CN102903896B - For the silicon-carbon composite cathode material of lithium ion battery, its preparation method and application - Google Patents
For the silicon-carbon composite cathode material of lithium ion battery, its preparation method and application Download PDFInfo
- Publication number
- CN102903896B CN102903896B CN201210404007.0A CN201210404007A CN102903896B CN 102903896 B CN102903896 B CN 102903896B CN 201210404007 A CN201210404007 A CN 201210404007A CN 102903896 B CN102903896 B CN 102903896B
- Authority
- CN
- China
- Prior art keywords
- silicon
- carbon
- lithium ion
- cathode material
- ion battery
- Prior art date
- Legal status (The legal status is an assumption and is not a legal conclusion. Google has not performed a legal analysis and makes no representation as to the accuracy of the status listed.)
- Expired - Fee Related
Links
- HBBGRARXTFLTSG-UHFFFAOYSA-N Lithium ion Chemical compound [Li+] HBBGRARXTFLTSG-UHFFFAOYSA-N 0.000 title claims abstract description 42
- 229910001416 lithium ion Inorganic materials 0.000 title claims abstract description 42
- 239000002153 silicon-carbon composite material Substances 0.000 title claims abstract description 36
- 239000010406 cathode material Substances 0.000 title claims abstract description 32
- 238000002360 preparation method Methods 0.000 title claims abstract description 23
- 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
- 239000002245 particle Substances 0.000 claims abstract description 10
- 239000002131 composite material Substances 0.000 claims abstract description 6
- OKTJSMMVPCPJKN-UHFFFAOYSA-N Carbon Chemical compound [C] OKTJSMMVPCPJKN-UHFFFAOYSA-N 0.000 claims description 34
- 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
- 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
- 238000001035 drying Methods 0.000 claims description 7
- 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
- 239000005720 sucrose Substances 0.000 claims description 4
- 239000012298 atmosphere Substances 0.000 claims description 3
- 238000001816 cooling Methods 0.000 claims description 3
- 229910021392 nanocarbon Inorganic materials 0.000 claims description 3
- 238000005507 spraying Methods 0.000 claims description 3
- XUIMIQQOPSSXEZ-UHFFFAOYSA-N Silicon Chemical compound [Si] XUIMIQQOPSSXEZ-UHFFFAOYSA-N 0.000 abstract description 25
- 239000010703 silicon Substances 0.000 abstract description 25
- 229910052710 silicon Inorganic materials 0.000 abstract description 25
- 239000000463 material Substances 0.000 abstract description 19
- 238000000034 method Methods 0.000 abstract description 16
- 230000008569 process Effects 0.000 abstract description 11
- 230000000694 effects Effects 0.000 abstract description 7
- 239000011258 core-shell material Substances 0.000 abstract description 5
- 230000007246 mechanism Effects 0.000 abstract description 5
- 230000007613 environmental effect Effects 0.000 abstract description 2
- 238000010276 construction Methods 0.000 abstract 1
- 238000006243 chemical reaction Methods 0.000 description 24
- IJGRMHOSHXDMSA-UHFFFAOYSA-N Atomic nitrogen Chemical compound N#N IJGRMHOSHXDMSA-UHFFFAOYSA-N 0.000 description 20
- 239000010410 layer Substances 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
- QVGXLLKOCUKJST-UHFFFAOYSA-N atomic oxygen Chemical compound [O] QVGXLLKOCUKJST-UHFFFAOYSA-N 0.000 description 5
- 239000006185 dispersion Substances 0.000 description 5
- 239000011261 inert gas Substances 0.000 description 5
- 229910052744 lithium Inorganic materials 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
- WHXSMMKQMYFTQS-UHFFFAOYSA-N Lithium Chemical compound [Li] WHXSMMKQMYFTQS-UHFFFAOYSA-N 0.000 description 4
- 239000002270 dispersing agent Substances 0.000 description 4
- 239000007789 gas Substances 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
- 239000002253 acid Substances 0.000 description 3
- 239000011247 coating layer Substances 0.000 description 3
- 239000000178 monomer Substances 0.000 description 3
- 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
- 206010013786 Dry skin Diseases 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
- 238000005516 engineering process Methods 0.000 description 2
- 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
- 230000000903 blocking effect Effects 0.000 description 1
- 230000003139 buffering effect Effects 0.000 description 1
- 150000001721 carbon Chemical class 0.000 description 1
- 230000008859 change Effects 0.000 description 1
- 238000009831 deintercalation Methods 0.000 description 1
- 210000001787 dendrite Anatomy 0.000 description 1
- 238000006253 efflorescence Methods 0.000 description 1
- 239000007772 electrode material Substances 0.000 description 1
- 238000004146 energy storage Methods 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
- 230000006872 improvement Effects 0.000 description 1
- 230000002687 intercalation Effects 0.000 description 1
- 238000009830 intercalation Methods 0.000 description 1
