CN110078134B - Preparation method of cobaltosic oxide for preparing lithium ion battery cathode material - Google Patents
Preparation method of cobaltosic oxide for preparing lithium ion battery cathode material Download PDFInfo
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- CN110078134B CN110078134B CN201910357204.3A CN201910357204A CN110078134B CN 110078134 B CN110078134 B CN 110078134B CN 201910357204 A CN201910357204 A CN 201910357204A CN 110078134 B CN110078134 B CN 110078134B
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- C01G51/00—Compounds of cobalt
- C01G51/04—Oxides; Hydroxides
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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
- 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
- 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
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- C01—INORGANIC CHEMISTRY
- C01P—INDEXING SCHEME RELATING TO STRUCTURAL AND PHYSICAL ASPECTS OF SOLID INORGANIC COMPOUNDS
- C01P2002/00—Crystal-structural characteristics
- C01P2002/70—Crystal-structural characteristics defined by measured X-ray, neutron or electron diffraction data
- C01P2002/72—Crystal-structural characteristics defined by measured X-ray, neutron or electron diffraction data by d-values or two theta-values, e.g. as X-ray diagram
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- C01—INORGANIC CHEMISTRY
- C01P—INDEXING SCHEME RELATING TO STRUCTURAL AND PHYSICAL ASPECTS OF SOLID INORGANIC COMPOUNDS
- C01P2004/00—Particle morphology
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- C—CHEMISTRY; METALLURGY
- C01—INORGANIC CHEMISTRY
- C01P—INDEXING SCHEME RELATING TO STRUCTURAL AND PHYSICAL ASPECTS OF SOLID INORGANIC COMPOUNDS
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- C01P2006/40—Electric properties
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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
- H01M2004/027—Negative electrodes
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- Y02E—REDUCTION OF GREENHOUSE GAS [GHG] EMISSIONS, RELATED TO ENERGY GENERATION, TRANSMISSION OR DISTRIBUTION
- Y02E60/00—Enabling technologies; Technologies with a potential or indirect contribution to GHG emissions mitigation
- Y02E60/10—Energy storage using batteries
Abstract
The invention discloses cobaltosic oxide for manufacturing a lithium ion battery cathode material and a preparation method thereof, wherein the cobaltosic oxide has a regular hexahedron porous structure, and the preparation method comprises the steps of adding ZIF67 powder into a mixed solvent of deionized water and ethanol, and carrying out ultrasonic treatment and stirring until the mixture is uniform to obtain a ZIF67 solution; and adding ammonium bicarbonate into the ZIF67 solution, uniformly stirring, carrying out hydrothermal reaction at 190 ℃ of 170-24 h, carrying out solid-liquid separation on the obtained product, and washing and drying the solid phase to obtain the cobaltosic oxide. Compared with the prior art, the invention has the following advantages: the volume expansion in the charge and discharge process of the lithium ion battery is relieved, the specific surface area of the material is improved, the full contact between the active material and lithium ions is promoted, and the electrochemical performance of the material is improved; the battery has good cycling stability, high cycling ratio capacity and excellent battery performance; the preparation method is simple, and the used raw materials are cheap and easy to obtain, thereby being beneficial to commercial application.
Description
Technical Field
The invention relates to the technical field of battery materials, in particular to cobaltosic oxide for manufacturing a lithium ion battery cathode material and a preparation method thereof.
Background
In recent years, lithium ion secondary batteries have become the most important and developed high-energy batteries because of their advantages of long cycle life, high specific energy, safety, no pollution, high operating voltage, and the like. At present, the theoretical capacity of the traditional commercial graphite carbon cathode material is only 372mA h g-1It is difficult to meet the energy requirements of fast-developing high-end consumer electronics (e.g., smart phones, wearable devices, etc.). And a transition metalCobalt oxide (CoO, Co)3O4) The theoretical specific capacity can reach 700--1The lithium ion battery has high theoretical specific capacity and good cycling stability, so that the lithium ion battery can meet the requirement of people on high-energy-density batteries at present. The cobaltosic oxide lithium ion battery is a secondary battery taking cobaltosic oxide as a negative electrode active material, and shows excellent lithium storage performance, but the battery volume expansion exists in the process of lithium ion intercalation and deintercalation, which influences the further improvement of the battery performance. The invention makes the material into porous shape, relieves the volume expansion, promotes the electrolyte to fully contact with the electrode material, and improves the electrochemical performance of the cathode material.
Disclosure of Invention
The invention aims to overcome the defects of the prior art and provides cobaltosic oxide for preparing a lithium ion battery cathode material and a preparation method thereof.
The invention is realized by the following technical scheme: the cobaltosic oxide used for manufacturing the lithium ion battery cathode material has a regular hexahedron porous structure.
