CN106450200B - A kind of CoS@nano cages and its preparation method and application - Google Patents
A kind of CoS@nano cages and its preparation method and application Download PDFInfo
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- CN106450200B CN106450200B CN201610931981.0A CN201610931981A CN106450200B CN 106450200 B CN106450200 B CN 106450200B CN 201610931981 A CN201610931981 A CN 201610931981A CN 106450200 B CN106450200 B CN 106450200B
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Abstract
The present invention provides a kind of CoS@nano cages and its preparation method and application, it is carbon source and cobalt source by synthesis cobalt-based metal-organic framework material (ZIF-67), the composite nano materials of CoS@nano cages can be prepared as presoma and sulphur powder dinectly bruning.Metal sulfide is solved in charge and discharge process, since volume change is excessive, leads to the collapsing of structure, the powdered of material, so that the problem of cyclical stability greatly reduces.Since nano cages are capable of providing more storage lithium gaps, improve the electric conductivity of integral material, and it can effectively alleviate volume change brought by lithium ion deintercalation, can also prevent the reunion of CoS particle, thus the composite material in terms of lithium ion battery electrode material with good application prospect.
Description
Technical field
The invention belongs to field of lithium ion battery, and in particular to a kind of CoS@nano cages and its preparation method and application.
Background technique
Lithium ion battery because its have it is small in size, light-weight, operating voltage is high, energy density is high, have extended cycle life, from
Discharge rate is small, memory-less effect, advantages of environment protection and be widely applied.Currently mobile electron is mainly used in set
The fields such as standby, national defense industry, electric car.Since the low specific capacity (theoretical value is only 372 m Ah/g) of carbon material limits significantly
The further development of lithium ion battery, so there is an urgent need to develop height ratio capacity negative electrode materials.Metal sulfide all have compared with
High theoretical specific capacity, and conduct electricity very well, it is a kind of lithium ion battery negative material with applications well prospect.But it is this kind of
Material is in charge and discharge process, since volume change is excessive, leads to the collapsing of structure, the powdered of material, so that cyclical stability
It greatly reduces.Research finds the carbon material of the special constructions such as nano cages, carbon mitron, can alleviate in cyclic process because of volume
The collapsing of structure caused by variation.Therefore, the present invention designs a kind of composite nano materials of CoS@nano cages, this compound
Material shows higher lithium storage content, excellent rate charge-discharge performance and cyclical stability.
There are not the preparation method of CoS@nano cages and its related patents report of the application in lithium battery also at present.
Summary of the invention
The purpose of the present invention is to provide a kind of CoS@nano cages and its preparation method and application, it is easy to operate, at
Sheet is low, with high purity, has excellent performance, and can largely synthesize.Metal sulfide is solved in charge and discharge process, due to volume change mistake
Greatly, lead to the collapsing of structure, the powdered of material, so that the problem of cyclical stability greatly reduces.Due to nano cages energy
It is enough that more storage lithium gaps are provided, the electric conductivity of integral material is improved, and can effectively alleviate lithium ion deintercalation and be brought
Volume change, the reunion of CoS particle can also be prevented, thus the composite material has in terms of lithium ion battery electrode material
Preferable application prospect.
To achieve the above object, the present invention adopts the following technical scheme:
The present invention by synthesis cobalt-based metal-organic framework material (ZIF-67) be carbon source and cobalt source, as presoma with
Cheap sulphur powder dinectly bruning can prepare the composite nano materials of CoS@nano cages.
A kind of preparation method of CoS@nano cages: specifically comprise the following steps:
1) preparation of ZIF-67 predecessor: by the Co (NO of 0.4-0.6 g3)2•6H2The 2-methylimidazole of O and 5.0- 6.5g
It is dissolved in the deionized water of 5-6 ml and 19-21 ml respectively, until completely dissolved by Co (NO3)2•6H2O solution is added drop-wise to dropwise
In 2-methylimidazole solution, 80-200 mg polyvinylpyrrolidone (PVP) then is added, 6-12 h is stirred at 25 DEG C, instead
It answers product in the drying after deionized water and ethanol washing 3 times, obtains Co@carbon through 550-650 DEG C of roasting 4-6 h in tube furnace and receive
Rice cage；
2) weigh 150-180 mg Co@nano cages and sulphur powder mixed grinding 30-40 minutes of 30-40 mg, will grind
Good sample tube furnace through 360-450 DEG C roasting 2-5 hours, obtained CoS@nano cages.
