CN107134565A - Combination electrode material and its preparation method and application - Google Patents
Combination electrode material and its preparation method and application Download PDFInfo
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- CN107134565A CN107134565A CN201710160786.7A CN201710160786A CN107134565A CN 107134565 A CN107134565 A CN 107134565A CN 201710160786 A CN201710160786 A CN 201710160786A CN 107134565 A CN107134565 A CN 107134565A
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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
- H01M4/362—Composites
- H01M4/366—Composites as layered products
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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
- H01M4/38—Selection of substances as active materials, active masses, active liquids of elements or alloys
- H01M4/386—Silicon or alloys based on silicon
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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
- H01M4/62—Selection of inactive substances as ingredients for active masses, e.g. binders, fillers
- H01M4/624—Electric conductive fillers
- H01M4/625—Carbon or graphite
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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
- H01M4/62—Selection of inactive substances as ingredients for active masses, e.g. binders, fillers
- H01M4/628—Inhibitors, e.g. gassing inhibitors, corrosion inhibitors
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- 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
Abstract
The present invention relates to a kind of preparation method of combination electrode material：CNT, silicon grain and water soluble organic substance are well mixed in water, then using spray dryer to being spray-dried；Dried product is carbonized under protective atmosphere at 700 1000 DEG C, after being mixed with sulphur powder, in 150 300 DEG C of heating in vacuum；Above-mentioned product is placed in carbon matrix precursor solution, the silicon-carbon nanometer tube composite materials of carbon matrix precursor cladding is obtained, it is then heated to 700 1000 DEG C under protective atmosphere, combination electrode material is obtained.The method of the present invention additionally provides a kind of combination electrode material, and the outer layer of combination electrode material is carbon-coating, and internal layer is silicon grain and CNT, and the particle diameter of combination electrode material is 1 20 μm.Present invention also offers application of the above-mentioned combination electrode material in lithium ion battery is prepared.The present invention prepares combination electrode material, its pattern is adjustable using sulphur as sacrifice layer using simple, efficient method, and with good cyclical stability.
Description
Technical field
The present invention relates to cell art, more particularly to a kind of combination electrode material and its preparation method and application.
Background technology
Current conventional energy resource is increasingly deficient, and the secondary cell for developing high-energy-density is extremely urgent, and silicium cathode is due to high ratio
Capacity, has attracted great concern.But it is due to that it has larger volumetric expansion (400%) and limited in charge and discharge process
Its application in actual production.
The main method for solving silicium cathode Problem of Failure at present is to provide expansion space for the expansion of silicon, but prior art
Not only complex process is difficult to, and easily pollutes environment, it is difficult to realize large-scale industrial production.In addition, there is research
It was found that, when silicon size reaches below 150nm, stress effect has not been to influence the principal element of performance of lithium ion battery.So
And up to the present, in Large Copacity, high-performance, long-life, low-cost silicon base lithium ion charging battery electrode developmental achievement also
There is no one kind extensive, low cost, industrialized technology of preparing.Therefore, find preparation technology it is simple and with good lithium from
The negative material of sub- storge quality turns into the key of development lithium ion battery.
The content of the invention
In order to solve the above technical problems, it is an object of the invention to provide a kind of combination electrode material and preparation method thereof and answering
With, the present invention prepares combination electrode material, its pattern is adjustable using sulphur simple substance as sacrifice layer using simple, efficient method, and
With good cyclical stability.
A kind of preparation method of combination electrode material of the present invention, comprises the following steps：
(1) CNT, silicon grain and water soluble organic substance are well mixed in water, obtain mixed solution, then make
Mixed solution is spray-dried with spray dryer；
(2) step (1) dried product is carbonized under protective atmosphere at 700-1000 DEG C, carbonization time is 1-
6h, after then being mixed with sulphur powder, in 150-300 DEG C of heating in vacuum, the heat time is 6-10h；
(3) product for obtaining step (2), which is placed in carbon matrix precursor solution, carries out the processing of surface bag carbon, obtains carbon matrix precursor
The silico-carbo nanometer tube composite materials of cladding, are then heated to 700-1000 DEG C by it under protective atmosphere, except desulfuration and to make carbon
Presoma is carbonized, and obtains combination electrode material.
Further, in step (1), the particle diameter of silicon grain is 50nm-1 μm.Silicon grain is silicon nanoparticle or micron
Silicon grain.
