CN108511719A - A kind of bivalve layer structural composite material, preparation method and the lithium ion battery comprising the composite material - Google Patents
A kind of bivalve layer structural composite material, preparation method and the lithium ion battery comprising the composite material Download PDFInfo
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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
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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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- 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
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- H01M4/624—Electric conductive fillers
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- H01M4/02—Electrodes composed of, or comprising, active material
- H01M4/62—Selection of inactive substances as ingredients for active masses, e.g. binders, fillers
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- H01M4/02—Electrodes composed of, or comprising, active material
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Abstract
The invention discloses a kind of bivalve layer structural composite material, preparation method and include the lithium ion battery of the composite material.Bivalve layer structural composite material includes nano-silicon kernel, and the core surface is equipped with the first clad and the second clad successively, and first clad is the nano-metal particle for being embedded in the core surface, and there are holes between nano-metal particle；Second clad is the outermost carbon coating layer of composite material.The present invention first coats one layer of metal hydroxides in silicon nanoparticle surface in situ, organic carbon coating is carried out to its surface again, while high temperature cabonization clad organic carbon, the metal hydroxides of first clad is decomposed into metal oxide first, nano metal simple substance particle is then reduced to by the carbon coating layer of the second clad, a large amount of hole is left, bivalve layer structural composite material is obtained.Present invention process is simple, when which is used for negative electrode of lithium ion battery, has very high specific capacity and excellent cycle performance.
Description
Technical field
The invention belongs to lithium ion battery negative material field, it is related to a kind of bivalve layer structural composite material, its preparation side
Method and the lithium ion battery comprising the composite material more particularly to a kind of double shell structurre silicon/Nanometer Copper/carbon compound cathode materials
Material, preparation method and the lithium ion battery comprising the composite negative pole material.
Background technology
Currently, commercialized ion secondary battery cathode material lithium is mostly that natural graphite, artificial graphite, interphase etc. are various
Graphite type material, although graphite type material has lot of advantages, such as abundant raw material, intercalation potential are low, good cycle.However
The theoretical capacity of graphite material only has 372mA h/g, cannot be satisfied current market and increasingly increases to lithium ion battery with high energy density
The demand added, to adapt to this turn of the market, it is necessary to develop a kind of negative material of novel high-energy metric density and replace graphite-like material
Material.Silicon materials are higher (4200mA h/g) as negative material theoretical specific capacity, and de- lithium potential plateau is relatively low, be most have it is uncommon
Hope that substituting graphite becomes the ideal chose of lithium cell cathode material of new generation.But silicium cathode is adjoint during de-/embedding lithium
Larger volume expansion (up to 300%), causes silicon particle to be crushed, dusting, so that material is lost activity, ultimately cause cyclicity
The deep fades of energy；In addition, the conductivity of silicon itself is not high, high rate performance is poor.These factors constrain silicon in lithium electricity jointly
Application in the negative material of pond.
For the above problem for solving present in silicium cathode, in recent years, researcher has carried out a large amount of exploration.On the one hand：
By silicon nanoscale, such as silicon nanowires, nano silicon particles and receive-micro-structure porous silicon can alleviate its body to a certain extent
Product effect, improves the cyclical stability of material；On the other hand：By silicon and stable mechanical performance and the preferable carbon-based material of electric conductivity
It is compound, the composite materials such as silicon/graphite, silicon/carbon nanotube, silicon/mesoporous carbon, silicon/graphene are prepared, composite material is not only increased
Overall conductivity, while can be effectively relieved silicon in charge and discharge process because volume expansion caused by stress.In addition, setting
The silicon based composite material of porous structure is counted, expansion space is reserved, can further alleviate silicium cathode material in charge and discharge process
Volume expansion, improve material circulation stability.
Although the method that a large amount of document report improves silica-base material chemical property, with commercialization graphite material phase
Than using the material prepared by these methods, its volume expansion is still larger, and cycle conservation rate is poor, far can not meet commercialization
The demand of negative material.
Invention content
To overcome the shortcomings of the prior art, the purpose of the present invention is to provide a kind of bivalve layer structure composites
Material, preparation method and the lithium ion battery comprising the composite material, especially a kind of double shell structurre silicon/Nanometer Copper/carbon
Composite negative pole material, preparation method and the lithium ion battery comprising the composite negative pole material.