Lithium ion battery assembling: CoS nano cages in mass ratio: polytetrafluoroethylene (PTFE): acetylene black=70-75:5-10:15-
1.3 cm are uniformly coated to after 20 mixed grindings2Copper sheet on do cathode, just extremely lithium metal, electrolyte are 1 M LiPF6's
EC+DEC+DMC (v/v/v of EC/DEC/DMC=1/1/1) solution.All assemblings carry out in the glove box full of argon gas.
Remarkable advantage of the invention is:
1) it solves metal sulfide in charge and discharge process, since volume change is excessive, leads to the collapsing of structure, material
Powdered, so that the problem of cyclical stability greatly reduces.
2) nano cages and the mutual of cobalt sulfide act synergistically so that carbon nano-cage loaded cobalt sulfide nano particle is in electrification
Preferable cycle performance can be possessed by learning in performance test.
3) since nano cages are capable of providing more storage lithium gaps, the electric conductivity of integral material is improved, and can have
Volume change brought by lithium ion deintercalation is alleviated on effect ground, can also prevent the reunion of CoS particle, thus the composite material is in lithium
In terms of ion battery electrode materials with good application prospect.
4) preparation method of the invention it is easy to operate, it is at low cost, with high purity, have excellent performance, can largely synthesize, it is obtained
CoS@nano cages specific capacity with higher.
Detailed description of the invention
Fig. 1 is the XRD spectrum of cobalt-based metal organic frame presoma (ZIF-67).
Fig. 2 is the X-ray powder diffraction analysis chart of CoS@nano cages.
Fig. 3 is the scanning electron microscope analysis figure of CoS@nano cages.
Fig. 4 is charge graph of the CoS@nano cages as cathode.
Fig. 5 is high rate performance figure of the CoS@nano cages under different current densities.
Fig. 6 is cyclic curve figure of the CoS@nano cages under 100 mA/g current densities.
Specific embodiment
The present invention is further illustrated by the following examples, but protection scope of the present invention is not limited to following reality
Apply example.
Embodiment 1
A kind of preparation method of CoS@nano cages: specifically comprise the following steps:
1) preparation of ZIF-67 predecessor: by the Co (NO of 0.4g3)2•6H2The 2-methylimidazole of O and 5.0g is dissolved in 5 respectively
In the deionized water of ml and 19 ml, until completely dissolved by Co (NO3)2•6H2O solution is added drop-wise to 2-methylimidazole solution dropwise
In, 80 mg polyvinylpyrrolidones (PVP) are then added, 6 h are stirred at 25 DEG C, reaction product is through deionized water and second
Alcohol is dry after washing 3 times, obtains Co@nano cages through 550 DEG C of 4 h of roasting in tube furnace；
2) weigh 150mg Co@nano cages and sulphur powder mixed grinding 30 minutes of 30 mg, ground sample is existed
Tube furnace roasts 2 hours through 360 DEG C, and CoS@nano cages are made.
Lithium ion battery assembling: CoS nano cages in mass ratio: polytetrafluoroethylene (PTFE): acetylene black=70:5:15 mixing is ground
1.3 cm are uniformly coated to after mill2Copper sheet on do cathode, just extremely lithium metal, electrolyte are 1 M LiPF6EC+DEC+
DMC (v/v/v of EC/DEC/DMC=1/1/1) solution.All assemblings carry out in the glove box full of argon gas.
Embodiment 2
A kind of preparation method of CoS@nano cages: specifically comprise the following steps:
1) preparation of ZIF-67 predecessor: by the Co (NO of 0.5 g3)2•6H2The 2-methylimidazole of O and 6.0g is dissolved in 5 respectively
In the deionized water of ml and 20 ml, until completely dissolved by Co (NO3)2•6H2O solution is added drop-wise to 2-methylimidazole solution dropwise
In, 150 mg polyvinylpyrrolidones (PVP) are then added, stir 10 h at 25 DEG C, reaction product through deionized water and
It is dry after ethanol washing 3 times, Co@nano cages are obtained through 600 DEG C of 5 h of roasting in tube furnace；
2) weigh 160mg Co@nano cages and sulphur powder mixed grinding 35 minutes of 35 mg, ground sample is existed
Tube furnace roasts 3 hours through 400 DEG C, and CoS@nano cages are made.
