CN102903896A - Silicon carbon composite negative electrode material for lithium ion battery as well as preparation method and applications of material - Google Patents
Silicon carbon composite negative electrode material for lithium ion battery as well as preparation method and applications of material Download PDFInfo
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- HBBGRARXTFLTSG-UHFFFAOYSA-N Lithium ion Chemical compound [Li+] HBBGRARXTFLTSG-UHFFFAOYSA-N 0.000 title claims abstract description 45
- 229910001416 lithium ion Inorganic materials 0.000 title claims abstract description 45
- 239000000463 material Substances 0.000 title claims abstract description 22
- 238000002360 preparation method Methods 0.000 title claims abstract description 20
- 239000011868 silicon-carbon composite negative electrode material Substances 0.000 title abstract 3
- 239000005543 nano-size silicon particle Substances 0.000 claims abstract description 48
- 229910003481 amorphous carbon Inorganic materials 0.000 claims abstract description 44
- 239000003575 carbonaceous material Substances 0.000 claims abstract description 25
- 239000002131 composite material Substances 0.000 claims abstract description 6
- 229910021392 nanocarbon Inorganic materials 0.000 claims abstract description 6
- OKTJSMMVPCPJKN-UHFFFAOYSA-N Carbon Chemical compound [C] OKTJSMMVPCPJKN-UHFFFAOYSA-N 0.000 claims description 34
- 239000002153 silicon-carbon composite material Substances 0.000 claims description 33
- 239000010406 cathode material Substances 0.000 claims description 29
- 229910052799 carbon Inorganic materials 0.000 claims description 23
- KRKNYBCHXYNGOX-UHFFFAOYSA-N citric acid Chemical compound OC(=O)CC(O)(C(O)=O)CC(O)=O KRKNYBCHXYNGOX-UHFFFAOYSA-N 0.000 claims description 18
- 229910021393 carbon nanotube Inorganic materials 0.000 claims description 10
- 239000002041 carbon nanotube Substances 0.000 claims description 10
- 239000002245 particle Substances 0.000 claims description 9
- 239000002134 carbon nanofiber Substances 0.000 claims description 8
- 238000005336 cracking Methods 0.000 claims description 8
- 238000010438 heat treatment Methods 0.000 claims description 8
- VNWKTOKETHGBQD-UHFFFAOYSA-N methane Chemical compound C VNWKTOKETHGBQD-UHFFFAOYSA-N 0.000 claims description 8
- 239000003960 organic solvent Substances 0.000 claims description 8
- 239000005011 phenolic resin Substances 0.000 claims description 5
- 229920001568 phenolic resin Polymers 0.000 claims description 5
- 229930006000 Sucrose Natural products 0.000 claims description 4
- CZMRCDWAGMRECN-UGDNZRGBSA-N Sucrose Chemical compound O[C@H]1[C@H](O)[C@@H](CO)O[C@@]1(CO)O[C@@H]1[C@H](O)[C@@H](O)[C@H](O)[C@@H](CO)O1 CZMRCDWAGMRECN-UGDNZRGBSA-N 0.000 claims description 4
- 238000005507 spraying Methods 0.000 claims description 4
- 239000005720 sucrose Substances 0.000 claims description 4
- 239000012298 atmosphere Substances 0.000 claims description 3
- 238000001816 cooling Methods 0.000 claims description 3
- XUIMIQQOPSSXEZ-UHFFFAOYSA-N Silicon Chemical compound [Si] XUIMIQQOPSSXEZ-UHFFFAOYSA-N 0.000 abstract description 24
- 239000010703 silicon Substances 0.000 abstract description 24
- 229910052710 silicon Inorganic materials 0.000 abstract description 24
- 238000000034 method Methods 0.000 abstract description 15
- 230000008569 process Effects 0.000 abstract description 11
- 230000003139 buffering effect Effects 0.000 abstract description 2
- 238000007599 discharging Methods 0.000 abstract 1
- 239000007773 negative electrode material Substances 0.000 abstract 1
- 239000011856 silicon-based particle Substances 0.000 abstract 1
- 238000006243 chemical reaction Methods 0.000 description 25
- 239000010410 layer Substances 0.000 description 21
- IJGRMHOSHXDMSA-UHFFFAOYSA-N Atomic nitrogen Chemical compound N#N IJGRMHOSHXDMSA-UHFFFAOYSA-N 0.000 description 20
- 229910052757 nitrogen Inorganic materials 0.000 description 10
- 238000013019 agitation Methods 0.000 description 8
- CSCPPACGZOOCGX-UHFFFAOYSA-N Acetone Chemical compound CC(C)=O CSCPPACGZOOCGX-UHFFFAOYSA-N 0.000 description 6
- 239000011157 advanced composite material Substances 0.000 description 6
- 238000001035 drying Methods 0.000 description 6
- 230000000694 effects Effects 0.000 description 6
- 229910052744 lithium Inorganic materials 0.000 description 6
- WHXSMMKQMYFTQS-UHFFFAOYSA-N Lithium Chemical compound [Li] WHXSMMKQMYFTQS-UHFFFAOYSA-N 0.000 description 5