In order to achieve the above object, the present invention uses following technical scheme：
In a first aspect, the present invention provides a kind of bivalve layer structural composite material, the composite material includes nano-silicon kernel,
The core surface is equipped with the first clad and the second clad successively, and first clad is to be embedded in the core surface
Nano-metal particle, second clad be the outermost carbon coating layer of composite material；Wherein, first clad
There are holes between nano-metal particle.
The bivalve layer structural composite material of the present invention may be simply referred to as double-deck nucleocapsid silicon/nano metal/carbon composite.
Its kernel is nano-silicon, and core surface is inlaid with a large amount of nano-metal particles (such as copper particle), and outer layer is the carbon coating of densification
Layer, there are holes between the nano-metal particle of the first clad.The metallic particles such as copper and kernel nano-silicon and outside in the structure
Layer carbon coating layer is in close contact, and plays function served as bridge, can be alleviated nano-silicon expansion and be promoted the conductivity of material.First
Hole between the nano-metal particle of clad is further that expansion space is reserved in the expansion of nano-silicon.Therefore, which uses
With excellent chemical property when negative electrode of lithium ion battery.
It is used as currently preferred technical solution below, but not as the limitation to technical solution provided by the invention, leads to
Following preferred technical solution is crossed, can preferably reach and realize the technical purpose and advantageous effect of the present invention.
Preferably, the nano-silicon is crystalline silicon.
Preferably, the median particle diameter of the nano-silicon be 50nm~120nm, such as 50nm, 65nm, 80nm, 90nm,
100nm, 105nm, 110nm or 120nm etc..
Preferably, the nano-metal particle is any one in copper nano particles, Nano-Zinc particle or nano iron particles
Kind or at least two combination, preferably nano copper particle.
Preferably, the grain size of the nano-metal particle is in 10nm~30nm, for example, 10nm, 15nm, 18nm, 20nm,
22nm, 25nm or 30nm etc..
Preferably, the carbon coating layer is agraphitic carbon, preferably includes resin carbon, coke, carbonaceous mesophase spherules, pitch and splits
Solve in carbon, Polymeric carbon or carbon fiber any one or at least two combination.
Preferably, the thickness of the carbon coating layer be 50nm~300nm, such as 50nm, 70nm, 80nm, 100nm,
125nm, 150nm, 170nm, 180nm, 200nm, 220nm, 240nm, 260nm or 300nm etc..
As the optimal technical scheme of composite material of the present invention, between the nano-metal particle of first clad
Hole width be 10nm~30nm, such as 10nm, 15nm, 20nm, 22nm, 24nm, 28nm or 30nm etc..
Preferably, the pore volume of the hole be 0.2cc/g~0.4cc/g, such as 0.2cc/g, 0.22cc/g,
0.25cc/g, 0.28cc/g, 0.3cc/g, 0.35cc/g or 0.4cc/g etc..
Second aspect, the present invention provides the preparation method of bivalve layer structural composite material as described in relation to the first aspect, described
Method includes the following steps：
(1) solution of silicon nanoparticle is prepared；
(2) solution for using the silicon nanoparticle of step (1), in the surface clad hydroxide of silicon nanoparticle,
Presoma one is obtained after drying；
(3) organic carbon coating is carried out to the presoma one of step (2), then calcined, obtain bivalve layer structural composite material.
The present invention method first silicon nanoparticle surface coat one layer of metal hydroxides, later again to its surface into
The organic carbon coating of row, while high temperature cabonization clad organic matter, the metal hydroxides of middle layer is decomposed into copper oxide first,
Metal simple-substance nano particle (such as copper nano particles) is then reduced to by carbon coating layer, leaves a large amount of hole, to obtain
Bivalve layer structural composite material, i.e., double-deck nucleocapsid silicon/nano metal/carbon composite.
As the optimal technical scheme of the method for the invention, the solution that step (1) prepares silicon nanoparticle uses method
One or method two in any one, wherein the method one includes：In a solvent by silicon nanoparticle dispersion, ultrasonic agitation,
Obtain the solution of silicon nanoparticle.
The method two includes：Silicon nanoparticle is distributed in solvent under conditions of ultrasonic agitation, continues to stir
0.5h~3h obtains the solution of silicon nanoparticle.
The solution of silicon nanoparticle prepared by the present invention is uniform or uniform dispersity.
Preferably, the solvent in the method one and method two independently is water, ethyl alcohol, propyl alcohol, isopropanol, butanol, third
Any one in ketone, ethyl acetate or N-Methyl pyrrolidone (N-methyl-2-pyrrolidone, NMP) or at least two
Mixed solvent.
