CN106374101B - A kind of Co3O4The preparation method and applications of@Co@nano cages - Google Patents
A kind of Co3O4The preparation method and applications of@Co@nano cages Download PDFInfo
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- CN106374101B CN106374101B CN201610823321.0A CN201610823321A CN106374101B CN 106374101 B CN106374101 B CN 106374101B CN 201610823321 A CN201610823321 A CN 201610823321A CN 106374101 B CN106374101 B CN 106374101B
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- 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
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Abstract
The invention discloses a kind of Co3O4The preparation method and applications of@Co@nano cages, pass through Co (NO3)2·6H2O solution is added drop-wise to dropwise in 2-methylimidazole solution, is stirred, and through centrifugation, washing, drying, step calcination charing and 200-230 DEG C of processing in air after reaction, Co is made3O4@Co@nano cages.Preparation method of the invention, it is easy to operate, at low cost, with high purity, have excellent performance, it can largely synthesize.Obtained Co3O4@Co@nano cages show higher coulombic efficiency and excellent cyclical stability, and discharge capacity reaches 1052mAh/g for the first time, and charging capacity reaches 851mAh/g, and coulombic efficiency is up to 81% for the first time；Under the current density of 0.2A/g after 100 cyclic processes, capacity may remain in 765mAh/g, show excellent cyclical stability.
Description
Technical field
The invention belongs to field of compound material, and in particular to a kind of Co3O4It the preparation method of@Co@nano cages and its answers
With.
Background technique
Lithium ion battery is because it has small in size, and light-weight, voltage is high, and self discharge is small, good rate capability, environment friend
It is good, the advantages that specific energy is high and be widely applied.Currently it is mainly used in mobile electronic device, national defense industry, electronic vapour
The fields such as vehicle.Electrode material is the core of lithium ion battery, and determines the key factor of performance of lithium ion battery.Mesh
Before, traditional graphite cathode material theoretical specific capacity is 372 mAh/g, has been unable to meet height ratio capacity lithium ion battery of new generation
The demand of negative electrode material.Transition metal oxide is due to theoretical capacity with higher and good chemical property and relatively low
The advantages that honest and clean cost, is expected to become ideal lithium ion battery negative material.But there are conductivities for transition metal oxide
Low, granule atomization and reunion in charge and discharge process, lithium ion insertion abjection and the disadvantages of the very big volume change that generates, cause
Its capacity attenuation is fast, high rate performance is poor and coulombic efficiency is low for the first time, these disadvantages limit their application.The group of electrode material
It is most important at, the influence of structure and pattern to its chemical property.By the design and optimization of synthesis route, construct
Transition metal oxide combination electrode material with special construction and pattern, can make it have excellent chemical property.
Summary of the invention
It is an object of the invention in view of the shortcomings of the prior art, providing a kind of Co3O4The preparation method of@Co@nano cages and
It is applied.The present invention prepares Co by synthesis cobalt-based metal organic frame3O4The composite Nano material of@Co@nano cages
Material, shows higher coulombic efficiency and excellent cyclical stability.
To achieve the above object, the present invention adopts the following technical scheme:
A kind of Co3O4The preparation method of@Co@nano cages, specifically includes the following steps:
(1) by the Co (NO of 0.35-0.5 g3)2·6H2The 2-methylimidazole of O and 4-6 g is dissolved in 4-6 ml and 18- respectively
In the deionized water of 22 ml, after being completely dissolved, Co (NO is obtained3)2·6H2O solution and 2-methylimidazole solution；
(2) Co (NO for obtaining step (1)3)2·6H2O solution is added drop-wise to dropwise in 2-methylimidazole solution, in 20-25
It stirs 4-12 h at DEG C to be reacted, the revolving speed of stirring is 90-130 r/min；
(3) reaction product is centrifuged and collected after reaction, and then gained is generated with deionized water and ethyl alcohol
Object is dry after respectively washing 3 times, then carries out step calcination charing, first roasts 2 h at 400 DEG C, then roasts at 600 DEG C
3h；
(4) by the 200-230 DEG C of processing 40-130 min in air of obtained substance after the charing of step (3) step calcination
Obtain Co3O4@Co@nano cages.