Further, in step (1), water soluble organic substance is polyvinylpyrrolidone, glucose or sucrose.Using water
Soluble organism forms carbon-coating as carbon source after carbonization, and silico-carbo nanotube composite construction, step can be prepared by one-step method
Simply, it is easy to manipulate.
Further, in step (1), the mass ratio of CNT, silicon grain and water soluble organic substance is 1-8:1:1-
20.By adjusting the ratio of CNT and silicon grain, the granular size of the combination electrode material ultimately formed can be adjusted.It is former
Because being that during spray drying, the solid-solid interface between different amounts of CNT and silicon grain has differences, therefore shape
Into the of different sizes of particle.
Preferably, in step (1), the mass ratio of CNT, silicon grain and water soluble organic substance is 3-1/3:1:20.
Further, in step (1), spray rate during spray drying is 5-15mL/min.
Further, in step (1), the inlet temperature of spray dryer is 120-160 DEG C, and outlet temperature is 70-90
℃。
Further, in step (2) and step (3), protective atmosphere is one kind or several in nitrogen, helium and argon gas
Kind.
Further, in step (2), the mass ratio of sulphur and the silicon grain in step (1) is 1-4:1.
Preferably, in step (2), the mass ratio of sulphur and the silicon grain in step (1) is 4:1.
In step (2), in 150-300 DEG C of heating in vacuum, sulphur can become liquid, be subsequently filled the seam of product after carbonization
In gap, to protect the destruction in follow-up temperature-rise period to product structure after carbonization.
Further, in step (3), product is placed in carbon matrix precursor solution, and the material in carbon matrix precursor can gather
Reaction is closed, in carbon pipe-one layer of silicon powder surface formation carbon matrix precursor layer.Further, in step (3), carbon matrix precursor solution is
Hydrochloric acid-dopamine solution, its pH value is 8.5.
Further, product step (2) obtained, which is placed in carbon matrix precursor solution, reacts 0.5-4h.Preferably, react
Time is 1h.
Further, in step (3), when being heated to 700-1000 DEG C under protective atmosphere, sulphur can become sulphur steam quilt
Remove, and carbon matrix precursor can be carbonized, and form carbon-coating.Preferably, in step (3), 900- is heated under protective atmosphere
1000 DEG C, except desulfuration and to make carbon matrix precursor be carbonized.
On the other hand, present invention also offers the combination electrode material prepared by a kind of use above method, compound electric
Pole material includes internal layer and is coated on the carbon outer layer of internal layer surface, and internal layer includes silicon grain and CNT, combination electrode material
Particle diameter be 1-20 μm.
It yet still another aspect, the combination electrode material prepared using the above method, which is also claimed, in the present invention is preparing lithium
Application in ion battery.
By such scheme, the present invention at least has advantages below：
Prepared using elemental sulfur as sacrifice layer with rule and the stable combination electrode material of property, and size can
Adjust, can mass produce；Using CNT as conductive network, the conduction of whole combination electrode on the one hand can be improved
Property, the still further aspect toughness certain because CNT has constituted in silicon grain is wrapped in by network, can alleviate silicon
Volumetric expansion problem；Combination electrode material prepared by the present invention, it is possible to increase the cyclical stability of electrode, can be widely used for electricity
The fields such as plating, electrolysis, solidification and crystallization.
Described above is only the general introduction of technical solution of the present invention, in order to better understand the technological means of the present invention,
And can be practiced according to the content of specification, below with presently preferred embodiments of the present invention and coordinate accompanying drawing describe in detail as after.