Preferably, the solvent in the method one and method two independently is the mixed solvent of water and alcohol, and molten to mix
The gross mass of agent is 100% meter, the mass percent of the alcohol is 50%~80%, such as 50%, 60%, 65%, 70%,
75% or 80% etc..
As the optimal technical scheme of the method for the invention, step (2) cladding is in-stiu coating, step (2) system
The concrete operations of standby presoma one include：The solution of water-soluble metal salt and silicon nanoparticle is mixed, pH to 2~5 is adjusted, is surpassed
Sound stirs, and aqueous slkali is then added, metal hydroxides is made to be embedded in the surface of silicon nanoparticle, stops as the pH=7 of solution
Aqueous slkali is only added, obtains presoma one.
In this optimal technical scheme, after the solution mixing of water-soluble metal salt and silicon nanoparticle, pH to 2~5, example are adjusted
Such as 2,3,4 or 5, preferably 3.It is acid, such as the hydrochloric acid of 0.5mol/L to adjust the conditioning agent that pH is used.
Preferably, during step (2) prepares presoma one, the water-soluble metal salt includes water-soluble copper salt, zinc
In salt or molysite any one or at least two combination.
Preferably, during step (2) prepares presoma one, the water-soluble metal salt and the silicon nanoparticle
The molar ratio of silicon nanoparticle in solution is 2~12, such as 2,2.3,2.5,3,4,5,6,7,8,10,11 or 12 etc., preferably
It is 10:3.
Preferably, during step (2) prepares presoma one, adjusted the time being stirred by ultrasonic after pH be 0.5h~
1h, preferably 0.5h.
Preferably, during step (2) prepares presoma one, the aqueous slkali is sodium hydroxide solution, the alkali soluble
The concentration of liquid is preferably 0.5mol/L.
Preferably, further include continuing to stir after stopping that aqueous slkali is added during step (2) prepares presoma one
0.5h and the step of filter.
As the optimal technical scheme of the method for the invention, step (3) the organic carbon method for coating is：In-situ polymerization
Any one in cladding, the hot carbon coating of situ solvent or liquid phase coating.
Preferably, in the method for in-situ polymerization cladding, polymer that in-situ polymerization coats include polyacrylic acid,
Polymerize phenolic resin or polymerize dopamine in any one or at least two combination.
Preferably, the concrete operations of in-situ polymerization cladding include：Presoma one is distributed in solvent, is then added
Reaction monomers are polymerize under the conditions of existing for oxidative initiator, and reaction monomers is made to polymerize on one surface of presoma
Reaction.For different types of reaction monomers, in order to obtain better polymerization effect, the pH value appropriate for adjusting slurry is needed,
It is the prior art, and details are not described herein again.
Preferably, in the method for the in-situ polymerization cladding, oxidative initiator is ammonium persulfate, sodium peroxydisulfate or dioxygen
In water any one or at least two combination.
Preferably, reaction monomers include in acrylic acid, aniline or DOPA amine monomers in the method for the in-situ polymerization cladding
Any one or at least two combination.
Preferably, the carbon-coated concrete operations of situ solvent heat include：Presoma one is distributed in solvent, then
Carbon source is added and forms slurry, obtained slurry is positioned over reaction a period of time in solvent thermal reaction kettle.
Preferably, in the carbon-coated method of the situ solvent heat, carbon source is any one in glucose sugar, sucrose or pitch
Kind or at least two combination.
Preferably, in the carbon-coated method of the situ solvent heat, the mass ratio of presoma one and carbon source is 1:(0.5~
, such as 1 2):0.5、1:0.8、1:1、1:1.5、1:1.7 or 1:2 etc., preferably 1:2.
Preferably, in the carbon-coated method of the situ solvent heat, carbon source is added and is stirred later, it is uniform to be formed
Slurry.
Preferably, in the carbon-coated method of the situ solvent heat, reaction temperature temperature is 100 DEG C~180 DEG C, such as
100 DEG C, 120 DEG C, 125 DEG C, 135 DEG C, 150 DEG C, 160 DEG C or 180 DEG C etc..
Preferably, in the carbon-coated method of situ solvent heat, the reaction time is 2h~10h, for example, 2h, 3h, 5h,
6h, 7h, 8h, 9h or 10h etc..