Co obtained3O4@Co@nano cages are as lithium ion battery negative material.Lithium ion battery assembling: in mass ratio
Co3O4@Co@nano cages: it polytetrafluoroethylene (PTFE): after acetylene black=75-85:5-10:10-15 mixed grinding, is uniformly coated to
1.3 cm2Copper sheet on do cathode, just extremely lithium metal, electrolyte are the EC+DEC+DMC solution of 1 M LiPF6, EC+DEC+
EC, DEC and DMC are 1:1:1 mixing by volume in DMC solution；All assemblings carry out in the glove box full of argon gas.
The beneficial effects of the present invention are: the present invention provides a kind of Co for the first time3O4The preparation method of@Co@nano cages,
Its is easy to operate, at low cost, with high purity, has excellent performance, and can largely synthesize.Obtained Co3O4@Co@nano cages are shown
Higher coulombic efficiency and excellent cyclical stability, discharge capacity is up to 1052 mAh/g for the first time, and charging capacity is up to 851 mAh/
G, coulombic efficiency is up to 81% for the first time；Under the current density of 0.2 A/g after 100 cyclic processes, capacity still may be used
765 mAh/g are maintained at, excellent cyclical stability is shown.
Detailed description of the invention
Fig. 1 is Co3O4The XRD diagram of@Co@nano cages；
Fig. 2 is Co3O4(a) low power and (b) high power SEM of@Co@nano cages are schemed；
Fig. 3 is Co3O4Charging and discharging curve of the@Co@carbon cage as cathode；
Fig. 4 is Co3O4Cyclic curve figure of the@Co@carbon cage as cathode.
Specific embodiment
Below in conjunction with specific embodiment, the present invention will be further described, but the present invention is not limited only to these embodiments.
Embodiment 1
A kind of Co3O4The preparation method of@Co@nano cages, specifically includes the following steps:
(1) by the Co (NO of 0.35 g3)2·6H2The 2-methylimidazole of O and 4 g be dissolved in respectively 4 ml and 18 ml go from
In sub- water, after being completely dissolved, Co (NO is obtained3)2·6H2O solution and 2-methylimidazole solution；
(2) Co (NO for obtaining step (1)3)2·6H2O solution is added drop-wise to dropwise in 2-methylimidazole solution, at 20 DEG C
4 h of lower stirring are reacted, and the revolving speed of stirring is 130 r/min；
(3) reaction product is centrifuged and collected after reaction, and then gained is generated with deionized water and ethyl alcohol
Object is dry after respectively washing 3 times, then carries out step calcination charing, first roasts 2 h at 400 DEG C, then roasts at 600 DEG C
3h；
(4) by the substance obtained after the charing of step (3) step calcination, 200 DEG C of 130 min of processing are obtained in air
Co3O4@Co@nano cages.
Co obtained3O4@Co@nano cages are as lithium ion battery negative material.Lithium ion battery assembling: in mass ratio
Co3O4@Co@nano cages: after acetylene black=75:5:10 mixed grinding, 1.3 cm polytetrafluoroethylene (PTFE): are uniformly coated to2Copper
On piece does cathode, and just extremely lithium metal, electrolyte are the EC+DEC+DMC solution of 1 M LiPF6, EC in EC+DEC+DMC solution,
DEC and DMC is 1:1:1 mixing by volume；All assemblings carry out in the glove box full of argon gas.
