CN108682830A - A kind of silicon-carbon composite cathode material of lithium ion battery and preparation method thereof - Google Patents
A kind of silicon-carbon composite cathode material of lithium ion battery and preparation method thereof Download PDFInfo
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- CN108682830A CN108682830A CN201810592172.0A CN201810592172A CN108682830A CN 108682830 A CN108682830 A CN 108682830A CN 201810592172 A CN201810592172 A CN 201810592172A CN 108682830 A CN108682830 A CN 108682830A
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- 239000002153 silicon-carbon composite material Substances 0.000 title claims abstract description 43
- 239000010406 cathode material Substances 0.000 title claims abstract description 42
- 238000002360 preparation method Methods 0.000 title claims abstract description 26
- 229910001416 lithium ion Inorganic materials 0.000 title claims abstract description 18
- HBBGRARXTFLTSG-UHFFFAOYSA-N Lithium ion Chemical compound [Li+] HBBGRARXTFLTSG-UHFFFAOYSA-N 0.000 title claims abstract description 16
- OKTJSMMVPCPJKN-UHFFFAOYSA-N Carbon Chemical compound [C] OKTJSMMVPCPJKN-UHFFFAOYSA-N 0.000 claims abstract description 93
- 229910021389 graphene Inorganic materials 0.000 claims abstract description 54
- 239000005543 nano-size silicon particle Substances 0.000 claims abstract description 37
- 239000010439 graphite Substances 0.000 claims abstract description 36
- 229910002804 graphite Inorganic materials 0.000 claims abstract description 35
- 238000005245 sintering Methods 0.000 claims abstract description 28
- 239000003795 chemical substances by application Substances 0.000 claims abstract description 18
- 239000011343 solid material Substances 0.000 claims abstract description 6
- 238000000034 method Methods 0.000 claims description 54
- 239000000463 material Substances 0.000 claims description 34
- 238000010438 heat treatment Methods 0.000 claims description 26
- 238000010792 warming Methods 0.000 claims description 19
- 229910052710 silicon Inorganic materials 0.000 claims description 17
- 239000010703 silicon Substances 0.000 claims description 17
- IJGRMHOSHXDMSA-UHFFFAOYSA-N Atomic nitrogen Chemical compound N#N IJGRMHOSHXDMSA-UHFFFAOYSA-N 0.000 claims description 15
- UHOVQNZJYSORNB-UHFFFAOYSA-N Benzene Chemical compound C1=CC=CC=C1 UHOVQNZJYSORNB-UHFFFAOYSA-N 0.000 claims description 12
- 239000002131 composite material Substances 0.000 claims description 12
- 239000007789 gas Substances 0.000 claims description 12
- 239000002245 particle Substances 0.000 claims description 12
- IAZDPXIOMUYVGZ-UHFFFAOYSA-N Dimethylsulphoxide Chemical compound CS(C)=O IAZDPXIOMUYVGZ-UHFFFAOYSA-N 0.000 claims description 8
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- 239000001099 ammonium carbonate Substances 0.000 claims description 8
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- 229910052757 nitrogen Inorganic materials 0.000 claims description 8
- XLYOFNOQVPJJNP-UHFFFAOYSA-N water Chemical compound O XLYOFNOQVPJJNP-UHFFFAOYSA-N 0.000 claims description 8
- ATRRKUHOCOJYRX-UHFFFAOYSA-N Ammonium bicarbonate Chemical compound [NH4+].OC([O-])=O ATRRKUHOCOJYRX-UHFFFAOYSA-N 0.000 claims description 7
- 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 7
- 229930006000 Sucrose Natural products 0.000 claims description 7
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- OKKJLVBELUTLKV-UHFFFAOYSA-N Methanol Chemical compound OC OKKJLVBELUTLKV-UHFFFAOYSA-N 0.000 claims description 6
- ZMXDDKWLCZADIW-UHFFFAOYSA-N N,N-Dimethylformamide Chemical compound CN(C)C=O ZMXDDKWLCZADIW-UHFFFAOYSA-N 0.000 claims description 6
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- 238000001694 spray drying Methods 0.000 claims description 5
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- NLXLAEXVIDQMFP-UHFFFAOYSA-N Ammonia chloride Chemical compound [NH4+].[Cl-] NLXLAEXVIDQMFP-UHFFFAOYSA-N 0.000 claims description 4
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- VLKZOEOYAKHREP-UHFFFAOYSA-N n-Hexane Chemical compound CCCCCC VLKZOEOYAKHREP-UHFFFAOYSA-N 0.000 claims description 4
- 229910021382 natural graphite Inorganic materials 0.000 claims description 4
- 229920001296 polysiloxane Polymers 0.000 claims description 4
- 238000002791 soaking Methods 0.000 claims description 4
- CTQNGGLPUBDAKN-UHFFFAOYSA-N O-Xylene Chemical compound CC1=CC=CC=C1C CTQNGGLPUBDAKN-UHFFFAOYSA-N 0.000 claims description 3
- 229910052786 argon Inorganic materials 0.000 claims description 3
- -1 trichloro ethylene ethyl alcohol Chemical compound 0.000 claims description 3
- SECXISVLQFMRJM-UHFFFAOYSA-N N-Methylpyrrolidone Chemical compound CN1CCCC1=O SECXISVLQFMRJM-UHFFFAOYSA-N 0.000 claims description 2
- 229920002472 Starch Polymers 0.000 claims description 2
- HMDDXIMCDZRSNE-UHFFFAOYSA-N [C].[Si] Chemical compound [C].[Si] HMDDXIMCDZRSNE-UHFFFAOYSA-N 0.000 claims description 2
- 150000001298 alcohols Chemical class 0.000 claims description 2
- 150000001335 aliphatic alkanes Chemical class 0.000 claims description 2