- 239000011159 matrix material Substances 0.000 description 1
- 239000002086 nanomaterial Substances 0.000 description 1
- 206010037844 rash Diseases 0.000 description 1
- 230000029058 respiratory gaseous exchange Effects 0.000 description 1
- 239000000126 substance Substances 0.000 description 1
- -1 such as Substances 0.000 description 1
- 238000010792 warming Methods 0.000 description 1
Classifications
-
- Y—GENERAL TAGGING OF NEW TECHNOLOGICAL DEVELOPMENTS; GENERAL TAGGING OF CROSS-SECTIONAL TECHNOLOGIES SPANNING OVER SEVERAL SECTIONS OF THE IPC; TECHNICAL SUBJECTS COVERED BY FORMER USPC CROSS-REFERENCE ART COLLECTIONS [XRACs] AND DIGESTS
- Y02—TECHNOLOGIES OR APPLICATIONS FOR MITIGATION OR ADAPTATION AGAINST CLIMATE CHANGE
- Y02E—REDUCTION OF GREENHOUSE GAS [GHG] EMISSIONS, RELATED TO ENERGY GENERATION, TRANSMISSION OR DISTRIBUTION
- Y02E60/00—Enabling technologies; Technologies with a potential or indirect contribution to GHG emissions mitigation
- Y02E60/10—Energy storage using batteries
Abstract
The present invention is applicable to field of new, provides a kind of silicon-carbon composite cathode material for lithium ion battery, its preparation method and application.This negative material is core-shell type composite construction, by nano-silicon be core, intermediate layer amorphous carbon and outermost layer One-dimensional nanoreticular carbon materials form.The wherein amorphous carbon in intermediate layer, forms the loose surface structure of scalability, the cycle performance of silicon and high rate performance is got a promotion; The network configuration that outermost One-dimensional nanoreticular carbon materials builds not only serves the effect of buffer mechanism stress, and provides Quick conductive passage for silicon active particle, further the cycle performance of raising silicon and high rate performance; Meanwhile, the three-dimensional conductive heat conduction network that One-dimensional nanoreticular carbon materials is formed, can be transmitted to surrounding space in time by the heat produced in battery discharge procedure, improves the security performance of battery.The present invention is used for that the silicon-carbon composite cathode material preparation method of lithium ion battery is simple for process, environmental protection and energy saving, with low cost, be easy to industrialization.
Description
Technical field
The invention belongs to field of new, particularly relate to a kind of silicon-carbon composite cathode material for lithium ion battery, its preparation method and application.
Background technology
, global warming surging in scarcity of resources, fossil price, subtract carbon emission, sustainable development and urban transportation blocking and under the large historical background such as motor vehicle emission is serious, the new chemical memory technology that to greatly develop using the energy storage electrokinetic cell be badly in need of as new-energy automobile, solar energy, wind energy etc. be representative, has become the emphasis of the common concern of countries in the world government and support.Lithium ion battery as Green Chemistry power supply is the secondary cell be most widely used at present, and range of needs is throughout fields such as electronic product, information industry, energy traffic and military project national defence.Negative material, as one of the critical material of lithium ion battery, plays vital effect to the raising of performance of lithium ion battery.
The lithium ion battery of Current commercial still mainly adopts graphite-like carbon negative pole material.But the theoretical specific capacity of graphite is only 372mAh/g, and intercalation potential platform is close to lithium metal, and quick charge or low temperature charging " analysing lithium " phenomenon easily occur and cause potential safety hazard, greatly constrain the development and application of lithium ion battery.In various non-carbon negative material, silicon has attracted the sight of more and more researcher with the advantage and potential of its uniqueness.Silicon and lithium can form a series of alloy, and the highest component can reach Li
4.4si, theoretical capacity is up to 4200mAh/g.Comparatively graphite is high for its slotting lithium current potential in addition, not easily forms dendrite, have higher security performance in charge and discharge process.But plug off in process at lithium, this kind of material volume change reaches more than 300%.The internal stress that serious volumetric expansion produces causes electrode material efflorescence and peels off, and its capacity declines rapidly, finally makes battery lose activity.For the consideration of extensive commercial application, the comprehensive silicon carbon negative pole material with nanostructure preparing high power capacity has development potentiality most.
