CN107863513A - A kind of closed cage structure Si-C composite material and preparation method thereof - Google Patents

A kind of closed cage structure Si-C composite material and preparation method thereof Download PDF

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CN107863513A
CN107863513A CN201711025115.6A CN201711025115A CN107863513A CN 107863513 A CN107863513 A CN 107863513A CN 201711025115 A CN201711025115 A CN 201711025115A CN 107863513 A CN107863513 A CN 107863513A
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silicon
composite material
materials
porous carbon
preparation
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CN107863513B (en
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谭强强
王鹏飞
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Institute of Process Engineering of CAS
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Hebei Aipuai Technology Development Co ltd
Institute of Process Engineering of CAS
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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
    • B—PERFORMING OPERATIONS; TRANSPORTING
    • B82—NANOTECHNOLOGY
    • B82Y—SPECIFIC USES OR APPLICATIONS OF NANOSTRUCTURES; MEASUREMENT OR ANALYSIS OF NANOSTRUCTURES; MANUFACTURE OR TREATMENT OF NANOSTRUCTURES
    • B82Y30/00—Nanotechnology for materials or surface science, e.g. nanocomposites
    • 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
    • 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
    • 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
    • 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
    • H01M4/48—Selection of substances as active materials, active masses, active liquids of inorganic oxides or hydroxides
    • H01M4/485—Selection of substances as active materials, active masses, active liquids of inorganic oxides or hydroxides of mixed oxides or hydroxides for inserting or intercalating light metals, e.g. LiTi2O4 or LiTi2OxFy
    • 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
    • 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
    • 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
    • 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 invention provides a kind of closed cage structure Si-C composite material and preparation method thereof.The closed cage structure Si-C composite material of the present invention is the hollow filling structural material of closed caged, and the core of the hollow filling structural material is the porous carbon materials of silicon materials filling；The silicon materials are filled in the porous carbon materials, and filling of the silicon materials in the porous carbon materials is with 50%~95% voidage；The outside of the porous carbon materials of the silicon materials filling is coated with carbon material, and it specifically comprises (SiOx)yC, wherein, 0≤x≤2,0 ＜ y≤1.The present invention closed cage structure Si-C composite material, as GND use during, isolated contact of the silicon materials with electrolyte, extended battery life, improved the volumetric properties and cycle performance of battery.

Description

A kind of closed cage structure Si-C composite material and preparation method thereof
Technical field
The invention belongs to Si-C composite material technical field, be related to a kind of closed cage structure Si-C composite material and its Preparation method.
Background technology
With the fast development of electric automobile, lithium ion battery material is obtained increasingly to be widely applied, and electric car is more Long course continuation mileage has the higher requirement of energy density, currently used negative electrode of lithium ion battery graphite material to lithium ion battery Expect increasingly its theoretical capacity of convergence (theoretical capacity 372mAh/g, 855mAh/cm3), utilize the electricity of graphite cathode Pond energy density is extremely difficult to 300wh/kg energy density target, such as further to realize that the breakthrough of energy density needs to apply Silicon based anode material with more height ratio capacity.
The theoretical embedding lithium capacity of silica-base material is 4200mAh/g, far above current other all negative materials.But silicon Serious bulk effect (up to 100-300%) be present, cause serious decay and peace in material during with lithium alloyage Full sex chromosome mosaicism.
For silicon bulk effect the problem of, main solution is at present：First, by silicon and flexible and performance Stable carrier is compound, buffers the Volume Changes of silicon, is the effective way for improving silicon class stability of material.CN103633306A is public A kind of silicon-carbon composite cathode material, including graphite particle in addition to silicon or silicon-containing particles have been opened, and including porous carbon layer, institute State silicon or silicon-containing particles are distributed near the graphite particle, the porous carbon layer is coated on the graphite particle and the silicon Or silicon-containing particles surface and be combined together both, the porous carbon layer is low crystalline carbon or amorphous carbon layer, silicon or is contained The size of silicon grain is less than the size of the graphite particle.The silicon-carbon composite cathode material has a loose structure, and material structure is steady It is fixed, there is high power capacity, high conduction performance and good cycle performance.