Brief description of the drawings
Fig. 1 is the SEM figures after Spray dried products carbonization in the embodiment of the present invention 1；
Fig. 2 is part-structure enlarged drawing in SEM figures in the embodiment of the present invention 1 after Spray dried products carbonization；
Fig. 3 is part-structure enlarged drawing in SEM figures in the embodiment of the present invention 1 after Spray dried products carbonization；
Fig. 4 is the SEM figures of carbon nanometer tube/silicon material filling elemental sulfur in the embodiment of the present invention 1；
Fig. 5 is part-structure enlarged drawing in the SEM figures of carbon nanometer tube/silicon material filling elemental sulfur in the embodiment of the present invention 1；
Fig. 6 is part-structure enlarged drawing in the SEM figures of carbon nanometer tube/silicon material filling elemental sulfur in the embodiment of the present invention 1；
Fig. 7 is the crystal structure test result of the product after the step of the embodiment of the present invention 1 (2) processing；
Fig. 8 is the SEM figures of combination electrode material prepared by the embodiment of the present invention 1；
Fig. 9 is the part-structure enlarged drawing in Fig. 8；
Figure 10 is the part-structure enlarged drawing in Fig. 9；
Figure 11 is that the combination electrode material of the preparation of the embodiment of the present invention 1 is used as the cycle performance of lithium ion battery negative material
Figure；
Figure 12 is that the mass ratio of CNT and silicon is respectively 1:The SEM figures of combination electrode material prepared by 3；
Figure 13 is that the mass ratio of CNT and silicon is respectively 1:The SEM figures of combination electrode material prepared by 2；
Figure 14 is that the mass ratio of CNT and silicon is respectively 1:The SEM figures of combination electrode material prepared by 1；
Figure 15 is that the mass ratio of CNT and silicon is respectively 2:The SEM figures of combination electrode material prepared by 1；
Figure 16 is that the mass ratio of CNT and silicon is respectively 3:The SEM figures of combination electrode material prepared by 1；
Figure 17 is the nitrogen adsorption curve for changing the combination electrode material prepared by the mass ratio of CNT and silicon.
Embodiment
With reference to the accompanying drawings and examples, the embodiment to the present invention is described in further detail.Implement below
Example is used to illustrate the present invention, but is not limited to the scope of the present invention.
Embodiment 1
(1) by silicon grain (particle diameter is 50-100nm), CNT, polyvinylpyrrolidone is according to 1:1:20 mass ratio
Mix, using Ultrasonic Cell Disruptor ultrasonic disperse 240min, be spray-dried after mixture is taken out in 100mL water, sprayed
Dry inlet temperature is 140 DEG C, and outlet temperature is 80 DEG C, and spray rate is 10mL/min.Product after spray drying is existed
It is heated to 700 DEG C in tube furnace to be carbonized, the heat time is with nitrogen as protection gas in 60min, tube furnace.
(2) taken out after stove is cooled to room temperature, be 4 according to the mass ratio of elemental sulfur and silicon grain:1 ratio is mixed,
Then under vacuum conditions, taken out after 6h, 300 DEG C of insulation 2h are incubated at 150 DEG C, obtain sulphur-carbon nanometer tube/silicon combination electrode
Material.
(3) above-mentioned electrode material is placed in pH=8.5 hydrochloric acid-dopamine solution to react and taken out after 1h, obtain poly- many
It, is then heated to 900 DEG C by the silico-carbo nanometer tube composite materials of bar amine cladding under nitrogen protection, except desulfuration and to make to gather
Dopamine is carbonized, and obtains combination electrode material.
Fig. 1-3 is the material SEM characterization results that step (1) is obtained, it can be seen that the silicon prepared using this method
Carbon composite electrode material average grain diameter is 5 μm, the inside for being embedded in CNT ball of silicon grain at random.
Fig. 4-6 is the SEM characterization results for the material that step (2) is obtained, it can be seen that elemental sulfur fully enters carbon
The inside of nanotube/silicon ball, original carbon nanometer tube/silicon ball internal interstices are blocked.Fig. 7 is the crystal structure that step (2) is obtained
Test chart, it can be seen that by handling, sulphur simple substance can be combined really in composite, in addition, by being combined, silicon
Crystal structure will not change.
Fig. 8-9 is the combination electrode material finally given after carbonization, as seen from the figure, carbon nanometer tube/silicon particle surface
Coated completely by carbon-coating.Figure 11 is its Electrochemical Characterization figure, and top curve represents coulombic efficiency, and lower curve is represented
Specific discharge capacity, abscissa represents cycle-index, it can be seen that (the 1C=4200mA/ under C/20 current density
G), circulation 1000 circle after still have 997mAh/g specific discharge capacity, its first coulombic efficiency be 53%.
