CN112744871B - Lithium cobaltate cathode material and preparation method thereof - Google Patents

Lithium cobaltate cathode material and preparation method thereof Download PDF

Info

Publication number
CN112744871B
CN112744871B CN201911063124.3A CN201911063124A CN112744871B CN 112744871 B CN112744871 B CN 112744871B CN 201911063124 A CN201911063124 A CN 201911063124A CN 112744871 B CN112744871 B CN 112744871B
Authority
CN
China
Prior art keywords
product
lithium cobaltate
lithium
positive electrode
mixing
Prior art date
Legal status (The legal status is an assumption and is not a legal conclusion. Google has not performed a legal analysis and makes no representation as to the accuracy of the status listed.)
Active
Application number
CN201911063124.3A
Other languages
Chinese (zh)
Other versions
CN112744871A (en
Inventor
白珍辉
安娜
凌仕刚
沙金
苏迎春
朱卫泉
Current Assignee (The listed assignees may be inaccurate. Google has not performed a legal analysis and makes no representation or warranty as to the accuracy of the list.)
Tianjin Guoan Mengguli New Material Technology Co ltd
Original Assignee
Tianjin Guoan Mengguli New Material Technology Co ltd
Priority date (The priority date is an assumption and is not a legal conclusion. Google has not performed a legal analysis and makes no representation as to the accuracy of the date listed.)
Filing date
Publication date
Application filed by Tianjin Guoan Mengguli New Material Technology Co ltd filed Critical Tianjin Guoan Mengguli New Material Technology Co ltd
Priority to CN201911063124.3A priority Critical patent/CN112744871B/en
Publication of CN112744871A publication Critical patent/CN112744871A/en
Application granted granted Critical
Publication of CN112744871B publication Critical patent/CN112744871B/en
Active legal-status Critical Current
Anticipated expiration legal-status Critical

Links

Images

Classifications

    • C—CHEMISTRY; METALLURGY
    • C01—INORGANIC CHEMISTRY
    • C01G—COMPOUNDS CONTAINING METALS NOT COVERED BY SUBCLASSES C01D OR C01F
    • C01G51/00—Compounds of cobalt
    • C01G51/40—Cobaltates
    • C01G51/42—Cobaltates containing alkali metals, e.g. LiCoO2
    • 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
    • C—CHEMISTRY; METALLURGY
    • C01—INORGANIC CHEMISTRY
    • C01P—INDEXING SCHEME RELATING TO STRUCTURAL AND PHYSICAL ASPECTS OF SOLID INORGANIC COMPOUNDS
    • C01P2004/00—Particle morphology
    • C01P2004/60—Particles characterised by their size
    • C01P2004/61—Micrometer sized, i.e. from 1-100 micrometer
    • 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
    • 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

Landscapes

  • Chemical & Material Sciences (AREA)
  • Inorganic Chemistry (AREA)
  • Organic Chemistry (AREA)
  • Chemical Kinetics & Catalysis (AREA)
  • Electrochemistry (AREA)
  • General Chemical & Material Sciences (AREA)
  • Battery Electrode And Active Subsutance (AREA)

Abstract

The invention discloses a lithium cobaltate positive electrode material and a preparation method thereof, wherein the preparation method of the lithium cobaltate positive electrode material comprises the following steps: mixing a cobalt source and a lithium source, and carrying out primary synthesis to obtain a product A; dispersing the product A in an organic solvent to obtain a suspension; putting the suspension into a microwave digestion instrument for treatment to obtain a product B; the product B is post-processed to obtain the lithium cobaltate cathode material, the lithium cobaltate cathode material is modified by a microwave method, the obtained lithium cobaltate cathode material has uniform particles, a lithium ion battery prepared from the lithium cobaltate cathode material has higher specific capacity and excellent cycle performance, and the preparation method has the advantages of simple process, no pollution, low energy consumption and wide application prospect.