- 235000012501 ammonium carbonate Nutrition 0.000 claims description 2
- 235000019270 ammonium chloride Nutrition 0.000 claims description 2
- BFNBIHQBYMNNAN-UHFFFAOYSA-N ammonium sulfate Chemical compound N.N.OS(O)(=O)=O BFNBIHQBYMNNAN-UHFFFAOYSA-N 0.000 claims description 2
- 229910052921 ammonium sulfate Inorganic materials 0.000 claims description 2
- 235000011130 ammonium sulphate Nutrition 0.000 claims description 2
- 229910021383 artificial graphite Inorganic materials 0.000 claims description 2
- 239000010426 asphalt Substances 0.000 claims description 2
- 239000008367 deionised water Substances 0.000 claims description 2
- 229910021641 deionized water Inorganic materials 0.000 claims description 2
- 150000002170 ethers Chemical class 0.000 claims description 2
- 238000004108 freeze drying Methods 0.000 claims description 2
- 239000011339 hard pitch Substances 0.000 claims description 2
- 125000004836 hexamethylene group Chemical group [H]C([H])([*:2])C([H])([H])C([H])([H])C([H])([H])C([H])([H])C([H])([H])[*:1] 0.000 claims description 2
- 239000012456 homogeneous solution Substances 0.000 claims description 2
- 150000002576 ketones Chemical class 0.000 claims description 2
- 239000013081 microcrystal Substances 0.000 claims description 2
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- 239000008107 starch Substances 0.000 claims description 2
- 235000019698 starch Nutrition 0.000 claims description 2
- YLQBMQCUIZJEEH-UHFFFAOYSA-N tetrahydrofuran Natural products C=1C=COC=1 YLQBMQCUIZJEEH-UHFFFAOYSA-N 0.000 claims description 2
- 229960002415 trichloroethylene Drugs 0.000 claims description 2
- UBOXGVDOUJQMTN-UHFFFAOYSA-N trichloroethylene Natural products ClCC(Cl)Cl UBOXGVDOUJQMTN-UHFFFAOYSA-N 0.000 claims description 2
- 238000001291 vacuum drying Methods 0.000 claims description 2
- YXFVVABEGXRONW-UHFFFAOYSA-N Toluene Chemical compound CC1=CC=CC=C1 YXFVVABEGXRONW-UHFFFAOYSA-N 0.000 claims 3
- VGGSQFUCUMXWEO-UHFFFAOYSA-N Ethene Chemical compound C=C VGGSQFUCUMXWEO-UHFFFAOYSA-N 0.000 claims 1
- 239000005977 Ethylene Substances 0.000 claims 1
- 238000000465 moulding Methods 0.000 claims 1
- 239000008096 xylene Substances 0.000 claims 1
- 238000011160 research Methods 0.000 abstract description 2
- 238000004146 energy storage Methods 0.000 abstract 1
- XUIMIQQOPSSXEZ-UHFFFAOYSA-N Silicon Chemical compound [Si] XUIMIQQOPSSXEZ-UHFFFAOYSA-N 0.000 description 15
- 238000003756 stirring Methods 0.000 description 14
- 238000004321 preservation Methods 0.000 description 13
- 238000001816 cooling Methods 0.000 description 8
- 238000001035 drying Methods 0.000 description 6
- 229910052799 carbon Inorganic materials 0.000 description 5
- 230000000052 comparative effect Effects 0.000 description 5
- 238000007873 sieving Methods 0.000 description 5
- 239000007787 solid Substances 0.000 description 5
- 239000002210 silicon-based material Substances 0.000 description 4
- WHXSMMKQMYFTQS-UHFFFAOYSA-N Lithium Chemical compound [Li] WHXSMMKQMYFTQS-UHFFFAOYSA-N 0.000 description 3
- VYPSYNLAJGMNEJ-UHFFFAOYSA-N Silicium dioxide Chemical compound O=[Si]=O VYPSYNLAJGMNEJ-UHFFFAOYSA-N 0.000 description 3
- 238000005253 cladding Methods 0.000 description 3
- 238000011065 in-situ storage Methods 0.000 description 3
- 229910052744 lithium Inorganic materials 0.000 description 3
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- 235000007164 Oryza sativa Nutrition 0.000 description 2
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- 238000012360 testing method Methods 0.000 description 2
- 239000003643 water by type Substances 0.000 description 2
- 239000006245 Carbon black Super-P Substances 0.000 description 1
- RYGMFSIKBFXOCR-UHFFFAOYSA-N Copper Chemical compound [Cu] RYGMFSIKBFXOCR-UHFFFAOYSA-N 0.000 description 1
- 241000196324 Embryophyta Species 0.000 description 1
- 229910013872 LiPF Inorganic materials 0.000 description 1
- 101150058243 Lipf gene Proteins 0.000 description 1
- AQLLBJAXUCIJSR-UHFFFAOYSA-N OC(=O)C[Na] Chemical compound OC(=O)C[Na] AQLLBJAXUCIJSR-UHFFFAOYSA-N 0.000 description 1
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- YZSKZXUDGLALTQ-UHFFFAOYSA-N [Li][C] Chemical compound [Li][C] YZSKZXUDGLALTQ-UHFFFAOYSA-N 0.000 description 1
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- 239000000443 aerosol Substances 0.000 description 1
- 150000001336 alkenes Chemical class 0.000 description 1
- BIGPRXCJEDHCLP-UHFFFAOYSA-N ammonium bisulfate Chemical class [NH4+].OS([O-])(=O)=O BIGPRXCJEDHCLP-UHFFFAOYSA-N 0.000 description 1
- PRKQVKDSMLBJBJ-UHFFFAOYSA-N ammonium carbonate Chemical class N.N.OC(O)=O PRKQVKDSMLBJBJ-UHFFFAOYSA-N 0.000 description 1
- 235000011162 ammonium carbonates Nutrition 0.000 description 1
- 238000004458 analytical method Methods 0.000 description 1
- 238000000889 atomisation Methods 0.000 description 1
- WQZGKKKJIJFFOK-VFUOTHLCSA-N beta-D-glucose Chemical compound OC[C@H]1O[C@@H](O)[C@H](O)[C@@H](O)[C@@H]1O WQZGKKKJIJFFOK-VFUOTHLCSA-N 0.000 description 1
- 230000015572 biosynthetic process Effects 0.000 description 1