- QVGXLLKOCUKJST-UHFFFAOYSA-N atomic oxygen Chemical compound [O] QVGXLLKOCUKJST-UHFFFAOYSA-N 0.000 description 5
- 239000011261 inert gas Substances 0.000 description 5
- 239000001301 oxygen Substances 0.000 description 5
- 229910052760 oxygen Inorganic materials 0.000 description 5
- 239000000725 suspension Substances 0.000 description 5
- 239000011258 core-shell material Substances 0.000 description 4
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- 230000007246 mechanism Effects 0.000 description 4
- 239000000758 substrate Substances 0.000 description 4
- SNRUBQQJIBEYMU-UHFFFAOYSA-N Dodecane Natural products CCCCCCCCCCCC SNRUBQQJIBEYMU-UHFFFAOYSA-N 0.000 description 3
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- 239000012299 nitrogen atmosphere Substances 0.000 description 3
- 230000004044 response Effects 0.000 description 3
- 229910021487 silica fume Inorganic materials 0.000 description 3
- 239000007921 spray Substances 0.000 description 3
- XKRFYHLGVUSROY-UHFFFAOYSA-N Argon Chemical compound [Ar] XKRFYHLGVUSROY-UHFFFAOYSA-N 0.000 description 2
- LFQSCWFLJHTTHZ-UHFFFAOYSA-N Ethanol Chemical compound CCO LFQSCWFLJHTTHZ-UHFFFAOYSA-N 0.000 description 2
- 230000008901 benefit Effects 0.000 description 2
- 210000004027 cell Anatomy 0.000 description 2
- 239000008367 deionised water Substances 0.000 description 2
- 229910021641 deionized water Inorganic materials 0.000 description 2
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- 229910002804 graphite Inorganic materials 0.000 description 2
- 239000010439 graphite Substances 0.000 description 2
- 239000002243 precursor Substances 0.000 description 2
- XLYOFNOQVPJJNP-UHFFFAOYSA-N water Chemical compound O XLYOFNOQVPJJNP-UHFFFAOYSA-N 0.000 description 2
- VYPSYNLAJGMNEJ-UHFFFAOYSA-N Silicium dioxide Chemical class O=[Si]=O VYPSYNLAJGMNEJ-UHFFFAOYSA-N 0.000 description 1
- DBMJMQXJHONAFJ-UHFFFAOYSA-M Sodium laurylsulphate Chemical group [Na+].CCCCCCCCCCCCOS([O-])(=O)=O DBMJMQXJHONAFJ-UHFFFAOYSA-M 0.000 description 1
- HMDDXIMCDZRSNE-UHFFFAOYSA-N [C].[Si] Chemical compound [C].[Si] HMDDXIMCDZRSNE-UHFFFAOYSA-N 0.000 description 1
- 239000000956 alloy Substances 0.000 description 1
- 229910045601 alloy Inorganic materials 0.000 description 1
- 229910052786 argon Inorganic materials 0.000 description 1
- 150000001721 carbon Chemical class 0.000 description 1
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- 238000004146 energy storage Methods 0.000 description 1
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- -1 for example Substances 0.000 description 1
- 239000001307 helium Substances 0.000 description 1
- 229910052734 helium Inorganic materials 0.000 description 1
- SWQJXJOGLNCZEY-UHFFFAOYSA-N helium atom Chemical compound [He] SWQJXJOGLNCZEY-UHFFFAOYSA-N 0.000 description 1
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Classifications
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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
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Abstract
The invention is applicable to the field of novel materials, and provides a silicon carbon composite negative electrode material for a lithium ion battery, as well as a preparation method and applications of the material. The negative electrode material is of a nuclear-shell-type composite structure, and consists of nano silicon in the core, amorphous carbon at the middle layer and a one-dimensional nano carbon material at the outermost layer, wherein the amorphous carbon at the middle layer forms an elastic loose surface structure, and thus the circulating performance and multiplying performance of silicon are improved; a network structure built by the one-dimensional nano carbon material at the outermost layer not only plays a role in buffering mechanical stress, but also provides a rapid electric conducting channel for active silicon particles, and improves the circulating performance and multiplying performance of silicon further; and meanwhile, a three-dimensional electric-conducting heat-conducting network formed by the one-dimensional nano carbon material can conduct heat generated by a battery during the discharging process to the space around, and the safety performance of the battery is improved. The preparation method of the silicon carbon composite negative electrode material for the lithium ion battery is simple and feasible in process, environment-friendly and energy-saving, low in cost, and easy for industrialization.