Preferably, the concrete operations of the liquid phase coating include：Presoma one is distributed in solvent, carbon source is then added
Slurry is formed, then is spray-dried；
Preferably, in the method for the liquid phase coating, solvent be deionized water, ethyl alcohol or isopropanol in any one or
At least two combination.
Preferably, in the method for the liquid phase coating, carbon source be in glucose sugar, sucrose or pitch any one or at least
Two kinds of combination.
Preferably, in the method for the liquid phase coating, the mass ratio of presoma one and carbon source is 1:(0.5~2), such as 1:
0.5、1:0.8、1:1、1:1.5、1:1.7 or 1:2 etc., preferably 1:2；
Preferably, in the method for the liquid phase coating, carbon source is added and is stirred later, to form uniform slurry.
Preferably, step (3) calcining carries out under protective gas protection.
Preferably, the protective gas include in nitrogen, helium, neon, argon gas or xenon any one or at least
Two kinds of combination.
Preferably, the temperature of step (3) described calcining be 600 DEG C~1000 DEG C, such as 600 DEG C, 650 DEG C, 700 DEG C, 800
DEG C, 850 DEG C, 900 DEG C or 1000 DEG C etc..
Preferably, the time of step (3) described calcining is 1h~6h, such as 1h, 2h, 3h, 3.5h, 4h, 5h or 6h etc..
As the further preferred technical solution of the method for the invention, the described method comprises the following steps：
(1) silicon nanoparticle that median particle diameter is 50nm~120nm is dispersed in the in the mixed solvent of water and alcohol, ultrasound is stirred
It mixes, obtains the solution of evenly dispersed silicon nanoparticle；
(2) by the solution of the aqueous solution of mantoquita and silicon nanoparticle, pH to 3 is adjusted, 0.5h is stirred by ultrasonic, is then added
The sodium hydroxide solution of 0.5mol/L makes Kocide SD be coated on the surface of silicon nanoparticle, stops adding as the pH=7 of solution
Enter sodium hydroxide solution, continues to stir 0.5h, filtering is dried to obtain presoma one；
(3) in-situ polymerization cladding is carried out to the presoma one of step (2), then 600 DEG C under the protection of protective gas
~1000 DEG C of calcining 1h~6h obtain bivalve layer structural composite material；
Wherein, the polymer that the in-situ polymerization coats is polyacrylic acid, polymerization phenolic resin or polymerization dopamine
In any one or at least two combination.
The third aspect, the present invention provide a kind of lithium ion battery electrode material, and the lithium ion battery electrode material is the
Bivalve layer structural composite material described in one side.
Preferably, the electrode material is negative material.
Compared with the prior art, the present invention has the advantages that：
(1) method of the invention coats one layer of metal hydroxides on silicon nanoparticle surface first, later again to its table
Face carries out organic carbon coating, and while high temperature cabonization clad organic carbon, the metal hydroxides of the first clad decomposes first
For metal oxide, nano metal simple substance particle (such as Nanometer Copper is then reduced to by the carbon coating layer of the second clad
Grain), a large amount of hole is left, to obtain bivalve layer structural composite material, i.e., double-deck nucleocapsid silicon/nano metal/carbon is multiple
Condensation material.
(2) method and process of the invention is simple, easy to operate, is suitble to industrialized production.
(3) bivalve of the invention layer structural composite material structure novel, kernel are nano-silicon, and the first clad is to inlay
In a large amount of nano-metal particles (such as copper particle) of core surface, the second clad is the carbon coating layer of densification, the first cladding
There are holes between the nano-metal particle of layer.The metallic particles such as copper and kernel nano-silicon and the second clad carbon packet in the structure
Coating is in close contact, and plays function served as bridge, can be alleviated nano-silicon expansion and be promoted the conductivity of material.First clad
Nano-metal particle between hole further be nano-silicon expansion reserve expansion space.Therefore, which has very high
Specific capacity and excellent cycle performance：0.1C discharge capacities are more than 1600mA h/g, and first charge-discharge efficiency is more than 89%, 50
Capacity is maintained at 95% or more after secondary cycle.
Description of the drawings
Fig. 1 a are the structural schematic diagram of sample prepared by the embodiment of the present invention 1, wherein 1- Nanometer Coppers, 2- nano-silicons, the holes 3-
Gap, 4- carbon coating layers.
Fig. 1 b are the SEM figures of sample prepared by the embodiment of the present invention 1.
Fig. 2 is the XRD diagram of sample prepared by the embodiment of the present invention 1.