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- 239000011889 copper foil Substances 0.000 description 1
- 125000004122 cyclic group Chemical group 0.000 description 1
- 230000007812 deficiency Effects 0.000 description 1
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- 239000012046 mixed solvent Substances 0.000 description 1
- 239000007773 negative electrode material Substances 0.000 description 1
- QJGQUHMNIGDVPM-UHFFFAOYSA-N nitrogen group Chemical group [N] QJGQUHMNIGDVPM-UHFFFAOYSA-N 0.000 description 1
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Classifications
-
- 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
- H01M4/36—Selection of substances as active materials, active masses, active liquids
- H01M4/58—Selection of substances as active materials, active masses, active liquids of inorganic compounds other than oxides or hydroxides, e.g. sulfides, selenides, tellurides, halogenides or LiCoFy; of polyanionic structures, e.g. phosphates, silicates or borates
- H01M4/583—Carbonaceous material, e.g. graphite-intercalation compounds or CFx
-
- 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 energy storage research field, more particularly to a kind of silicon-carbon composite cathode material of lithium ion battery and preparation method thereof, which includes the following steps：（1）Graphene presoma, the agent that froths, graphite, nano-silicon are uniformly mixed, it is dry, obtain solid material；（2）Above-mentioned solid material is compacted into green body by press mold former；（3）Compacting green body is heat-treated, high temperature sintering obtains silicon-carbon composite cathode material；The silicon-carbon composite cathode material that preparation method of the present invention is obtained is applied to lithium ion battery, has higher charge specific capacity and excellent stable circulation performance.
Description
Technical field
The present invention relates to field of lithium ion battery, in particular it relates to a kind of lithium ion battery silicon-carbon composite negative pole
Material and preparation method thereof
Background technology
Commercial Li-ion battery negative material is mainly graphite cathode material at present, however as electric vehicle and large size
The raising of requirement of the equipment to battery energy density, graphite cathode material cannot due to its low theoretical capacity (372mAh/g)
Meet actual demand, therefore is badly in need of developing a kind of negative material of high-energy density.
Silicon is due to high theoretical capacity (4200mAh/g) and lower removal lithium embedded potential (＜ 0.05V), and voltage is flat
Platform is slightly above graphite, and in charge and discharge, difficulty causes silicon face to analyse lithium, and security performance is more preferable and is considered to have next-generation replacement stone
The Potential feasibility of black negative material.However silicon as lithium ion battery negative material when equally exist problem, in charge and discharge
In electric cyclic process, lithium ion is embedded and deviates to cause the expansion and contraction of material volume generation 300%, generated machinery
Stress can lead to the gradual dusting of material and structure collapses, ultimately cause active material and fall off in collector, lead to lithium ion battery
Cycle performance substantially reduces.In addition, since silicon is semi-conducting material, poor conductivity further limits silicon and is applied to lithium ion
Cell negative electrode material.Therefore materials conductive rate can not only be improved by urgently finding one kind, while silicon materials volume can also be inhibited swollen
It is swollen, and then improve the host material of chemical property.
Graphene due to its unique flexible two-dimension plane structure, the conductivity and specific surface area of superelevation and be considered " bright
Star " material, therefore by the way that graphene and nano-silicon are compounded to form graphene/nanometer silicon composite, can not only alleviate and receive
Volume expansion of the rice silicon in charge and discharge process, and the conductivity of material can be improved, so as to improve the electrochemistry of material
Energy.
However, the existing published method for preparing graphene/nanometer silicon composite is mostly to use first to prepare graphene
The technique compound with silicon materials afterwards can cause with high costs and be unable to industrialization.(the Journal of Physical such as Huang
Chemistry Letters,2012,3(13):1824) atomization is used to prepare the aerosol of graphene and silicon by pre-processing
The composite material of the fold graphene and silicon that prepare nucleocapsid structure with calcining should have recycled in button cell 200 weeks after specific volume
Measure undamped phenomenon.Guo(ChemicalCommunications,2012,48(16):2198-200) using freeze-drying and heat
Restoring method prepares Si-C composite material, and nano-silicon is embedded in graphene nano on piece in the composite material.
