CN105870439B - A kind of preparation method and applications of porous cobaltosic oxide - Google Patents
A kind of preparation method and applications of porous cobaltosic oxide Download PDFInfo
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- CN105870439B CN105870439B CN201610253390.2A CN201610253390A CN105870439B CN 105870439 B CN105870439 B CN 105870439B CN 201610253390 A CN201610253390 A CN 201610253390A CN 105870439 B CN105870439 B CN 105870439B
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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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- 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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- 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
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Abstract
The invention discloses a kind of preparation method and applications of porous cobaltosic oxide.The preparation method concretely comprises the following steps：（1）Cobalt salt and imdazole derivatives are dissolved in organic solvent and the mixed solution of deionized water, stirred, forms mixed solution；（2）By step（1）Obtained mixed solution, which is placed in hydrothermal reaction kettle, to be sealed, and in 20 DEG C of -190 DEG C of reaction 2-48 hours, is naturally cooled to room temperature, is centrifuged out solid, wash, dehydration, obtain cobaltosic oxide predecessor；（3）By step（2）Obtained predecessor is calcined in air atmosphere, is cooled to room temperature and is produced porous cobaltosic oxide.Preparation method of the present invention is simple, easily operated, reproducible, and the porous cobaltosic oxide particle that this method is prepared is uniform, specific surface area is big, purity is high, and the cobaltosic oxide of preparation has good application prospect in lithium ion battery electrode material field.
Description
Technical field
The invention belongs to the preparation of inorganic material and application field, and in particular to a kind of preparation side of porous cobaltosic oxide
Method and its application.
Background technology
As the energy storage system of low-carbon green, lithium ion battery because its energy density is big, memory-less effect, the circulation longevity
The features such as life is long and environment-friendly, has obtained favor and the extensive concern of researcher and industrial quarters, has turned into every country in the world
The research field competitively developed.Lithium ion battery industry is increasingly ripe in recent years, is widely used in mobile phone, computer, automobile etc.
In various products, improved as performance of lithium ion battery improves constantly, the research of lithium ion battery negative material is also suggested more
High request.
Cobaltosic oxide（Co3O4）Physics and chemical property with uniqueness, such as have layer structure and good electrochemistry
Performance, have a very wide range of applications, have been a great concern in fields such as catalysis, electrochemistry and sensors.Four oxidations three
The pattern and size of cobalt material have important influence to its performance and application, therefore study four oxidations three of synthesis different-shape
Cobalt nanostructured is to improve the key of its performance.Porous cobaltosic oxide can greatly increase effective contact area and contribute to electronics
Transmission, using a kind of simple and easy method control synthesis different-grain diameter size, have porous the four of good chemical property
Co 3 O has significance.
The content of the invention
It is an object of the invention to provide a kind of preparation method of porous cobaltosic oxide, preparation method is simple, is easy to grasp
Make, be reproducible, the porous cobaltosic oxide particle that this method is prepared is uniform, specific surface area is big, purity is high.
Another object of the present invention is to provide application of the porous cobaltosic oxide as lithium ion battery electrode material.
Technical scheme of the invention for the proposition that solves the above problems：
A kind of preparation method of porous cobaltosic oxide, it is characterised in that using following steps：
（1）Cobalt salt and imdazole derivatives are dissolved in organic solvent and the mixed solution of deionized water, stirred, is formed mixed
Close homogeneous solution；Wherein the volume ratio of organic solvent and deionized water is 0.5-3：1, the concentration of cobalt salt in the solution is 0.1-
0.25moL/L, the concentration of imdazole derivatives in the solution are 0.05-0.5moL/L；
（2）By step（1）Obtained mixed solution, which is placed in hydrothermal reaction kettle, to be sealed, in 20 DEG C of -190 DEG C of reactions
2-48 hours, room temperature is naturally cooled to, be centrifuged out solid, washed, dehydration, obtain cobaltosic oxide predecessor；
（3）By step（2）Obtained predecessor is calcined in air atmosphere, 350-600 DEG C of calcining 1-10h, is cooled to room
Temperature produces porous cobaltosic oxide.
