 55min, cooling to 5 ℃, filtering, washing for 4 times by using absolute ethyl alcohol and pure water respectively, drying for 7 hours at the temperature of 5Pa and-5 ℃ to prepare the thiophene diester, and mixing the thiophene diester, the acetone and the absolute ethyl alcohol according to the mass ratio of 1: 4: 4, uniformly mixing to prepare a thiophene diester solution, placing the modified magnetic particles in the thiophene diester solution with the mass being 18 times that of the modified magnetic particles, irradiating the modified magnetic particles by ultraviolet light with the wavelength of 350W and 360nm at 25 ℃, stirring and reacting for 3 hours at the speed of 800r/min, taking out the modified magnetic particles, washing the modified magnetic particles for 4 times respectively by absolute ethyl alcohol and pure water, and drying the modified magnetic particles for 7 hours at the temperature of 5Pa and-5 ℃ to prepare the deposition film.
Examples of effects
Table 1 below gives the results of performance analysis of the electricity storage effect and the charge and discharge life of the cathode material for lithium batteries using examples 1 to 3 of the present invention and comparative examples 1 to 4.
TABLE 1
| Capacity of battery | Capacity retention rate | Capacity of battery | Capacity retention rate | ||
| Example 1 | 431Wh | 98.3％ | Comparative example 1 | 328Wh | 93.2％ |
| Example 1 | 432Wh | 98.4％ | Comparative example 2 | 376Wh | 95.4％ |
| Example 1 | 429Wh | 98.1％ | Comparative example 3 | 364Wh | 97.9％ |
| Comparative example 4 | 428Wh | 89.5％ |
As can be seen from the comparison of the experimental data of examples 1, 2, 3 and comparative example 1 in table 1, the battery capacity and capacity retention rate of examples 1, 2, 3 are high compared with comparative example 1, which indicates that once suspension is performed, a metal organic framework network is formed on the surface of the modified magnetic particles, the magnetic center is protected and prevented from losing, and the charge and discharge life of the cathode material is prolonged; examples 1, 2, 3 have higher battery capacity and capacity retention than comparative example 2, which illustrates that the magnetic particles are uniformly dispersed and modified in a magnetic suspension manner, and the surface reaction of the magnetic particles can be more sufficient compared with stirring, so that the electricity storage effect and the charge-discharge life of the cathode material for the lithium battery are improved; compared with experimental data of examples 1, 2 and 3 and comparative example 3, the experimental data show that the batteries of examples 1, 2 and 3 and comparative example 3 have high capacity, which indicates that the ester group of the thiophene diester can protect hydroxyl groups from mutual combination and aggregation of modified magnetic particles so as to reduce the subsequent generation of charge and discharge sites compared with the polymerization deposition of 3, 4-dihydroxy thiophene, meanwhile, the ester group is hydrolyzed to generate hydroxyl and acetic acid, and the generated acetic acid overflows to form pores, so that the charge and discharge sites are fully exposed, and the charge and discharge effect of the cathode material is increased; the experimental data comparison of examples 1, 2 and 3 with comparative example 4 shows that the capacity retention rate of examples 1, 2 and 3 with comparative example 4 is high, which indicates that compared with the polymerization performance of direct stirring, the modified magnetic particles in the cathode material obtained by secondary magnetic suspension are more uniformly dispersed, the natural magnetic field of the modified magnetic particles can interact with the magnetic field generated by current during charging and discharging to generate vibration, the vibration is better, lithium peroxide and other non-conductive metal oxides attached to the cathode material are prevented from being used by the battery, and the performance charging and discharging life of the prepared cathode material is prolonged.
It will be evident to those skilled in the art that the invention is not limited to the details of the foregoing illustrative embodiments, and that the present invention may be embodied in other specific forms without departing from the spirit or essential attributes thereof. The present embodiments are therefore to be considered in all respects as illustrative and not restrictive, the scope of the invention being indicated by the appended claims rather than by the foregoing description, and all changes which come within the meaning and range of equivalency of the claims are therefore intended to be embraced therein. Any reference sign in a claim should not be construed as limiting the claim concerned.
Claims (10)
1. A cathode material for a lithium battery is characterized by mainly comprising the following components in parts by weight: 10-12 parts of modified magnetic particles, 21-25 parts of thiophene diester, 300-400 parts of phosphoric acid trichloride solution and 30-40 parts of sodium hydrosulfide.
2. The cathode material for a lithium battery as claimed in claim 1, wherein the modified magnetic particles are prepared by reacting magnetic particles with trimesic acid.
3. The cathode material for a lithium battery as claimed in claim 2, wherein the magnetic particles are prepared by reacting ferric chloride, ferrous chloride and aqueous ammonia, and then reacting with oleic acid.
4. The cathode material for a lithium battery as claimed in claim 3, wherein the thiophene diester is prepared by reacting 3, 4-thiophenehydroxy group with acetic acid.
5. A preparation method of a cathode material for a lithium battery is characterized by mainly comprising the following preparation steps:
(1) preparation of magnetic microparticles: reacting ferric chloride, ferrous chloride and ammonia water, and adding oleic acid to react to prepare magnetic particles;
(2) primary magnetic suspension: adding the magnetic particles into a trimesic acid solution, suspending the magnetic particles through a magnetic field, and reacting to obtain modified magnetic particles;
(3) secondary magnetic suspension and polymerization deposition: reacting 3, 4-dihydroxythiophene with acetic acid to form thiophene diester, suspending and dispersing the modified magnetic particles through a magnetic field, and adding the thiophene diester to carry out polymerization deposition to prepare a deposition film;
(4) and (3) vulcanization: hydrolyzing the deposited film to form hydroxyl and acetic acid, converting the hydroxyl on the deposited film into chlorine, reacting with sodium hydrosulfide to replace the chlorine into sulfhydryl, and converting the two sulfhydryl into a disulfide bond to prepare the cathode material for the lithium battery.
