CN108767220A - Si-C composite material and preparation method, cell negative electrode material and battery - Google Patents
Si-C composite material and preparation method, cell negative electrode material and battery Download PDFInfo
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- CN108767220A CN108767220A CN201810510703.7A CN201810510703A CN108767220A CN 108767220 A CN108767220 A CN 108767220A CN 201810510703 A CN201810510703 A CN 201810510703A CN 108767220 A CN108767220 A CN 108767220A
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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
- H01M4/36—Selection of substances as active materials, active masses, active liquids
- H01M4/58—Selection of substances as active materials, active masses, active liquids of inorganic compounds other than oxides or hydroxides, e.g. sulfides, selenides, tellurides, halogenides or LiCoFy; of polyanionic structures, e.g. phosphates, silicates or borates
- H01M4/583—Carbonaceous material, e.g. graphite-intercalation compounds or CFx
- H01M4/587—Carbonaceous material, e.g. graphite-intercalation compounds or CFx for inserting or intercalating light metals
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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 provides a kind of Si-C composite material and preparation method, cell negative electrode material and batteries, it is related to battery technology field, Si-C composite material is hollow microsphere structure, including shell and cavity, shell coats cavity, shell is mainly combined by silicon and carbon, and the outer diameter of shell is 1-10 μm, and the internal diameter of shell is 0.1-5 μm, the wall thickness of shell is 0.1-3 μm, the technical issues of alleviating elemental silicon poorly conductive, and there are larger volume variation in charge and discharge process, leading to poor circulation.Si-C composite material provided by the invention can not only provide space by cavity for the volume change that silicon generates in charge and discharge process, to which silicon volume expansion and structure collapses problem in charge and discharge process be effectively relieved, the cyclical stability and battery capacity of battery are improved；And can also be acted synergistically by silicon-carbon, improve the electric conductivity of composite material.
Description
Technical field
The present invention relates to battery technology field more particularly to a kind of Si-C composite material and preparation method, battery cathode materials
Material and battery.
Background technology
Lithium ion battery negative material in current practice is still based on traditional graphite material, actual specific capacity
It has been difficult to be promoted capacity is further already close to the theoretical value of its 372mAh/g.
Further to promote the energy density of lithium ion battery, meets growing power battery demand, develop new
Negative material system is imperative.Elemental silicon has very high specific capacity (4200mAh/g) and moderate voltage platform (0.4V
vs Li/Li+), specific capacity is almost ten times of the theoretical specific capacity of natural graphite or more, has preferable application prospect
Negative material, it has also become the hot spot of current research.
But elemental silicon poorly conductive, and there are larger volume changes in charge and discharge process, and material is caused to be easy knot
Structure caves in, dusting and then falls off from collector so that the specific capacity sharp-decay during charge and discharge cycles.
In view of this, special propose the present invention.
Invention content
One of the objects of the present invention is to provide a kind of Si-C composite materials, to alleviate elemental silicon poorly conductive, and are filling
There are larger volume changes in discharge process, cause material to be easy structure collapses, dusting and then fall off from collector so that
The technical issues of specific capacity sharp-decay during charge and discharge cycles.
Si-C composite material provided by the invention, the Si-C composite material are hollow microsphere structure, the tiny balloon
Including shell and cavity, the shell coats the cavity, and the shell includes silicon and carbon.
Further, the outer diameter of the shell is 1-10 μm, and the internal diameter of the shell is 0.1-5 μm, the wall of the shell
Thickness is 0.1-3 μm.
Further, silicone content is 30-90wt% in the shell.
The second object of the present invention is to provide a kind of preparation method of Si-C composite material, include the following steps：
(a) SiO is provided2The solution of colloidal sol and monomer containing C element, and form it into containing SiO2With the reality of polymer
Heart microballoon；
(b) solid microsphere is sintered, obtains the SiO with cavity2/ C microballoons；
(c) by SiO2/ C microballoons are reduced to the Si-C composite material with hollow microsphere structure, wherein the tiny balloon
Including shell and cavity, the shell coats the cavity, and the shell includes silicon and carbon.
Further, the polymer is copolymer, and the monomer includes the first monomer and second comonomer, wherein
In step (a), first by SiO2Then colloidal dispersion is added second comonomer and is total in the first monomer solution
It is poly-, it obtains containing SiO2With the solid microsphere of polymer, wherein contain C element in the first monomer and/or second comonomer；
Preferably, first monomer in urea, melamine, phenol, resorcinol and 3- amino-phenols extremely
Few one kind；And/or
Preferably, the second comonomer is selected from least one of the low-carbon aldehyde of C1-C6；
Further, in step (b), when being sintered, the first heating rate with 2-5 DEG C/min is by temperature by room temperature liter
Then temperature is warming up to 330-380 DEG C to 180-220 DEG C with the heating rate of 0.5-1 DEG C/min, so again with the liter of 2-5 DEG C/min
Warm rate is warming up to 700-800 DEG C and keeps the temperature 6-10 hours.