Description

Lithium cobaltate positive electrode material and preparation method thereof
Technical Field
The invention belongs to the technical field of lithium ion secondary batteries, and particularly relates to a lithium cobaltate positive electrode material and a preparation method thereof.
Background
The lithium ion battery has the advantages of high energy density, high working voltage, long cycle life, no memory effect, environmental friendliness and the like, and is widely applied to portable electronic equipment such as mobile phones, notebook computers, digital cameras and the like and electric automobiles.
With the rapid development of science and technology, 3C electronic products such as mobile phones gradually develop towards miniaturization and multi-functionalization, higher requirements are put forward on the service life and service life of lithium ion batteries, and simultaneously higher requirements are put forward on the cycle performance of the anode material.
Disclosure of Invention
In order to overcome the above problems, the present inventors have conducted intensive studies to design a lithium cobaltate positive electrode material and a method for preparing the same, the method for preparing the lithium cobaltate positive electrode material comprising: mixing a cobalt source and a lithium source, and carrying out primary synthesis to obtain a product A; dispersing the product A in an organic solvent to obtain a suspension; putting the suspension into a microwave digestion instrument for processing to obtain a product B; the product B is post-processed to obtain the lithium cobaltate cathode material, the lithium cobaltate cathode material is modified by a microwave method, the obtained lithium cobaltate cathode material has uniform particles, a lithium ion battery prepared from the lithium cobaltate cathode material has high specific capacity and excellent cycle performance, and the preparation method has the advantages of simple process, no pollution, low energy consumption and wide application prospect, thereby completing the invention.
The invention aims to provide a preparation method of a lithium cobaltate positive electrode material, which comprises the following steps:
step 1, mixing a cobalt source and a lithium source, and carrying out primary synthesis to obtain a product A;
step 2, dispersing the product A in an organic solvent to obtain a suspension;
step 3, putting the suspension into a microwave digestion instrument for treatment to obtain a product B;
and 4, carrying out post-treatment on the product B to obtain the lithium cobaltate cathode material.
In step 1, the cobalt source is a cobalt compound, the lithium source is a lithium compound, and the molar ratio of Li element in the lithium source to Co element in the cobalt source, li/Co = (1-1.2): 1.
in the step 4, the lithium source is one or more selected from lithium carbonate, lithium nitrate, lithium hydroxide, lithium oxalate, lithium acetate, lithium oxide and lithium chloride.
Wherein, in the step 1, the temperature of the first synthesis is 800-1050 ℃, preferably 900-1050 ℃.
In the step 2, the organic solvent is selected from one or more of ethanol, methanol, acetone, ethylene glycol and glycerol, and the weight ratio of the product A to the organic solvent is 1: (5 to 20), preferably 1: (8-15).
In the step 3, the microwave digestion instrument is a high-flux microwave digestion extraction synthesis workstation.
Wherein in the step 3, the treatment temperature is 100-400 ℃ and the treatment time is 10-90 min in a microwave digestion instrument.
In step 4, the median particle diameter D of the lithium cobaltate cathode material 50 2 to 10 mu m.
Wherein the lithium cobaltate cathode material has a median particle diameter D 50 Is 3-8 μm.
Another aspect of the present invention provides a lithium cobaltate positive electrode material prepared by the method according to the first aspect of the present invention.
The invention has the following beneficial effects:
(1) The preparation method of the lithium cobaltate positive electrode material is also a modification method of the lithium cobaltate positive electrode material, and a high-flux microwave digestion extraction synthesis workstation is adopted to carry out microwave modification on the lithium cobaltate material, so that the cycle performance of the lithium cobaltate positive electrode material is improved;
(2) The lithium cobaltate positive electrode material prepared by the method has uniform particles and good dispersibility, and the gram capacity and the cycle performance are superior to those of the traditional lithium cobaltate positive electrode material (which is not processed by a microwave digestion instrument), for example, the capacity retention rate of a lithium ion battery prepared by the lithium cobaltate positive electrode material prepared by the method, which circulates for 50 weeks under the conditions of 25 ℃ and 4.65V voltage, is improved by more than 10 percent compared with that of the traditional lithium cobaltate positive electrode material, the cycle performance of the lithium cobaltate positive electrode material is obviously improved, and the service life of the lithium cobaltate positive electrode material is prolonged;
(3) Under the conditions that the temperature is 25 ℃ and the voltage is 4.65V, the capacity retention rate of the lithium cobaltate cathode material prepared by the method is more than 85%, preferably more than 87%, more preferably more than 88% and even up to 88.87% after 50-week circulation;
(4) The preparation method of the lithium cobaltate cathode material provided by the invention has the advantages of simple process, no pollution, low energy consumption and suitability for large-scale popularization.
Drawings
Fig. 1 shows an SEM image of the lithium cobaltate positive electrode material obtained in example 1;
fig. 2 shows an SEM image of the lithium cobaltate positive electrode material obtained in comparative example 1;
FIG. 3 shows specific discharge capacity versus cycle number curves for coin cells prepared from the lithium cobaltate positive electrode materials obtained in example 1 and comparative example 1;
fig. 4 shows the capacity retention rate of coin cells prepared from the lithium cobaltate positive electrode materials obtained in example 1 and comparative example 1 as a function of the number of cycles.
Detailed Description
The invention is explained in more detail below with reference to the drawings and preferred embodiments. The features and advantages of the present invention will become more apparent from the description.
The invention provides a preparation method of a lithium cobaltate positive electrode material, which comprises the following steps:
step 1, mixing a cobalt source and a lithium source, and carrying out primary synthesis to obtain a product A.
According to the present invention, in step 1, the cobalt source is a cobalt-containing compound, preferably one or more selected from cobaltosic oxide, cobalt hydroxide, cobalt carbonate, cobalt nitrate and cobalt chloride, more preferably cobaltosic oxide or cobalt carbonate, such as cobaltosic oxide.