Chinese patent CN201510252804.5 discloses a kind of preparation method of graphene-based silicon-carbon composite cathode material,
The preparation method step is：The graphene particles of three-dimensional shape are prepared first, and then nano-silicon is deposited on stone by the method for deposition
Black alkene surface, not only complex process, of high cost, and the nano-silicon deposited is easily reunited in sintering process, leads to electricity
The cycle performance of pole material declines.
Chinese patent CN201710544133.9 discloses a kind of preparation of graphene-silicon carbon lithium ion battery cathode
Method, the preparation method step are：The once-combined material of the graphene coated of silicon nanoparticle, carbon coating and carbonization and batch mixing；
However this method graphene and silicon sand grinding process easily lead to silicon and are oxidized to silica, to reduce the appearance of silicon based composite material
Amount.
Invention content
In view of the deficiencies of the prior art, one of the objects of the present invention is to provide a kind of preparations of silicon-carbon composite cathode material
Method, this method can realize and uniformly be coated to nano silicon material while preparing graphene, compared with prior art,
This method has the characteristics that easy to operate, of low cost.
In order to achieve the above object, the present invention uses following technical scheme：
A kind of preparation method of silicon-carbon composite cathode material, includes the following steps：
It uniformly mixes, is dried to obtain Step 1: graphene presoma, the agent that froths, graphite, nano-silicon are dispersed in solvent
Solid material；
Step 2: the solid material that step 1 obtains is compacted into green body by press mold former；
Step 3: under protective gas atmosphere, the green body that step 2 obtains is heat-treated, then high temperature sintering,
Obtain silicon-carbon composite cathode material.
Preferably, the step 3 the specific steps are the green bodies for obtaining step 2 to be placed in agglomerating plant, protecting
Property gas atmosphere under, be warming up to 150~180 DEG C first, keep the temperature 2~5h, then proceed to be warming up to 800~1800 DEG C and be burnt
Knot, sintering time are 1~5h, and cooled to room temperature obtains silicon-carbon composite cathode material.
Preferably, the weight part ratio of graphene presoma described in step 1, the agent that froths, graphite and nano-silicon be (1~
1.8)：(7~18)：(0.5~1.5)：(5~12)；Further preferably (1~1.5)：(7~15)：(0.5~1)：(5~
10), particularly preferably (1~1.5)：(5~10)：(0.5~0.8)：(7~9).
Preferably, the graphene presoma is the one kind or two or more combination in sucrose, glucose, starch or pitch,
Further preferably glucose or pitch；
Preferably, the pitch is the one kind or two or more combination in hard pitch, emulsified asphalt or soft pitch.
Preferably, the graphite is artificial graphite, micro crystal graphite or the one kind or two or more combination of natural graphite, further
Preferred natural graphite, the shape of the graphite are a kind in sheet, spherical or spherical shape.
Preferably, the median particle diameter (D of the graphite50) it is 8~18 μm, such as 8 μm, 9 μm, 10 μm, 11 μm, 12 μm, 14 μ
M, 16 μm, 17 μm, 17.5 μm, 17.8 μm or 17.9 μm etc., further preferably 8~12 μm, particularly preferred 10~12 μm.
Preferably, the agent that froths described in step 1 is 1 in ammonium sulfate, ammonium chloride, ammonium nitrate, ammonium carbonate or ammonium hydrogen carbonate
Kind or combination of more than two kinds.
Preferably, solvent described in step 1 be deionized water, alcohols, ethers, alkanes, ketone, aromatics, further
Preferably methanol, ethyl alcohol, n-butanol, ethylene glycol, isopropanol, acetone, N-Methyl pyrrolidone, n-hexane, hexamethylene, benzene, first
1 in benzene, dimethylbenzene, styrene, dichloromethane, trichloro ethylene ethyl alcohol, dimethylformamide, dimethyl sulfoxide (DMSO) or tetrahydrofuran
Kind or combination of more than two kinds.
Preferably, the median particle diameter (D of the nano-silicon50) be 5~170nm, such as 5nm, 10nm, 20nm, 42nm,
66nm, 80nm, 100nm, 120nm, 130nm, 140nm, 155nm, 165nm or 169nm etc., further preferably 30~130nm,
Particularly preferably 50~80nm.
Preferably, method dry described in step 1 can be the drying means of this field routine, further preferably cold
It is lyophilized a kind in dry, vacuum drying, spray drying；
Preferably, the temperature of the drying be 60~100 DEG C, further preferably 60~90 DEG C, particularly preferably 70~
80℃。
Preferably, the pressure of press mold former described in step 2 is 7~50mPa, further preferably 8~20mPa, spy
It You Xuanwei not 8~10mPa；
Present invention research learns that being compacted the pressure size of green body influences the formation of final composite material very big, pressure mistake
Conference leads to composite material densification, and the graphene presoma of molten condition cannot flow around in sintering process, in turn
Cause nano-silicon and graphite surface in composite material that cannot uniformly be coated；
Preferably, the dwell time of press mold former described in step 2 be 1~10min, further preferably 2~
8min, particularly preferred 3~6min；
Preferably, sintering process described in step 3 carries out under protective atmosphere, and the protective atmosphere is nitrogen or argon
Gas；
Preferably, the heating rate that the heat treatment process is warming up in step 3 is 0.5~10 DEG C/min, further excellent
It is selected as 2~8 DEG C/min, particularly preferred 3~6 DEG C/min.
