CN109065866A - A kind of silicon-carbon composite cathode material and preparation method thereof based on silsesquioxane - Google Patents

A kind of silicon-carbon composite cathode material and preparation method thereof based on silsesquioxane Download PDF

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CN109065866A
CN109065866A CN201810872409.0A CN201810872409A CN109065866A CN 109065866 A CN109065866 A CN 109065866A CN 201810872409 A CN201810872409 A CN 201810872409A CN 109065866 A CN109065866 A CN 109065866A
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silsesquioxane
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silicon
composite
vinyl
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CN109065866B (en
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涂文懋
白子瑜
唐浩林
朱君可
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Wuhan University of Technology WUT
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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
    • 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
    • H01M4/38—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
    • H01M4/62—Selection of inactive substances as ingredients for active masses, e.g. binders, fillers
    • H01M4/624—Electric conductive fillers
    • H01M4/625—Carbon or graphite
    • 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 belongs to new energy materials fields, it specifically discloses a kind of preparation method of silicon-carbon composite cathode material (Si@C) based on silsesquioxane polymer presoma: first mixing vinyl silsesquioxane with styrene, it is copolymerized under initiator effect, using resulting polymers as persursor material, be successively carbonized, magnesiothermic reduction, removal impurity obtain Si@C negative electrode material.In gained negative electrode material of the invention, silicon and carbon form uniformly compound clad structure, and are conducive to construct nanoaperture structure, can effectively improve lithium ion battery specific discharge capacity and cyclical stability；And the preparation method being related to is simple, and it is reproducible, a new approaches can be provided for the preparation of the efficient negative electrode material of lithium ion battery.

Description

A kind of silicon-carbon composite cathode material and preparation method thereof based on silsesquioxane
Technical field
The invention belongs to novel energy resource material technology fields, and in particular to a kind of based on silsesquioxane polymer presoma Silicon-carbon composite cathode material and preparation method thereof.
Background technique
With the continuous consumption of fossil energy, renewable and clean energy resource becomes countries in the world focus of attention, however this There are localities and unstability for a little energy, it is difficult to effectively be utilized on a large scale.Thus, the conversion of clean energy resource with deposit Storage also just becomes the most important thing of current new energy field development.Wherein, lithium ion battery has energy as energy storage device The advantages that density is big, good cycling stability, and operating voltage is high, is widely used in portable electronic product field.This is but also open Hair high capacity, high stability and cheap new type lithium ion battery material become current research hotspot.
Key components of the negative electrode material as lithium ion battery, largely determine the performance of battery.It passes The graphite cathode material electric conductivity and stability of system are preferable, but its theoretical capacity only has 370mAhg-1.Its reason of silicium cathode material Reach 4200mAhg by capacity-1, it is more than ten times of graphite cathode, and its intercalation potential is moderate, abundant raw materials.However, silicon is negative There is up to 300% bulk effect and poor conduction during alloying reaction occurs with lithium ion in pole material Property, which also limits the commercial applications of silicon materials.It is more that patent CN201010581833.3 discloses a kind of lithium ion battery use Hole carbon nano-fiber negative electrode material and preparation method, negative electrode material are to combine preparation gained with carbon heat through electrostatic spinning technique. Patent CN201611174374.0 discloses a kind of lithium ion battery silicium cathode, and negative electrode active material includes graphite and titanium dioxide Silicon.But the porous carbon negative pole material component used is single, does not make full use of the advantage of the high capacity of silicon based anode material；Silicon Graphite and silica are bonded by organic solvent in negative electrode active material, and only simple mixing, does not form Even clad structure is unable to deformation of buffers active substance during removal lithium embedded.In addition, for existing Si@C composite, Use inorganic silicon materials as silicon source mostly, the uniformity that silicon and carbon are distributed in preparation gained composite material is not high, in charge and discharge The problems such as bad there are cyclical stability in electric process.
Summary of the invention
It is a primary object of the present invention in view of the deficienciess of the prior art, providing a kind of silicon based on silsesquioxane The preparation method of carbon compound cathode materials, using silsesquioxane nanostructure frame can In-situ reaction the advantages of, preparation is equal Even compound silicon-carbon clad structure, can effectively improve the specific discharge capacity and cyclical stability of battery；And the preparation side being related to Method is simple, easy to operate, is suitble to promote and apply.