According to the present invention, in step 1, the lithium source is a lithium-containing compound, preferably one or more of lithium carbonate, lithium nitrate, lithium hydroxide, lithium oxalate, lithium acetate, lithium oxide and lithium chloride, more preferably lithium carbonate or lithium hydroxide, such as lithium carbonate.
According to the present invention, in step 1, the particle size of the lithium source is in the nanometer range; the particle size of the cobalt source is 1-8 μm, preferably 4-5 μm, and the lithium source with the particle size can be selected to enable the finally prepared cathode material to have the advantage of high compaction density, so that the obtained cathode material is high in specific capacity and good in cycle performance.
According to the present invention, the cobalt source and the lithium source are mixed, and the mixing manner is not particularly limited, but is preferably a mixing manner commonly used in the art.
According to the invention, the cobalt source and the lithium source are mixed by high-speed mixing and/or ball-milling, for example in a high-speed mixer and/or a planetary ball mill.
According to the present invention, in step 1, the molar ratio of Li element in the lithium source to Co element in the cobalt source, li/Co = (1 to 1.2): 1, preferably Li/Co = (1 to 1.1): 1, more preferably, li/Co = (1 to 1.02): 1.
according to the present invention, in step 1, it is preferable that the lithium source and the cobalt source are uniformly mixed in a dry condition, and it is preferable that high speed mixing is performed and then ball milling mixing is performed.
According to the invention, the mixing speed of the high-speed mixing is 1000-2000 r/min, preferably 1200-1800 r/min, more preferably 1500r/min; the mixing time is 30 to 150s, preferably 50 to 120s, more preferably 80 seconds.
According to the invention, the mixing speed of ball milling mixing is 600-1000 r/min, preferably 700-900 r/min, more preferably 850r/min; the mixing time is 1 to 5 hours, preferably 2 to 4 hours, more preferably 3 hours.
According to a preferred embodiment of the present invention, in step 1, a dopant is further added, and the dopant is mixed with a lithium source and a cobalt source, wherein the dopant contains Mg element, preferably one or more of magnesium carbonate, magnesium nitrate and magnesium hydroxide.
According to a further preferred embodiment of the present invention, the molar ratio of Mg element in the dopant to Co element in the cobalt source is (0 to 0.01): 1.
according to the invention, the Mg-containing dopant is added to improve the cycle performance, such as cycle retention rate and cycle stability, of the final product lithium cobaltate cathode material.
According to the invention, in step 1, a cobalt source and a lithium source are uniformly mixed and then subjected to one-time synthesis, and the one-time synthesis is a high-temperature calcination process, wherein the temperature of the one-time synthesis (high-temperature calcination) is 800-1050 ℃, preferably 900-1050 ℃, more preferably 950 ℃, and the calcination time is 6-12 h, preferably 8-10 h, for example 8h.
According to the present invention, in step 1, the primary synthesis is performed in an oxygen atmosphere, preferably an oxygen atmosphere having an oxygen concentration of 90% or more, preferably 95% or more, and more preferably 97% or more. For example, the primary synthesis is carried out in a muffle furnace.
According to the invention, in the step 1, the product A is obtained after the lithium source and the cobalt source are mixed and synthesized at one time, and the product A is modified to obtain the lithium cobaltate cathode material with excellent cycle performance.
The inventor finds that the product A is processed by the microwave digestion instrument, so that the cycle performance of the lithium cobaltate anode material can be improved, and the microwave digestion instrument can rapidly and uniformly heat the product A under the microwave condition, so that the product A is modified.
And 2, dispersing the product A in an organic solvent to obtain a suspension.
In the invention, in step 2, when the product A is subjected to microwave digestion, the product A needs to be prepared and dispersed in an organic solvent to prepare a suspension.
According to the present invention, in step 2, the organic solvent is preferably selected from one or more of ethanol, methanol, acetone, ethylene glycol and glycerol, preferably ethanol, such as absolute ethanol.
According to the invention, in step 2, the dispersing mode is preferably ultrasonic dispersing, preferably, the power of the ultrasonic dispersing is 600W, and the frequency of the ultrasonic is 40000Hz; the ultrasonic dispersion time is 5 to 60min, preferably 10 to 30min, and more preferably 10min. The power and frequency are inherent to the apparatus and a uniform and useful suspension is obtained at the dispersion time.
According to the invention, in the step 2, the mass ratio of the product A to the organic solvent is 1: (5 to 20), preferably 1: (8 to 15), for example, 1. When the mass ratio of the two components is too large, the dispersion tends to be uneven, and when the mass ratio is too small, the experiment speed is affected.
And 3, putting the turbid liquid into a microwave digestion instrument for treatment to obtain a product B.
According to the invention, in the step 3, the suspension of the product A obtained in the step 2 is placed into a microwave digestion instrument for treatment, and is taken out after the treatment is finished and the cooling is carried out, so as to obtain a product B, wherein the microwave digestion instrument is preferably a high-flux microwave digestion extraction synthesis workstation, preferably the model is SINEO MDS-10, the suspension is added into a digestion tank of the high-flux microwave digestion extraction synthesis workstation, absolute ethyl alcohol with the same mass as the solvent in the digestion tank is added into a main control tank, and the liquid level of the absolute ethyl alcohol is not more than two thirds of that of a reaction tank.
According to the invention, in step 3, the suspension is treated in a microwave digestion instrument, wherein the treatment temperature is 100-400 ℃, preferably 200-350 ℃, and more preferably 300 ℃; and/or
The treatment time is 10 to 90min, preferably 20 to 60min, for example 30min; and/or
The treatment power is 2000 to 3000W, preferably 2500W.
According to the invention, the microwave digestion instrument can carry out microwave digestion on the product A in the suspension, so that rapid and uniform heating is realized, the product A is crushed, the granularity of the product A is reduced, the particles are more uniform, the dispersibility is good, and the capacity and the cycle retention rate of the final lithium cobaltate anode material are improved.
And 4, carrying out post-treatment on the product B to obtain the lithium cobaltate positive electrode material.
According to the invention, in step 4, the post-treatment of the product B comprises drying, crushing and sieving the product B.
According to the invention, the drying of the product B is carried out by a drying method commonly used in the field, the pulverization is preferably carried out by air flow pulverization, and the sieving mesh number is preferably 200-500 meshes, for example 300 meshes, so as to obtain the lithium cobaltate cathode material.