The Si/C composite negative pole material that processability is excellent, key is how to obtain rational material structure.The silicon grain of micro/nano level is uniformly distributed or completely coated by carbon, and carbonaceous buffering matrix forms good order wire circuit and has rational hole or Rotating fields with the breathing of controls Si in charge and discharge process, while material monolithic there is rock-steady structure.But the Si-C composite material of preparation is at present difficult to the structural stability keeping activated silica material in lithium ion deintercalation process, causes cyclical stability, high rate performance and security performance undesirable, limits 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 the technical problem that in prior art, Si-C composite material cyclical stability, high rate performance and security performance are undesirable; And this is used for the silicon-carbon composite cathode material preparation method of 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, comprises nucleome and is coated on intermediate layer and the outermost layer of nucleome successively, this nucleome be nano-silicon, this intermediate layer is amorphous carbon, and this is outermost is One-dimensional nanoreticular carbon materials.
And,
The 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 organic solvent, microwave heating 2 ~ 180 minutes under inert atmosphere and temperature are 300 ~ 600 DEG C of conditions after drying, cooling obtain amorphous carbon clad nano silicon grain, this organic carbon source be selected from citric acid, phenolic resins, sucrose one or more;
Be scattered in organic solution by this amorphous carbon clad nano silicon grain, One-dimensional nanoreticular carbon materials, cracking of spraying at 100 ~ 400 DEG C of temperature, obtains the silicon-carbon composite cathode material for lithium ion battery.
The present invention further provides the application of the above-mentioned silicon-carbon composite cathode material for lithium ion battery in 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, forms the loose surface structure of scalability, for Lithium-ion embeding silicon substrate material provides inflatable cushion space, the cycle performance of silicon and high rate performance is got a promotion; The network configuration that outer field One-dimensional nanoreticular carbon materials builds not only serves the effect of buffer mechanism stress, and provides Quick conductive passage for silicon active particle, further the cycle performance of raising silicon and high rate performance; Meanwhile, the three-dimensional conductive heat conduction network that One-dimensional nanoreticular carbon materials is formed, can be transmitted to surrounding space in time by the heat produced in battery discharge procedure, improves the security performance of battery.The present invention is used for that the silicon-carbon composite cathode material preparation method of lithium ion battery is simple for process, environmental protection and energy saving, with low cost, be easy to industrialization.
Embodiment
In order to make object of the present invention, technical scheme and advantage clearly understand, 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, be not intended to limit the present invention.
The embodiment of the present invention provides a kind of silicon-carbon composite cathode material for lithium ion battery, this negative material is core-shell type three-layer composite structure, comprise nucleome and be coated on intermediate layer and the outermost layer of nucleome successively, this nucleome is nano-silicon, this intermediate layer is amorphous carbon, and this outermost layer is One-dimensional nanoreticular carbon materials.
That is, embodiment of the present invention negative material, is made up of the particulate of core shell structure, this core shell structure comprises three-layer composite structure, nucleome and be coated on intermediate layer and the outermost layer of nucleome successively, 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 core 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 made up of amorphous carbon, forms the loose surface structure of scalability, for Lithium-ion embeding silicon substrate material provides inflatable cushion space, the cycle performance of silicon and high rate performance is got a promotion.
This outermost layer is One-dimensional nanoreticular carbon materials, such as, 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 build and form network configuration, not only serve the effect of buffer mechanism stress, and provide Quick conductive passage for silicon active particle, improve cycle performance and the high rate performance of silicon further; Meanwhile, the three-dimensional conductive heat conduction network that this outer One-dimensional nanoreticular carbon materials is formed, can be transmitted to surrounding space in time by the heat produced in battery discharge procedure, improve 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, forms the loose surface structure of scalability, for Lithium-ion embeding silicon substrate material provides inflatable cushion space, the cycle performance of silicon and high rate performance is got a promotion; The network configuration that outer field One-dimensional nanoreticular carbon materials builds not only serves the effect of buffer mechanism stress, and provides Quick conductive passage for silicon active particle, further the cycle performance of raising silicon and high rate performance; Meanwhile, the three-dimensional conductive heat conduction network that One-dimensional nanoreticular carbon materials is formed, can be transmitted to surrounding space in time by the heat produced in battery discharge procedure, improves the security performance of battery.