To achieve the above object, the technical solution adopted by the present invention are as follows:
A kind of preparation method of the silicon-carbon composite cathode material based on silsesquioxane, it the following steps are included:
1) azo-bis-isobutyl cyanide is added in styrene, is uniformly mixed, obtain mixed solution；
2) vinyl silsesquioxane is dissolved in mixed solution obtained by step 1), is uniformly mixed, and carry out deoxygenation Freezing, obtains anaerobic mixture；
3) in an inert atmosphere, gained anaerobic mixture is reacted under water-bath and stirring condition；Then into Row washing, dry, grinding, obtains the styrene copolymerized plural gel powder of vinyl silsesquioxane-；
4) gained vinyl silsesquioxane-styrene copolymerized plural gel powder is placed in inert atmosphere and calcined, Obtain SiOx@C composite；
5) by magnesium powder and SiOx@C composite is mixed, and is placed in progress magnesiothermic reduction reaction in argon atmosphere, is obtained Si@ C composite；
6) Si C composite is washed through salt acid soak, it is dry, it is ground to the silicon-carbon Compound Negative based on silsesquioxane Pole material (Si@C negative electrode material).
In above scheme, the vinyl silsesquioxane (vinyl-POSS) is selected from divinyl silsesquioxane, four Vinyl silsesquioxane, six vinyl silsesquioxanes, one in octavinyl-polyhedral oligomeric silsesquioxane (eight vinyl-POSS) Kind.
In above scheme, the mass ratio of the vinyl silsesquioxane and styrene is 1:(5~25)；Two isobutyl of azo The mass ratio of cyanogen and vinyl silsesquioxane is 1:(1.25~2).
In above scheme, the deoxygenation refrigeration operation, which is placed in liquid nitrogen, to be carried out.
In above scheme, reaction temperature described in step 3) is 60~75 DEG C, and the time is 2~4h.
In above scheme, drying temperature described in step 3) is 70~85 DEG C, and the time is 6~8h.
In above scheme, calcination temperature described in step 4) is 800~1100 DEG C, and soaking time is 3~5h；Heating rate For 3~5 DEG C/min.
In above scheme, magnesium powder described in step 5) and SiOxThe mass ratio of@C composite is 1:(0.5~0.8).
In above scheme, magnesiothermic reduction reaction temperature described in step 5) is 650~750 DEG C, and soaking time is 2~4h； Heating rate is 3~5 DEG C/min.
In above scheme, inert atmosphere described in step 4) is nitrogen or argon gas.
In above scheme, drying temperature described in step 6) is 90~100 DEG C, and the time is 6~8h.
In above scheme, in the hydrochloric acid soaking step, the concentration of hydrochloric acid used is 1~2mol/L.
According to the silicon-carbon composite cathode material based on silsesquioxane prepared by above scheme, it can express and excellent electric discharge Specific capacity and cyclical stability.
The principle of the present invention: the present invention is different in azo two using vinyl silsesquioxane and styrene as polymerized monomer Under the initiation of fourth cyanogen, free radicals copolymerization reaction occurs, using gained silsesquioxane polymer as persursor material, then through carbon Change, magnesiothermic reduction processing, obtains Si@C composite；In the material system, using vinyl silsesquioxane as silicon source, introduce vertical Cube nanostructure frame provides more active sites for the insertion of lithium ion, improves embedding lithium capacity, and nanometer frame Be conducive to introduce nano pore structure in Si/C composite material, be conducive to deformation of buffers active substance during removal lithium embedded Problem；Styrene carries out In-situ reaction as carbon source, with vinyl silsesquioxane, forms the clad structure of carbon packet silicon, is mentioning On the basis of high gained conductivity of composite material and capacitance, it can also further alleviate the volume expansion of silicon materials, significantly improve The cyclical stability of battery.
Compared with prior art, beneficial effects of the present invention:
1) compared with traditional Si@C negative electrode material, present invention firstly provides be with vinyl silsesquioxane based polyalcohol Presoma is advantageously implemented cellular structure nanosizing with clad structure in the synchronous building of Si/C composite material, is obviously improved institute Obtain the chemical property of composite material.
2) composite material uses In-situ reaction means, after being carbonized, the carbon of nanoaperture and cladding in silicon structure The bulk effect of layer double buffering silicon materials makes gained composite material that good capacity can still be maintained to keep in later cycles Rate.