Embodiment 2
A kind of Co3O4The preparation method of@Co@nano cages, specifically includes the following steps:
(1) by the Co (NO of 0.5 g3)2·6H2The 2-methylimidazole of O and 6 g are dissolved in the deionization of 6 ml and 22 ml respectively
In water, after being completely dissolved, Co (NO is obtained3)2·6H2O solution and 2-methylimidazole solution；
(2) Co (NO for obtaining step (1)3)2·6H2O solution is added drop-wise to dropwise in 2-methylimidazole solution, at 25 DEG C
12 h of lower stirring are reacted, and the revolving speed of stirring is 90 r/min；
(3) reaction product is centrifuged and collected after reaction, and then gained is generated with deionized water and ethyl alcohol
Object is dry after respectively washing 3 times, then carries out step calcination charing, first roasts 2 h at 400 DEG C, then roasts at 600 DEG C
3h；
(4) by the substance obtained after the charing of step (3) step calcination, 230 DEG C of 40 min of processing obtain Co in air3O4@
Co@nano cages.
Co obtained3O4@Co@nano cages are as lithium ion battery negative material.Lithium ion battery assembling: in mass ratio
Co3O4@Co@nano cages: after acetylene black=85:10:15 mixed grinding, 1.3 cm polytetrafluoroethylene (PTFE): are uniformly coated to2's
Cathode is done on copper sheet, just extremely lithium metal, electrolyte is the EC+DEC+DMC solution of 1 M LiPF6, in EC+DEC+DMC solution
EC, DEC and DMC are 1:1:1 mixing by volume；All assemblings carry out in the glove box full of argon gas.
Embodiment 3
A kind of Co3O4The preparation method of@Co@nano cages, specifically includes the following steps:
(1) by the Co (NO of 0.42 g3)2·6H2The 2-methylimidazole of O and 5 g be dissolved in respectively 5 ml and 20 ml go from
In sub- water, after being completely dissolved, Co (NO is obtained3)2·6H2O solution and 2-methylimidazole solution；
(2) Co (NO for obtaining step (1)3)2·6H2O solution is added drop-wise to dropwise in 2-methylimidazole solution, at 22 DEG C
8 h of lower stirring are reacted, and the revolving speed of stirring is 110 r/min；
(3) reaction product is centrifuged and collected after reaction, and then gained is generated with deionized water and ethyl alcohol
Object is dry after respectively washing 3 times, then carries out step calcination charing, first roasts 2 h at 400 DEG C, then roasts at 600 DEG C
3h；
(4) by the substance obtained after the charing of step (3) step calcination, 215 DEG C of 85 min of processing obtain Co in air3O4@
Co@nano cages.
Co obtained3O4@Co@nano cages are as lithium ion battery negative material.Lithium ion battery assembling: in mass ratio
Co3O4@Co@nano cages: after acetylene black=80:7.5:12.5 mixed grinding, 1.3 cm polytetrafluoroethylene (PTFE): are uniformly coated to2
Copper sheet on do cathode, just extremely lithium metal, electrolyte are the EC+DEC+DMC solution of 1 M LiPF6, EC+DEC+DMC solution
Middle EC, DEC and DMC are 1:1:1 mixing by volume；All assemblings carry out in the glove box full of argon gas.
It can be seen that the main diffraction peak of prepared sample is attributed to spinelle from Fig. 1 X-ray powder diffraction analysis chart
Co3O4(JCPDS PDF#42-1467), in addition there are a small amount of metal Co(PDF#15-0806), illustrate that prepared sample is four
The compound of Co 3 O and a small amount of cobalt simple substance.The material of compound is polyhedron after calcining carbonization as can be seen from Figure 2
Pattern, partial size is in 400-600 nm or so；Can be seen that from its high power SEM figure be uniform-distribution with above carbon cage cobaltosic oxide and
Cobalt simple substance also can be observed carbon cage and notch occurs, thus illustrate that carbon cage is hollow structure.In the present invention, can by revolving speed come
Adjust the size of predecessor partial size.If the charging and discharging curve figure of Fig. 3 can be seen that, Co3O4The discharge capacity for the first time of@Co@nano cages
Up to 1052 mAh/g, charging capacity is up to 851 mAh/g, and coulombic efficiency is up to 81% for the first time.From the circulation figure of Fig. 4 it is found that 0.2
Under the current density of A/g after 100 cyclic processes, capacity may remain in 765 mAh/g, show excellent
Cyclical stability.