Fig. 3 is all charging and discharging curves of head that battery made of cathode is used for using sample prepared by the embodiment of the present invention 1.
Fig. 4 is the cyclic curve that battery made of cathode is used for using sample prepared by the embodiment of the present invention 1.
Specific implementation mode
Technical solution to further illustrate the present invention below with reference to the accompanying drawings and specific embodiments.
The negative material of each embodiment and comparative example is tested using following methods：
1. grain size of the present invention using 2000 test material particle size ranges of Malvern laser particle analyzer MS and
The average grain diameter of feed particles.
2. using the structure of X-ray diffractometer X ' Pert Pro, PANalytical test materials.
3. being cut using surface topography, granular size and the particle of Hitachi, Ltd's S4800 scanning electron microscope observation sample
Face.
4. testing charge-discharge property using following methods：
By the negative material of each embodiment and comparative example, conductive agent and binder by mass percentage 80:10:10 are dissolved in
It is mixed in solvent, obtained mixed slurry is coated in copper foil current collector, and cathode pole piece is made in vacuum drying；Then by 1mol/
LiPF6/EC+DMC+EMC (the v/v=1 of L:1:1) electrolyte, SK (12 μm) diaphragm, shell assemble CR2016 using common process
Button cell, electrochemical property test current density 1C are equal to 1000mA h/g.
Embodiment 1
(1) nano-silicon that median particle diameter is 100nm is scattered in the in the mixed solvent of ethyl alcohol and deionized water, ethyl alcohol and gone
The mass ratio of ionized water is 8:2,1h is stirred by ultrasonic, obtains presoma suspension A.
(2) it is 10 to be added into presoma suspension A under stirring condition with nanometer silicon mol ratio:3 copper sulphate solid, it
The hydrochloric acid solution that 0.5mol/L is added dropwise in the backward solution adjusts the PH=3 of solution, is stirred by ultrasonic after 0.5h to continuation thereto
The sodium hydroxide solution of 0.5mol/L is slowly added dropwise, copper particle is made to be changed into Kocide SD and is uniformly wrapped on silicon nanoparticle
Surface stops that sodium hydroxide solution is added dropwise as the PH=7 of solution, continues to filter after stirring 0.5h, presoma is obtained after dry
One.
(3) presoma one that step (2) obtains is scattered in deionized water, is added and one mass ratio of presoma thereto
It is 1:2 glucose sugar, is spray-dried it after stirring 0.5h, by 850 DEG C under an inert gas of the product after spray drying
It is burnt into 2h, the sample sifter after firing is got into double-deck nucleocapsid silicon/Nanometer Copper/carbon composite, to the negative material sample
Product are detected, and the results are shown in Table 1.
Fig. 1 a are the structural schematic diagram of sample prepared by the present embodiment 1, wherein 1- Nanometer Coppers, 2- nano-silicons, and 3- holes,
4- carbon coating layers.
Fig. 1 b are the SEM figures of sample prepared by the present embodiment 1, and as seen from the figure, sample surfaces have coated one layer of densification
Carbon-coating.
Fig. 2 is the XRD diagram that the present embodiment 1 prepares sample, and the diffraction maximum of apparent silicon, copper and carbon can be observed from figure.
Fig. 3 is all charging and discharging curves of head that battery made of cathode is used for using sample prepared by the present embodiment 1, from charge and discharge
Electric curve is it is found that the material initial charge capacity is 1605mA h/g, and coulombic efficiency is 89% for the first time.
Fig. 4 is the cyclic curve that battery made of cathode is used for using sample prepared by the present embodiment 1, which exists
Capacity retention ratio is 95.6% after 50 cycles under the current density of 1C, and the surface material has excellent stable circulation
Property.
Embodiment 2
(1) nano-silicon that median particle diameter is 100nm is scattered in the in the mixed solvent of ethyl alcohol and deionized water, ethyl alcohol and gone
The mass ratio of ionized water is 8:3,1h is stirred by ultrasonic, obtains presoma suspension A.
(2) it is 10 to be added into presoma suspension A under stirring condition with nanometer silicon mol ratio:3 copper chloride solid, it
The hydrochloric acid solution that 0.5mol/L is added dropwise in the backward solution adjusts the PH=3 of solution, continues to delay thereto after 0.5h is stirred by ultrasonic
The slow sodium hydroxide solution that 0.5mol/L is added dropwise, makes copper particle be changed into Kocide SD and is uniformly wrapped on the table of silicon nanoparticle
Face stops that sodium hydroxide solution is added dropwise as the PH=7 of solution, continues to filter after stirring 0.5h, presoma one is obtained after dry.