According to the invention, a product A is obtained through one-time synthesis, wherein the product A is an unmodified lithium cobaltate positive electrode material, and then the product A is modified through a microwave treatment method, so that the obtained lithium cobaltate positive electrode material is a microwave modified lithium cobaltate positive electrode material.
According to the invention, in the step 4, the particle size distribution range of the obtained lithium cobaltate positive electrode material is 1-15 μm. The obtained meso-position particles of the lithium cobaltate cathode materialDiameter D 50 Is 2 to 10 μm, preferably 3 to 8 μm, and more preferably (5. + -. 0.5) μm.
The lithium cobaltate positive electrode material obtained by the preparation method provided by the invention has uniform particles and good dispersibility, and the gram capacity and the cycle performance are superior to those of the traditional lithium cobaltate positive electrode material (which is not processed by a microwave digestion instrument), for example, the cycle retention rate of a lithium ion battery prepared from the lithium cobaltate positive electrode material prepared by the invention after 50 cycles at 25 ℃ and 4.65V is improved by more than 10% compared with that of the traditional lithium cobaltate positive electrode material, the cycle performance of the lithium cobaltate positive electrode material is obviously improved, and the service life of the lithium cobaltate positive electrode material is prolonged.
A second aspect of the present invention provides a lithium cobaltate positive electrode material, preferably prepared by the method of the first aspect of the present invention.
The lithium ion battery prepared from the lithium cobaltate positive electrode material obtained by the preparation method has the cycle retention rate of more than 85%, preferably more than 87%, more preferably more than 88% and even up to 88.18% after 50 weeks of cycle under the conditions of 25 ℃ and 4.65V of voltage.
Examples
Example 1 (
Weighing 400g of dried cobaltosic oxide and 186.8g of lithium carbonate, adding the weighed materials into a high-speed mixer, mixing the materials at a high speed for 80s at a rotating speed of 1500r/min, then adding the materials into a planetary ball mill for uniform mixing, ball-milling and mixing the materials at a rotating speed of 850r/min for 3h, after the mixing is finished, putting the mixture into a muffle furnace for primary synthesis, and calcining the mixture at a high temperature of 950 ℃ for 8h to obtain a product A;
adding 50g of the product A into 400g of absolute ethyl alcohol, and performing ultrasonic treatment to obtain a suspension;
and (3) moving the suspension into a digestion tank of a high-flux microwave digestion extraction synthesis workstation, adding absolute ethyl alcohol with equal mass into a main control tank, setting the processing temperature of the microwave digestion workstation to be 300 ℃ and the processing time to be 30min, setting the processing temperature of the microwave digestion workstation to be 300 ℃, moving out of the workstation after cooling, and obtaining a product B.
And drying the product B, and screening the product B through a 300-mesh sieve after jet milling to obtain the final product lithium cobaltate cathode material.
Scanning electron microscope test is carried out on the obtained lithium cobaltate positive electrode material, the obtained SEM image is shown in figure 1, as can be seen from figure 1, the obtained lithium cobaltate positive electrode material has uniform particles, good dispersibility and particle size distribution of 1.657-11.198 micrometers, and D of the lithium cobaltate positive electrode material is measured 50 It was 4.706. Mu.m. The agglomeration of the positive electrode material particles is opened, and the particle size is reduced. The obtained positive electrode material has improved compaction density, and the capacity and the cycle retention rate of the obtained positive electrode material can be improved.
Example 2
Weighing 400g of dried cobaltosic oxide and 186.8g of lithium carbonate, adding the weighed materials into a high-speed mixer, mixing the materials at a high speed for 70s at a rotating speed of 1600r/min, then adding the materials into a planetary ball mill for uniform mixing, ball-milling and mixing the materials for 3h at a rotating speed of 850r/min, after the mixing is finished, putting the mixture into a muffle furnace for one-time synthesis, and calcining the mixture at a high temperature of 950 ℃ for 8h to obtain a product A;
adding 50g of the product A into 400g of absolute ethyl alcohol, and performing ultrasonic treatment to obtain a suspension;
and (3) moving the suspension into a digestion tank of a high-flux microwave digestion extraction synthesis workstation, adding absolute ethyl alcohol with equal mass into a main control tank, setting the processing temperature of the microwave digestion workstation to be 300 ℃ and the processing time to be 20min, setting the processing temperature of the microwave digestion workstation to be 300 ℃, moving out of the workstation after cooling, and obtaining a product B.
And drying the product B, and screening the product B through a 300-mesh sieve after jet milling to obtain the final product lithium cobaltate cathode material.
Scanning electron microscope testing is carried out on the obtained lithium cobaltate positive electrode material, the obtained lithium cobaltate positive electrode material is measured to have uniform particles, good dispersibility and 1.657-11.2 mu m of particle size distribution, and the D of the lithium cobaltate positive electrode material is measured 50 Was 4.719. Mu.m.
Example 3 ()
Weighing 400g of dried cobaltosic oxide and 186.8g of lithium carbonate, adding the weighed materials into a high-speed mixer, mixing the materials at a high speed for 80s at a rotating speed of 1500r/min, then adding the materials into a planetary ball mill for uniform mixing, ball-milling and mixing the materials at a rotating speed of 850r/min for 3h, after the mixing is finished, putting the mixture into a muffle furnace for primary synthesis, and calcining the mixture at a high temperature of 950 ℃ for 8h to obtain a product A;
adding 50g of the product A into 400g of absolute ethyl alcohol, and performing ultrasonic treatment to obtain a suspension;
and (3) transferring the suspension into a digestion tank of a high-flux microwave digestion extraction synthesis workstation, adding 400g of absolute ethyl alcohol into a main control tank, setting the processing temperature of the microwave digestion workstation to be 400 ℃ and the processing time to be 30min, after the processing is finished, cooling, and then transferring out of the workstation to obtain a product B.
And drying the product B, and screening the product B through a 300-mesh sieve after jet milling to obtain the final product lithium cobaltate cathode material.
Scanning electron microscope testing is carried out on the obtained lithium cobaltate positive electrode material, the obtained lithium cobaltate positive electrode material has uniform particles, good dispersibility and particle size of 1.288-14.371 mu m, and D of the lithium cobaltate positive electrode material is measured 50 It was 4.171. Mu.m.
Example 4