Further, in step (c), SiO is restored using reducing agent2/ C microballoons；
Preferably, reducing agent is magnesium, iron, copper or manganese.
The third object of the present invention is to provide a kind of cell negative electrode material, including silicon-carbon composite wood provided by the invention
Material.
The fourth object of the present invention is to provide a kind of battery, including Si-C composite material provided by the invention or the present invention
The cell negative electrode material of offer.
For Si-C composite material provided by the invention by being arranged to internal be cavity, cavity outer cladding includes the outer of silicon and carbon
The hollow microsphere structure of shell can not only provide space by cavity for the volume change that silicon generates in charge and discharge process, from
And silicon volume expansion and structure collapses problem in charge and discharge process is effectively relieved, the cyclical stability and battery for improving battery hold
Amount；And can also be acted synergistically by silicon-carbon, improve the electric conductivity of composite material.
The preparation method of Si-C composite material provided by the invention is mutually tied using polymerisation induced colloid aggregation with sintering schedule
It closes, prepares the Si-C composite material with hollow microsphere structure, it is simple for process, it is easy to operate, it is big raw that industrialization can be suitable for
Production improves production efficiency.
Cell negative electrode material provided by the invention using Si-C composite material provided by the invention as negative electrode active material,
Effectively increase the cyclical stability and battery capacity of battery.
Battery provided by the invention, using Si-C composite material provided by the invention as negative electrode active material or using this
The cell negative electrode material provided is invented as negative material, effectively increases the cyclical stability and battery capacity of battery.
Description of the drawings
It, below will be to specific in order to illustrate more clearly of the specific embodiment of the invention or technical solution in the prior art
Embodiment or attached drawing needed to be used in the description of the prior art are briefly described, it should be apparent that, in being described below
Attached drawing is some embodiments of the present invention, for those of ordinary skill in the art, before not making the creative labor
It puts, other drawings may also be obtained based on these drawings.
Fig. 1 is the SEM figures for the Si-C composite material that the embodiment of the present invention 3 provides；
Fig. 2 is SEM figure of the Si-C composite material shown in Fig. 1 after focused ion beam (FIB) incision；
Fig. 3 is the battery that provides of embodiment 19 first charge-discharge curve at 0.1C；
Fig. 4 is the test song that the battery that embodiment 19 and comparative example 5 provide carries out 300 circle loop tests at 0.1C respectively
Line chart.
Specific implementation mode
Technical scheme of the present invention is clearly and completely described below in conjunction with attached drawing, it is clear that described implementation
Example is a part of the embodiment of the present invention, instead of all the embodiments.Based on the embodiments of the present invention, ordinary skill
The every other embodiment that personnel are obtained without making creative work, shall fall within the protection scope of the present invention.
According to the first aspect of the invention, the present invention provides a kind of Si-C composite material, the Si-C composite materials
For hollow microsphere structure, the tiny balloon includes shell and cavity, and the shell coats the cavity, and the shell includes silicon
And carbon.
For Si-C composite material provided by the invention by being arranged to internal be cavity, cavity is coated with the shell of silicon and carbon
Hollow microsphere structure, space can not only be provided by cavity for the volume change that silicon generates in charge and discharge process, to
Silicon volume expansion and structure collapses problem in charge and discharge process is effectively relieved, the cyclical stability and battery for improving battery hold
Amount；And can also be acted synergistically by silicon-carbon, improve electric conductivity.
In the preferred embodiment of the present invention, the outer diameter of the shell is 1-10 μm, and the internal diameter of the shell is
0.1-5 μm, the wall thickness of the shell is 0.1-3 μm.
In the present invention, the typical but non-limiting outer diameter of shell as 1,1.5,2,2.5,3,3.5,4,4.5,5,
5.5,6,6.5,7,7.5,8,8.5,9,9.5 or 10 μm.
The typical but non-limiting internal diameter of shell be 0.1,0.2,0.3,0.4,0.5,0.6,0.7,0.8,0.9,1,
1.2,1.5,1.8,2,2.5,3,3.5,4,4.5 or 5 μm.
The wall thickness of shell as 0.1,0.2,0.3,0.4,0.5,0.6,0.7,0.8,0.9,1,1.2,1.5,1.8,2,
2.2,2.5,2.8 or 3 μm.