3) compared to traditional Si@C composite, under conditions of identical silicone content, battery capacity is significantly improved.
4) preparation method of the present invention is simple, and dual structure in Si/C composite material can be realized using single step reaction Building, and this method repetitive rate is high, is suitble to promote and apply.
Detailed description of the invention
Fig. 1 is the photoelectron spectroscopy figure that the embodiment of the present invention 1 prepares Si@C negative electrode material.
Fig. 2 is the scanning electron microscope (SEM) photograph that the embodiment of the present invention 1 prepares Si@C negative electrode material.
Fig. 3 is the curve of double curvature that the embodiment of the present invention 1 prepares Si@C negative electrode material.
Specific embodiment
In order to better understand the content of the present invention, it is further illustrated below with reference to specific example.But it should refer to Out, implementation of the invention is not limited to following several embodiments.
Embodiment 1
A kind of preparation method of the silicon-carbon composite cathode material based on silsesquioxane polymer presoma, including walk as follows It is rapid:
1) 1.2g azo-bis-isobutyl cyanide is added in 10ml styrene, stirs 10min, obtains mixed solution；
2) 1.8g divinyl silsesquioxane is dissolved in mixed solution obtained by step 1), stirs 15min, is placed in liquid Deoxygenation is carried out in nitrogen and freezes 30min, obtains anaerobic mixture；
3) under inert gas (argon gas) environment, by anaerobic mixture obtained by step 2) under 65 DEG C of water-baths, stirring conditions React 3h；Then filtering and washing is carried out with ethyl alcohol, it is total to obtain divinyl silsesquioxane-styrene by 80 DEG C of dry 6h, grinding Poly- plural gel powder；
4) gained divinyl silsesquioxane-styrene copolymerized plural gel powder is placed in Ar gas atmosphere 1100 DEG C Lower calcining 3h (heating rate is 3 DEG C/min), obtains SiOx@C composite；
5) by 2g magnesium powder and 1g SiOx@C composite is mixed, and is placed in 650 DEG C of calcining 2h in Ar gas atmosphere and (is risen Warm speed is 3 DEG C/min), obtain Si@C composite；
6) Si@C composite is impregnated into the oxide that 4h removes excessive magnesium powder and magnesium through 1mol/L HCl, then through going Ion water washing, 100 DEG C of dry 6h, grinding are to get silicon-carbon composite cathode material (the Si C cathode material based on silsesquioxane Material).
The present embodiment products therefrom is carried out to XPS Analysis, morphology analysis and electro-chemical test analysis respectively: Fig. 1 is the photoelectron spectroscopy figure of Si@C negative electrode material obtained by this example (presence at the peak 100.4eV characterizes Si-C key), it can be seen that Products therefrom of the present invention is Si-C composite material rather than the mixture of simple silicon-carbon mixing；Fig. 2 is Si@C obtained by this example Negative electrode material scanning electron microscope (SEM) photograph, it can be seen that gained composite material has the composite construction of bulk multi-hole；Fig. 3 is obtained by this example The curve of double curvature of Si@C negative electrode material, test result show in current density 5Ag-1Under, capacity maintains 400mAhg-1, work as electricity Current density reforms into 200mAg-1When, capacity can still restore to 800mAhg-1；And gained Si@C negative electrode material have compared with Good high rate performance and reversible capacity.
Composite material obtained by this example of 35mg is weighed in agate grinding, 10mg acetylene black, mixed grinding 0.5h is added.Claim Amount 5mg PVDF is dissolved in 250ul NMP, is ultrasonically treated 1.5h；Mixture after mixed grinding is added to and has dissolved PVDF's In NMP, continues ultrasound 1.5h, obtain evenly dispersed slurries.The slurries are coated on copper foil, through 70 DEG C of dry 12h, through beating Hole assembles lithium-ion button battery and carries out electro-chemical test.
The result shows that being reached using the lithium ion battery of the preparation of Si@C negative electrode material obtained by the present embodiment in first circle capacity 1423mAhg-1, hence it is evident that be higher than comparative sample (by the preparation-obtained Si@C composite negative pole material of this example through hf etching, go Resulting porous carbon negative pole material after impurity) first circle 812mAhg-1Capacity, and capacity still can be with after 1600 circulations It is maintained at 418mAhg-1, there is good cyclical stability.