Weighing 400g of dried cobaltosic oxide and 186.8g of lithium carbonate, adding the weighed materials into a high-speed mixer, mixing the materials at a high speed for 80s at a rotating speed of 1600r/min, then adding the materials into a planetary ball mill, uniformly mixing the materials, mixing the materials for 3 hours at a mixing speed of 850r/min, putting the mixture into a muffle furnace to perform one-time synthesis after the mixture is completely mixed, and calcining the mixture at a high temperature of 1000 ℃ for 8 hours to obtain a product A;
adding 50g of the product A into 400g of absolute ethyl alcohol, and performing ultrasonic treatment to obtain a suspension;
and (3) moving the suspension into a digestion tank of a high-flux microwave digestion extraction synthesis workstation, adding 400g of absolute ethyl alcohol into a main control tank, setting the processing temperature of the microwave digestion workstation to 300 ℃ and the processing time to 30min, setting the processing temperature of the microwave digestion workstation to 300 ℃, cooling, and moving out of the workstation to obtain a product B.
And drying the product B, and screening the product B through a 300-mesh sieve after jet milling to obtain the final product lithium cobaltate cathode material.
For the obtained cobaltThe lithium cobaltate positive electrode material is tested by a scanning electron microscope, the obtained lithium cobaltate positive electrode material has uniform particles, good dispersibility and particle diameter of 1.654-12.723 mu m, and the D of the lithium cobaltate positive electrode material is measured 50 It was 4.978. Mu.m.
Example 5
Weighing 400g of dried cobaltosic oxide and 186.8g of lithium carbonate, adding the weighed materials into a high-speed mixer, mixing the materials at a high speed for 80s at a rotating speed of 1500r/min, then adding the materials into a planetary ball mill for uniform mixing, ball-milling and mixing the materials for 3h at a rotating speed of 850r/min, after the mixing is finished, putting the mixture into a muffle furnace for primary synthesis, and calcining the mixture at a high temperature of 850 ℃ for 8h to obtain a product A;
adding 50g of the product A into 400g of absolute ethyl alcohol, and performing ultrasonic treatment to obtain a suspension;
and (3) moving the suspension into a digestion tank of a high-flux microwave digestion extraction synthesis workstation, adding 400g of absolute ethyl alcohol into a main control tank, setting the processing temperature of the microwave digestion workstation to 300 ℃ and the processing time to 30min, setting the processing temperature of the microwave digestion workstation to 300 ℃, moving out of the workstation after cooling, and obtaining a product B.
And drying the product B, and screening the product B through a 300-mesh sieve after jet milling to obtain the final product lithium cobaltate cathode material.
Scanning electron microscope testing is carried out on the obtained lithium cobaltate positive electrode material, the obtained lithium cobaltate positive electrode material has uniform particles, good dispersibility and particle size of 1.48-10.055 mu m, and D of the lithium cobaltate positive electrode material is measured 50 It was 4.337. Mu.m.
Comparative example
Comparative example 1
Weighing 400g of dried cobaltosic oxide and 186.8g of lithium carbonate, adding the weighed materials into a high-speed mixer, mixing the materials at a high speed for 80s at a rotating speed of 1500r/min, then adding the materials into a planetary ball mill for uniform mixing, ball-milling and mixing the materials at a rotating speed of 850r/min for 3h, after the mixing is finished, putting the mixture into a muffle furnace for primary synthesis, and calcining the mixture at a high temperature of 950 ℃ for 8h to obtain a product A.
The product A is used as the final product lithium cobaltate cathode material obtained in the comparative example 1.
The obtained lithium cobaltate cathode material is subjected to scanning electron microscope test, the obtained SEM image is shown in fig. 2, and as can be seen from fig. 2, the obtained cathode material has a larger particle size.
Examples of the experiments
The lithium cobaltate positive electrode materials obtained in the embodiment 1 and the comparative example 1 are respectively used as the positive electrode of the lithium ion battery, the lithium sheet is used as the negative electrode, the button battery is assembled, a blue-electricity system is adopted for testing, the specific capacity and the cycle retention rate of the battery after 50 times of charge and discharge cycles are tested under the conditions that the temperature is 25 ℃ and the voltage is 4.65V, the relation curve of the discharge specific capacity and the cycle frequency of the obtained battery is shown in figure 3, and the relation curve of the cycle retention rate and the cycle frequency of the obtained battery is shown in figure 4.
As can be seen from fig. 3, the specific discharge capacity of the battery prepared from the lithium cobaltate positive electrode material obtained in example 1 is higher than that of the battery prepared from the lithium cobaltate positive electrode material obtained in comparative example 1, the first specific discharge capacities of the batteries prepared from the lithium cobaltate positive electrode materials obtained in example 1 and comparative example 1 are 205.6mAh/g and 204.3mAh/g, respectively, with the increase of cycle times, the specific discharge capacity of the battery prepared from the lithium cobaltate positive electrode material obtained in comparative example 1 decreases rapidly, after 50 cycles, the specific discharge capacity of the battery prepared from the lithium cobaltate positive electrode material obtained in example 1 is 181.3mAh/g, and the specific discharge capacity of the battery prepared from the lithium cobaltate positive electrode material obtained in comparative example 1 is 150.5mAh/g.
As can be seen from fig. 4, the capacity retention ratio of the battery prepared from the lithium cobaltate positive electrode material obtained in example 1 was higher than that of comparative example 1. The cycle retention rate of the battery prepared from the lithium cobaltate positive electrode material in the comparative example 1 is reduced faster with the increase of the cycle number, and after 50 cycles, the capacity retention rate of the battery prepared from the lithium cobaltate positive electrode material obtained in the example 1 is 88.18%, while the capacity retention rate of the battery prepared from the lithium cobaltate positive electrode material in the comparative example 1 is 73.64%.
The invention has been described in detail with reference to the preferred embodiments and illustrative examples. It should be noted, however, that these specific embodiments are only illustrative of the present invention and do not limit the scope of the present invention in any way. Various modifications, equivalent substitutions and alterations can be made to the technical contents and embodiments of the present invention without departing from the spirit and scope of the present invention, and these are within the scope of the present invention. The scope of the invention is defined by the appended claims.