In the preferred embodiment of the present invention, silicone content is 30-90wt% in shell.
The present invention typical but non-limiting embodiment in, in shell silicone content as 30wt%, 32wt%,
35wt%, 38wt%, 40wt%, 42wt%, 45wt%, 48wt%, 50wt%, 52wt%, 55wt%, 58wt%, 60wt%,
62wt%, 65wt%, 68wt%, 70wt%, 72wt%, 75wt%, 78wt%, 80wt%, 82wt%, 85wt%, 88wt%
Or 90wt%.
It is demonstrated experimentally that when silicone content is less than 30wt% in shell, the energy density of battery is too low, when silicone content in shell
When more than 90%, it is difficult to form good tiny balloon.
According to the second aspect of the invention, the present invention provides a kind of preparation methods of Si-C composite material, including such as
Lower step：
(a) SiO is provided2The solution of colloidal sol and monomer containing C element, and form it into containing SiO2With the reality of polymer
Heart microballoon；
(b) solid microsphere is sintered, obtains the SiO with cavity2/ C microballoons；
(c) by SiO2/ C microballoons are reduced to the Si-C composite material with cavity, wherein the tiny balloon includes shell
And cavity, the shell coat the cavity, the shell includes silicon and carbon.
The preparation method of Si-C composite material provided by the invention is mutually tied using polymerisation induced colloid aggregation with sintering schedule
It closes, prepares the Si-C composite material with hollow microsphere structure, it is simple for process, it is easy to operate, it is big raw that industrialization can be suitable for
Production improves production efficiency.
The Si-C composite material that the preparation method of the Si-C composite material provided through the invention is prepared, can not only
Space is provided for the volume change that silicon generates in charge and discharge process by cavity, and can also be acted synergistically by silicon-carbon, is carried
High conduction performance improves the cycle of battery to which silicon volume expansion and structure collapses problem in charge and discharge process be effectively relieved
Stability and battery capacity.
In the preferred embodiment of the present invention, polymer is copolymer, and monomer includes that single monomer and second are single
Body, wherein
In step (a), first by SiO2Then colloidal dispersion is added second comonomer and is total in the first monomer solution
It is poly-, it obtains containing SiO2With the solid microsphere of polymer, wherein contain C element in the first monomer and/or second comonomer.
By first by SiO2Colloidal dispersion adds second comonomer and is copolymerized in the first monomer solution, so that SiO2
Inside the polymer microballoon that colloidal sol is evenly distributed on the first monomer and second comonomer polymerization generates.
In the preferred embodiment of the present invention, the first monomer is selected from urea, melamine, phenol, resorcinol
At least one of with 3- amino-phenols.
In the preferred embodiment of the present invention, second comonomer is selected from least one of C1-C6 low-carbon aldehyde.
In the typical but non-limiting embodiment of the present invention, the first monomer and second comonomer copolymerization generate three dimensional network
Shape structural polymer, obtains containing SiO2With the solid microsphere of polymer, SiO is formed convenient for being subsequently sintered2/ C microballoons.
In the preferred embodiment of the present invention, the molar ratio of the first monomer and second comonomer is 1：1-2.
In the typical but non-limiting embodiment of the present invention, the first monomer and second comonomer mole are such as 1:
0.5、1:0.6、1:0.7、1:0.8、1:0.9、1:1、1:1.1、1:1.2、1:1.3、1:1.4、1:1.5、1:1.6、1:1.7、1:
1.8,1:1.9 or 1:2.
By the way that the quality of the first monomer and second comonomer is limited to 1:(1-2), so that the first monomer and second comonomer
The reaction was complete, and the polymer of generation can be by SiO2Colloidal sol coats completely.
In a kind of typical but non-limiting embodiment of the present invention, in step (b), SiO2 and polymerization will be contained
The solid microsphere of object is sintered in inertia or reducing atmosphere, makes polymer carbonization, SiO2Colloidal sol is shunk, and is obtained with cavity
SiO2/ C microballoons.
When the solid microsphere containing SiO2 and polymer is sintered in inertia or reducing atmosphere, it is coated on SiO2It is molten
Polymerization outside glue is carbonized at high temperature, leaves C element, the SiO inside polymer microballoon2Evaporation of the solvent in colloidal sol so that
SiO2Colloidal sol is shunk, to obtain the SiO with cavity2/ C microballoons.