The embodiment of the present invention provides the above-mentioned silicon-carbon composite cathode material preparation method for lithium ion battery further, comprises the steps:
Step S01, prepares amorphous carbon clad nano silicon grain:
Be scattered in organic solvent by silicon nanoparticle and organic carbon source, microwave heating 2 ~ 180 minutes under inert atmosphere and temperature are 300 ~ 600 DEG C of conditions after drying, cooling obtains amorphous carbon clad nano silicon grain.This organic carbon source be selected from citric acid, phenolic resins, sucrose one or more;
Step S02, prepares nano-silicon/amorphous carbon/One-dimensional nanoreticular carbon materials composite material:
Be scattered in organic solution by described amorphous carbon clad nano silicon grain, One-dimensional nanoreticular carbon materials, cracking of spraying at 100 ~ 400 DEG C of temperature, obtains the silicon-carbon composite cathode material for lithium ion battery.
In step S01, this organic carbon source is selected from one or more in citric acid, phenolic resins, sucrose.This organic solvent is selected from the one in absolute ethyl alcohol, acetone or 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 are added to organic solvent, make silicon nanoparticle and organic carbon source dispersed in organic solvent by ultrasonic wave and mechanical agitation mode.By the solution drying process after dispersion, obtain the structure of organic carbon source clad nano silicon grain, i.e. amorphous carbon clad nano silicon grain presoma, such as, dry in 100 DEG C of baking ovens.
Then this amorphous carbon clad nano silicon grain precursor is placed in microwave reaction chamber, vacuumize and to make in burner hearth absolute pressure lower than 1kPa, vacuumize again after passing into inert gas to normal pressure, repeat this process more than three times, the oxygen in reaction chamber is got rid of clean.
Then open microwave, first pass into the inert gas of flowing before opening microwave in reaction chamber, to remove the oxygen remained in reaction chamber.In the embodiment of the present invention, inert gas such as, nitrogen, helium, argon gas etc.
While opening microwave, keep passing into of above-mentioned inert gas, after unlatching microwave, the circulation of inert gas is 20 ~ 200sccm, such as, 100sccm, is adjusted to 300 ~ 600 DEG C by microwave heating by the temperature of reaction chamber, such as, 400 DEG C, then keep 2 ~ 180 minutes under said temperature condition, carry out microwave reaction.By microwave heating to said temperature, the organic carbon source generation cracking in amorphous carbon clad nano silicon grain precursor, forms carbon monomer, and this carbon monomer forms coating layer, is coated on nano-silicon periphery, in carbon monomer coating layer, forms loose structure.
After having reacted, system temperature is cooled to room temperature, namely obtains amorphous carbon clad nano silicon grain.
In step S02, this One-dimensional nanoreticular carbon materials is selected from the one in carbon nano-tube or carbon nano-fiber, and this organic solvent is selected from the one in absolute ethyl alcohol, acetone soln or deionized water, further, also add appropriate dispersant in this step, this dispersant is dodecyl sodium sulfate.By adding dispersant, make uniform doping between nano-carbon material and 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 are added to appropriate organic solvent, by ultrasonic process and each 20 ~ 60 minutes of mechanical agitation, make each component dispersed, obtain homodisperse suspension.This suspension to be sprayed at 100 ~ 400 DEG C of temperature cracking, obtain the silicon-carbon composite cathode material for lithium ion battery.
The embodiment of the present invention is used for the silicon-carbon composite cathode material preparation method of lithium ion battery, by using organic carbon source clad nano silicon, coated one deck carbon nano-tube or carbon nano-fiber again, obtain comprising nucleome, intermediate layer and outer field core-shell type particle, wherein, the amorphous carbon in intermediate layer, forms the loose surface structure of scalability, for Lithium-ion embeding silicon substrate material provides inflatable cushion space, the cycle performance of silicon and high rate performance are got a promotion; The network configuration that outer field One-dimensional nanoreticular carbon materials builds not only serves the effect of buffer mechanism stress, and provides Quick conductive passage for silicon active particle, further the cycle performance of raising silicon and high rate performance; Meanwhile, the three-dimensional conductive heat conduction network that One-dimensional nanoreticular carbon materials is formed, can be transmitted to surrounding space in time by the heat produced in battery discharge procedure, improves the security performance of battery.
The embodiment of the present invention provides the application of the above-mentioned silicon-carbon composite cathode material for lithium ion battery in lithium ion battery further.