(3) presoma one that step (2) obtains is scattered in deionized water, it is 1 that mass ratio is added thereto:2.5
Aniline monomer, the hydrochloric acid solution that a concentration of 0.5Mol/L is added dropwise thereto adjust its PH to 5 or so, are added and aniline quality later
Than being 5:3 ammonium persulfate powder stirs filtration drying after 8h, the obtained presoma after drying is warming up to 900 DEG C, heat preservation
2h, cooled to room temperature, screening obtain double-deck nucleocapsid silicon/Nanometer Copper/carbon composite, to the negative electrode material sample into
Row detection, the results are shown in Table 1.
Embodiment 3
(1) nano-silicon that median particle diameter is 100nm is scattered in ethyl alcohol/deionized water in the mixed solvent, ethyl alcohol and go from
The mass ratio of sub- water is 1:1,1h is stirred by ultrasonic, obtains presoma suspension A.
(2) it is 10 to be added into presoma suspension A under stirring condition with nanometer silicon mol ratio:3 copper chloride solid, it
The hydrochloric acid solution that 0.5mol/L is added dropwise in the backward solution adjusts the PH=3 of solution, continues to delay thereto after 0.5h is stirred by ultrasonic
The slow sodium hydroxide solution that 0.5mol/L is added dropwise, makes copper particle be changed into Kocide SD and is uniformly wrapped on the table of silicon nanoparticle
Face stops that sodium hydroxide solution is added dropwise as the PH=7 of solution, continues to filter after stirring 0.5h, presoma one is obtained after dry.
(3) presoma one for obtaining step (2) and pitch in mass ratio 55:45 ratio is dispersed in butanol solution
In, it is spray-dried after stirring 30min, it is 10 μm of presomas two to obtain median particle diameter.Then obtained presoma two is put
It is placed in batch-type furnace, is passed through nitrogen, be warming up to 850.0 DEG C with 3.0 DEG C/min heating rates, keep the temperature 2.0h, naturally cool to room
Temperature, screening obtain double-deck nucleocapsid silicon/Nanometer Copper/carbon composite, are detected, the results are shown in Table to the negative electrode material sample
1。
Embodiment 4
In addition to the following contents, other preparation methods and condition are same as Example 1：
The median particle diameter of step (1) nano-silicon is 50nm, and the time of ultrasonic agitation is 0.5h；
The pH=4 of hydrochloric acid conditioning solution is added dropwise in step (2)；
Step (3) is burnt into 6h for 650 DEG C under an inert gas.
Embodiment 5
In addition to step (3), other preparation methods and condition are same as Example 1：
The concrete operations of step (3) are：The presoma one that step (2) is obtained and glucose in mass ratio 50:100 ratio
Example is dispersed in deionized water solution, be placed on 180 DEG C of reaction 6h in hydrothermal reaction kettle after stirring 30min, is waited for it
It is 8 μm of presomas two that filtration drying, which obtains median particle diameter, after natural cooling.Then obtained presoma two is positioned over batch-type furnace
In, it is passed through nitrogen, 750.0 DEG C are warming up to 3.0 DEG C/min heating rates, keeps the temperature 2.0h, cooled to room temperature, screening obtains
Double-deck nucleocapsid silicon/Nanometer Copper/carbon composite.
Embodiment 6
In addition to copper chloride is replaced with zinc chloride, other preparation methods and condition are same as Example 1.
Comparative example 1
(1) nano-silicon that median particle diameter is 100nm is scattered in ethyl alcohol/deionized water (mass ratio 1:1) mixed solvent
In, 1h is stirred by ultrasonic, obtains presoma suspension A.
(2) it is 1 that the drive body suspension A for obtaining step 1, which is added thereto under agitation with nano-silicon mass ratio,:2
Glucose sugar, stir 0.5h after it is spray-dried, by the product after spray drying under an inert gas 850 DEG C firing
Sample sifter after firing is got nucleocapsid silicon/carbon composite, is detected to the negative electrode material sample, as a result by 2h
It is shown in Table 1.
Table 1
By finding out known to each embodiment and comparative example, double-deck nucleocapsid silicon/nanometer of various embodiments of the present invention preparation
Metal/carbon composite material has excellent chemical property, and in the negative material of comparative example, nanogold is not present in core surface
Metal particles, also without gap between nucleocapsid, coulombic efficiency and poor circulation for the first time.