Preferably, the temperature of heat treatment process described in step 3 is 160~180 DEG C；
Preferably, the soaking time of heat treatment process described in step 3 is 3~5h；
Preferably, the heating rate that the sintering process is warming up in step 3 is 0.5~10 DEG C/min, further preferably
For 2~8 DEG C/min, particularly preferred 3~6 DEG C/min.
Preferably, the sintering temperature of sintering process described in step 3 be 900~1200 DEG C, further preferably 900~
1100℃；
Preferably, the sintering time of sintering process described in step 3 is 2~5h, further preferably 2~4h；
Preferably, the preparation method of the silicon-carbon composite cathode material, includes the following steps：
Be stirred Step 1: graphene presoma is added to the agent that froths in solvent, formed homogeneous solution, then to
Graphite is added in solution and nano-silicon uniformly mixes, it is dry, obtain mixed material；
Step 2: being compacted the mixed material that step 1 obtains to obtain green body by press mold former；
Step 3: the green body that step 1 obtains is placed in sintering furnace, under the atmosphere of protective gas, first with heating
0.5~10 DEG C/min of rate is warming up to 150~180 DEG C, and soaking time is 2~5h, then with 0.5~10 DEG C/min of heating rate
It is continuously heating to 800~1800 DEG C to be sintered, sintering time is 1~5h, and cooled to room temperature obtains silicon-carbon composite cathode
Material.
The present invention first mixes graphene presoma, the agent that froths, graphite and nano-silicon even in liquid phase, then dries, obtains
To mixed material, wherein in the mixed material, graphene presoma is coated on the surface of nano-silicon and graphite, froths simultaneously
Agent is dispersed in each material；Then mixed material is compacted by press mold former obtain green body；It is described by mixed material
Being compacted into the process of green body contributes to：A, froth agent and the graphene presoma plane-plane contact in green body, is blown with maximally utilizing
The pressure that infusion generates when being decomposed in subsequent high temperature sintering process, the graphene presoma of stripping cladding nano-silicon in situ；b、
The agent that froths can be dispersed in surface or the inner layer of graphene precursor；C, nano-silicon is dispersed in graphene table in situ
To avoid being aoxidized between face and graphene sheet layer；D, nano-silicon is avoided to reunite in sintering stage；Finally green body is carried out
Heat treatment, high temperature sintering, obtain silicon-carbon composite cathode material；The sintering process is to prepare the critical process of graphene,
Graphene presoma described in one stage heat treatment process is molten condition, and bond energy is minimum between molecule and spacing is maximum, simultaneously
The molecular layer that the gas pressure that agent is generated in this temperature decomposable process that froths can pull open molten condition prepares monomolecular layer, with
The raising molecular layer for second stage temperature is gradually carbonized to graphitization, and graphene is finally made.
It should be noted that the temperature of first stage heat treatment process must be with graphene presoma in the sintering process
The softening point temperature of material and the decomposition temperature for the agent that froths are foundation, as the softening point temperature of graphene presoma glucose is
110 DEG C, the decomposition temperature for the agent ammonium nitrate that froths is 120 DEG C, then the temperature of the heat treatment process of first stage need to be set in 120-
130 DEG C, and the holding temperature of the sintering process of second stage is preferably set to 1000 DEG C or more, to be more conducive to the stone of agraphitic carbon
Mo Hua.
Another object of the present invention is to provide a kind of Si-C composite material being prepared by the above method, the composite woods
Material is nucleocapsid structure, wherein kernel is combined by graphite with the nano-silicon for being coated on graphite surface, shell by graphene and
The uniform nano-silicon being dispersed between graphene sheet layer is constituted；It is the structure of silicon-carbon composite cathode material of the present invention as shown in Figure 1
Schematic diagram.
Preferably, the nanometer silicone content for being distributed in graphite surface is less than 50%, the institute between embedded graphene sheet layer
It states nano-silicon and is higher than 50%, such distribution mode, which is remarkably improved the electric conductivity of composite material and reduces nano silicon material, is filling
The Volumetric expansion of discharge process.
Preferably, in the silicon-carbon composite cathode material nano-silicon 3~25%wt of content, graphene be 1~10%wt,
Graphite is 20~70%wt.
Preferably, the graphene in the silicon-carbon composite cathode material is made by graphene presoma is thermally treated；
Preferably, the median particle diameter (D of the silicon-carbon composite cathode material50) be 8~20 μm, such as 8 μm, 9 μm, 10 μm,
11 μm, 12 μm, 14 μm, 16 μm, 18 μm, 19.5 μm, 19.7 μm or 19.9 μm etc., further preferably 13~15 μm；
Preferably, the specific surface area of the silicon-carbon composite cathode material is 1~20m2/ g, further preferably 1~12m2/
G, particularly preferably 1~3m2/g；
The third object of the present invention is to provide a kind of lithium ion battery, and the lithium ion battery includes by above-mentioned preparation side
The silicon-carbon composite cathode material made from method.
Advantageous effect
Compared with prior art,
(1) while preparation method of the present invention realizes the preparation of graphene with coated Si materials process, integration is (i.e.
Silicon materials are uniformly coated while preparing graphene), it is first prepared after graphene compared with the method for cladding silicon materials with existing, preparation
Technique is simpler, and does not need sulfuric acid, the reagents such as potassium permanganate, environmentally friendly, of low cost, is suitble to industrialization.