Below in conjunction with specific embodiment, the 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 chooses 1g nano silica fume, 10g citric acid is scattered in ethanolic solution, and ultrasonic adding after mechanical agitation is disperseed dries the presoma obtaining amorphous carbon clad nano silicon in 100 DEG C of baking ovens;
2) presoma of dried amorphous carbon clad nano silicon is placed in reaction chamber, vacuumizes and make absolute pressure in burner hearth lower than 1kPa, vacuumize again after logical nitrogen to normal pressure, repeat this process three times.The nitrogen of flowing is first passed in reaction chamber, to remove the oxygen remained in reaction chamber before opening microwave;
3) open gas flow bottle valve, pass into the nitrogen that flow is 100sccm, use microwave heating reaction chamber, when temperature rises to reaction temperature 400 DEG C fast, after question response 30min, close microwave, whole reaction system is cooled to room temperature in a nitrogen atmosphere, obtains amorphous carbon clad nano silicon grain;
4) the amorphous carbon clad nano silicon grain obtained first time, the acid of 0.01g dodecane sulfo group are received and 0.8g carbon nano-tube is mixed in appropriate ethanolic solution.Mixed liquor through ultrasonic add mechanical agitation dispersion 60min after, finely dispersed suspension is obtained silicon/amorphous carbon/carbon nano-tube advanced composite material (ACM) in 220 DEG C 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 chooses 1g nano silica fume, 20g phenolic resins is dissolved in appropriate acetone soln, ultrasonic add mechanical agitation dispersion after in 80 DEG C of baking ovens, dry the presoma obtaining amorphous carbon clad nano silicon;
2) presoma of dried amorphous carbon clad nano silicon is placed in reaction chamber, vacuumizes and make absolute pressure in burner hearth lower than 1kPa, vacuumize again after logical nitrogen to normal pressure, repeat this process three times.The nitrogen of flowing is first passed in reaction chamber, to remove the oxygen remained in reaction chamber before opening microwave;
3) open gas flow bottle valve, pass into the nitrogen that flow is 100sccm.Use microwave heating reaction chamber, when temperature rises to reaction temperature 500 DEG C fast, after question response 60min, close microwave, whole reaction system is cooled to room temperature in a nitrogen atmosphere, obtains amorphous carbon clad nano silicon grain;
4) the amorphous carbon clad nano silicon grain obtained first time, the acid of 0.02g dodecane sulfo group are received and 1.5g average diameter is that 100nm carbon nano-fiber is mixed in appropriate ethanolic solution.Mixed liquor through ultrasonic add mechanical agitation dispersion 60min after, finely dispersed suspension is obtained silicon/amorphous carbon/carbon nano-fiber advanced composite material (ACM) in 220 DEG C of high-temperature spray cracking dryings.
Embodiment 3
1) the present embodiment chooses 2g nano silica fume, 10g citric acid is scattered in ethanolic solution, and ultrasonic adding after mechanical agitation is disperseed dries the presoma obtaining amorphous carbon clad nano silicon in 100 DEG C of baking ovens;
2) presoma of dried amorphous carbon clad nano silicon is placed in reaction chamber, vacuumizes and make absolute pressure in burner hearth lower than 1kPa, vacuumize again after logical nitrogen to normal pressure, repeat this process three times.The nitrogen of flowing is first passed in reaction chamber, to remove the oxygen remained in reaction chamber before opening microwave;
3) open gas flow bottle valve, pass into the nitrogen that flow is 100sccm.Use microwave heating reaction chamber, when temperature rises to reaction temperature 600 DEG C fast, after question response 60min, close microwave, whole reaction system is cooled to 100 DEG C in a nitrogen atmosphere, obtains amorphous carbon clad nano silicon grain;
4) the amorphous carbon clad nano silicon grain obtained first time, the acid of 0.01g dodecane sulfo group are received and 1g carbon nano-tube is mixed in appropriate ethanolic solution.Mixed liquor through ultrasonic add mechanical agitation dispersion 60min after, finely dispersed suspension is obtained spherical silicon/amorphous carbon/carbon nano-tube advanced composite material (ACM) in 300 DEG C of high-temperature spray cracking drying.
The foregoing is only preferred embodiment of the present invention, not in order to limit the present invention, all any amendments done within the spirit and principles in the present invention, equivalent replacement and improvement etc., all should be included within protection scope of the present invention.