Description
Technical field
The invention belongs to field of new, relate in particular to a kind of silicon-carbon composite cathode material for lithium ion battery, its preparation method and application.
Background technology
, global warming surging at scarcity of resources, fossil price, subtract that carbon emission, sustainable development and urban transportation are stopped up and the large historical background such as motor vehicle emission is serious under, greatly develop take as the energy storage electrokinetic cell of the urgent needs such as new-energy automobile, solar energy, the wind energy new chemical memory technology as representative, become the emphasis of the common concern of countries in the world government and support.Lithium ion battery as the Green Chemistry power supply is the secondary cell that is most widely used at present, and range of needs spreads all over the fields such as electronic product, information industry, energy traffic and military project national defence.Negative material is as one of critical material of lithium ion battery, and the raising of performance of lithium ion battery is played vital effect.
Current business-like lithium ion battery still mainly adopts the graphite-like carbon negative pole material.Yet the theoretical specific capacity of graphite only is 372mAh/g, and embedding lithium current potential platform is near lithium metal, and quick charge or low temperature charging " analysing lithium " phenomenon easily occur cause potential safety hazard, have greatly restricted the development and application of lithium ion battery.In the various non-carbon negative pole materials, silicon has attracted more and more researchers' sight with its unique advantage and potentiality.Silicon and lithium can form a series of alloys, and the highest component can reach Li
4.4Si, theoretical capacity is up to 4200mAh/g.Its slotting lithium current potential is high than graphite in addition, is difficult in the charge and discharge process forming dendrite, has higher security performance.But, to insert at lithium and to take off in the process, this class material volume changes and reaches more than 300%.The internal stress that serious volumetric expansion produces causes the electrode material efflorescence and peels off, and its capacity descends rapidly, and battery is lost activity.For the consideration of extensive commercial application, the comprehensive silicon carbon negative pole material with nanostructure of preparation high power capacity has development potentiality most.
The Si/C composite negative pole material that processability is good, key are how to obtain rational material structure.The silicon grain of micro/nano level evenly distributes or is coated fully by carbon, carbonaceous buffering matrix form good order wire circuit and rational hole is arranged or layer structure with the breathing of control Si in charge and discharge process, material monolithic has rock-steady structure simultaneously.But the Si-C composite material of preparation takes off the structural stability that is difficult to keep the activated silica material in the embedding process at lithium ion at present, causes cyclical stability, high rate performance and security performance undesirable, has limited its practical application.
Summary of the invention
In view of this, the object of the present invention is to provide a kind of silicon-carbon composite cathode material for lithium ion battery, solve Si-C composite material cyclical stability, high rate performance and the undesirable technical problem of security performance in the prior art; And the silicon-carbon composite cathode material preparation method that should be used for lithium ion battery.
The present invention is achieved in that
A kind of silicon-carbon composite cathode material for lithium ion battery, this negative material is nucleocapsid structure, comprise nucleome and be coated on successively intermediate layer and the outermost layer of nucleome, this nucleome be nano-silicon, this intermediate layer is amorphous carbon, and this is outermost to be One-dimensional nanoreticular carbon materials.