Step（1）Described in cobalt salt be selected from cobalt oxalate, cobalt nitrate, cobalt acetate or hydration cobalt acetate, described imidazoles spreads out
Biology is benzimidazole or 2-methylimidazole, and described organic solvent is selected from isopropanol, ethylene glycol or DMF.
Preferably, step（1）Described in organic solvent and deionized water volume ratio be 1：1, cobalt salt is in the solution
Concentration is 0.8moL/L, and the concentration of imdazole derivatives in the solution is 0.8moL/L.
Preferably, step（2）Described in mixed solution be placed in hydrothermal reaction kettle and seal, it is small in 180 DEG C of reactions 6
When.
Step（2）Middle centrifugal rotational speed is 5000-7000r/min, centrifugation time 5-10min.
Preferably, step（3）Described in calcining heat be 450 DEG C, calcination time 5h.
Application of the porous cobaltosic oxide in lithium ion battery electrode material a kind of prepared by above-mentioned preparation method.
Beneficial effect
（1）The invention provides a kind of method of the porous cobaltosic oxide of solvent structure, preparation method is simple, is easy to
Operation, it is reproducible, by adjusting the species and proportioning of cobalt salt, imdazole derivatives and organic solvent, and reaction temperature and time,
Make cobaltosic oxide particle size controllable, average grain diameter is 5 μm to 15 μm, and cobaltosic oxide particle is uniform, specific surface area is big, pure
Degree is high, is advantageous to the infiltration and diffusion of electrolyte, is easy to the transmission of lithium ion.
（2）The porous cobaltosic oxide that the present invention obtains is applied to lithium ion battery negative material, and charge/discharge capacity is high, follows
The ring life-span is good, high-rate discharge ability is good, and under 400mA/g current densities, specific discharge capacity is up to after circulation in 100 weeks
1650mAh/g。
Brief description of the drawings
Fig. 1 is the flying-spot microscope for the porous cobaltosic oxide that the embodiment of the present invention 1 synthesizes（SEM）Photo；
Fig. 2 is the X-ray diffraction for the porous cobaltosic oxide that the embodiment of the present invention 1 synthesizes（XRD）Collection of illustrative plates；
Fig. 3 is the cycle life figure for the porous cobaltosic oxide electrode that the embodiment of the present invention 4 synthesizes；
Fig. 4 is the high rate performance curve for the porous cobaltosic oxide electrode that the embodiment of the present invention 4 synthesizes.
Embodiment
Embodiment is set forth below, and the present invention will be described, but the invention is not limited in these embodiments.
Embodiment 1
5mmoL six is hydrated cobalt acetate and 2.5mmoL benzimidazoles are dissolved in 30mL isopropanols and 20mL deionized waters
In mixed solution, stirring at room temperature forms mixed solution, and mixed solution is placed in hydrothermal reaction kettle and sealed, 20
Reacted 48 hours at DEG C, obtained product is washed with 20mL deionized waters, 5000r/min centrifugations 10min obtains solid, repeats three
Secondary above-mentioned washing process, the dehydration of 20ml absolute ethyl alcohols is added in obtained solid, obtains cobaltosic oxide predecessor.Before obtaining
Drive thing to calcine in air atmosphere, 350 DEG C are calcined 10 hours, are cooled to room temperature and are produced porous cobaltosic oxide.Porous four oxidation
The ESEM of three cobalts（SEM）Spectrogram is shown in accompanying drawing 1, it can be seen that product morphology is regular, about 5 μm of the size of product；It is more
The X-ray diffraction of hole cobaltosic oxide（XRD）See accompanying drawing 2, it can be seen that products obtained therefrom purity is high, well-crystallized.