Claims (8)
1. the silicon-carbon composite cathode material preparation method for lithium ion battery, described silicon-carbon composite cathode material is nucleocapsid structure, comprise nucleome and be coated on intermediate layer and the outermost layer of nucleome successively, described nucleome is nano-silicon, described intermediate layer is amorphous carbon, and described outermost layer is One-dimensional nanoreticular carbon materials;
Described silicon-carbon composite cathode material preparation method comprises the steps:
Silicon nanoparticle and organic carbon source are scattered in organic solvent, microwave heating 2 ~ 180 minutes under inert atmosphere and temperature are 300 ~ 600 DEG C of conditions after drying, cooling obtain amorphous carbon clad nano silicon grain, described organic carbon source be selected from citric acid, phenolic resins, sucrose one or more;
Be scattered in organic solution by described amorphous carbon clad nano silicon grain, nano-carbon material, cracking of spraying at 100 ~ 400 DEG C of temperature, obtains the silicon-carbon composite cathode material for lithium ion battery.
2., as claimed in claim 1 for the silicon-carbon composite cathode material preparation method of lithium ion battery, it is characterized in that, the weight ratio of described silicon nanoparticle and organic carbon source is 20:1 ~ 1:20.
3., as claimed in claim 1 for the silicon-carbon composite cathode material preparation method of lithium ion battery, it 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.
4., as claimed in claim 1 for the silicon-carbon composite cathode material preparation method of lithium ion battery, it is characterized in that, the particle diameter of described nano-silicon is 10 ~ 100nm.
5., as claimed in claim 1 for the silicon-carbon composite cathode material preparation method of lithium ion battery, it is characterized in that, described amorphous carbon is porous carbon.
6. the silicon-carbon composite cathode material preparation method for lithium ion battery as described in any one of claim 1,4,5, is characterized in that, the thickness in described intermediate layer is 1 ~ 80nm.
7., as claimed in claim 1 for the silicon-carbon composite cathode material preparation method of lithium ion battery, it is characterized in that, described nano-carbon material is selected from carbon nano-tube or carbon nano-fiber.
8., as claimed in claim 1 for the silicon-carbon composite cathode material preparation method of lithium ion battery, it is characterized in that, described nano-silicon is 10 ~ 90% at the percentage by weight of composite material.
Priority Applications (1)
| Application Number | Priority Date | Filing Date | Title |
|---|---|---|---|
| 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 |
Applications Claiming Priority (1)
| Application Number | Priority Date | Filing Date | Title |
|---|---|---|---|
| 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 |
Publications (2)
| Publication Number | Publication Date |
|---|---|
| CN102903896A CN102903896A (en) | 2013-01-30 |
| CN102903896B true CN102903896B (en) | 2015-07-29 |
Family
ID=47576036
Family Applications (1)
| Application Number | Title | Priority Date | Filing Date |
|---|---|---|---|
| CN201210404007.0A Expired - Fee Related CN102903896B (en) | 2012-10-22 | 2012-10-22 | For the silicon-carbon composite cathode material of lithium ion battery, its preparation method and application |
Country Status (1)
| Country | Link |
|---|---|
| CN (1) | CN102903896B (en) |
Families Citing this family (31)
| Publication number | Priority date | Publication date | Assignee | Title |
|---|---|---|---|---|
| CN103346324B (en) * | 2013-06-28 | 2016-07-06 | 中国科学院宁波材料技术与工程研究所 | Lithium ion battery cathode material and its preparation method |
| CN103762379A (en) * | 2014-01-28 | 2014-04-30 | 泉州劲鑫电子有限公司 | High-capacity lithium ion battery and production process thereof |
| CN103904335B (en) * | 2014-04-21 | 2016-02-17 | 哈尔滨工业大学 | A kind of lithium ion battery negative material |
| CN104332632B (en) * | 2014-08-22 | 2017-01-11 | 新乡市远东电子科技股份有限公司 | Lithium ion battery silicon-carbon negative electrode material and preparation method thereof |
| CN105591109B (en) * | 2014-11-14 | 2018-03-09 | 青岛灵科新能源有限公司 | carbon material and preparation method thereof and lithium ion battery |
| CN104617261B (en) * | 2015-01-23 | 2017-01-18 | 福建翔丰华新能源材料有限公司 | Method for preparing composite cathode material of silicon-carbon nanotube of lithium ion battery |