In the preferred embodiment of the present invention, in step (b), when being sintered, first with the liter of 2-5 DEG C/min
Warm rate by temperature by room temperature to 180-220 DEG C, be then warming up to 330-380 DEG C with the heating rate of 0.5-1 DEG C/min,
So 700-800 DEG C is warming up to the heating rate of 2-5 DEG C/min again and keeps the temperature 6-10 hours.
In the typical but non-limiting embodiment of the present invention, in step (b), by once heating up sintering temperature
Degree is increased to 180-220 DEG C from room temperature, and then secondary temperature elevation is finally warming up to 700-800 DEG C and keeps the temperature three times to 330-380 DEG C
6-10 hours, lead to the SiO generated to avoid because of too fast heating2/ C microballoon existing defects.
In the present invention, the typical but non-limiting heating rate once to heat up is as being 2,2.5,3,3.5,4,4.5 or 5
℃/min；The typical but non-limiting heating rate of secondary temperature elevation is as being 0.5,0.6,0.7,0.8,0.9,1 DEG C/min；Three times
The typical but non-limiting heating rate of heating is as being 2,2.5,3,3.5,4,4.5 or 5 DEG C/min.
In the present invention, the typical but non-limiting temperature after primary heating as 180,185,190,195,200,
205,210,215 or 220 DEG C；Typical but non-limiting temperature after secondary temperature elevation as 330,335,340,345,350,
355,360,365,370,375 or 380 DEG C；Typical but non-limiting temperature after heating up three times as 700,705,710,
715,720,725,730,735,740,745,750,755,760,765,770,775,780,785,790,795 or 800 DEG C.
In the present invention, typical but non-limiting soaking time after heating up three times as 6,6.5,7,7.5,8,8.5,
9,9.5 or 10h.
In the preferred embodiment of the present invention, in step (c), SiO is restored using reducing agent2/ C microballoons.
SiO is restored by using reducing agent2/ C microballoons so that SiO2Reduction, obtains the Si-C composite material with cavity.
In the preferred embodiment of the present invention, reducing agent is at least one of magnesium, iron, copper or manganese, especially
When reducing agent is magnesium, reduction effect is more preferably.
In the preferred embodiment of the present invention, SiO2The mass ratio of/C microballoons and reducing agent is 1:(1-5).
In the typical but non-limiting embodiment of the present invention, SiO2The quality of/C microballoons and reducing agent is such as 1:
1,1:1.5,1:2,1:2.5,1:3,1:3.5,1:4,1:4.5 or 1:5；Especially work as SiO2The mass ratio of/C microballoons and reducing agent
It is 1：When (2-3), reduction effect is more preferably.
In the preferred embodiment of the present invention, in step (c), first by SiO2/ C microballoons are mixed with reducing agent,
Then it is sintered 6-20 hours at 700-800 DEG C, obtains the Si-C composite material with hollow-core construction.
In the typical but non-limiting embodiment of the present invention, sintering temperature as 700,710,720,730,740,
750,760,770,780,790 or 800 DEG C；Sintering time is as being 6,7,8,9,10,11,12,13,14,15,16,17,18,19
Or 20h.
In the preferred embodiment of the present invention, SiO2Colloidal sol according toMethod is prepared.
Stober methods are a kind of physico-chemical process of synthesis monodisperse silicon particle, by WernerEt al. most
It first finds, generally refers to by the way that the method for generating silicon nanoparticle is added in ethyl alcohol and ammonium hydroxide in TEOS.
In the preferred embodiment of the present invention, SiO2Colloidal sol is prepared in accordance with the following steps：By ammonium hydroxide and positive silicic acid
Ethyl ester is sequentially added in solvent and is uniformly mixed, and is stirred, and reaction generates SiO2Colloidal sol.
In the preferred embodiment of the present invention, a concentration of 0.01-0.5mol/L of ethyl orthosilicate, ammonium hydroxide it is dense
Degree is 0.1-2mol/L.
In the present invention, the typical but non-limiting concentration of ethyl orthosilicate as 0.01,0.02,0.03,0.04,
0.05、0.08、0.1、0.12、0.15、0.18、0.2、0.22、0.25、0.28、0.3、0.32、0.35、0.38、0.4、0.42、
0.45,0.48 or 0.5mol/L；The typical but non-limiting concentration of ammonium hydroxide as 0.1,0.2,0.3,0.4,0.5,0.6,
0.7,0.8,0.9,1,1.1,1.2,1.3,1.4,1.5,1.6,1.7,1.8,1.9 or 2mol/L.
In the preferred embodiment of the present invention, solvent is the mixed solution of water or water and ethyl alcohol.
In present invention further optimization embodiment, in the mixed solution of water and ethyl alcohol, the volume ratio of water and ethyl alcohol
For 1-25:1.