Second, substituting silicon materials using silica, silica has less bulk effect, can effectively alleviated, still Silica reduce further the electric conductivity of material.CN105609743A discloses a kind of SiOxThe system of/C/CNT composites Preparation Method.This method has obtained one by way of adding carbon nanotube conducting network (CNT) and directly pouring into culture dish film forming Kind novel silicon/carbon composite construction, this structure include：Graphite framework material, amorphous silicon oxide SiOx, carbon nanotube conducting net Network.The composite of the invention solves the reuniting effect of nano silicon material, it is therefore prevented that the rapid decay of battery specific capacity；Without fixed Conformal silicon oxide forms SiO with graphitex/ C-structure, huge stress effect caused by nano-silicon volumetric expansion/contraction can be buffered, improved The cycle life of battery；CNT is distributed in SiOxIn/C-structure, preferably silicon and carbon can be linked together, formation is led Electric network structure, the electric conductivity of composite is enhanced, improve the high rate performance of battery.
Third, silicon materials or Si-C composite material are made into porous material, the hole of porous material is the volume of silicon materials Expansion provides buffering, the Volume Changes of overall electrode is controlled in rational scope, while silicon high power capacity is kept, carries Its high cyclical stability.CN106848199A disclose a kind of lithium ion cell nano silicon/porous carbon compound cathode materials and its Preparation method and application, composite negative pole material are the hollow fillings being made up of porous nano silicon grain kernel and porous carbon layer shell Structural material, its preparation method are after alusil alloy powder Surface coating organic polymer layers, carry out carbonization treatment, carbonization production Thing is by acid etch to remove aluminium and to carbon-coating pore-creating, produce nano-silicon/porous carbon compound cathode materials；Preparation method letter Single, low cost, meet large-scale production, and the composite negative pole material prepared can prepare lithium ion battery, show higher Capacity, excellent circulation and high rate performance.
However, the silicon or silicon carbon material of loose structure, by silicon exposed to the surface of electrode material directly and electrolyte contacts, SEI films are generated in cyclic process, simultaneously because bulk effect, SEI is constantly broken, regrows, causes the continuous of specific capacity Decay.
The content of the invention
In view of the shortcomings of the prior art, an object of the present invention is to provide a kind of closed cage structure silicon-carbon compound Material, as GND use during, isolated contact of the silicon materials with electrolyte, extended battery life, Improve the volumetric properties and cycle performance of battery.
To use following technical scheme up to this purpose, the present invention：
A kind of closed cage structure Si-C composite material, the closed cage structure Si-C composite material are closed The hollow filling structural material of caged, the core of the hollow filling structural material are the porous carbon materials of silicon materials filling；Institute Silicon materials are stated to be filled in the porous carbon materials, filling of the silicon materials in the porous carbon materials have 50%~ 95% voidage；The outside of the porous carbon materials of the silicon materials filling is coated with carbon material, and it specifically comprises (SiOx)yC, wherein, 0≤x≤2,0 ＜ y≤1.It should be noted that filling of the silicon materials in the porous carbon materials has 50%~95% voidage, after referring to that the silicon materials are filled in the porous carbon materials, porous carbon materials there remains 50%~95% voidage, bulk effect of the hole for silicon materials in cathode of lithium battery application provide very big buffering, Such as remaining voidage is 50%, 55%, 60%, 65%, 70%, 75%, 80%, 85%, 90%, 95%.
The porous carbon materials are porous carbon or absorbent charcoal material, and the silicon materials are silicon and/or silica.