Embodiment 2
By silicon grain (particle diameter is 50-100nm), CNT, glucose is according to 1/3-3:1:1 mass ratio is in 100mL
Mix, using Ultrasonic Cell Disruptor ultrasonic disperse 240min, be spray-dried after mixture is taken out in water, spray drying is entered
Mouth temperature is 140 DEG C, and outlet temperature is 80 DEG C, and spray rate is 5mL/min.Product after spray drying is added in tube furnace
Heat is carbonized to 900 DEG C, and the heat time is with nitrogen as protecting gas in 60min, tube furnace.Figure 12-16 is CNT
Mass ratio with silicon is respectively 1:3、1:2、1:1、2:1、3:The SEM figures of combination electrode material prepared by 1, can from figure
Go out, with the increase of CNT, the hole of particle surface increases, and Figure 17 is the nitrogen adsorption curve of above-mentioned material, in figure
SiNPs represents silicon grain, and MWCNTs represents CNT, it can be seen that CNT increase, the increase of its specific surface area.
Described above is only the preferred embodiment of the present invention, is not intended to limit the invention, it is noted that for this skill
For the those of ordinary skill in art field, without departing from the technical principles of the invention, can also make it is some improvement and
Modification, these improvement and modification also should be regarded as protection scope of the present invention.
Claims (10)
1. a kind of preparation method of combination electrode material, it is characterised in that comprise the following steps：
(1) CNT, silicon grain and water soluble organic substance are well mixed in water, obtain mixed solution, then using spray
Mist drying machine is spray-dried to the mixed solution；
(2) step (1) dried product is carbonized under protective atmosphere at 700-1000 DEG C, then mixed with sulphur powder
Afterwards, in 150-300 DEG C of heating in vacuum；
(3) product obtained in step (2) is placed in carbon matrix precursor solution and carries out the processing of surface bag carbon, obtain carbon matrix precursor bag
The silico-carbo nanometer tube composite materials covered, are then heated to 700-1000 DEG C by it under protective atmosphere, except desulfuration and to make before carbon
Body carbonization is driven, the combination electrode material is obtained.
2. the preparation method of combination electrode material according to claim 1, it is characterised in that：In step (1), the silicon
The particle diameter of particle is 50nm-1 μm.
3. the preparation method of combination electrode material according to claim 1, it is characterised in that：In step (1), the water
Soluble organism is polyvinylpyrrolidone, glucose or sucrose.
4. the preparation method of combination electrode material according to claim 1, it is characterised in that：In step (1), the carbon
The mass ratio of nanotube, silicon grain and water soluble organic substance is 1-8:1:1-20.
5. the preparation method of combination electrode material according to claim 1, it is characterised in that：In step (1), spraying is dry
Spray rate when dry is 5-15mL/min.
6. the preparation method of combination electrode material according to claim 1, it is characterised in that：In step (1), spraying is dry
The inlet temperature of dry machine is 120-160 DEG C, and outlet temperature is 70-90 DEG C.
7. the preparation method of combination electrode material according to claim 1, it is characterised in that：In step (2) and step (3)
In, protective atmosphere is the one or more in nitrogen, helium and argon gas.
8. the preparation method of combination electrode material according to claim 1, it is characterised in that：In step (2), the sulphur
Mass ratio with the silicon grain in step (1) is 1-4:1.
9. the combination electrode material prepared by a kind of method according to any one of claim 1-8, it is characterised in that：Institute
Stating combination electrode material includes internal layer and the carbon outer layer for being coated on the internal layer surface, and the internal layer includes silicon grain and carbon nanometer
Pipe, the particle diameter of the combination electrode material is 1-20 μm.
10. the combination electrode material prepared by the method any one of claim 1-8 is in lithium ion battery is prepared
Application.
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Cited By (2)
| Publication number | Priority date | Publication date | Assignee | Title |
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| CN108039465A (en) * | 2017-12-01 | 2018-05-15 | 西安交通大学苏州研究院 | Combination electrode material and its preparation method and application |
| CN109473665A (en) * | 2018-11-23 | 2019-03-15 | 浙江众泰汽车制造有限公司 | A kind of nano silica-base material and its preparation method and application |
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| CN108039465A (en) * | 2017-12-01 | 2018-05-15 | 西安交通大学苏州研究院 | Combination electrode material and its preparation method and application |
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| CN109473665A (en) * | 2018-11-23 | 2019-03-15 | 浙江众泰汽车制造有限公司 | A kind of nano silica-base material and its preparation method and application |
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Application publication date: 20170905 |