And,
Above-mentioned silicon-carbon composite cathode material preparation method for lithium ion battery comprises the steps:
Silicon nanoparticle and organic carbon source are scattered in the organic solvent, be microwave heating 2 ~ 180 minutes under 300 ~ 600 ℃ of conditions in inert atmosphere and temperature after dry, cooling obtains amorphous carbon clad nano silicon grain, and this organic carbon source is selected from one or more of citric acid, phenolic resins, sucrose;
This amorphous carbon clad nano silicon grain, One-dimensional nanoreticular carbon materials are scattered in the organic solution, and the cracking of spraying under 100 ~ 400 ℃ of temperature obtains the silicon-carbon composite cathode material for lithium ion battery.
The present invention further provides above-mentioned silicon-carbon composite cathode material for lithium ion battery in the application of lithium ion battery.
The present invention is used for the silicon-carbon composite cathode material of lithium ion battery, the amorphous carbon in intermediate layer, and the loose surface structure of formation scalability provides inflatable cushion space for lithium ion embeds the silicon substrate material, and the cycle performance of silicon and high rate performance are got a promotion; The network configuration that outer field One-dimensional nanoreticular carbon materials makes up has not only played the effect of buffer mechanism stress, and for the silicon active particle provides the Quick conductive passage, further improves cycle performance and the high rate performance of silicon; Simultaneously, the three-dimensional conductive and heat-conductive network that One-dimensional nanoreticular carbon materials forms can in time be transmitted to surrounding space with the heat that produces in the battery discharge procedure, improves the security performance of battery.The present invention is simple for process for the silicon-carbon composite cathode material preparation method of lithium ion battery, environmental protection and energy saving, with low cost, is easy to industrialization.
Embodiment
In order to make purpose of the present invention, technical scheme and advantage clearer, below in conjunction with embodiment, the present invention is further elaborated.Should be appreciated that specific embodiment described herein only in order to explain the present invention, is not intended to limit the present invention.
The embodiment of the invention provides a kind of silicon-carbon composite cathode material for lithium ion battery, this negative material is the core-shell type three-layer composite structure, comprise nucleome and be coated on successively intermediate layer and the outermost layer of nucleome, this nucleome is nano-silicon, this intermediate layer is amorphous carbon, and this outermost layer is One-dimensional nanoreticular carbon materials.
That is to say, embodiment of the invention negative material is by the ultrafine particles composition of core-shell type structure, this core-shell type structure comprises three-layer composite structure, nucleome and be coated on successively intermediate layer and the outermost layer of nucleome, and this nucleome is nano-silicon, this intermediate layer is amorphous carbon, and this outermost layer is One-dimensional nanoreticular carbon materials.
This nucleome is nano-silicon, and the particle diameter of this nano-silicon is preferably 10 ~ 100nm, and also, the particle diameter of this nucleome is 10-100nm.
This intermediate layer is coated on this nucleome surface, and the thickness in this intermediate layer is 1 ~ 80nm, and material is amorphous carbon.This amorphous carbon is preferably porous carbon.This coating layer is comprised of amorphous carbon, forms the loose surface structure of scalability, provides inflatable cushion space for lithium ion embeds the silicon substrate material, and the cycle performance of silicon and high rate performance are got a promotion.
This outermost layer is One-dimensional nanoreticular carbon materials, for example, and carbon nano-tube or carbon nano-fiber.By selecting the skin of carbon nano-tube or carbon nano-fiber, this carbon nano-tube or carbon nano-fiber make up and form network configuration, not only play the effect of buffer mechanism stress, and for the silicon active particle provides the Quick conductive passage, further improved cycle performance and the high rate performance of silicon; Simultaneously, the three-dimensional conductive and heat-conductive network that this skin One-dimensional nanoreticular carbon materials forms can in time be transmitted to surrounding space with the heat that produces in the battery discharge procedure, improves the security performance of battery.
The present invention is used for the silicon-carbon composite cathode material of lithium ion battery, the amorphous carbon in intermediate layer, and the loose surface structure of formation scalability provides inflatable cushion space for lithium ion embeds the silicon substrate material, and the cycle performance of silicon and high rate performance are got a promotion; The network configuration that outer field One-dimensional nanoreticular carbon materials makes up has not only played the effect of buffer mechanism stress, and for the silicon active particle provides the Quick conductive passage, further improves cycle performance and the high rate performance of silicon; Simultaneously, the three-dimensional conductive and heat-conductive network that One-dimensional nanoreticular carbon materials forms can in time be transmitted to surrounding space with the heat that produces in the battery discharge procedure, improves the security performance of battery.