Claims (3)

1. A preparation method of a lithium cobaltate positive electrode material is characterized by comprising the following steps:
step 1, mixing a cobalt source and a lithium source at a high speed, then ball-milling and mixing, carrying out primary synthesis at the temperature of 900-1050 ℃ for 8-10 h to obtain a product A,
the mixing speed of high-speed mixing is 1200-1800 r/min, the mixing time is 50-120 s, the mixing speed of ball milling mixing is 600-1000 r/min, and the mixing time is 2-4 h;
step 2, dispersing the product A in an organic solvent to obtain a suspension;
step 3, placing the suspension into a microwave digestion instrument for processing, wherein the microwave digestion instrument is a high-flux microwave digestion extraction synthesis workstation, the processing temperature is 200-350 ℃, and the processing time is 20-60 min, so as to obtain a product B;
and 4, carrying out post-treatment on the product B to obtain a lithium cobaltate positive electrode material, wherein the post-treatment comprises drying, crushing and sieving, and the median particle diameter D of the lithium cobaltate positive electrode material 50 Is in the range of 2 to 10 μm,
in step 1, the cobalt source is cobaltosic oxide, the lithium source is lithium carbonate, and the molar ratio of the Li element in the lithium source to the Co element in the cobalt source, i/Co = (1-1.2): 1,
in the step 2, the organic solvent is ethanol, and the weight ratio of the product A to the organic solvent is 1: (5-20).
2. The method according to claim 1, wherein in step 2, the weight ratio of the product A to the organic solvent is 1: (8 to 15).
3. The method according to claim 1, wherein the lithium cobaltate positive electrode materialMedian particle diameter D of the material 50 Is 3-8 μm.
CN201911063124.3A 2019-10-31 2019-10-31 Lithium cobaltate cathode material and preparation method thereof Active CN112744871B (en)