Second object of the present invention is to provide a kind of preparation method of closed cage structure Si-C composite material, wrapped Include following steps：
1) silicon tetrachloride is dissolved in the anhydrous ethane solution that silicon tetrachloride is made in anhydrous ethane, porous carbon materials are added Impregnated into the anhydrous ethane solution of silicon tetrachloride, filter, heat after obtain Si-C composite material A；
2) the Si-C composite material A for obtaining step 1) is added in reductant solution, and it is clear that detergent is added after stirring reaction Wash, obtain Si-C composite material B；
3) organic carbon source is added in the Si-C composite material B that step 2) obtains, ball milling, calcining, obtains closed caged Structure Si-C composite material.
In step 1), the mass concentration that the silicon tetrachloride is dissolved in anhydrous ethane is 0.1~10mol/L, such as described Silicon tetrachloride be dissolved in mass concentration in anhydrous ethane for 0.1mol/L, 0.5mol/L, 0.8mol/L, 1mol/L, 2mol/L, 2.5mol/L、3mol/L、3.5mol/L、4mol/L、4.5mol/L、5mol/L、5.5mol/L、6mol/L、6.5mol/L、 7mol/L、7.5mol/L、8mol/L、8.5mol/L、9mol/L、9.5mol/L、10mol/L。
Preferably, the mol ratio of the silicon tetrachloride and the porous carbon materials is (0:1)~(1:, such as described four 1) The mol ratio of silicon chloride and the porous carbon materials is 0:1、0.1:1、0.2:1、0.3:1、0.4:1、0.5:1、0.6:1、0.7: 1、0.8:1、0.9:1、1:1。
Preferably, the time of the dipping is 0.5~5h, for example, the time of dipping be 0.5h, 1h, 1.5h, 2h, 2.5h, 3h、3.5h、4h、4.5h、5h。
Preferably, the temperature of the heating is 100~200 DEG C, unnecessary solvent volatilization after heating.Such as the temperature of heating For 100 DEG C, 110 DEG C, 120 DEG C, 130 DEG C, 140 DEG C, 150 DEG C, 160 DEG C, 170 DEG C, 180 DEG C, 190 DEG C, 200 DEG C.
After step 1) dipping, filtering, heating, Si-C composite material A is obtained, Si-C composite material A is carbon and silicon Oxide composite, wherein, silicon tetrachloride is changed into the oxide of silicon.
In step 2), the reducing agent is tetrahydrofuran solution, the diethyl ether solution and dioxygen of aluminium lithium hydride of aluminium lithium hydride One kind in water.
Preferably, in step 2), the mol ratio of the aluminium lithium hydride and the silicon tetrachloride is (1:1)~(3:1), such as The mol ratio of aluminium lithium hydride and the silicon tetrachloride is 1:1、1.5:1、2:1、2.5:1、3:1.
Preferably, in step 2), the mol ratio of the hydrogen peroxide and the silicon tetrachloride is (2:1)~(6:, such as institute 1) The mol ratio for stating hydrogen peroxide and the silicon tetrachloride is 2:1、2.5:1、3:1、3.5:1、4:1、4.5:1、5:1、5.5:1、6:1.
Preferably, in step 2), time of the reaction is 0.5~5h, for example, the time of reaction be 0.5h, 1h, 1.5h, 2h、2.5h、3h、3.5h、4h、4.5h、5h。
Preferably, in step 2), the detergent is absolute methanol or absolute ethyl alcohol.
After the reduction of step 2) reducing agent, Si-C composite material A is changed into Si-C composite material B, and Si-C composite material B is carbon With the composite of elemental silicon, wherein, the oxide of silicon is reduced to elemental silicon.
In step 3), the quality of the organic carbon source is the 1/5~1/20 of the quality of porous carbon materials described in step 1), Such as 1/5,1/6,1/7,1/8,1/9,1/ that the quality of the organic carbon source is the quality of porous carbon materials described in step 1) 10、1/11、1/12、1/13、1/14、1/15、1/16、1/17、1/18、1/19、1/20。
Preferably, in step 3), the organic carbon source is selected from sucrose, cellulose, acetate fiber, cyclodextrin and phenolic resin One kind or at least two.