It is 19.7% through the silicon rate in Si@C composite negative pole material manufactured in the present embodiment known to atomic absorption spectrum.And with Silicon monoxide is silicon source, sucrose is carbon source, and the Si@C composite being prepared in situ through high-energy ball milling, pyrolysis contains in identical silicon Under amount, first circle capacity is 1120mAhg-1, capacity is reduced to 385mAhg after 100 circulations-1。
Embodiment 2
A kind of preparation method of the silicon-carbon composite cathode material based on silsesquioxane polymer presoma, including walk as follows It is rapid:
1) 1g azo-bis-isobutyl cyanide is added in 10ml styrene, stirs 15min, obtains mixed solution；
2) 1.5g tetravinyl silsesquioxane is dissolved in mixed solution obtained by step 1), stirs 10min, is placed in liquid Deoxygenation is carried out in nitrogen and freezes 30min, obtains anaerobic mixture；
3) under inert gas (argon gas) environment, by anaerobic mixture obtained by step 2) under 65 DEG C of water-baths, stirring conditions React 3h；Then filtering and washing is carried out with ethyl alcohol, it is total to obtain tetravinyl silsesquioxane-styrene by 80 DEG C of dry 6h, grinding Poly- plural gel powder；
4) gained tetravinyl silsesquioxane-styrene copolymerized plural gel powder is placed in Ar gas atmosphere 800 DEG C Lower calcining 3h (heating rate is 3 DEG C/min), obtains SiOx@C composite；
5) by 1.5g magnesium powder and 1g SiOx@C composite is mixed, and 700 DEG C of calcining 2h in Ar gas atmosphere are placed in (heating rate is 3 DEG C/min), obtains Si@C composite；
6) Si@C composite is impregnated into the oxide that 4h removes excessive magnesium powder and magnesium through 1mol/L HCl, then through going Ion water washing, 100 DEG C of dry 6h, grinding are to get silicon-carbon composite cathode material (the Si C cathode material based on silsesquioxane Material).
Composite material obtained by 35mg the present embodiment is weighed in agate grinding, 10mg acetylene black, mixed grinding 0.5h is added. It weighs 5mg PVDF and is dissolved in 250ul NMP, be ultrasonically treated 1.5h；Mixture after mixed grinding is added to and has dissolved PVDF NMP in, continue ultrasound 1.5h, obtain evenly dispersed slurries.The slurries are coated on copper foil, through 70 DEG C of dry 12h, warp Punching assembling lithium-ion button battery carries out electro-chemical test.
The result shows that being reached using the lithium ion battery of the preparation of Si@C negative electrode material obtained by the present embodiment in first circle capacity 1482mAhg-1, and capacity still may remain in 435mAhg after 1800 circulations-1, there is good cyclical stability.
Embodiment 3
A kind of preparation method of the silicon-carbon composite cathode material based on silsesquioxane polymer presoma, including walk as follows It is rapid:
1) 0.6g azo-bis-isobutyl cyanide is added in 10ml styrene, stirs 20min, obtains mixed solution；
2) six vinyl silsesquioxane of 1g is dissolved in mixed solution obtained by step 1), stirs 15min, is placed in liquid nitrogen Middle progress deoxygenation freezes 30min, obtains anaerobic mixture；
3) under inert gas (argon gas) environment, by anaerobic mixture obtained by step 2) under 65 DEG C of water-baths, stirring conditions React 3h；Then filtering and washing is carried out with ethyl alcohol, it is total to obtain six vinyl silsesquioxanes-styrene by 80 DEG C of dry 6h, grinding Poly- plural gel powder；
4) six vinyl silsesquioxane of gained-styrene copolymerized plural gel powder is placed in Ar gas atmosphere 900 DEG C Lower calcining 3h (heating rate is 3 DEG C/min), obtains SiOx@C composite；
5) by 1.25g magnesium powder and 1g SiOx@C composite is mixed, and 750 DEG C of calcining 2h in Ar gas atmosphere are placed in (heating rate is 3 DEG C/min), obtains Si@C composite；
6) Si@C composite is impregnated into the oxide that 4h removes excessive magnesium powder and magnesium through 1mol/L HCl, then through going Ion water washing, 100 DEG C of dry 6h, grinding are to get silicon-carbon composite cathode material (the Si C cathode material based on silsesquioxane Material).