The present invention typical but non-limiting embodiment in, solvent be water and ethyl alcohol mixed solution, and water with
The volume ratio of ethyl alcohol is 1:1,2:1,5:1,8:1,10:1,12:1,15:1,18:1,20:1,22:1 or 25:1.
In the preferred embodiment of the present invention, SiO is being prepared2When colloidal sol, mixing time is 2-4 hours, stirring
Temperature is 25-90 DEG C.
Preparing SiO2When colloidal sol, typical but non-limiting time of stirring as 2,2.2,2.5,2.8,3,3.2,
3.5,3.8 or 4h, whipping temp is as being 25,30,35,40,45,50,55,60,65,70,75,80,85 or 90 DEG C.
According to the third aspect of the present invention, the present invention provides a kind of cell negative electrode material, including it is provided by the invention
Si-C composite material, conductive agent and adhesive.
Cell negative electrode material provided by the invention using Si-C composite material provided by the invention as negative electrode active material,
Effectively increase the cyclical stability and battery capacity of battery.
In the preferred embodiment of the present invention, conductive agent is selected from graphite, carbon black, acetylene black, graphene, carbon fiber
With one kind or at least two in carbon nanotube.
In the preferred embodiment of the present invention, adhesive is selected from Vingon, soluble poly tetrafluoroethene, fourth
Benzene rubber, hydroxypropyl methyl cellulose, methylcellulose, carboxymethyl cellulose, polyvinyl alcohol, acrylonitrile copolymer, alginic acid
One kind in sodium, chitosan and chitosan derivatives or at least two.
According to the fourth aspect of the present invention, the present invention provides a kind of battery, including silicon-carbon provided by the invention are compound
Material or cell negative electrode material provided by the invention.
Battery provided by the invention, using Si-C composite material provided by the invention as negative electrode active material or using this
The cell negative electrode material provided is invented as negative material, effectively increases the cyclical stability and battery capacity of battery.
Technical solution provided by the invention is further described with reference to embodiment and comparative example.
Embodiment 1
A kind of Si-C composite material is present embodiments provided, is hollow microsphere structure, shell is combined by silicon-carbon, Si
Content accounting is 30wt%, is prepared by the following method：
(s) SiO is prepared2Colloidal sol
Ammonium hydroxide and TEOS are sequentially added water and ethyl alcohol, and (mass ratio of water and ethyl alcohol is 1:1) in mixed solution, wherein
A concentration of 0.01mol/L of TEOS, a concentration of 0.1mol/L of ammonium hydroxide are stirred to react 48 hours, and heating temperature is 90 DEG C, until molten
Liquid becomes leucosol suspension, obtains SiO2Colloidal sol；
(a) it prepares and contains SiO2With the solid microsphere of polymer
In SiO2Urea and formaldehyde are sequentially added in colloidal sol, and the pH value for adjusting reaction system is 0.5, is stirred evenly, instead
It answers, centrifuge washing is obtained containing SiO2With the solid microsphere of polymer, the wherein molar ratio of urea and formaldehyde is 1:1, SiO2It is molten
The volume ratio of glue and reaction system is 1:15；
(b) SiO is prepared2/ C microballoons
SiO will be contained2It is placed in the solid microsphere of polymer in the tube furnace of inertia or reducing atmosphere, with 2 DEG C/min's
Heating rate by temperature by room temperature to 200 DEG C, then 350 DEG C are warming up to the heating rate of 1 DEG C/min, then again with 2
DEG C/heating rate of min is warming up to 750 DEG C and keeps the temperature 8 hours, obtain the SiO with cavity structure2/ C microballoons；
(c) Si/C composite materials are prepared
By SiO2/ C microballoons are with Mg powder with 1：1 mass ratio uniformly mixes, and is placed in the tube furnace of inertia or reducing atmosphere,
It is sintered 6 hours at being 750 DEG C in temperature, carries out magnesiothermic reduction reaction, then washed with dilute HCl and remove extra Mg powder, obtained
Si/C composite materials.