In step 3), the speed of the ball milling is 100~300rpm, for example, the speed of the ball milling be 100rpm, 110rpm、120rpm、130rpm、140rpm、150rpm、160rpm、170rpm、180rpm、190rpm、200rpm、210rpm、 220rpm、230rpm、240rpm、250rpm、260rpm、270rpm、280rpm、290rpm、300rpm；The time of the ball milling Time for 0.5~10h, such as the ball milling is 0.5h, 1h, 2h, 3h, 4h, 5h, 6h, 7h, 8h, 9h, 10h.
In step 3), the calcining is carried out in inert atmosphere or reducing atmosphere.
Preferably, the inert atmosphere is blanket of nitrogen or argon atmospher, and the reducing atmosphere is hydrogen atmosphere；In indifferent gas Generated in atmosphere for the silicon materials of partial oxidation and the compound of carbon, generate Si-C composite material under reducing atmosphere.
Preferably, the temperature of the calcining be 800~1000 DEG C, such as calcining time for 800 DEG C, 850 DEG C, 900 DEG C, 950℃、1000℃；The time of the calcining is 3~12h, for example, the time of calcining be 3h, 4h, 5h, 6h, 7h, 8h, 9h, 10h, 11h、12h、13h。
After step 3), closed cage structure Si-C composite material is obtained after organic carbon source cladding.
Further, in step 2), after reducing agent reduces, the oxide of silicon is reduced to elementary silicon nano particle, obtains The particle diameter of the nano silicon particles arrived is 2nm~20nm, the nano particle of small particle, enhances the electric transmission of silicon grain；Such as The particle diameter of nano silicon particles be 2nm, 3nm, 4nm, 5nm, 6nm, 7nm, 8nm, 9nm, 10nm, 11nm, 12nm, 13nm, 14nm, 15nm、16nm、17nm、18nm、19nm、20nm。
As the preferred scheme of the present invention, a kind of preparation method of closed cage structure Si-C composite material, including such as Lower step：
1) silicon tetrachloride is dissolved in anhydrous ethane and mass concentration is made as the anhydrous of 0.1~10mol/L silicon tetrachloride Ethane solution, by porous carbon materials add into the anhydrous ethane solution of silicon tetrachloride dipping 0.5~5h, the silicon tetrachloride with The mol ratio of the porous carbon materials is (0:1)~(1:1), filter, obtain Si-C composite material A after heating；
2) the Si-C composite material A for obtaining step 1) is added in reductant solution, and the reducing agent is aluminium lithium hydride Tetrahydrofuran solution, aluminium lithium hydride diethyl ether solution and hydrogen peroxide in one kind；The aluminium lithium hydride and the silicon tetrachloride Mol ratio is (1:1)~(3:1), or the mol ratio of the hydrogen peroxide and the silicon tetrachloride is (2:1)~(6:1), stirring is anti- Detergent cleaning is added after answering 0.5~5h, obtains Si-C composite material B；
3) organic carbon source is added in the Si-C composite material B that step 2) obtains, the quality of the organic carbon source is step 1) the 1/5~1/20 of the quality of porous carbon materials described in；0.5~10h of ball milling is carried out with 100~300rpm ball milling speed, 800~1000 DEG C of 3~12h of temperature calcination in inert atmosphere or reducing atmosphere, obtain closed cage structure silicon-carbon and answer Condensation material.
Compared with prior art, beneficial effects of the present invention are：
(1) closed cage structure Si-C composite material of the invention, silicon materials are coated with carbon material, ensures that material is being made Electrolyte does not contact with silicon materials during for GND use, and the surface of silicon materials does not generate SEI films, process recycling In, the rupture of the SEI films on silicon materials surface is not had, is regenerated, thus consumption lithium ion will not be continued, extend the battery longevity Life.
(2) closed cage structure Si-C composite material of the invention, silicon materials are coated with carbon material, meanwhile, silicon materials It is completely in the hole of cage structure, carbon material cladding silicon materials have 50%~95% porosity, and hole is that silicon materials exist Bulk effect in cathode of lithium battery application provides very big buffering.