| CN105161695A (en) * | 2015-06-12 | 2015-12-16 | 南通彩都新能源科技有限公司 | Spherical active material particles for lithium ion battery negative electrode, preparation method and application of spherical active material particles |
| CN104953122B (en) * | 2015-06-30 | 2017-09-19 | 深圳清华大学研究院 | Nano-silicone wire/carbon composite negative pole material and preparation method and its lithium ion battery |
| CN105006554B (en) * | 2015-07-27 | 2017-11-28 | 深圳市国创新能源研究院 | A kind of silicon-carbon composite cathode material of lithium ion battery and preparation method thereof |
| CN105118974A (en) * | 2015-08-20 | 2015-12-02 | 浙江理工大学 | Silicon-based negative electrode material and preparation method thereof |
| CN105304875A (en) * | 2015-09-30 | 2016-02-03 | 苏州大学 | Preparation method of lithium ion battery composite cathode material |
| CN105406039B (en) * | 2015-11-03 | 2018-03-30 | 山东精工电子科技有限公司 | A kind of silicon-carbon cathode slurry and preparation method thereof |
| CN105428614B (en) * | 2015-11-06 | 2017-03-15 | 盐城工学院 | A kind of nitrogen-doping porous composite negative pole material and preparation method thereof |
| CN107302082A (en) * | 2016-04-15 | 2017-10-27 | 华为技术有限公司 | Silicium cathode material and preparation method thereof, cathode pole piece and lithium ion battery |
| CN106099079A (en) | 2016-08-26 | 2016-11-09 | 宁德时代新能源科技股份有限公司 | Secondary battery negative electrode material, preparation method thereof and battery containing negative electrode material |
| CN106941170A (en) * | 2017-04-24 | 2017-07-11 | 广东烛光新能源科技有限公司 | A kind of silicon-carbon cathode material and preparation method thereof |
| CN107010938B (en) * | 2017-04-28 | 2020-08-04 | 郑州大学 | Method for inhibiting growth of magnesia-alumina spinel nano-particles at high temperature |
| CN110323418A (en) * | 2018-03-30 | 2019-10-11 | 中国石油化工股份有限公司 | Si-C composite material and its preparation method and application |
| EP3788666A4 (en) * | 2018-04-30 | 2022-01-19 | Lyten, Inc. | Lithium ion battery and battery materials |
| CN109148851B (en) * | 2018-08-16 | 2021-07-06 | 武汉理工大学 | Silicon-carbon composite negative electrode material modified by double carbon structure and preparation method thereof |
| CN109920990B (en) * | 2019-03-01 | 2022-02-11 | 贵州大学 | Preparation method for preparing silicon-metal-carbon composite material by microwave |
| CN110649254B (en) * | 2019-09-06 | 2020-12-25 | 成都新柯力化工科技有限公司 | Lithium battery silicon-carbon negative electrode composite material and preparation method thereof |
| CN111326723B (en) * | 2020-02-26 | 2021-11-05 | 博尔特新材料(银川)有限公司 | Silicon-carbon composite negative electrode material for lithium ion battery and preparation method thereof |
| CN111244430B (en) * | 2020-03-11 | 2021-06-15 | 武汉理工大学 | Silicon-carbon composite negative electrode material with double-wall core-shell structure and preparation and application thereof |
| CN111755680B (en) * | 2020-07-06 | 2022-09-20 | 马鞍山科达普锐能源科技有限公司 | Silicon-carbon negative electrode material for lithium ion battery and preparation method thereof |
| CN112125294B (en) * | 2020-09-21 | 2022-04-19 | 陕西煤业化工技术研究院有限责任公司 | Coal-based silicon-carbon composite negative electrode material and preparation method thereof |
| CN112142060B (en) * | 2020-09-21 | 2022-04-19 | 陕西煤业化工技术研究院有限责任公司 | Coal-based silicon-carbon composite negative electrode material and preparation method thereof |
| CN112133898B (en) * | 2020-09-21 | 2022-04-19 | 陕西煤业化工技术研究院有限责任公司 | Silicon-based negative electrode material and preparation method thereof |
| US11735745B2 (en) | 2021-06-16 | 2023-08-22 | Lyten, Inc. | Lithium-air battery |
| CN113732013A (en) * | 2021-08-27 | 2021-12-03 | 昆明理工大学 | Microwave catalytic treatment method for waste photovoltaic module and silicon-carbon composite material obtained by microwave catalytic treatment method |
| CN116936750A (en) * | 2023-09-18 | 2023-10-24 | 季华实验室 | Lithium ion battery negative electrode plate, preparation method thereof, negative electrode plate slurry and lithium ion battery |
Citations (1)
| Publication number | Priority date | Publication date | Assignee | Title |
|---|---|---|---|---|
| CN101439972A (en) * | 2007-11-21 | 2009-05-27 | 比亚迪股份有限公司 | Silicon-carbon composite material, preparation thereof, battery cathode and lithium ionic cell |
Family Cites Families (1)
| Publication number | Priority date | Publication date | Assignee | Title |
|---|---|---|---|---|