Embodiment 2
A kind of Si-C composite material is present embodiments provided, is hollow microsphere structure, shell is combined by silicon-carbon, Si
Content accounting is 90wt%, is prepared by the following method：
(s) SiO is prepared2Colloidal sol
Ammonium hydroxide and TEOS are sequentially added water and ethyl alcohol, and (mass ratio of water and ethyl alcohol is 1:1) in mixed solution, wherein
A concentration of 0.5mol/L of TEOS, a concentration of 2mol/L of ammonium hydroxide are stirred to react 2 hours, and heating temperature is 25 DEG C, until solution becomes
At leucosol suspension, SiO is obtained2Colloidal sol；
(a) it prepares and contains SiO2With the solid microsphere of polymer
In SiO2Urea and formaldehyde are sequentially added in colloidal sol, and the pH value for adjusting reaction system is 2, is stirred evenly, and is reacted,
Centrifuge washing is obtained containing SiO2With the solid microsphere of polymer, the wherein molar ratio of urea and formaldehyde is 1:2, SiO2Colloidal sol with
The volume ratio of reaction system is 1:2；
(b) SiO is prepared2/ C microballoons
SiO will be contained2It is placed in the solid microsphere of polymer in the tube furnace of inertia or reducing atmosphere, with 5 DEG C/min's
Heating rate by temperature by room temperature to 200 DEG C, be then warming up to 350 DEG C with the heating rate of 0.5 DEG C/min, then again with
The heating rate of 5 DEG C/min is warming up to 800 DEG C and keeps the temperature 8 hours, obtains the SiO with cavity structure2/ C microballoons；
(c) Si/C composite materials are prepared
By SiO2/ C microballoons are with Mg powder with 1：5 mass ratio uniformly mixes, and is placed in the tube furnace of inertia or reducing atmosphere,
It is sintered 6 hours at being 750 DEG C in temperature, carries out magnesiothermic reduction reaction, then washed with dilute HCl and remove extra Mg powder, obtained
Si/C composite materials.
Embodiment 3
A kind of Si-C composite material is present embodiments provided, is hollow microsphere structure, shell is combined by silicon-carbon, Si
Content accounting is 60wt%, is prepared by the following method：
(s) SiO is prepared2Colloidal sol
Ammonium hydroxide and TEOS are sequentially added water and ethyl alcohol, and (mass ratio of water and ethyl alcohol is 1:1) in mixed solution, wherein
A concentration of 0.2mol/L of TEOS, a concentration of 1mol/L of ammonium hydroxide are stirred to react 20 hours, and heating temperature is 45 DEG C, until solution
Become leucosol suspension, obtains SiO2Colloidal sol；
(a) it prepares and contains SiO2With the solid microsphere of polymer
In SiO2Urea and formaldehyde are sequentially added in colloidal sol, and the pH value for adjusting reaction system is 1, is stirred evenly, and is reacted,
Centrifuge washing is obtained containing SiO2With the solid microsphere of polymer, the wherein molar ratio of urea and formaldehyde is 1:1.8, SiO2Colloidal sol
Volume ratio with reaction system is 1:5；
(b) SiO is prepared2/ C microballoons
SiO will be contained2It is placed in the solid microsphere of polymer in the tube furnace of inertia or reducing atmosphere, with 5 DEG C/min's
Heating rate by temperature by room temperature to 200 DEG C, be then warming up to 350 DEG C with the heating rate of 0.5 DEG C/min, then again with
The heating rate of 5 DEG C/min is warming up to 800 DEG C and keeps the temperature 8 hours, obtains the SiO with cavity structure2/ C microballoons；
(c) Si/C composite materials are prepared
By SiO2/ C microballoons are with Mg powder with 1：2 mass ratio uniformly mixes, and is placed in the tube furnace of inertia or reducing atmosphere,
It is sintered 6 hours at being 750 DEG C in temperature, carries out magnesiothermic reduction reaction, then washed with dilute HCl and remove extra Mg powder, obtained
Si/C composite materials.
Embodiment 4
Present embodiments provide a kind of Si-C composite material, the present embodiment with embodiment 3 the difference is that, silicone content
It is 10%.
Embodiment 5
Present embodiments provide a kind of Si-C composite material, the present embodiment with embodiment 3 the difference is that, silicone content
It is 99%.
Embodiment 6
Present embodiments provide a kind of Si-C composite material, the present embodiment with embodiment 3 the difference is that, in step
(a) in, the molar ratio of urea and formaldehyde is 1:0.5.
Embodiment 7
A kind of Si-C composite material is present embodiments provided, the Si-C composite material that the present embodiment is provided with embodiment 3
Preparation method the difference is that, in step (a), the molar ratio of urea and formaldehyde is 1:5.
Embodiment 8
A kind of Si-C composite material is present embodiments provided, the Si-C composite material that the present embodiment is provided with embodiment 3
Preparation method the difference is that, in step (c), SiO2The mass ratio of/C tiny balloons and Mg powder is 1:0.5.