Priority Applications (1)

Application Number Priority Date Filing Date Title
CN201911063124.3A CN112744871B (en) 2019-10-31 2019-10-31 Lithium cobaltate cathode material and preparation method thereof

Applications Claiming Priority (1)

Application Number Priority Date Filing Date Title
CN201911063124.3A CN112744871B (en) 2019-10-31 2019-10-31 Lithium cobaltate cathode material and preparation method thereof

Publications (2)

Publication Number Publication Date
CN112744871A CN112744871A (en) 2021-05-04
CN112744871B true CN112744871B (en) 2022-12-13

Family

ID=75644954

Family Applications (1)

Application Number Title Priority Date Filing Date
CN201911063124.3A Active CN112744871B (en) 2019-10-31 2019-10-31 Lithium cobaltate cathode material and preparation method thereof

Country Status (1)

Country Link
CN (1) CN112744871B (en)

Citations (6)

* Cited by examiner, † Cited by third party
Publication number Priority date Publication date Assignee Title
JP2005519840A (en) * 2002-03-26 2005-07-07 カウンシル・オブ・サイエンティフィック・アンド・インダストリアル・リサーチ Solid phase heating synthesis method of lithium cobaltate
CN103618080A (en) * 2013-12-19 2014-03-05 长沙矿冶研究院有限责任公司 Pretreatment method of cobaltosic oxide for preparing high-voltage lithium cobalt oxide, high-voltage lithium cobalt oxides anode material and preparation method of high-voltage lithium cobalt oxide
CN103702934A (en) * 2011-06-27 2014-04-02 新加坡国立大学 An approach for manufacturing efficient mesoporous nano-composite positive electrode limn1-xfexpo4 materials
CN103746114A (en) * 2014-01-29 2014-04-23 厦门钨业股份有限公司 Preparation method for lithium cobalt oxide anode material
CN105731549A (en) * 2016-01-25 2016-07-06 山东玉皇新能源科技有限公司 Preparation method and application of high-purity lithium cobalt oxide cathode material
CN105958039A (en) * 2016-07-12 2016-09-21 广东工业大学 Preparation method of modified lithium nickel manganese oxide cathode material, and high-voltage lithium ion battery