| CN100499215C (en) * | 2003-11-04 | 2009-06-10 | 上海杉杉科技有限公司 | Preparing method for carbon negative material of lithium ion battery |
-
2012
- 2012-10-22 CN CN201210404007.0A patent/CN102903896B/en not_active Expired - Fee Related
Patent Citations (1)
| Publication number | Priority date | Publication date | Assignee | Title |
|---|---|---|---|---|
| CN101439972A (en) * | 2007-11-21 | 2009-05-27 | 比亚迪股份有限公司 | Silicon-carbon composite material, preparation thereof, battery cathode and lithium ionic cell |
Also Published As
| Publication number | Publication date |
|---|---|
| CN102903896A (en) | 2013-01-30 |
Similar Documents
| Publication | Publication Date | Title |
|---|---|---|
| CN102903896B (en) | For the silicon-carbon composite cathode material of lithium ion battery, its preparation method and application | |
| CN106876689B (en) | Nitrogen-doped graphene-silicon composite negative electrode material, preparation method thereof and lithium ion battery | |
| CN103346325B (en) | A kind of lithium ion battery negative material, its preparation method and lithium ion battery | |
| CN102769139A (en) | Preparation method of high power capacity lithium ion battery cathode material | |
| CN102969489A (en) | Silicon-carbon composite material, preparation method of silicon-carbon composite material, and lithium ion battery containing silicon-carbon composite material | |
| CN103427073A (en) | Preparation method of mesoporous Si/C composite microsphere as lithium battery negative electrode material | |
| CN102447112A (en) | Silicon-carbon composite material, preparation method thereof and cathode material containing same as well as lithium ion battery | |
| CN105826527A (en) | Porous silicon-carbon composite material and preparation method and application thereof | |
| CN102437318A (en) | Preparation method for silicon-carbon composite material, prepared silicon-carbon composite material, lithium ion battery anode containing silicon-carbon composite material and battery | |
| CN111129466B (en) | High-performance positive electrode material, preparation method thereof and application thereof in lithium ion battery | |
| CN103346302A (en) | Lithium battery silicon-carbon nanotube composite cathode material as well as preparation method and application thereof | |
| CN104752698A (en) | Silicon carbon composite material for lithium ion battery cathode, and preparation method of composite material | |
| CN101859886A (en) | Lithium ion battery anode material and preparation method thereof | |
| CN110323073B (en) | Preparation method and application of oxygen-doped cobalt nickel phosphide-reduced graphene oxide composite material | |
| CN108565408A (en) | A kind of lithium ion battery negative material and preparation method thereof | |
| CN107845797A (en) | A kind of lithium ion battery nano-silicone wire/carbon composite negative pole material and preparation method thereof | |
| CN104638253A (en) | Preparation method of Si and C-RG core-shell composite material used as cathode of lithium ion battery | |
| CN105280889B (en) | A kind of lithium ion battery silicon composite cathode material and preparation method thereof | |
| CN105140481A (en) | Preparation method of high-capacity lithium-ion battery anode material | |
| CN109309199B (en) | Preparation method of lithium ion battery cathode red phosphorus/carbon nanotube composite material | |
| CN104617301B (en) | Preparation method of large-size graphene/graphite composite negative pole material | |
| CN106025241A (en) | Graphene aerogel loaded lithium iron phosphate porous composite material and preparation method thereof | |
| CN102969509A (en) | Preparation method of lithium ion battery silicon carbon composite material | |
| CN104868159A (en) | Preparation method for modified graphite anode material | |
| CN110380021A (en) | A kind of TiO of organic conductive polymer/carbon dual cladding2(B) negative electrode material and preparation method thereof |
Legal Events
| Date | Code | Title | Description |
|---|---|---|---|
| C06 | Publication | ||
| PB01 | Publication | ||
| C10 | Entry into substantive examination | ||
| SE01 | Entry into force of request for substantive examination | ||
| C14 | Grant of patent or utility model | ||
| GR01 | Patent grant | ||
| CF01 | Termination of patent right due to non-payment of annual fee |
Granted publication date: 20150729 |
|
| CF01 | Termination of patent right due to non-payment of annual fee |