The embodiment of the invention further provides above-mentioned silicon-carbon composite cathode material preparation method for lithium ion battery, comprises the steps:
Step S01, preparation amorphous carbon clad nano silicon grain:
Silicon nanoparticle and organic carbon source are scattered in the organic solvent, are microwave heating 2 ~ 180 minutes under 300 ~ 600 ℃ of conditions in inert atmosphere and temperature after dry, and cooling obtains amorphous carbon clad nano silicon grain.This organic carbon source is selected from one or more of citric acid, phenolic resins, sucrose;
Step S02, preparation nano-silicon/amorphous carbon/One-dimensional nanoreticular carbon materials composite material:
Described amorphous carbon clad nano silicon grain, One-dimensional nanoreticular carbon materials are scattered in the organic solution, and the cracking of spraying under 100 ~ 400 ℃ of temperature obtains the silicon-carbon composite cathode material for lithium ion battery.
Among the step S01, this organic carbon source is selected from one or more in citric acid, phenolic resins, the sucrose.This organic solvent is selected from a kind of in absolute ethyl alcohol, acetone or the deionized water.The particle diameter of this silicon nanoparticle is 10 ~ 100nm.The weight ratio of this silicon nanoparticle and organic carbon source is 20:1 ~ 1:20.After silicon nanoparticle and organic carbon source be added to organic solvent, make silicon nanoparticle and organic carbon source Uniform Dispersion in organic solvent with ultrasonic wave and mechanical agitation mode.With the dry processing of the solution after disperseing, obtain the structure of organic carbon source clad nano silicon grain, namely amorphous carbon clad nano silicon grain presoma is for example dried in 100 ℃ of baking ovens.
Then this amorphous carbon clad nano silicon grain precursor is placed the microwave reaction chamber, vacuumize and make the interior absolute pressure of burner hearth be lower than 1kPa, pass into inert gas and to normal pressure, vacuumize again, repeat this process more than three times, the oxygen in the reaction chamber is got rid of clean.
Then open microwave, open before the microwave and pass into first mobile inert gas in the reaction chamber, remain in oxygen in the reaction chamber with removal.In the embodiment of the invention inert gas for example, nitrogen, helium, argon gas etc.
When opening microwave, keep passing into of above-mentioned inert gas, the circulation of inert gas is 20 ~ 200sccm behind the unlatching microwave, for example, 100sccm is adjusted to 300 ~ 600 ℃ by microwave heating with the temperature of reaction chamber, for example, 400 ℃, then under the said temperature condition, kept 2 ~ 180 minutes, carry out microwave reaction.To above-mentioned temperature, the organic carbon source generation cracking in the amorphous carbon clad nano silicon grain precursor forms the carbon monomer by microwave heating, and this carbon monomer forms coating layer, is coated on the nano-silicon periphery, forms loose structure in carbon monomer coating layer.
After reaction is finished, system temperature is cooled to room temperature, namely obtains amorphous carbon clad nano silicon grain.
Among the step S02, this One-dimensional nanoreticular carbon materials is selected from a kind of in carbon nano-tube or the carbon nano-fiber, and this organic solvent is selected from a kind of in absolute ethyl alcohol, acetone soln or the deionized water, further, also add an amount of dispersant in this step, this dispersant is dodecyl sodium sulfate.By adding dispersant, make uniform doping between nano-carbon material and the amorphous carbon clad nano silicon grain.The weight ratio of this amorphous carbon clad nano silicon grain and One-dimensional nanoreticular carbon materials is 10:1 ~ 1:10.After this amorphous carbon clad nano silicon, One-dimensional nanoreticular carbon materials and dispersant be added to an amount of organic solvent, by ultrasonic processing and mechanical agitation each 20 ~ 60 minutes, make each component Uniform Dispersion, obtain homodisperse suspension.With the cracking of under 100 ~ 400 ℃ of temperature, spraying of this suspension, obtain the silicon-carbon composite cathode material for lithium ion battery.