Composite material obtained by 35mg the present embodiment is weighed in agate grinding, 10mg acetylene black, mixed grinding 0.5h is added； It weighs 5mg PVDF and is dissolved in 250ul NMP, be ultrasonically treated 1.5h.Mixture after mixed grinding is added to and has dissolved PVDF NMP in, continue ultrasound 1.5h, obtain evenly dispersed slurries.The slurries are coated on copper foil, through 70 DEG C of dry 12h, warp Punching assembling lithium-ion button battery carries out electro-chemical test.
The result shows that being reached using the lithium ion battery of the preparation of Si@C negative electrode material obtained by the present embodiment in first circle capacity 1441mAhg-1, and capacity still may remain in 423mAhg after 1900 circulations-1, there is good cyclical stability.
Embodiment 4
A kind of preparation method of the silicon-carbon composite cathode material based on silsesquioxane polymer presoma, including walk as follows It is rapid:
1) 0.2g azo-bis-isobutyl cyanide is added in 10ml styrene, stirs 20min, obtains mixed solution；
2) 0.4g octavinyl-polyhedral oligomeric silsesquioxane is dissolved in mixed solution obtained by step 1), stirs 10min, is placed in liquid Deoxygenation is carried out in nitrogen and freezes 30min, obtains anaerobic mixture；
3) under inert gas (argon gas) environment, by anaerobic mixture obtained by step 2) under 65 DEG C of water-baths, stirring conditions React 3h；Then filtering and washing is carried out with ethyl alcohol, it is total to obtain octavinyl-polyhedral oligomeric silsesquioxane-styrene by 80 DEG C of dry 6h, grinding Poly- plural gel powder；
4) gained octavinyl-polyhedral oligomeric silsesquioxane-styrene copolymerized plural gel powder is placed in Ar gas atmosphere 1000 DEG C Lower calcining 3h (heating rate is 3 DEG C/min), obtains SiOx@C composite；
5) by 1.4g magnesium powder and 1g SiOx@C composite is mixed, and 750 DEG C of calcining 2h in Ar gas atmosphere are placed in (heating rate is 3 DEG C/min), obtains Si@C composite；
6) Si@C composite is impregnated into the oxide that 4h removes excessive magnesium powder and magnesium through 1mol/L HCl, then through going Ion water washing, 100 DEG C of dry 6h, grinding are to get silicon-carbon composite cathode material (the Si C cathode material based on silsesquioxane Material).
Composite material obtained by 35mg the present embodiment is weighed in agate grinding, 10mg acetylene black, mixed grinding 0.5h is added； It weighs 5mg PVDF and is dissolved in 250ul NMP, be ultrasonically treated 1.5h.Mixture after mixed grinding is added to and has dissolved PVDF NMP in, continue ultrasound 1.5h, obtain evenly dispersed slurries.The slurries are coated on copper foil, through 70 DEG C of dry 12h, warp Punching assembling lithium-ion button battery carries out electro-chemical test.
The result shows that being reached using the lithium ion battery of the preparation of Si@C negative electrode material obtained by the present embodiment in first circle capacity 1506mAhg-1, and capacity still may remain in 457mAhg after 2000 circulations-1, there is good cyclical stability.
Comparative example
A kind of porous carbon negative pole material, preparation method include the following steps:
1) 1.2g azo-bis-isobutyl cyanide is added in 10ml styrene, stirs 10min, obtains mixed solution；
2) 1.8g divinyl silsesquioxane is dissolved in mixed solution obtained by step 1), stirs 15min, is placed in liquid Deoxygenation is carried out in nitrogen and freezes 30min, obtains anaerobic mixture；
3) under inert gas (argon gas) environment, by anaerobic mixture obtained by step 2) under 65 DEG C of water-baths, stirring conditions React 3h；Then filtering and washing is carried out with ethyl alcohol, it is total to obtain divinyl silsesquioxane-styrene by 80 DEG C of dry 6h, grinding Poly- plural gel powder；
4) gained divinyl silsesquioxane-styrene copolymerized plural gel powder is placed in Ar gas atmosphere 1100 DEG C Lower calcining 3h (heating rate is 3 DEG C/min), obtains SiOx@C composite；
5) by 2g magnesium powder and 1g SiOx@C composite is mixed, and is placed in 650 DEG C of calcining 2h in Ar gas atmosphere and (is risen Warm speed is 3 DEG C/min), obtain Si@C composite；
6) Si@C composite is impregnated into the oxide that 4h removes excessive magnesium powder and magnesium through 1mol/L HCl, then through going Ion water washing, 100 DEG C of dry 6h, grinding are to get silicon-carbon composite cathode material (the Si C cathode material based on silsesquioxane Material).