Embodiment 2
3mmoL cobalt acetates and 1.5mmoL benzimidazoles are dissolved in 10mLN, N-dimethylformamide and 20mL deionized waters
Mixed solution in, at room temperature stirring form mixed solution, mixed solution is placed in hydrothermal reaction kettle and sealed,
Being reacted 48 hours under room temperature condition, obtained product is washed with 20mL deionized waters, 7000r/min centrifugations 5min obtains solid,
Above-mentioned washing process in triplicate, the dehydration of 20ml absolute ethyl alcohols is added in obtained solid, obtains cobaltosic oxide predecessor.Will
Obtained predecessor is calcined in air atmosphere, and 350 DEG C are calcined 10 hours, are cooled to room temperature and are produced porous cobaltosic oxide.
Embodiment 3
10mmol cobalt oxalates and 20mmol 2-methylimidazoles are dissolved in the mixing of 30ml ethylene glycol and 10ml deionized waters
In solution, homogeneous solution is stirred to obtain at room temperature.Obtained homogeneous solution is put into hydrothermal reaction kettle and sealed, in 190 DEG C of insulations
6h is reacted, obtained product is washed with 20mL deionized waters, 7000r/min centrifugations 5min obtains solid, above-mentioned washing process weight
It is multiple to add the dehydration of 20ml absolute ethyl alcohols three times, in obtained solid, obtain cobaltosic oxide predecessor.By obtained predecessor in sky
Atmosphere encloses middle calcining, 600 DEG C of calcining 1h, is cooled to room temperature and produces porous cobaltosic oxide.
Embodiment 4
5mmol cobalt nitrates and 5mmol benzimidazoles are dissolved in 20ml isopropanols and the mixed solution of 20ml deionized waters
In, homogeneous solution is stirred to obtain at room temperature.Obtained homogeneous solution is put into hydrothermal reaction kettle and sealed, in 180 DEG C of insulation reactions
6h, obtained product is washed with 20mL deionized waters, 7000r/min centrifugations 5min obtains solid, above-mentioned washed in triplicate
Journey；It is dehydrated in middle addition 20ml absolute ethyl alcohols, obtains cobaltosic oxide predecessor.By obtained predecessor in air atmosphere
450 DEG C of calcining 5h, are cooled to room temperature and produce porous cobaltosic oxide.Fig. 3 is porous four oxidation three that the embodiment of the present invention 4 synthesizes
The cycle life figure of cobalt electrode, Fig. 4 are the high rate performance curve for the porous cobaltosic oxide electrode that the embodiment of the present invention 4 synthesizes.
The cobaltosic oxide various performance parameters detection being prepared in embodiment is carried out as follows：
Specific surface area/mesh size：Specific surface area and pore analysis（BET）；
Particle diameter：Field emission scanning electron microscope（FESEM）；
Cobaltosic oxide content/metal cation content：Energy dispersive spectrometer（EDS）.
The porous cobaltosic oxide obtained to above-described embodiment carries out measured performance parameter, and data are as follows：
Porous cobaltosic oxide performance parameter in the embodiment of table 1
The performance evaluation mode of porous cobaltosic oxide prepared by the present invention：Porous four oxidation three prepared by the present invention
Cobalt, super P-Li conductive blacks and PVDF adhesives are respectively according to 8:1:1 ratio is fully ground mixing, and is tuned into and is homogenized
Material, coat on Cu paper tinsels, dry, compacting.2025 are assembled into the glove box of high-purity argon gas (purity is more than 99.99%) atmosphere
Type button cell (H2O contents are less than 1ppm, O2Content is less than 3ppm), wherein metal lithium sheet is as negative pole.
To porous C o3O4The electrode of preparation carries out electrochemical property test, and Fig. 3 is its charge and discharge under 400mA/g current densities
Electric curve, it can be found from figure, discharge capacity is about 1601 mAhg first for it-1, initial charge capacity is about 1282mAhg-1,
Capacity is higher；After activation after a while, capacity keeps stable, and specific discharge capacity is up to 1650mAhg after circulation in 100 weeks-1, and the coulombic efficiency circulated every time is all higher than 99%, it is shown that excellent capability retention.It is forthright in order to further study its times
Can, test respectively under 200-3200mA/g current density conditions, the specific capacity changing rule of material, as seen from Figure 4：In electricity
In the range of current density 200-2200mA/g, its capacity keeps high value, when current density increases to 3200mA/g, its capacity
Decay is obvious, but current density reverts to 200mA/g, and its capacity can increase sharply again, and specific discharge capacity reaches 1600mAh/g.