(2) in preparation method of the present invention, green body is obtained using compacting equipment, passes through base in heat treatment process in the first stage
The graphene presoma that pressure when generating gas removes coated Si in situ is decomposed in the agent that froths in body, not only makes nano-silicon always
Graphene internal layer without because high temperature sintering reunite, and nano silicon material energy it is uniform be dispersed in graphene sheet layer it
Between, the good mechanical performance of the graphene and electric conductivity can effectively alleviate the deformational stress of silicon, excellent electric conductivity and lead
It is hot that quick electronics conduction and heat evacuation are provided so that the silicon-carbon composite cathode material that preparation method of the present invention obtains has height
Specific capacity and excellent cyclical stability, charge specific capacity under 1C current densities be 625.35mAh/g, recycle 300 weeks
Capacity retention ratio is 85.01%.
Description of the drawings
Fig. 1 is the structural schematic diagram of silicon-carbon composite cathode material of the present invention；
Fig. 2 is the cycle performance curve graph for the silicon-carbon composite cathode material that embodiment 1 obtains；
Specific implementation mode
With reference to specific embodiment, the present invention will be described in further detail, but is not intended to limitation to the present invention
Protection domain.
Embodiment 1
1g sucrose and 10g ammonium carbonates are dissolved in 30mL deionized waters and stir 30 minutes, and it is 10 μm that 3gD50, which is then added,
It after graphite and the nano-silicon that 0.5g D50 are 50nm stir 1h, is placed in air dry oven, is arranged 90 DEG C, dry 12h obtains block
Above-mentioned blocks of solid is compacted into green body by shape body by press mold former, and pressure used is 8mPa, pressurize 3min.It is above-mentioned
Green body is placed in tube furnace flat-temperature zone, under nitrogen protection with 2 DEG C/min of heating rate be warming up to 300 DEG C heat preservation 3h after, then after
It is continuous to be warming up to 1000 DEG C of heat preservation 3h, it is finally naturally cooling to room temperature, takes out sample, the sieving of above-mentioned sample broke is obtained into intermediate value
The silicon-carbon composite cathode material that grain size D50 is 12.5 μm
Embodiment 2
1g sucrose and 10g ammonium nitrate are dissolved in 30mL water and stir 30 minutes, and the graphite that 3g D50 are 10 μm is then added
After stirring 1h with 0.5g D50 for the nano-silicon of 80nm, it is placed in air dry oven, 85 DEG C of above-mentioned solution of drying obtain blocks,
Above-mentioned blocks of solid is compacted into green body by press mold former, and pressure used is 10mPa, pressurize 6min.Above-mentioned green body is set
In tube furnace flat-temperature zone, after being warming up to 120 DEG C of heat preservation 3h under nitrogen protection with 2 DEG C/min of heating rate, then proceed to heat up
To 1000 DEG C of heat preservation 3h, it is finally naturally cooling to room temperature, takes out sample, the sieving of above-mentioned sample broke is obtained into median particle diameter
The silicon-carbon composite cathode material that D50 is 12.5 μm.
Embodiment 3
2g glucose and 10g ammonium hydrogen sulfates are dissolved in 30mL water and stir 30min, then be added 3g10 μm graphite and
After the nano-silicon that 0.5g D50 are 80nm stirs 2h, 90 DEG C of air dry ovens dry above-mentioned solution and obtain blocks, above-mentioned bulk
Body is compacted into green body by press mold former, and pressure used is 10mPa, pressurize 3min.Above-mentioned green body is placed in tube furnace perseverance
Warm area, above-mentioned green body are placed in tube furnace flat-temperature zone, are warming up to 220 DEG C of heat preservation 3h under nitrogen protection with 2 DEG C/min of heating rate
Afterwards, it then proceedes to be warming up to 1000 DEG C of heat preservation 3h, is finally naturally cooling to room temperature, takes out sample, above-mentioned sample broke is sieved
Obtain the silicon-carbon composite cathode material that median particle diameter D50 is 12.5 μm.
Embodiment 4
10g glucose and 80g ammonium hydrogen carbonate are dissolved in 120mL water and stir 4h, and 30g10 μm of graphite and 5g is then added
After the nano-silicon that D50 is 80nm stirs 1h, it is placed in drying in spray drying device, discharge port temperature is 110 DEG C, obtains bulk
Blocks of solid is compacted into green body by body by press mold former, and pressure used is 20mPa, pressurize 3min.Above-mentioned green body is set
In the flat-temperature zone of box atmosphere furnace, above-mentioned green body is placed in tube furnace flat-temperature zone, under nitrogen protection with heating rate 2 DEG C/min liters
After temperature to 150 DEG C of heat preservation 3h, then proceedes to be warming up to 1000 DEG C of heat preservation 3h, be finally naturally cooling to room temperature, be naturally cooling to room
Temperature takes out sample, and the sieving of above-mentioned sample broke is obtained the silicon-carbon composite cathode material that median particle diameter D50 is 12.5 μm.