Comparative example 1
This comparative example provides a kind of Si-C composite material, is microspheroidal, is combined by silicon and carbon, and silicon is core, carbon
For shell, and Si content accountings are 60wt%, the preparation method that preparation method is provided with embodiment 3 the difference is that,
Urea and formaldehyde will be sequentially added in silica flour, and carries out polymerisation and sintering successively, and the silicon-carbon for obtaining solid microsphere structure is multiple
Condensation material.
Comparative example 2
This comparative example provides a kind of tin-carbon composite, and structure is identical as the Si-C composite material that embodiment 3 provides,
Its with embodiment 3 the difference is that, shell is combined by tin carbon.
Embodiment 9-16
Embodiment 10-18 each provides a kind of cell negative electrode material, and the silicon-carbon provided respectively with embodiment 1-8 is compound
Material is negative electrode active material, while further including carbon black and Vingon (PVDF), and the mass ratio of three is 90%:
5%:5%.
Comparative example 3-4
Comparative example 3-4 each provides a kind of cell negative electrode material, the silicon-carbon composite wood provided respectively with comparative example 1-2
Material is negative electrode active material, while further including carbon black and Vingon (PVDF), and the mass ratio of three is 90%:5%:
5%.
Embodiment 17-24
Embodiment 17-24 each provides a kind of battery, the Electrode Negative material that cathode is provided by embodiment 9-16 respectively
Material is coated on copper foil and is prepared.
Comparative example 5-6
Comparative example 5-6 each provides a kind of battery, and cathode is applied by the electrode anode material that comparative example 4-6 is provided respectively
It is overlying on copper foil and is prepared.
Test example 1
The Si-C composite material that embodiment 3 provides is scanned Electronic Speculum test, Fig. 1 is silicon provided in an embodiment of the present invention
The SEM of carbon composite schemes；Fig. 2 is that SEM of the Si-C composite material shown in Fig. 1 after focused ion beam (FIB) incision schemes knot
Fruit is as depicted in figs. 1 and 2, and the Si-C composite material that embodiment 3 provides is the internal micro-sphere structure with cavity, outer diameter between
Between 1 μm and 10 μm, this illustrate the Si-C composite material can by the cavity inside Si-C composite material be silicon in charge and discharge
The volume change generated in the process provides space, and silicon volume expansion and structure collapses problem in charge and discharge process is effectively relieved,
As can be seen from the figure the Si-C composite material has larger particle scale simultaneously, can effectively improve compacted density and volume
Energy density, to effectively improve the cyclical stability and battery capacity of battery.
Test example 2
The battery that embodiment 19 (using the Si-C composite material that embodiment 3 provides for negative electrode active material) provides is existed
First charge-discharge test is carried out under 0.1C, test results are shown in figure 3, from figure 3, it can be seen that the battery that embodiment 19 provides is first
Secondary charge/discharge capacity can reach 1200
MAh/g, the Si-C composite material that this explanation uses embodiment 3 to provide have for battery made of negative electrode active material
Higher first charge-discharge capacity.
Test example 3
The battery that embodiment 19 and comparative example 5 are provided carries out 300 loop tests at 0.1C respectively, and test result is such as
Shown in Fig. 4, from fig. 4, it can be seen that the cycle performance for the battery that embodiment 19 provides is significantly higher than the battery of the offer of comparative example 5,
This illustrates that the battery that embodiment 19 provides uses the Si-C composite material that embodiment 3 provides for negative electrode active material, due to
There is cavity, to provide space for the volume change that silicon generates in charge and discharge process, effectively inside the Si-C composite material
Alleviate silicon volume expansion and structure collapses problem in charge and discharge process, improves the cyclical stability and battery capacity of battery.
Test example 4
It provides embodiment 17-24 and comparative example 5-6 to battery and constant current charge-discharge test is carried out with the current density of 0.1C, survey
It is 25 DEG C to try temperature, and test result is as shown in table 1.
1 battery charging and discharging test data table of table
From table 1, embodiment 17-19 can be seen that the head for the battery that embodiment 17-19 is provided with the comparison of comparative example 5
Secondary cycle specific capacity is above 1200mAh/g, and capacity retention remains above 94% after 300 cycles, this explanation is used when battery
When the Si-C composite material with cavity structure that embodiment 1-3 is provided is negative electrode active material, electricity is not only significantly improved
Pond specific capacity, and significantly improve the cyclical stability of battery.