7) prepared Si@C negative electrode material HF is impregnated into 12h, washing, 100 DEG C of dry 8h are ground to get porous carbon Material (comparative sample).
Porous carbon materials obtained by this comparative example of 35mg are weighed in agate grinding, 10mg acetylene black, mixed grinding is added 0.5h；It weighs 5mg PVDF and is dissolved in 250ul NMP, be ultrasonically treated 1.5h.Mixture after mixed grinding is added to dissolution In the NMP of PVDF, continues ultrasound 1.5h, obtain evenly dispersed slurries.The slurries are coated on copper foil, through 70 DEG C of dryings 12h carries out electro-chemical test through punching assembling lithium-ion button battery.
The result shows that being using the lithium ion battery first circle capacity of porous carbon negative pole material preparation obtained by this comparative example 812mAhg-1, and capacity is stable at 410mAhg after 300 circulations-1。
Obviously, above-described embodiment is only intended to clearly illustrate made example, and is not the limitation to embodiment.It is right For those of ordinary skill in the art, can also make on the basis of the above description it is other it is various forms of variation or It changes.There is no necessity and possibility to exhaust all the enbodiments.And the obvious variation or change therefore amplified It moves within still in the protection scope of the invention.

Claims (10)

1. a kind of preparation method of the silicon-carbon composite cathode material based on silsesquioxane, it the following steps are included:
1) azo-bis-isobutyl cyanide is added in styrene, is uniformly mixed, obtain mixed solution；
2) vinyl silsesquioxane is dissolved in mixed solution obtained by step 1), is uniformly mixed, and carry out deoxygenation freezing, Obtain anaerobic mixture；
3) in an inert atmosphere, gained anaerobic mixture is reacted under water-bath and stirring condition；Then it is washed It washs, dry, grinding obtains the styrene copolymerized plural gel powder of vinyl silsesquioxane-；
4) gained vinyl silsesquioxane-styrene copolymerized plural gel powder is placed in inert atmosphere and calcined, obtained SiOx@C composite；
5) by magnesium powder and SiOx@C composite is mixed, and is placed in progress magnesiothermic reduction reaction in argon atmosphere, it is compound to obtain Si@C Material；
6) Si C composite is washed through salt acid soak, dry, grinding obtains the silicon-carbon composite cathode based on silsesquioxane Material.
2. preparation method according to claim 1, which is characterized in that the vinyl silsesquioxane is selected from divinyl One of silsesquioxane, tetravinyl silsesquioxane, six vinyl silsesquioxanes, octavinyl-polyhedral oligomeric silsesquioxane.
3. preparation method according to claim 1, which is characterized in that the matter of the vinyl silsesquioxane and styrene Amount is than being 1:(5~25)；The mass ratio of azo-bis-isobutyl cyanide and vinyl silsesquioxane is 1:(1.25~2).
4. preparation method according to claim 1, which is characterized in that reaction temperature described in step 3) is 60~75 DEG C, Time is 2~4h.
5. preparation method according to claim 1, which is characterized in that calcination temperature described in step 4) is 800~1100 DEG C, soaking time is 3~5h.
6. preparation method according to claim 1, which is characterized in that magnesium powder described in step 5) and SiOx@C composite Mass ratio be 1:(0.5~0.8).
7. preparation method according to claim 1, which is characterized in that magnesiothermic reduction reaction temperature described in step 5) is 650~750 DEG C, soaking time is 2~4h.
8. preparation method according to claim 1, which is characterized in that inert atmosphere described in step 4) is nitrogen or argon Gas.
9. preparation method according to claim 1, which is characterized in that in the hydrochloric acid soaking step, the hydrochloric acid of use is dense Degree is 1~2mol/L.
10. the silicon-carbon composite cathode material based on silsesquioxane made from any one of claim 1~9 preparation method.
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CN112038625A (en) * 2020-08-14 2020-12-04 合肥国轩高科动力能源有限公司 Lithium titanate negative electrode material and preparation method thereof
CN115148975A (en) * 2022-07-29 2022-10-04 合肥综合性国家科学中心能源研究院(安徽省能源实验室) Silicon oxide/carbon negative electrode material of self-supporting lithium ion battery and preparation method

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