(3) the nano silicon particles particle diameter that liquid phase reduction of the present invention obtains is between 2nm~20nm, the nanometer of small particle Grain, enhance the electric transmission of silicon grain.
(4) in obtained closed cage structure Si-C composite material of the invention, silicon is with simple substance or partial oxide Form is present, and the theoretical capacity of silicon is higher, can greatly improve the volumetric properties and cycle performance of battery, and volumetric properties are up to 1580.8mAh/g, 300 weeks capability retentions of cycle performance are up to 97.6%, and electric conductivity is up to 348S/m；And silica (SiOx) with having the bulk effect smaller than elemental silicon during lithium alloyage, material can be reduced in use Internal stress, alleviate the pulverizing problem of material.
Brief description of the drawings
Fig. 1 is the structural representation of the closed cage structure Si-C composite material of the present invention.
Reference is as follows：
1- porous carbon materials；2- silicon materials；3- carbon materials.
Embodiment
Further illustrate technical scheme below in conjunction with the accompanying drawings and by embodiment.
As shown in figure 1, a kind of closed cage structure Si-C composite material, closed cage structure Si-C composite material are The hollow filling structural material of closed caged, the core of hollow filling structural material are the porous carbon materials that silicon materials 2 are filled 1；Silicon materials are filled out 2 and filled in the hole of porous carbon materials 1, and filling of the silicon materials 2 in porous carbon materials 1 is with 50%~95% Voidage；The outside for the porous carbon materials 1 that silicon materials 2 are filled is coated with carbon material 3, and carbon material 3 is organic carbon source material, and it has Body composition is (SiOx)yC, wherein, 0≤x≤2,0 ＜ y≤1.
Embodiment 1
153.84g silicon tetrachlorides are scattered in the anhydrous ethane of 1L and obtain solution A；Then 30.768g porous carbons are added to molten In liquid A；2h is stirred, is then filtrated to get the porous carbon of absorption silicon tetrachloride, 100 DEG C of heating, to the porous carbon after processing 65.2 hydrogen peroxide 5h of middle dropwise addition, then filter, filter cake are washed with absolute ethyl alcohol, remove unnecessary hydrogen peroxide, obtain solid B, solid 30.768g sucrose is added in body B, with 300rpm ball milling speed ball milling 2h, compound C is obtained, compound C is placed in 900 DEG C of hydrogen 5h is calcined under gas atmosphere, it is final to obtain closing cage structure silicon/carbon composite.
Embodiment 2
15.384g silicon tetrachlorides are scattered in the anhydrous ethane of 1L and obtain solution A；Then 1.5384g activated carbons are added to molten In liquid A；1.5h is stirred, is then filtrated to get the activated carbon of absorption silicon tetrachloride, 120 DEG C of heating, to the activity after processing The diethyl ether solution 6h of 3.3 aluminium lithium hydrides is added dropwise in charcoal, then filters, filter cake is washed with absolute ethyl alcohol, removes unnecessary aluminium lithium hydride Diethyl ether solution, obtain solid B, in solid B add 1.5384g glucose, with 100rpm ball milling speed ball milling 3h, mixed Material C is closed, compound C is placed under 950 DEG C of argon gas atmospheres and calcines 6h, it is final to obtain closing cage structure silica/carbon composite wood Material.
Embodiment 3
30.768g silicon tetrachlorides are scattered in the anhydrous ethane of 1L and obtain solution A；Then 1.5384g porous carbons are added to molten In liquid A；2h is stirred, is then filtrated to get the porous carbon of absorption silicon tetrachloride, 130 DEG C of heating, to the porous carbon after processing The middle tetrahydrofuran solution 7h that 6.5 aluminium lithium hydrides are added dropwise, then filters, filter cake is washed with absolute ethyl alcohol, removes unnecessary aluminium hydrogenation The tetrahydrofuran solution of lithium, solid B is obtained, 1.5384g celluloses are added in solid B, with 150rpm ball milling speed ball milling 4h, Compound C is obtained, compound C is placed under 1000 DEG C of nitrogen atmospheres and calcines 7h, it is final to obtain closing cage structure silica/carbon Composite.