Applicant states that the present invention illustrates the method detailed of the present invention, but the present invention not office by above-described embodiment
It is limited to above-mentioned method detailed, that is, does not mean that the present invention has to rely on above-mentioned method detailed and could implement.Technical field
Technical staff it will be clearly understood that any improvement in the present invention, equivalence replacement and auxiliary element to each raw material of product of the present invention
Addition, the selection etc. of concrete mode, all fall within protection scope of the present invention and the open scope.
Claims (10)
1. a kind of bivalve layer structural composite material, which is characterized in that the composite material includes nano-silicon kernel, the kernel table
Face is equipped with the first clad and the second clad successively, and first clad is the nano metal for being embedded in the core surface
Particle, second clad are the outermost carbon coating layer of composite material；
Wherein, there are holes between the nano-metal particle of first clad.
2. composite material according to claim 1, which is characterized in that the nano-silicon is crystalline silicon；
Preferably, the median particle diameter of the nano-silicon is 50nm~120nm；
Preferably, the nano-metal particle be nano copper particle, Nano-Zinc particle or nano iron particles in any one or
At least two combination, preferably nano copper particle；
Preferably, the grain size of the nano-metal particle is in 10nm~30nm；
Preferably, the carbon coating layer is agraphitic carbon, preferably includes resin carbon, coke, carbonaceous mesophase spherules, pitch cracking
In carbon, Polymeric carbon or carbon fiber any one or at least two combination；
Preferably, thickness 50nm~300nm of the carbon coating layer.
3. composite material according to claim 1 or 2, which is characterized in that the width of the hole is 10nm~30nm；
Preferably, the pore volume of the hole is 0.2cc/g~0.4cc/g.
4. the preparation method of layer structural composite material in bivalve as described in any one of claims 1-3, which is characterized in that the side
Method includes the following steps：
(1) solution of silicon nanoparticle is prepared；
(2) solution for using the silicon nanoparticle of step (1), it is dry in the surface clad hydroxide of silicon nanoparticle
After obtain presoma one；
(3) organic carbon coating is carried out to the presoma one of step (2), then calcined, obtain bivalve layer structural composite material.
5. according to the method described in claim 4, it is characterized in that, the solution that step (1) prepares silicon nanoparticle uses method
One or method two in any one, wherein the method one includes：In a solvent by silicon nanoparticle dispersion, ultrasonic agitation,
Obtain the solution of silicon nanoparticle；
The method two includes：Silicon nanoparticle is distributed in solvent under conditions of ultrasonic agitation, continue stir 0.5h~
3h obtains the solution of silicon nanoparticle；
Preferably, the solvent in the method one and method two independently is water, ethyl alcohol, propyl alcohol, isopropanol, butanol, acetone, second
In acetoacetic ester or N-Methyl pyrrolidone any one or at least two mixed solvent；
Preferably, the solvent in the method one and method two independently is the mixed solvent of water and alcohol, and with mixed solvent
Gross mass is 100% meter, and the mass percent of the alcohol is 50%~80%.
6. method according to claim 4 or 5, which is characterized in that step (2) cladding is in-stiu coating, step (2)
The concrete operations for preparing presoma one include：The solution of water-soluble metal salt and silicon nanoparticle is mixed, pH to 2~5 is adjusted,
Ultrasonic agitation, is then added aqueous slkali, metal hydroxides is made to be embedded in the surface of silicon nanoparticle, as the pH=7 of solution
Stop that aqueous slkali is added, obtains presoma one；
Preferably, during step (2) prepares presoma one, the water-soluble metal salt include water-soluble copper salt, zinc salt or
In molysite any one or at least two combination；
Preferably, during step (2) prepares presoma one, in the solution of the water-soluble metal salt and silicon nanoparticle
The molar ratio of silicon nanoparticle is 2~12, preferably 10:3；
Preferably, during step (2) prepares presoma one, using acid for adjusting pH；
Preferably, during step (2) prepares presoma one, pH to 3 is adjusted；
Preferably, during step (2) prepares presoma one, it is 0.5h~1h to have adjusted the time being stirred by ultrasonic after pH,
Preferably 0.5h；
Preferably, during step (2) prepares presoma one, the aqueous slkali is sodium hydroxide solution, the aqueous slkali
Concentration is preferably 0.5mol/L；
Preferably, further include continuing to stir 0.5h after stopping that aqueous slkali is added during step (2) prepares presoma one
And the step of filtering.