The invention also provides a preparation method of the cobaltosic oxide, which comprises the following steps:
step one, adding ZIF67 powder into a mixed solvent of deionized water and ethanol, and carrying out ultrasonic treatment and stirring uniformly to obtain a ZIF67 solution;
and step two, adding ammonium bicarbonate into the ZIF67 solution obtained in the step one, uniformly stirring, carrying out hydrothermal reaction for 8-24h at the temperature of 190 ℃ below zero, carrying out solid-liquid separation on the obtained product, and washing and drying the solid phase to obtain the cobaltosic oxide.
As a further improvement to the above scheme, in the first step, the dosage ratio of ZIF67, deionized water and absolute ethyl alcohol is 40 mg: 5-25 mL: 5-25 mL.
As a further improvement to the above scheme, the dosage ratio of ammonium bicarbonate in the second step to the ZIF67 solution is 25-60 mg: 30 mL.
As a further improvement to the scheme, in the second step, a centrifugal separation mode is adopted for solid-liquid separation, the centrifugal rotation speed in the centrifugal separation is 6000-10000rpm, and the drying temperature is 40-80 ℃.
Compared with the prior art, the invention has the following advantages: the cobaltosic oxide with the cubic porous structure designed and synthesized in the invention relieves the volume expansion of the lithium ion battery in the charging and discharging processes due to the porous structure, improves the specific surface area of the material, promotes the full contact of the active material and lithium ions, and improves the electrochemical performance of the material; the porous structure formed by corroding the cheap raw material ammonium bicarbonate can relieve volume expansion, the specific surface area is high, the obtained battery has better cycling stability and high cycling specific capacity, and the battery performance is excellent; the preparation method is simple, and the used raw materials are cheap and easy to obtain, thereby being beneficial to commercial application.
Drawings
FIG. 1 is an SEM photograph of tricobalt tetraoxide of a cubic porous structure obtained in example 1;
FIG. 2 is a TEM photograph of tricobalt tetroxide of a cubic porous structure obtained in example 1;
FIG. 3 is an XRD photograph of tricobalt tetraoxide having a cubic porous structure obtained in example 1;
FIG. 4 is a graph showing the cell performance of the regular hexahedral porous structure cobaltosic oxide obtained in example 1;
FIG. 5 is an SEM photograph of cubic cobaltosic oxide obtained in example 2;
FIG. 6 is a TEM photograph of cubic tricobalt tetroxide obtained in example 2;
FIG. 7 is a graph showing the cell performance of cubic tricobalt tetroxide obtained in example 2;
Detailed Description
The following examples are given for the detailed implementation and specific operation of the present invention, but the scope of the present invention is not limited to the following examples.
Example 1:
the present example prepares cobaltosic oxide with a cubic porous structure according to the following steps:
1. adding 10ml of deionized water and 20ml of absolute ethyl alcohol into a 40ml reaction kettle, uniformly stirring, adding 40mg of ZIF-67 into the solution, and ultrasonically stirring until the ZIF-67 is dispersed to form a uniform ZIF-67 solution;
2. mixing ammonium bicarbonate and a ZIF-67 solution according to a mass volume ratio of 40:30, uniformly stirring, and carrying out hydrothermal reaction for 15h at 180 ℃; and placing the obtained product in a centrifugal tube for centrifugal separation at the speed of 9000rmp, then carrying out centrifugal washing for three times by using ethanol, and drying at 60 ℃ to obtain the target product of the cobaltosic oxide with the regular hexahedral porous structure.
Fig. 1 and fig. 2 are SEM photographs and TEM photographs of the target product obtained in this example, respectively, from which it can be seen that the material has a cubic porous structure in a microscopic view, and from the TEM photographs, it can be seen that the material has good uniformity and porosity, which ensures that the material has a large specific surface area, and is beneficial to improving the battery performance.
FIG. 3 is an XRD picture of the target product obtained in this example, which shows that the characteristic peak of the material is completely consistent with the peak of cobaltosic oxide, and proves that the material is Co3O4。
The battery performance of the target product obtained in this example was tested using a blue cell test system:
uniformly mixing the cobaltosic oxide nano material with the cubic porous structure, ketjen black and PVDF according to the mass ratio of 7:2:1, and dissolving the mixture in an NMP solution to prepare slurry; uniformly coating the obtained slurry on a copper foil current collector to prepare a working electrode; the polypropylene film is taken as a diaphragm, and the electrolyte is 1M LiPF containing EC, DMC and DEC (volume ratio of 3: 4: 3)6The addition amount of the electrolyte is 160 mu l; assembling a 2032 button cell in a glove box filled with argon according to the sequence of 'negative electrode shell, lithium sheet, diaphragm, electrolyte, working electrode, gasket, backing ring and positive electrode shell', wherein the test voltage range is 0.01V-3.0V vs Li+/Li。
FIG. 4 shows the cycle of the target product obtained in this exampleRing performance, test magnification 0.5A g-1It can be seen that the specific discharge capacity of the first loop of the sample is 1551.3mA h g-11439.1mA h g is still held after 300 cycles-1The reversible specific capacity, the average capacity attenuation rate per circle is only 0.0354%, which shows that the cycle performance is excellent.