The foregoing is merely presently preferred embodiments of the present invention, all equivalent changes done according to scope of the present invention patent with
Modification, is all covered by the present invention.
Claims (4)
1. a kind of Co3O4The preparation method of@Co@nano cages, it is characterised in that: specifically includes the following steps:
(1) by the Co (NO of 0.35-0.5 g3)2·6H2The 2-methylimidazole of O and 4-6 g is dissolved in 4-6 ml and 18-22 ml respectively
Deionized water in, after being completely dissolved, obtain Co (NO3)2·6H2O solution and 2-methylimidazole solution；
(2) Co (NO for obtaining step (1)3)2·6H2O solution is added drop-wise to dropwise in 2-methylimidazole solution, at 20-25 DEG C
Stirring 4-12 h is reacted；
(3) reaction product is centrifuged and collected after reaction, it is then each to gained product with deionized water and ethyl alcohol
It is dry after washing 3 times, then carry out step calcination charing；The step calcination carbonization process are as follows: first roast 2 at 400 DEG C
Then h roasts 3h at 600 DEG C；
(4) by the substance obtained after the charing of step (3) step calcination, 200-230 DEG C of processing 40-130 min is obtained in air
Co3O4@Co@nano cages.
2. Co according to claim 13O4The preparation method of@Co@nano cages, it is characterised in that: stirring in step (2)
Revolving speed be 90-130 r/min.
3. Co made from a kind of preparation method as described in claim 13O4The application of@Co@nano cages, it is characterised in that: institute
State Co3O4@Co@nano cages are as lithium ion battery negative material.
4. application according to claim 3, it is characterised in that: lithium ion battery assembling: Co in mass ratio3O4@Co@carbon is received
Rice cage: after acetylene black=75-85:5-10:10-15 mixed grinding, 1.3 cm polytetrafluoroethylene (PTFE): are uniformly coated to2Copper sheet
On do cathode, just extremely lithium metal, electrolyte are the EC+DEC+DMC solution of 1 M LiPF6, EC in EC+DEC+DMC solution,
DEC and DMC is 1:1:1 mixing by volume；All assemblings carry out in the glove box full of argon gas.
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| 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 |
| CN107159297B (en) * | 2017-06-21 | 2020-03-27 | 黑龙江大学 | Double-function oxygen catalyst cobalt/cobaltosic oxide/nitrogen carbon composite material and preparation method thereof |
| CN107437617B (en) * | 2017-08-28 | 2019-11-26 | 武汉理工大学 | A kind of surface modification method, gained richness lithium material and application improving rich lithium material chemical property |
| CN108325529B (en) * | 2018-01-26 | 2020-03-27 | 新疆大学 | Photocatalytic water oxidation catalyst and preparation method thereof |
| CN110284153B (en) * | 2018-03-19 | 2021-06-01 | 天津大学 | Cobalt/cobaltous oxide porous nanosheet array composite material and preparation method and application thereof |
| 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 |
| CN110364710A (en) * | 2019-07-02 | 2019-10-22 | 华南理工大学 | High-performance manganese-based zinc ion battery positive electrode material and preparation method and application thereof |
| CN114853567B (en) * | 2022-06-16 | 2023-07-25 | 南京工业大学 | Catalyst for preparing low-carbon alcohol by converting carbon dioxide, and preparation method and application thereof |
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| CN102842710A (en) * | 2012-07-18 | 2012-12-26 | 上海大学 | Preparation method of Co3O4/graphene nanocomposite material |
| CN103094559B (en) * | 2013-01-31 | 2015-07-29 | 湘潭大学 | A kind of Co 3o 4/ C lithium ion battery cathode material and its preparation method |
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