Patent Citations (6)

* Cited by examiner, † Cited by third party
Publication number Priority date Publication date Assignee Title
JP2005519840A (en) * 2002-03-26 2005-07-07 カウンシル・オブ・サイエンティフィック・アンド・インダストリアル・リサーチ Solid phase heating synthesis method of lithium cobaltate
CN103702934A (en) * 2011-06-27 2014-04-02 新加坡国立大学 An approach for manufacturing efficient mesoporous nano-composite positive electrode limn1-xfexpo4 materials
CN103618080A (en) * 2013-12-19 2014-03-05 长沙矿冶研究院有限责任公司 Pretreatment method of cobaltosic oxide for preparing high-voltage lithium cobalt oxide, high-voltage lithium cobalt oxides anode material and preparation method of high-voltage lithium cobalt oxide
CN103746114A (en) * 2014-01-29 2014-04-23 厦门钨业股份有限公司 Preparation method for lithium cobalt oxide anode material
CN105731549A (en) * 2016-01-25 2016-07-06 山东玉皇新能源科技有限公司 Preparation method and application of high-purity lithium cobalt oxide cathode material
CN105958039A (en) * 2016-07-12 2016-09-21 广东工业大学 Preparation method of modified lithium nickel manganese oxide cathode material, and high-voltage lithium ion battery

Non-Patent Citations (1)

* Cited by examiner, † Cited by third party
Title
雷圣辉等.《锂电池正极材料钴酸锂的改性研究进展》.《湖南有色金属》.2009, *

Also Published As

Publication number Publication date
CN112744871A (en) 2021-05-04

Similar Documents

Publication Publication Date Title
CN107369823B (en) Artificial graphite composite negative electrode material for lithium ion battery and preparation method thereof
CN102386384B (en) Spherical hard carbon lithium ion battery cathode material and preparation method thereof
CN106711461A (en) Spherical porous silicon/carbon composite material as well as preparation method and application thereof
CN102050437A (en) Carbon composite material, and preparation method and application thereof
CN111029578B (en) Modified hard carbon negative electrode material and preparation method thereof
JP2005310744A (en) Cathode activator for nonaqueous lithium secondary battery, manufacturing method of the same, and nonaqueous lithium secondary battery using the cathode activator
CN111653759A (en) Silicon-based composite material and preparation method thereof
CN113903896B (en) Secondary particle hard carbon composite material and preparation method and application thereof
CN114725349B (en) Preparation of modified positive electrode material of lithium ion battery and application of prepared material
CN114477130A (en) Method for preparing hard carbon negative electrode material for sodium ion battery by adopting porous material
CN112110448A (en) Nitrogen-doped carbon and nano-silicon composite anode material and preparation method thereof
CN114314580A (en) Composite graphite negative electrode material and preparation method and application thereof
CN102347481A (en) Superfine spherical graphite as well as preparation method and application thereof
CN102709548A (en) Multi-element cathode material for lithium ion battery and preparation method for multi-element cathode material
CN115332500A (en) Preparation method and application of high-capacity battery active material
CN115249799A (en) Rosin-based nitrogen-doped coated hard carbon negative electrode material of sodium ion battery and preparation method of rosin-based nitrogen-doped coated hard carbon negative electrode material
CN106486650A (en) A kind of Delanium/silicon composite cathode material and preparation method thereof
CN112744871B (en) Lithium cobaltate cathode material and preparation method thereof
CN110931792B (en) Coated silicon-based material and preparation method thereof
CN105810938B (en) A kind of high discharge voltage plateau method for preparing anode material of lithium-ion battery
CN104505502B (en) Lithium titanate composite negative material for lithium ion battery and preparation method of lithium titanate composite negative material
CN116666589A (en) Nano silicon carbon composite negative electrode material with core-shell structure, and preparation method and application thereof
CN110571422A (en) Modified high-nickel anode material and preparation method thereof, high-nickel anode slurry, battery cell, lithium ion battery and power utilization equipment
CN115775875A (en) High-nickel positive electrode material, preparation method thereof and lithium ion battery
CN114709383A (en) Modified lithium ion battery anode material and preparation method and application thereof

Legal Events

Date Code Title Description
PB01 Publication
PB01 Publication
SE01 Entry into force of request for substantive examination
SE01 Entry into force of request for substantive examination
GR01 Patent grant
GR01 Patent grant