Example 2
In this example, a cobaltosic oxide material having a cubic structure was prepared in the same manner as in example 1, except that ammonium bicarbonate was mixed with the ZIF-67 solution in a mass to volume ratio of 60:30 and stirred uniformly.
Fig. 5 and fig. 6 are SEM photograph and TEM photograph of the target product obtained in this example, respectively, from which it can be seen that the material granular feeling is prominent, the material has a regular hexahedral structure, and the material has no pore distribution, which is not beneficial to lithium ion transmission.
The battery performance of the objective product obtained in this example was tested in the same manner as in example 1. FIG. 7 shows the cycle performance of the target product obtained in this example, with a test magnification of 0.5A g-1From the figure, it can be clearly observed that the specific capacity of the battery negative electrode material is rapidly attenuated, and the cycling stability is poor.
Compared with the negative electrode material in the embodiment 1, the negative electrode material in the embodiment 2 has no porous structure, and has the advantages of fast battery performance attenuation and frequent fluctuation in the cycle process, which is not beneficial to the practical application in the lithium ion battery. However, the anode material of example 1 has a relatively smooth cycle and good reversibility, resulting in a long cycle life.
Comparative analysis was performed with example 1 to confirm that the performance of the cubic porous structure obtained in example 1 was superior.
The above description is only for the purpose of illustrating the preferred embodiments of the present invention and is not to be construed as limiting the invention, and any modifications, equivalents and improvements made within the spirit and principle of the present invention are intended to be included within the scope of the present invention.
Claims (2)
1. A preparation method of cobaltosic oxide for manufacturing a lithium ion battery cathode material is characterized by comprising the following steps of: the cobaltosic oxide has a regular hexahedral porous structure; the cobaltosic oxide is obtained by the following preparation method:
step one, adding ZIF67 powder into a mixed solvent of deionized water and ethanol, and carrying out ultrasonic treatment and stirring uniformly to obtain a ZIF67 solution;
step two, adding ammonium bicarbonate into the ZIF67 solution obtained in the step one, uniformly stirring, carrying out hydrothermal reaction for 8-24h at the temperature of 190 ℃ and 170 ℃, carrying out solid-liquid separation on the obtained product, and washing and drying the solid phase to obtain the cobaltosic oxide;
in the first step, the dosage ratio of ZIF67, deionized water and absolute ethyl alcohol is 40 mg: 5-25 mL: 5-25 mL; the dosage ratio of the ammonium bicarbonate to the ZIF67 solution in the second step is 25-40 mg: 30 mL.
2. The method of preparing cobaltosic oxide according to claim 1, wherein: in the second step, the solid-liquid separation adopts a centrifugal separation mode, the centrifugal rotation speed in the centrifugal separation is 6000-10000rpm, and the drying temperature is 40-80 ℃.
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Citations (3)
| Publication number | Priority date | Publication date | Assignee | Title |
|---|---|---|---|---|
| CN103011306A (en) * | 2013-01-04 | 2013-04-03 | 南京工业大学 | Method for preparing nanometer-level cube-like cobaltosic oxide |
| CN103855385A (en) * | 2014-02-24 | 2014-06-11 | 清华大学 | Preparation method of cobaltosic oxide with high-magnification-performance micro-nano structure |
| CN109319846A (en) * | 2018-12-06 | 2019-02-12 | 怀化学院 | The preparation method of cobalt carbonate and the preparation method of cobaltosic oxide |
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Patent Citations (3)
| Publication number | Priority date | Publication date | Assignee | Title |
|---|---|---|---|---|
| CN103011306A (en) * | 2013-01-04 | 2013-04-03 | 南京工业大学 | Method for preparing nanometer-level cube-like cobaltosic oxide |
| CN103855385A (en) * | 2014-02-24 | 2014-06-11 | 清华大学 | Preparation method of cobaltosic oxide with high-magnification-performance micro-nano structure |
| CN109319846A (en) * | 2018-12-06 | 2019-02-12 | 怀化学院 | The preparation method of cobalt carbonate and the preparation method of cobaltosic oxide |
Non-Patent Citations (1)
| Title |
|---|
| A controllable ionic liquid-assisted hydrothermal route to prepare CoCO3 crystals and their conversion to porous Co3O4;Haobo Li et al.;《Crystal Research & Technology》;20111125;第47卷(第1期);第25-30页 * |
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