Embodiment 4
76.92g silicon tetrachlorides are scattered in the anhydrous ethane of 0.1L and obtain solution A；Then 5.769g activated carbons are added to molten In liquid A；2.5h is stirred, is then filtrated to get the activated carbon of absorption silicon tetrachloride, 140 DEG C of heating, to the activity after processing 65.2 hydrogen peroxide 8h are added dropwise in charcoal, then filter, filter cake is washed with absolute ethyl alcohol, remove unnecessary hydrogen peroxide, obtain solid B, 5.769g acetate fibers are added in solid B, with 200rpm ball milling speed ball milling 5h, compound C is obtained, compound C is placed in 800 8h is calcined under DEG C hydrogen atmosphere, it is final to obtain closing cage structure silicon/carbon composite.
Embodiment 5
153.84g silicon tetrachlorides are scattered in the anhydrous ethane of 1L and obtain solution A；Then 19.23g porous carbons are added to solution In A；3h is stirred, is then filtrated to get the porous carbon of absorption silicon tetrachloride, 160 DEG C of heating, into the porous carbon after processing The diethyl ether solution 9h of 65.2 aluminium lithium hydrides is added dropwise, then filters, filter cake is washed with absolute ethyl alcohol, removes the second of unnecessary aluminium lithium hydride Ethereal solution, solid B is obtained, 19.23g cyclodextrin is added in solid B, with 250rpm ball milling speed ball milling 6h, obtains compound C, compound C is placed under 850 DEG C of argon gas atmospheres and calcines 9h, it is final to obtain closing cage structure silica/carbon composite.
Embodiment 6
307.68g silicon tetrachlorides are scattered in the anhydrous ethane of 1L and obtain solution A；Then 46.152g activated carbons are added to molten In liquid A；4h is stirred, is then filtrated to get the activated carbon of absorption silicon tetrachloride, 180 DEG C of heating, to the activated carbon after processing The middle tetrahydrofuran solution 10h that 130.3 aluminium lithium hydrides are added dropwise, then filters, filter cake is washed with absolute ethyl alcohol, remove unnecessary aluminium hydrogen Change the tetrahydrofuran solution of lithium, obtain solid B, 46.152g phenolic resin is added in solid B, with 300rpm ball milling speed balls 7h is ground, compound C is obtained, compound C is placed under 825 DEG C of nitrogen atmospheres and calcines 10h, it is final to obtain closing cage structure oxidation Silicon/carbon composite.
Embodiment 7
307.68g silicon tetrachlorides are scattered in the anhydrous ethane of 0.5L and obtain solution A；Then 53.844g porous carbons are added to In solution A；5h is stirred, is then filtrated to get the porous carbon of absorption silicon tetrachloride, 200 DEG C of heating, to porous after processing 390.9 hydrogen peroxide 11h are added dropwise in carbon, then filter, filter cake is washed with absolute ethyl alcohol, remove unnecessary hydrogen peroxide, obtain solid B, 53.844g sucrose is added in solid B, with 150rpm ball milling speed ball milling 8h, compound C is obtained, compound C is placed in 975 11h is calcined under DEG C hydrogen atmosphere, it is final to obtain closing cage structure silicon/carbon composite.
Embodiment 8
1538.4g silicon tetrachlorides are scattered in the anhydrous ethane of 2L and obtain solution A；Then 153.84g activated carbons are added to molten In liquid A；0.5h is stirred, is then filtrated to get the activated carbon of absorption silicon tetrachloride, 150 DEG C of heating, to the activity after processing The diethyl ether solution 12h of 977.3 aluminium lithium hydrides is added dropwise in charcoal, then filters, filter cake is washed with absolute ethyl alcohol, removes unnecessary aluminium hydrogenation The diethyl ether solution of lithium, solid B is obtained, 153.84g glucose is added in solid B, with 200rpm ball milling speed ball milling 9h, is obtained Compound C, compound C is placed under 925 DEG C of argon gas atmospheres and calcines 12h, final acquisition closing cage structure silica/carbon is compound Material.