Lithium ion battery assembling: CoS nano cages in mass ratio: polytetrafluoroethylene (PTFE): acetylene black=72:8:18 mixing is ground
1.3 cm are uniformly coated to after mill2Copper sheet on do cathode, just extremely lithium metal, electrolyte are 1 M LiPF6EC+DEC+
DMC (v/v/v of EC/DEC/DMC=1/1/1) solution.All assemblings carry out in the glove box full of argon gas.
Embodiment 3
A kind of preparation method of CoS@nano cages: specifically comprise the following steps:
1) preparation of ZIF-67 predecessor: by the Co (NO of 0.6 g3)2•6H2The 2-methylimidazole of O and 6.5g is dissolved in 6 respectively
In the deionized water of ml and 21 ml, until completely dissolved by Co (NO3)2•6H2O solution is added drop-wise to 2-methylimidazole solution dropwise
In, 200 mg polyvinylpyrrolidones (PVP) are then added, stir 12 h at 25 DEG C, reaction product through deionized water and
It is dry after ethanol washing 3 times, Co@nano cages are obtained through 650 DEG C of 6 h of roasting in tube furnace；
2) weigh 180 mg Co@nano cages and sulphur powder mixed grinding 40 minutes of 40 mg, ground sample is existed
Tube furnace roasts 5 hours through 450 DEG C, and CoS@nano cages are made.
Lithium ion battery assembling: CoS nano cages in mass ratio: polytetrafluoroethylene (PTFE): acetylene black=75:10:20 mixing
1.3 cm are uniformly coated to after grinding2Copper sheet on do cathode, just extremely lithium metal, electrolyte are 1 M LiPF6EC+DEC
+ DMC (v/v/v of EC/DEC/DMC=1/1/1) solution.All assemblings carry out in the glove box full of argon gas.
Fig. 1 is the XRD spectrum of cobalt-based metal organic frame presoma (ZIF-67), is penetrated from the X- of Fig. 2 CoS@nano cages
Line powder diffraction analysis figure can be seen that the peak position of CoS fits like a glove with standard spectrum (PDF#65-3418), illustrate prepared
Sample is cobalt sulfide.It can be seen that obtained CoS@nano cages particle size in 400- from Fig. 3 scanning electron microscope analysis figure
700 um or so, CoS nanoparticle (20-30 nm) are more uniformly supported on nano cages, it was further observed that individual carbon cages
There is notch, thus illustrates that carbon cage is hollow structure.The mutual synergistic effect of nano cages and cobalt sulfide is so that nano cages are negative
Preferable cycle performance can be possessed in electrochemical property test by carrying cobalt sulfide nano particle.Fig. 4 is CoS@nano cages conduct
The charging curve of cathode, voltage tester scope are 0.4 V-3V, it can be seen that the initial charge capacity of CoS@nano cages is up to 331.5
mAh/g.Fig. 5 is high rate performance figure of the CoS@nano cages under different current densities, in 100 mA/g, 200 mA/g, 500
Under mA/g, 1000 m A/g, 2000 m A/g and 5000 mA/g current densities, corresponding reversible specific capacity is respectively 337
It is non-to illustrate that the material has by m Ah/g, 333 m Ah/g, 315 mA/g, 294 Ah/g, 262m Ah/g and 200 m Ah/g
The high rate performance of Chang Youyi.As shown in fig. 6, the figure is cyclic curve of the CoS@nano cages under 100 mA/g current densities
Figure, the initial charge specific capacity of CoS@nano cages are 373 m Ah/g, and after circulation 200 is enclosed, reversible specific capacity can still be stablized
In 290 m Ah/g, good cyclical stability is shown.Since nano cages are capable of providing more storage lithium gaps, improve
The electric conductivity of integral material, and can effectively alleviate volume change brought by lithium ion deintercalation, CoS can also be prevented
Son reunion, thus the composite material in terms of lithium ion battery electrode material with good application prospect.
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 (2)
1. a kind of preparation method of CoS@nano cages, which is characterized in that specific step is as follows:
1) preparation of ZIF-67 predecessor: by the Co (NO of 0.4-0.6 g3)2•6H2The 2-methylimidazole of O and 5.0- 6.5g is distinguished
It is dissolved in the deionized water of 5-6 ml and 19-21 ml, until completely dissolved by Co (NO3)2•6H2O solution is added drop-wise to 2- first dropwise
In base imidazole solution, 80-200 mg polyvinylpyrrolidone is then added, 6-12 h is stirred at 25 DEG C, reaction product is passing through
It is dry after deionized water and ethanol washing 3 times, Co@nano cages are obtained through 550-650 DEG C of roasting 4-6 h in tube furnace；
2) weigh 150-180 mg Co@nano cages and sulphur powder mixed grinding 30-40 minutes of 30-40 mg, will be ground
Sample tube furnace through 360-450 DEG C roasting 2-5 hours, be made CoS@nano cages.