By the comparison of embodiment 17-19 and embodiment 20-21 as can be seen that following for the first time for the battery that embodiment 20 provides
Ring specific capacity is substantially less than embodiment 17-19, and the capacity retention for the battery that embodiment 21 provides is substantially less than embodiment 17-
19, the Si-C composite material as negative electrode active material that this explanation is used when battery, silicone content is too high or too low can shadow
The specific capacity of cycle for the first time and capacity retention for ringing battery, i.e., in Si-C composite material, when silicone content is 30-90wt%, system
Specific capacity had not only been recycled for the first time with good at battery, but also there is good cyclical stability, and comprehensive performance is more preferably.
It can be seen that the head for the battery that embodiment 22-23 is provided by the comparison of embodiment 17-19 and embodiment 22-23
Secondary cycle specific capacity and capacity retention ratio are slightly less than embodiment 17-19, this explanation, when preparing Si-C composite material, first
The molar ratio of monomer and second comonomer is 1:When 1-2, manufactured Si-C composite material is as battery made of negative electrode active material
Cycle performance it is more stable, battery capacity conservation rate is more preferably.
It can be seen that the cycle for the first time for the battery that embodiment 24 provides by the comparison of embodiment 17-19 and embodiment 24
Specific capacity and cyclical stability are below embodiment 17-19, this explanation is when the part silicon in Si-C composite material is with oxide shape
Formula exists, and when not being completely reduced, the specific capacity of cycle for the first time and cyclical stability of manufactured battery can decline.
By embodiment 17-19 with the comparison of comparative example 2 as can be seen that following for the first time for the battery that embodiment 17-19 is provided
Ring specific capacity and cyclical stability are above documents 2, this explanation uses negative electrode active of the Si-C composite material as battery
The specific capacity of cycle for the first time and cyclical stability of battery made of material are above using tin-carbon composite as negative electrode active
The battery of substance.
Finally it should be noted that：The above embodiments are only used to illustrate the technical solution of the present invention., rather than its limitations；To the greatest extent
Present invention has been described in detail with reference to the aforementioned embodiments for pipe, it will be understood by those of ordinary skill in the art that：Its according to
So can with technical scheme described in the above embodiments is modified, either to which part or all technical features into
Row equivalent replacement；And these modifications or replacements, various embodiments of the present invention technology that it does not separate the essence of the corresponding technical solution
The range of scheme.
Claims (10)
1. a kind of Si-C composite material, which is characterized in that the Si-C composite material is hollow microsphere structure, the tiny balloon
Including shell and cavity, the shell coats the cavity, and the shell includes silicon and carbon.
2. Si-C composite material according to claim 1, which is characterized in that the outer diameter of the shell is 1-10 μm, described
The internal diameter of shell is 0.1-5 μm, and the wall thickness of the shell is 0.1-3 μm.
3. Si-C composite material according to claim 1, which is characterized in that silicone content is 30-90wt% in the shell.
4. a kind of preparation method of Si-C composite material, which is characterized in that include the following steps：
(a) SiO is provided2The solution of colloidal sol and monomer containing C element, and form it into containing SiO2It is solid micro- with polymer
Ball；
(b) solid microsphere is sintered, obtains the SiO with cavity2/ C microballoons；
(c) by the SiO2/ C microballoons are reduced to the Si-C composite material with hollow microsphere structure, wherein
The tiny balloon includes shell and cavity, and the shell coats the cavity, and the shell includes silicon and carbon.
5. preparation method according to claim 4, which is characterized in that the polymer is copolymer, and the monomer includes
First monomer and second comonomer, wherein
In step (a), first by SiO2Then colloidal dispersion is added the second comonomer and carries out in first monomer solution
Copolymerization, obtains containing SiO2With the solid microsphere of polymer；Wherein, contain C in first monomer and/or the second comonomer
Element.
6. preparation method according to claim 5, which is characterized in that first monomer is selected from urea, melamine, benzene
At least one of phenol, resorcinol and 3- amino-phenols；And/or
One kind in low-carbon aldehyde of the second comonomer selected from C1-C6.
7. preparation method according to claim 4, which is characterized in that in step (b), when being sintered, first with 2-5
DEG C/heating rate of min by temperature by room temperature to 180-220 DEG C, be then warming up to the heating rate of 0.5-1 DEG C/min
330-380 DEG C, then 700-800 DEG C is warming up to the heating rate of 2-5 DEG C/min again and keeps the temperature 6-10 hours.
8. preparation method according to claim 4, which is characterized in that in step (c), SiO is restored using reducing agent2/C
Microballoon, the reducing agent are magnesium, iron, copper or manganese.
9. a kind of cell negative electrode material, which is characterized in that including any Si-C composite material of claims 1 to 3.
10. a kind of battery, including the battery described in the claims 1 to 3 any Si-C composite material or claim 9 are negative
Pole material.
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