Embodiment 9
4922.88g silicon tetrachlorides are scattered in the anhydrous ethane of 4L and obtain solution A；Then 246.144g porous carbons are added to In solution A；1h is stirred, is then filtrated to get the porous carbon of absorption silicon tetrachloride, 160 DEG C of heating, to porous after processing The tetrahydrofuran solution 13h of 3127.5 aluminium lithium hydrides is added dropwise in carbon, then filters, washs filter cake with absolute ethyl alcohol, it is unnecessary to remove The tetrahydrofuran solution of aluminium lithium hydride, solid B is obtained, 246.144g celluloses are added in solid B, with 100rpm ball milling speeds Ball milling 10h, compound C is obtained, compound C is placed under 875 DEG C of nitrogen atmospheres and calcines 4h, it is final to obtain closing cage structure oxygen SiClx/carbon composite.
Embodiments of the invention 1-9 material property is tested, experimental result is as shown in table 1.
Table 1
In the obtained closed cage structure Si-C composite material of the present invention, silicon materials are coated with carbon material, ensure material Material electrolyte during being used as GND does not contact with silicon materials, and the surface of silicon materials does not generate SEI films, then follows During ring, the rupture of the SEI films on silicon materials surface is not had, is regenerated, thus will not continue consumption lithium ion, extend Battery life；Meanwhile silicon materials are completely in the hole of cage structure, carbon material cladding silicon materials have 50%~95% hole Gap rate, bulk effect of the hole for silicon materials in cathode of lithium battery application provide very big buffering；Silicon is with simple substance or part The form of oxide is present, and the theoretical capacity of silicon is higher, can greatly improve the volumetric properties and cycle performance of material, hypovolemic 1580.8mAh/g can be up to, 300 weeks capability retentions of cycle performance are up to 97.6%, and electric conductivity is up to 348S/m.
The present invention illustrates the detailed process equipment of the present invention and technological process by above-described embodiment, but the present invention is not Above-mentioned detailed process equipment and technological process are confined to, that is, does not mean that the present invention has to rely on above-mentioned detailed process equipment and work Skill flow could be implemented.Person of ordinary skill in the field is it will be clearly understood that any improvement in the present invention, to product of the present invention The equivalence replacement of each raw material and the addition of auxiliary element, the selection of concrete mode etc., all fall within protection scope of the present invention and public affairs Within the scope of opening.

Claims (10)

  1. A kind of 1. closed cage structure Si-C composite material, it is characterised in that the closed cage structure silicon-carbon composite wood Expect the hollow filling structural material for closed caged, the core of the hollow filling structural material is the porous of silicon materials filling Carbon material；The silicon materials are filled in the porous carbon materials, filling tool of the silicon materials in the porous carbon materials There is 50%~95% voidage；The outside of the porous carbon materials of the silicon materials filling is coated with carbon material, its concrete composition For (SiOx)yC, wherein, 0≤x≤2,0 ＜ y≤1.
  2. 2. closed cage structure Si-C composite material according to claim 1, it is characterised in that the porous carbon materials For porous carbon or absorbent charcoal material, the silicon materials are silicon and/or silica.
  3. A kind of 3. preparation method of closed cage structure Si-C composite material as claimed in claim 1, it is characterised in that bag Include following steps：
    1) silicon tetrachloride is dissolved in the anhydrous ethane solution that silicon tetrachloride is made in anhydrous ethane, porous carbon materials are added to four Impregnated in the anhydrous ethane solution of silicon chloride, filter, heat after obtain Si-C composite material A；
    2) the Si-C composite material A for obtaining step 1) is added in reductant solution, and detergent cleaning is added after stirring reaction, is obtained To Si-C composite material B；
    3) organic carbon source is added in the Si-C composite material B that step 2) obtains, ball milling, calcining, obtains closed cage structure Si-C composite material.