The embodiment of the invention is used for the silicon-carbon composite cathode material preparation method of lithium ion battery, by using organic carbon source clad nano silicon, coat again one deck carbon nano-tube or carbon nano-fiber, obtain comprising nucleome, intermediate layer and outer field core-shell type particle, wherein, the amorphous carbon in intermediate layer, the loose surface structure of formation scalability, provide inflatable cushion space for lithium ion embeds the silicon substrate material, the cycle performance of silicon and high rate performance are got a promotion; The network configuration that outer field One-dimensional nanoreticular carbon materials makes up has not only played the effect of buffer mechanism stress, and for the silicon active particle provides the Quick conductive passage, further improves cycle performance and the high rate performance of silicon; Simultaneously, the three-dimensional conductive and heat-conductive network that One-dimensional nanoreticular carbon materials forms can in time be transmitted to surrounding space with the heat that produces in the battery discharge procedure, improves the security performance of battery.
The embodiment of the invention further provides the application of above-mentioned silicon-carbon composite cathode material for lithium ion battery at lithium ion battery.
Below in conjunction with specific embodiment above-mentioned silicon-carbon composite cathode material preparation method for lithium ion battery is described in detail.
Embodiment 1
The preparation method of the Si-C composite material of the present embodiment comprises following concrete steps:
1) the present embodiment is chosen the 1g nano silica fume, the 10g citric acid is scattered in the ethanolic solution, and the ultrasonic mechanical agitation that adds is disperseed the rear presoma that obtains amorphous carbon clad nano silicon of drying in 100 ℃ of baking ovens;
2) presoma with dried amorphous carbon clad nano silicon places reaction chamber, vacuumizes to make the interior absolute pressure of burner hearth be lower than 1kPa, and logical nitrogen vacuumizes to normal pressure again, repeats this process three times.Open before the microwave and pass into first mobile nitrogen in the reaction chamber, remain in oxygen in the reaction chamber with removal;
3) open the gas flow bottle valve, pass into the nitrogen that flow is 100sccm, use the microwave heating reaction chamber, when temperature rises to 400 ℃ of reaction temperatures fast, behind the question response 30min, close microwave, whole reaction system is cooled to room temperature under nitrogen atmosphere, obtain amorphous carbon clad nano silicon grain;
4) with the amorphous carbon clad nano silicon grain that obtains for the first time, the acid of 0.01g dodecane sulfo group receives and the 0.8g carbon nano-tube is mixed in an amount of ethanolic solution.Mixed liquor through ultrasonic add mechanical agitation and disperse 60min after, finely dispersed suspension is obtained silicon/amorphous carbon/carbon nano-tube advanced composite material (ACM) in 220 ℃ of high-temperature spray cracking dryings.
Embodiment 2
The preparation method of the Si-C composite material of the present embodiment comprises following concrete steps:
1) the present embodiment is chosen the 1g nano silica fume, 20g phenolic resins is dissolved in an amount of acetone soln, and the ultrasonic mechanical agitation that adds is disperseed the rear presoma that obtains amorphous carbon clad nano silicon of drying in 80 ℃ of baking ovens;
2) presoma with dried amorphous carbon clad nano silicon places reaction chamber, vacuumizes to make the interior absolute pressure of burner hearth be lower than 1kPa, and logical nitrogen vacuumizes to normal pressure again, repeats this process three times.Open before the microwave and pass into first mobile nitrogen in the reaction chamber, remain in oxygen in the reaction chamber with removal;
3) open the gas flow bottle valve, pass into the nitrogen that flow is 100sccm.Use the microwave heating reaction chamber, when temperature rises to 500 ℃ of reaction temperatures fast, behind the question response 60min, close microwave, whole reaction system is cooled to room temperature under nitrogen atmosphere, obtain amorphous carbon clad nano silicon grain;
4) the amorphous carbon clad nano silicon grain, the acid of 0.02g dodecane sulfo group that obtain are for the first time received and the 1.5g average diameter is that the 100nm carbon nano-fiber is mixed in an amount of ethanolic solution.Mixed liquor through ultrasonic add mechanical agitation and disperse 60min after, finely dispersed suspension is obtained silicon/amorphous carbon/carbon nano-fiber advanced composite material (ACM) in 220 ℃ of high-temperature spray cracking dryings.