6. The method of claim 5, wherein the method of preparing the cathode material for a lithium battery essentially comprises the steps of:
(1) preparation of magnetic microparticles: mixing ferric chloride, ferrous chloride and pure water according to a mass ratio of 5: 2: 20-5: 2: 25, uniformly mixing, heating to 80-90 ℃ in a nitrogen atmosphere, stirring for 3-5 min at 1500-2000 r/min, adding ammonia water with the mass fraction of 50% 2-3 times that of iron chloride, continuously stirring for 15-20 min at 1500-2000 r/min, adding oleic acid with the mass of 0.8-1.2 times that of iron chloride, continuously stirring for 8-12 min at 1500-2000 r/min, collecting by using a magnet, washing for 3-5 times by using pure water, drying for 4-6 h at 60-70 ℃ in a nitrogen atmosphere to prepare magnetic particles;
(2) primary magnetic suspension: mixing trimesic acid, absolute ethyl alcohol and pure water according to a mass ratio of 1: 4: 4-1: 8: 8, uniformly mixing to prepare a trimesic acid solution, placing magnetic particles in the trimesic acid solution with the mass 15-20 times that of the magnetic particles, applying an alternating magnetic field to enable the magnetic particles to be suspended and dispersed, reacting for 3-4 hours under the condition of 30-40 kHz ultrasonic oscillation at 60-70 ℃, filtering, and washing for 3-5 times by using absolute ethyl alcohol and pure water in sequence to prepare modified magnetic particles;
(3) secondary magnetic suspension and polymerization deposition: mixing thiophene diester, acetone and absolute ethyl alcohol according to a mass ratio of 1: 3: 3-1: 5: 5, uniformly mixing to prepare a thiophene diester solution, placing modified magnetic particles in the thiophene diester solution with the mass 15-20 times that of the modified magnetic particles, applying an alternating magnetic field to enable the modified magnetic particles to be suspended and dispersed, irradiating the modified magnetic particles for 3-4 hours at the temperature of 20-30 ℃ by using ultraviolet light with the wavelength of 350-380 nm, taking out the modified magnetic particles, washing the modified magnetic particles for 3-5 times by using absolute ethyl alcohol and pure water respectively, and drying the modified magnetic particles for 6-8 hours at the temperature of 1-10 Pa and-10-1 ℃ to prepare a deposition film;
(4) and (3) vulcanization: hydrolyzing and chloridizing the deposited film, then placing the film into pure water with the mass 15-20 times of that of the deposited film, adding sodium hydrosulfide with the mass 1.1-1.3 times of that of the deposited film, reacting for 70-90 min under the nitrogen atmosphere at 80-90 ℃ and the ultrasonic oscillation condition of 30-40 kHz, cooling to 10-20 ℃, adding hydrogen peroxide with the mass fraction of 10-15% of that of 0.9-1.3 times of that of the deposited film, reacting for 20-30 min under the ultrasonic oscillation condition of 10-20 ℃ and 30-40 kHz, taking out, washing for 3-5 times by using pure water, and drying for 6-8 h under the conditions of 1-10 Pa, minus 10-minus 1 ℃ to obtain the cathode material for the lithium battery.
7. The method for preparing a cathode material for a lithium battery as claimed in claim 6, wherein the alternating magnetic field in steps (2) and (3) is parallel to the gravitational field and is formed by passing an alternating current through an iron core electromagnet, the coil has 50 turns, the voltage is 36V, and the frequency is 50 Hz.
8. The method of claim 7, wherein the thiophene diester of step (3) is prepared by: mixing 3, 4-dihydroxythiophene with 45-50% of sulfuric acid solution in a mass ratio of 1: 10-1: 15 are sequentially added into a flask and uniformly mixed, then acetic acid with the mass of 0.8-1.2 times that of 3, 4-dihydroxythiophene is added, the flask is heated until the solution in the flask boils, the temperature is regulated to 100 ℃, the solution is kept for 50-60 min, the solution is cooled to 1-10 ℃ and filtered, absolute ethyl alcohol and pure water are respectively used for washing for 3-5 times, and the product is dried for 6-8 hours under the conditions of 1-10 Pa, minus 10-minus 1 ℃ to prepare the product.
9. The method of claim 8, wherein the hydrolysis in step (4) is performed by: placing the film in a sodium hydroxide solution with the mass fraction of 5-8% and the mass of 15-20 times that of the deposited film, reacting for 3-4 h at the temperature of 60-70 ℃ under the condition of 30-40 kHz ultrasonic oscillation, taking out the film, and washing for 3-5 times by using a hydrochloric acid solution with the mass fraction of 1%.
10. The method of claim 9, wherein the chlorination in step (4) is performed by: placing the film in a phosphorus trichloride solution 15-20 times of the mass of the deposited film, reacting for 40-50 min under the conditions of 60-70 ℃ and 30-40 kHz ultrasonic oscillation, taking out, and washing for 3-5 times by using pure water; the phosphorus trichloride solution is prepared from phosphorus trichloride and a hydrochloric acid solution with the mass fraction of 20% in a mass ratio of 1: 5-1: 8, mixing uniformly.
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