  4. 4. preparation method according to claim 3, it is characterised in that in step 1), the silicon tetrachloride is dissolved in anhydrous second Mass concentration in alkane is 0.1~10mol/L；
    Preferably, the mol ratio of the silicon tetrachloride and the porous carbon materials is (0:1)~(1:1)；
    Preferably, the time of the dipping is 0.5~5h；
    Preferably, the temperature of the heating is 100~200 DEG C.
  5. 5. the preparation method according to claim 3 or 4, it is characterised in that in step 2), the reducing agent is aluminium lithium hydride Tetrahydrofuran solution, aluminium lithium hydride diethyl ether solution and hydrogen peroxide in one kind；
    Preferably, in step 2), the mol ratio of the aluminium lithium hydride and the silicon tetrachloride is (1:1)~(3:1)；
    Preferably, in step 2), the mol ratio of the hydrogen peroxide and the silicon tetrachloride is (2:1)~(6:1)；
    Preferably, in step 2), the time of the reaction is 0.5~5h；
    Preferably, in step 2), the detergent is absolute methanol or absolute ethyl alcohol.
  6. 6. according to the preparation method described in one of claim 3-5, it is characterised in that in step 3), the matter of the organic carbon source Measure 1/5~1/20 of the quality for porous carbon materials described in step 1)；
    Preferably, in step 3), the organic carbon source is selected from the one of sucrose, cellulose, acetate fiber, cyclodextrin and phenolic resin Kind or at least two.
  7. 7. according to the preparation method described in one of claim 3-6, it is characterised in that in step 3), the speed of the ball milling is 100~300rpm, the time of the ball milling is 0.5~10h.
  8. 8. according to the preparation method described in one of claim 3-7, it is characterised in that in step 3), the calcining is in inertia Carried out in atmosphere or reducing atmosphere；
    Preferably, the inert atmosphere is blanket of nitrogen or argon atmospher, and the reducing atmosphere is hydrogen atmosphere；
    Preferably, the temperature of the calcining is 800~1000 DEG C, and the time of the calcining is 3~12h.
  9. 9. according to the preparation method described in one of claim 3-8, it is characterised in that in step 2), after reducing agent reduces To simple substance nano silicon particles, the particle diameter of the simple substance nano silicon particles is 2nm~20nm.
  10. 10. according to the preparation method described in one of claim 3-9, it is characterised in that the preparation method comprises the following steps：
    1) silicon tetrachloride is dissolved in the anhydrous ethane that the silicon tetrachloride that mass concentration is 0.1~10mol/L is made in anhydrous ethane Solution, by porous carbon materials add into the anhydrous ethane solution of silicon tetrachloride dipping 0.5~5h, the silicon tetrachloride with it is described The mol ratio of porous carbon materials is (0:1)~(1:1), filter, obtain Si-C composite material A after heating；
    2) the Si-C composite material A for obtaining step 1) is added in reductant solution, and the reducing agent is the tetrahydrochysene of aluminium lithium hydride Tetrahydrofuran solution, aluminium lithium hydride diethyl ether solution and hydrogen peroxide in one kind；Mole of the aluminium lithium hydride and the silicon tetrachloride Than for (1:1)~(3:1), or the mol ratio of the hydrogen peroxide and the silicon tetrachloride is (2:1)~(6:1), stirring reaction 0.5 Detergent cleaning is added after~5h, obtains Si-C composite material B；
    3) organic carbon source is added in the Si-C composite material B that step 2) obtains, the quality of the organic carbon source is in step 1) The 1/5~1/20 of the quality of the porous carbon materials；0.5~10h of ball milling is carried out with 100~300rpm ball milling speed, lazy 800~1000 DEG C of 3~12h of temperature calcination, obtains closed cage structure silicon-carbon composite wood in property atmosphere or reducing atmosphere Material.
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CN113506864A (en) * 2021-04-12 2021-10-15 南京睿扬光电技术有限公司 Silicon monoxide composite material for lithium ion battery and preparation method thereof
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