Embodiment 3
1) the present embodiment is chosen the 2g nano silica fume, the 10g citric acid is scattered in the ethanolic solution, and the ultrasonic mechanical agitation that adds is disperseed the rear presoma that obtains amorphous carbon clad nano silicon of drying in 100 ℃ of baking ovens;
2) presoma with dried amorphous carbon clad nano silicon places reaction chamber, vacuumizes to make the interior absolute pressure of burner hearth be lower than 1kPa, and logical nitrogen vacuumizes to normal pressure again, repeats this process three times.Open before the microwave and pass into first mobile nitrogen in the reaction chamber, remain in oxygen in the reaction chamber with removal;
3) open the gas flow bottle valve, pass into the nitrogen that flow is 100sccm.Use the microwave heating reaction chamber, when temperature rises to 600 ℃ of reaction temperatures fast, behind the question response 60min, close microwave, whole reaction system is cooled to 100 ℃ under nitrogen atmosphere, obtain amorphous carbon clad nano silicon grain;
4) with the amorphous carbon clad nano silicon grain that obtains for the first time, the acid of 0.01g dodecane sulfo group receives and the 1g carbon nano-tube is mixed in an amount of ethanolic solution.Mixed liquor through ultrasonic add mechanical agitation and disperse 60min after, finely dispersed suspension is obtained spherical silicon/amorphous carbon/carbon nano-tube advanced composite material (ACM) in 300 ℃ of high-temperature spray cracking dryings.
The above only is preferred embodiment of the present invention, not in order to limiting the present invention, all any modifications of doing within the spirit and principles in the present invention, is equal to and replaces and improvement etc., all should be included within protection scope of the present invention.
Claims (10)
1. silicon-carbon composite cathode material that is used for lithium ion battery, it is characterized in that: described negative material is nucleocapsid structure, comprise nucleome and be coated on successively intermediate layer and the outermost layer of nucleome, described nucleome is nano-silicon, described intermediate layer is amorphous carbon, and described outermost layer is One-dimensional nanoreticular carbon materials.
2. the silicon-carbon composite cathode material for lithium ion battery as claimed in claim 1 is characterized in that, the particle diameter of described nano-silicon is 10 ~ 100nm.
3. the silicon-carbon composite cathode material for lithium ion battery as claimed in claim 1 is characterized in that, described amorphous carbon is porous carbon.
4. such as each described silicon-carbon composite cathode material for lithium ion battery of claim 1 ~ 3, it is characterized in that, the thickness in described intermediate layer is 1 ~ 80nm.
5. the silicon-carbon composite cathode material for lithium ion battery as claimed in claim 1 is characterized in that, described nano-carbon material is selected from carbon nano-tube or carbon nano-fiber.
6. the silicon-carbon composite cathode material for lithium ion battery as claimed in claim 1 is characterized in that, described nano-silicon is 10 ~ 90% at the percentage by weight of composite material.
7. such as each described silicon-carbon composite cathode material preparation method for lithium ion battery of claim 1 ~ 6, comprise the steps:
Silicon nanoparticle and organic carbon source are scattered in the organic solvent, be microwave heating 2 ~ 180 minutes under 300 ~ 600 ℃ of conditions in inert atmosphere and temperature after dry, cooling obtains amorphous carbon clad nano silicon grain, and described organic carbon source is selected from one or more of citric acid, phenolic resins, sucrose;
Described amorphous carbon clad nano silicon grain, nano-carbon material are scattered in the organic solution, and the cracking of spraying under 100 ~ 400 ℃ of temperature obtains the silicon-carbon composite cathode material for lithium ion battery.
8. the silicon-carbon composite cathode material preparation method for lithium ion battery as claimed in claim 7 is characterized in that, the weight ratio of described silicon nanoparticle and organic carbon source is 20:1 ~ 1:20.
9. the silicon-carbon composite cathode material preparation method for lithium ion battery as claimed in claim 7 is characterized in that, the weight ratio of described amorphous carbon clad nano silicon grain and One-dimensional nanoreticular carbon materials is 10:1 ~ 1:10.
10. such as the application of each described silicon-carbon composite cathode material for lithium ion battery of claim 1 ~ 7 at lithium ion battery.
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| Application Number | Priority Date | Filing Date | Title |
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| CN201210404007.0A CN102903896B (en) | 2012-10-22 | 2012-10-22 | For the silicon-carbon composite cathode material of lithium ion battery, its preparation method and application |
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| CN201210404007.0A CN102903896B (en) | 2012-10-22 | 2012-10-22 | For the silicon-carbon composite cathode material of lithium ion battery, its preparation method and application |
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| CN102903896A true CN102903896A (en) | 2013-01-30 |
| CN102903896B CN102903896B (en) | 2015-07-29 |
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