Claims (6)
1. a kind of preparation method of porous cobaltosic oxide, it is characterised in that using following steps：
（1）Cobalt salt and imdazole derivatives are dissolved in organic solvent and the mixed solution of deionized water, stirred, it is equal to form mixing
Even solution；Wherein the volume ratio of organic solvent and deionized water is 0.5-3：1, the concentration of cobalt salt in the solution is 0.1-
0.25moL/L, the concentration of imdazole derivatives in the solution are 0.05-0.5moL/L；
（2）By step（1）Obtained mixed solution, which is placed in hydrothermal reaction kettle, to be sealed, in 20 DEG C of -190 DEG C of reaction 2-48
Hour, room temperature is naturally cooled to, is centrifuged out solid, is washed, dehydration, obtains cobaltosic oxide predecessor；
（3）By step（2）Obtained predecessor is calcined in air atmosphere, 350-600 DEG C of calcining 1-10h, is cooled to room temperature i.e.
Obtain porous cobaltosic oxide；
Wherein step（1）Described in imdazole derivatives be benzimidazole or 2-methylimidazole.
A kind of 2. preparation method of porous cobaltosic oxide according to claim 1, it is characterised in that step（1）Described in
Cobalt salt be selected from cobalt oxalate, cobalt nitrate, cobalt acetate or hydration cobalt acetate.
A kind of 3. preparation method of porous cobaltosic oxide according to claim 1, it is characterised in that step（1）Described in
Organic solvent be selected from isopropanol, ethylene glycol or DMF.
A kind of 4. preparation method of porous cobaltosic oxide according to claim 1, it is characterised in that step（2）Described in
Mixed solution be placed in hydrothermal reaction kettle and seal, react 6h at 180 DEG C.
A kind of 5. preparation method of porous cobaltosic oxide according to claim 1, it is characterised in that step（2）Middle centrifugation
Rotating speed is 5000-7000r/min, centrifugation time 5-10min.
A kind of 6. preparation method of porous cobaltosic oxide according to claim 1, it is characterised in that step（3）Described in
Calcining heat be 450 DEG C, calcination time 5h.
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Families Citing this family (7)
| Publication number | Priority date | Publication date | Assignee | Title |
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| CN106450288A (en) * | 2016-11-04 | 2017-02-22 | 济南大学 | Preparation method and application of porous cobalt oxide |
| CN106946789B (en) * | 2017-04-05 | 2019-12-10 | 哈尔滨工业大学 | two-dimensional porous metal cobalt complex and preparation method and application thereof |
| CN107819125A (en) * | 2017-11-02 | 2018-03-20 | 济南大学 | A kind of preparation method of straw bundle shape cobaltosic oxide and its application in lithium ion battery |
| CN109809498A (en) * | 2019-02-03 | 2019-05-28 | 复旦大学 | A kind of three-dimensional multistage hole cobaltosic oxide material and its preparation method and application |
| CN112635755B (en) * | 2020-12-22 | 2021-12-07 | 江西理工大学 | In-situ growth surface coordination polymerization reaction for preparing hollow Co3O4Method of nanosphere |
| CN115028208B (en) * | 2022-07-22 | 2024-06-25 | 衢州华友钴新材料有限公司 | Tricobalt tetraoxide material, preparation method, positive electrode and lithium battery |
| CN115745010B (en) * | 2022-09-23 | 2023-08-11 | 唐山师范学院 | Cobalt oxide/multi-wall carbon nano tube composite material and preparation method and application thereof |
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Application publication date: 20160817 Assignee: SHANDONG ZHONGCHA HEAVY INDUSTRY MACHINERY Co.,Ltd. Assignor: University of Jinan Contract record no.: X2020370000009 Denomination of invention: Preparation method and application of porous Co3O4 Granted publication date: 20180316 License type: Exclusive License Record date: 20200717 |
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