Embodiment 5
10g sucrose and 80g ammonium hydrogen carbonate are dissolved in 120mL water and stir 4h, and 30g10 μm of graphite and 5g is then added
After the nano-silicon that D50 is 100nm stirs 1h, it is placed in drying in spray drying device, discharge port temperature is 110 DEG C, obtains bulk
Above-mentioned blocks of solid is compacted into green body by body by press mold former, and pressure used is 15mPa, pressurize 5min.Above-mentioned base
Body is placed in the flat-temperature zone of box atmosphere furnace, and above-mentioned green body is placed in tube furnace flat-temperature zone, under nitrogen protection with 2 DEG C of heating rate/
After min is warming up to 150 DEG C of heat preservation 3h, then proceedes to be warming up to 1000 DEG C of heat preservation 3h, be finally naturally cooling to room temperature and be sieved to obtain the final product
To silicon-carbon composite cathode material.
Embodiment 6
10g sucrose and 70g ammonium hydrogen carbonate are dissolved in 120mL water and stir 4h, and 24g10 μm of graphite and 4.5g is then added
After the nano-silicon that D50 is 50nm stirs 1h, it is placed in drying in spray drying device, discharge port temperature is 120 DEG C, obtains bulk
Blocks of solid is compacted into green body by body by press mold former, and pressure used is 10mPa, and pressurize is 3min minutes.Above-mentioned base
Body is placed in the flat-temperature zone of box atmosphere furnace, and above-mentioned green body is placed in tube furnace flat-temperature zone, under nitrogen protection with 2 DEG C of heating rate/
After min is warming up to 150 DEG C of heat preservation 3h, then proceedes to be warming up to 1000 DEG C of heat preservation 3h, be finally naturally cooling to room temperature, take out sample
Product, it is 12.5 μm of silicon-carbon composite cathode materials that the sieving of above-mentioned sample broke, which is obtained median particle diameter D50,.
Comparative example 1
1g sucrose is dissolved in 30mL deionized waters and stirs 30 minutes, and the graphite and 0.5g that 3g D50 are 10 μm is then added
It after the nano-silicon that D50 is 50nm stirs 1h, is placed in air dry oven, is arranged 90 DEG C, dry 12h obtains blocks.Above-mentioned piece
Shape body is placed in tube furnace flat-temperature zone, after being warming up to 1000 DEG C of heat preservation 3h with 2 DEG C/min of heating rate, is naturally cooling to room temperature, takes
Go out sample, the sieving of above-mentioned sample broke is obtained into silicon-carbon cathode material, median particle diameter is 12.5 μm.
Electrochemistry cycle performance test, tool are carried out to silicon-carbon composite cathode material prepared by Examples 1 to 6 and comparative example 1
Steps are as follows for body：Material prepared by Example 1~6 and comparative example 1 is as negative material, with conductive agent (Super-P), bonding
Agent carboxymethyl sodium cellulosate (CMC) is mixed according to 90: 6: 4 mass ratio, and suitable pure water is added and is slurred as dispersant
Material is coated on copper foil, and vacuum dried, roll-in, is prepared into negative plate；Anode uses metal lithium sheet, uses 1mol/L's
6 three component mixed solvents of LiPF press EC: DMC: EMC=1: 1: 1 (v/v) mixing electrolyte, use microporous polypropylene membrane for every
Film is assembled into the German Braun inert atmosphere glove box System Co., Ltd MB200B type glove boxes full of argon gas
CR2025 type button cells.The charge-discharge test of button cell is on Shanghai Chen Hua CHI760E battery test systems, in room temperature item
Part, 1C constant current charge-discharges, charging/discharging voltage are limited in 0.005~1.5V.
The Electrochemical results of silicon-carbon composite cathode material prepared by Examples 1 to 6 and comparative example 1 are as shown in table 1.
Table 1
As seen from the results in Table 1, there is excellent cyclical stability and high rate performance using material prepared by the method for the present invention,
Charge specific capacity under 1C current densities is 625.35mAh/g, and charge specific capacity is 531.59mAh/g after recycling 300 weeks, is held
Conservation rate is measured up to 85.01%.In Si-C composite material prepared by the method for the present invention, pass through the gas pressure institute caused by agent that froths
The raising that graphene is conducive to the conductivity of entire composite material is prepared, it is first to be conducive to the deintercalation depth of lithium ion
The raising of secondary efficiency for charge-discharge and specific capacity；In addition graphene can effectively inhibit the volume expansion of nano-silicon structure is avoided to collapse
It collapses, greatly improves the cycle life of lithium ion battery；And the agraphitic carbon cladding that comparative example 1 is generated only by glucose is received
Rice silicon inhibits volume expansion, and the conductivity of agraphitic carbon is not high.
Applicant states that the present invention illustrates detailed process equipment and the technological process of the present invention by above-described embodiment,
But the invention is not limited in above-mentioned detailed process equipment and technological processes, that is, it is above-mentioned detailed not mean that the present invention has to rely on
Process equipment and technological process could be implemented.Person of ordinary skill in the field it will be clearly understood that any improvement in the present invention,
The addition of equivalence replacement and auxiliary element to each raw material of product of the present invention, the selection etc. of concrete mode all fall within the present invention's
Within protection domain and the open scope.
Claims (10)
1. a kind of preparation method of silicon-carbon composite cathode material, which is characterized in that include the following steps：
It is uniformly mixed Step 1: graphene presoma, the agent that froths, graphite, nano-silicon are dispersed in solvent, is dried to obtain solid
Material；
Step 2: the solid material that step 1 obtains is compacted into green body by press mold former；
Step 3: under the atmosphere of protective gas, the green body that step 2 obtains is heat-treated, then high temperature sintering, is obtained
To silicon-carbon composite cathode material.