2. CoS@nano cages made from a kind of preparation method as described in claim 1.
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| CN108630947B (en) * | 2017-03-15 | 2020-10-02 | 中国科学院福建物质结构研究所 | Preparation method of cobalt sulfide/carbon nano catalyst of rechargeable zinc-air battery |
| CN107978745B (en) * | 2017-11-21 | 2020-08-14 | 华南师范大学 | High-capacity carbon nanotube composite cobalt sulfide negative electrode material and preparation and application thereof |
| CN108295881B (en) * | 2018-01-29 | 2020-02-04 | 中南大学 | Co4N/N-doped carbon hollow nano cage composite material and preparation method and application thereof |
| CN108745381B (en) * | 2018-06-07 | 2020-10-09 | 南开大学 | Method for preparing cobalt sulfide catalyst by taking MOF as substrate |
| CN108948365B (en) * | 2018-06-28 | 2021-03-09 | 浙江工业大学 | Method for preparing two-dimensional MOF (Metal organic framework) derivative sulfide by utilizing template method |
| CN108706573B (en) * | 2018-08-20 | 2020-01-31 | 南京大学 | graphene-based hollow cobalt sulfide nanocrystalline capable of efficiently activating persulfate and preparation method thereof |
| CN111416119A (en) * | 2019-01-07 | 2020-07-14 | 北京大学 | Ultra-high dispersion Co-containing3S4Nanoparticle porous carbon and carbon nanotube sponge hybrid and preparation method and application thereof |
| CN110400918B (en) * | 2019-06-11 | 2022-06-10 | 南开大学 | Preparation method of cobalt-sulfur compound/sulfur-doped carbon composite material |
| CN110311131A (en) * | 2019-06-28 | 2019-10-08 | 江苏大学 | Aluminium ion battery, its positive electrode and production method |
| CN110734097B (en) * | 2019-10-23 | 2022-03-04 | 中国人民解放军国防科技大学 | ZIF 67-containing derived composite carbon material lithium-sulfur battery positive electrode material, preparation method thereof, positive electrode plate containing positive electrode material and lithium-sulfur battery |
| CN110783549B (en) * | 2019-11-07 | 2022-05-31 | 吉林大学 | Polypyrrole-coated sulfur-doped cobalt-based carbon nanocage material, and preparation method and application thereof |
| CN111933933A (en) * | 2020-07-31 | 2020-11-13 | 广东凯金新能源科技股份有限公司 | Novel lithium ion battery cathode material and preparation method thereof |
| CN111933934A (en) * | 2020-07-31 | 2020-11-13 | 广东凯金新能源科技股份有限公司 | Battery negative electrode material and preparation method thereof |
| CN112366298B (en) * | 2020-10-19 | 2021-10-08 | 杭州职业技术学院 | Carbon-assembled zinc sulfide cobalt sulfide hollow nano polyhedral framework material and preparation and application thereof |
| CN113066964B (en) * | 2021-03-15 | 2022-04-19 | 南昌大学 | Double-metal phosphide-inlaid carbon hollow nano cage and preparation method and application thereof |
| CN115566161B (en) * | 2022-09-20 | 2023-07-28 | 东莞理工学院 | Preparation method of sulfur-rich polymer hierarchical pore carbon nano cage composite material and application of sulfur-rich polymer hierarchical pore carbon nano cage composite material in lithium sulfur battery |
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| CN103236542A (en) * | 2013-04-17 | 2013-08-07 | 浙江大学 | Preparation method for lithium-sulfur battery positive electrode material adopting metal-organic framework material as sulfur carrier |
| KR101597970B1 (en) * | 2014-03-10 | 2016-02-26 | 연세대학교 산학협력단 | Preparing method of alloy catalyst using poly dopamine coating and alloy catalyst thereby |
| CN105552392A (en) * | 2016-01-06 | 2016-05-04 | 复旦大学 | Cobalt diselenide/graphite carbon composite material, namely oxygen reduction catalyst, and preparation method thereof |
| CN105977467A (en) * | 2016-07-01 | 2016-09-28 | 北京工业大学 | Preparation method for preparing Co3O4@CoP composite electrode based on MOF template |
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