7. according to claim 4-6 any one of them methods, which is characterized in that step (3) the organic carbon method for coating is：
Any one in in-situ polymerization cladding, the hot carbon coating of situ solvent or liquid phase coating；
Preferably, in the method for the in-situ polymerization cladding, the polymer that in-situ polymerization coats includes polyacrylic acid, polyphenyl
Amine, polymerization phenolic resin or polymerize dopamine in any one or at least two combination；
Preferably, the concrete operations of in-situ polymerization cladding include：Presoma one is distributed in solvent, reaction is then added
Monomer is polymerize under the conditions of existing for oxidative initiator, makes reaction monomers that polymerisation occur on one surface of presoma；
Preferably, in the method for the in-situ polymerization cladding, oxidative initiator is in ammonium persulfate, sodium peroxydisulfate or hydrogen peroxide
Any one or at least two combination；
Preferably, in the method for the in-situ polymerization cladding, reaction monomers include appointing in acrylic acid, aniline or DOPA amine monomers
It anticipates a kind of or at least two combinations；
Preferably, the carbon-coated concrete operations of situ solvent heat include：Presoma one is distributed in solvent, is then added
Carbon source forms slurry, and obtained slurry is positioned in solvent thermal reaction kettle and is reacted；
Preferably, in the carbon-coated method of situ solvent heat, carbon source be in glucose sugar, sucrose or pitch any one or
At least two combination；
Preferably, in the carbon-coated method of the situ solvent heat, the mass ratio of presoma one and carbon source is 1:(0.5~2), it is excellent
It is selected as 1:2；
Preferably, in the carbon-coated method of the situ solvent heat, carbon source is added and is stirred later, to form uniform slurry
Material；
Preferably, in the carbon-coated method of the situ solvent heat, reaction temperature is 100 DEG C~180 DEG C；
Preferably, in the carbon-coated method of the situ solvent heat, the reaction time is 2h~10h；
Preferably, the concrete operations of the liquid phase coating include：Presoma one is distributed in solvent, carbon source is then added and is formed
Slurry, then be spray-dried；
Preferably, in the method for the liquid phase coating, solvent be deionized water, ethyl alcohol or isopropanol in any one or at least
Two kinds of combination；
Preferably, in the method for the liquid phase coating, carbon source is any one or at least two in glucose sugar, sucrose or pitch
Combination；
Preferably, in the method for the liquid phase coating, the mass ratio of presoma one and carbon source is 1:(0.5~2), preferably 1:2；
Preferably, in the method for the liquid phase coating, carbon source is added and is stirred later, to form uniform slurry.
8. according to claim 4-7 any one of them methods, which is characterized in that step (3) calcining is in protective gas
Protection is lower to be carried out；
Preferably, the protective gas includes any one in nitrogen, helium, neon, argon gas or xenon or at least two
Combination；
Preferably, the temperature of step (3) described calcining is 600 DEG C~1000 DEG C；
Preferably, the time of step (3) described calcining is 1h~6h.
9. according to claim 4-8 any one of them methods, which is characterized in that the described method comprises the following steps：
(1) silicon nanoparticle that median particle diameter is 50nm~120nm is dispersed in the in the mixed solvent of water and alcohol, is stirred by ultrasonic,
Obtain the solution of evenly dispersed silicon nanoparticle；
(2) by the solution of the aqueous solution of mantoquita and silicon nanoparticle, pH to 3 is adjusted, 0.5h is stirred by ultrasonic, is then added
The sodium hydroxide solution of 0.5mol/L makes Kocide SD be coated on the surface of silicon nanoparticle, stops adding as the pH=7 of solution
Enter sodium hydroxide solution, continues to stir 0.5h, filtering obtains presoma one after dry；
(3) to the presoma one of step (2) carry out in-situ polymerization cladding, then 600 DEG C under the protection of protective gas~
1000 DEG C of calcining 1h~6h obtain bivalve layer structural composite material；
Wherein, the polymer that the in-situ polymerization coats is in polyacrylic acid, polymerization phenolic resin or polymerization dopamine
Any one or at least two combination.
10. a kind of lithium ion battery electrode material, which is characterized in that the lithium ion battery electrode material is claim 1-3
Any one of them bivalve layer structural composite material；
Preferably, the electrode material is negative material.
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