2. preparation method according to claim 1, which is characterized in that graphene presoma described in step 1 froths
The weight part ratio of agent, graphite, nano-silicon is（1~1.8）：（7~18）：（0.5~1.5）：（5~12）, further preferably（1~
1.5）：（7~15）：（0.5~1）：（5~10）, particularly preferably（1~1.5）：（5~10）：（0.5~0.8）：（7~9）.
3. preparation method according to claim 1 or 2, which is characterized in that the temperature being heat-treated described in step 3 is
160~180 DEG C；
Preferably, the soaking time of the heat treatment is 2~5h；
Preferably, the sintering temperature of the sintering process is 900~1200 DEG C, further preferably 900~1100 DEG C；
Preferably, the sintering time of the sintering process is 2~5h, further preferably 2~4h；
Preferably, the protective gas is nitrogen or argon gas.
4. according to claim 1-3 any one of them preparation methods, which is characterized in that the graphene presoma be sucrose,
One kind or two or more combination in glucose, starch or pitch, further preferably glucose or pitch；
Preferably, the pitch is the one kind or two or more combination in hard pitch, emulsified asphalt or soft pitch；
Preferably, it is described froth agent be ammonium sulfate, ammonium chloride, ammonium nitrate, ammonium carbonate or ammonium hydrogen carbonate in a kind or 2 kinds with
On combination；
Preferably, the solvent be deionized water, alcohols, ethers, alkanes, ketone, aromatics, further preferably methanol,
Ethyl alcohol, n-butanol, ethylene glycol, isopropanol, acetone, N-Methyl pyrrolidone, n-hexane, hexamethylene, benzene,toluene,xylene, benzene
1 kind or 2 kinds in ethylene, dichloromethane, trichloro ethylene ethyl alcohol, dimethylformamide, dimethyl sulfoxide (DMSO) or tetrahydrofuran with
On combination.
5. according to claim 1-4 any one of them preparation methods, which is characterized in that dry method described in step 1
For a kind in freeze-drying, vacuum drying or spray drying.
6. according to claim 1-5 any one of them preparation methods, which is characterized in that the molding of press mold described in step 2 is set
Standby pressure is 7~50mPa, further preferably 8~20mPa, particularly preferably 8~10mPa；
Preferably, the dwell time of the press mold former is 1~10min, further preferably 2~8min, particularly preferred 3
~6min.
7. a kind of preparation method of silicon-carbon composite cathode material, which is characterized in that include the following steps：
It is stirred Step 1: graphene presoma is added to the agent that froths in solvent, homogeneous solution is formed, then to solution
Middle addition graphite and nano-silicon are stirred, dry, obtain mixed material；
Step 2: the mixed material that step 1 obtains, which is put into compacting in press mold former, obtains green body；
Step 3: the green body of compacting is placed in sintering furnace, under the atmosphere of protective gas, first with heating rate 0.5~
10 DEG C/min is warming up to 150~180 DEG C, and soaking time is 2~5h, then continues to heat up with 0.5~10 DEG C/min of heating rate
It is sintered to 800~1800 DEG C, sintering time is 1~5h, and cooled to room temperature obtains silicon-carbon composite cathode material.
8. preparation method according to claim 7, which is characterized in that be warming up to the heating rate of heat treatment process
For 2~8 DEG C/min, further preferred 3~6 DEG C/min；
Preferably, the heating rate for being warming up to sintering process is 2~8 DEG C/min, further preferably 3~6 DEG C/min.
9. a kind of silicon-carbon composite cathode material, which is characterized in that the composite material is by any one of the claim 1-8 sides
Prepared by method, the silicon-carbon composite cathode material is nucleocapsid structure, wherein kernel is by graphite and the nanometer for being coated on graphite surface
Silicon is combined, and shell is made of graphene and the uniform nano-silicon being dispersed between graphene sheet layer；
Preferably, the nanometer silicone content for being distributed in graphite surface is less than 50%, the nanometer between embedded graphene sheet layer
Silicone content is higher than 50%；
Preferably, the graphite is artificial graphite, micro crystal graphite or the one kind or two or more combination of natural graphite, further preferably
Natural graphite；
Preferably, the shape of the graphite is a kind in sheet, spherical or spherical shape；
Preferably, the median particle diameter of the graphite（D50）It is 8 ~ 18 μm, further preferably 8 ~ 12 μm, particularly preferred 10 ~ 12 μm；
Preferably, the median particle diameter of the nano-silicon（D50）For 5 ~ 170nm, further preferably 30 ~ 130nm, particularly preferably
50~80nm；
Preferably, nanometer 3 ~ 25%wt of silicone content in the silicon-carbon composite cathode material, graphene be 1 ~ 10%wt, graphite be 20 ~
70%wt；
Preferably, the median particle diameter of the silicon-carbon composite cathode material（D50）Be 8 ~ 20 μm, for example, 8 μm, 9 μm, 10 μm, 11 μm,
12 μm, 14 μm, 16 μm, 18 μm, 19.5 μm, 19.7 μm or 19.9 μm etc., further preferably 13 ~ 15 μm；
Preferably, the specific surface area of the silicon-carbon composite cathode material is 1 ~ 20m2/ g, further preferably 1 ~ 12m2/ g, especially
Preferably 1 ~ 3m2/g。
10. a kind of lithium ion battery, which is characterized in that the lithium ion battery includes the silicon-carbon Compound Negative described in claim 9
Pole material.
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