CN109216689A - A kind of Si-C composite material and preparation method thereof and lithium ion battery - Google Patents
A kind of Si-C composite material and preparation method thereof and lithium ion battery Download PDFInfo
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- CN109216689A CN109216689A CN201811252495.1A CN201811252495A CN109216689A CN 109216689 A CN109216689 A CN 109216689A CN 201811252495 A CN201811252495 A CN 201811252495A CN 109216689 A CN109216689 A CN 109216689A
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- silicon
- carbon
- composite material
- conductive agent
- lithium ion
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- 239000002153 silicon-carbon composite material Substances 0.000 title claims abstract description 39
- HBBGRARXTFLTSG-UHFFFAOYSA-N Lithium ion Chemical compound [Li+] HBBGRARXTFLTSG-UHFFFAOYSA-N 0.000 title claims abstract description 28
- 229910001416 lithium ion Inorganic materials 0.000 title claims abstract description 28
- 238000002360 preparation method Methods 0.000 title claims abstract description 14
- 239000000463 material Substances 0.000 claims abstract description 49
- 239000006258 conductive agent Substances 0.000 claims abstract description 24
- 239000005543 nano-size silicon particle Substances 0.000 claims abstract description 22
- 238000005253 cladding Methods 0.000 claims abstract description 17
- 239000011159 matrix material Substances 0.000 claims abstract description 16
- 229910003481 amorphous carbon Inorganic materials 0.000 claims abstract description 11
- 239000011248 coating agent Substances 0.000 claims abstract description 11
- 238000000576 coating method Methods 0.000 claims abstract description 11
- 239000007773 negative electrode material Substances 0.000 claims abstract description 8
- OKTJSMMVPCPJKN-UHFFFAOYSA-N Carbon Chemical compound [C] OKTJSMMVPCPJKN-UHFFFAOYSA-N 0.000 claims description 45
- 238000000034 method Methods 0.000 claims description 29
- 229910052799 carbon Inorganic materials 0.000 claims description 25
- KRKNYBCHXYNGOX-UHFFFAOYSA-N citric acid Chemical compound OC(=O)CC(O)(C(O)=O)CC(O)=O KRKNYBCHXYNGOX-UHFFFAOYSA-N 0.000 claims description 15
- 238000010438 heat treatment Methods 0.000 claims description 15
- 229910002804 graphite Inorganic materials 0.000 claims description 13
- IJGRMHOSHXDMSA-UHFFFAOYSA-N Atomic nitrogen Chemical compound N#N IJGRMHOSHXDMSA-UHFFFAOYSA-N 0.000 claims description 12
- 238000001354 calcination Methods 0.000 claims description 11
- 239000010439 graphite Substances 0.000 claims description 10
- 239000000203 mixture Substances 0.000 claims description 9
- LFQSCWFLJHTTHZ-UHFFFAOYSA-N Ethanol Chemical compound CCO LFQSCWFLJHTTHZ-UHFFFAOYSA-N 0.000 claims description 8
- 239000002041 carbon nanotube Substances 0.000 claims description 6
- 229910021393 carbon nanotube Inorganic materials 0.000 claims description 6
- 229910052757 nitrogen Inorganic materials 0.000 claims description 6
- KXGFMDJXCMQABM-UHFFFAOYSA-N 2-methoxy-6-methylphenol Chemical compound [CH]OC1=CC=CC([CH])=C1O KXGFMDJXCMQABM-UHFFFAOYSA-N 0.000 claims description 5
- 239000002202 Polyethylene glycol Substances 0.000 claims description 5
- 239000004372 Polyvinyl alcohol Substances 0.000 claims description 5
- 229910021383 artificial graphite Inorganic materials 0.000 claims description 5
- 229910021389 graphene Inorganic materials 0.000 claims description 5
- 239000003273 ketjen black Substances 0.000 claims description 5
- 229910021382 natural graphite Inorganic materials 0.000 claims description 5
- 229920001568 phenolic resin Polymers 0.000 claims description 5
- 239000005011 phenolic resin Substances 0.000 claims description 5
- 229920001223 polyethylene glycol Polymers 0.000 claims description 5
- 229920002451 polyvinyl alcohol Polymers 0.000 claims description 5
- 238000007873 sieving Methods 0.000 claims description 5
- WQZGKKKJIJFFOK-GASJEMHNSA-N Glucose Natural products OC[C@H]1OC(O)[C@H](O)[C@@H](O)[C@@H]1O WQZGKKKJIJFFOK-GASJEMHNSA-N 0.000 claims description 4
- 235000021355 Stearic acid Nutrition 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
- 229930006000 Sucrose Natural products 0.000 claims description 4
- 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 claims description 4
- 239000008103 glucose Substances 0.000 claims description 4
- QIQXTHQIDYTFRH-UHFFFAOYSA-N octadecanoic acid Chemical compound CCCCCCCCCCCCCCCCCC(O)=O QIQXTHQIDYTFRH-UHFFFAOYSA-N 0.000 claims description 4
- OQCDKBAXFALNLD-UHFFFAOYSA-N octadecanoic acid Natural products CCCCCCCC(C)CCCCCCCCC(O)=O OQCDKBAXFALNLD-UHFFFAOYSA-N 0.000 claims description 4
- 239000011295 pitch Substances 0.000 claims description 4
- 235000019422 polyvinyl alcohol Nutrition 0.000 claims description 4
- 239000004800 polyvinyl chloride Substances 0.000 claims description 4
- 229920000915 polyvinyl chloride Polymers 0.000 claims description 4
- 239000008117 stearic acid Substances 0.000 claims description 4
- 239000005720 sucrose Substances 0.000 claims description 4
- 238000002791 soaking Methods 0.000 claims description 3
- 238000005507 spraying Methods 0.000 claims description 3
- 230000015572 biosynthetic process Effects 0.000 claims description 2
- 235000015165 citric acid Nutrition 0.000 claims description 2
- 238000001694 spray drying Methods 0.000 claims description 2
- VGGSQFUCUMXWEO-UHFFFAOYSA-N Ethene Chemical compound C=C VGGSQFUCUMXWEO-UHFFFAOYSA-N 0.000 claims 1
- 240000000111 Saccharum officinarum Species 0.000 claims 1
- 235000007201 Saccharum officinarum Nutrition 0.000 claims 1
- LYCAIKOWRPUZTN-UHFFFAOYSA-N ethylene glycol Substances OCCO LYCAIKOWRPUZTN-UHFFFAOYSA-N 0.000 claims 1
- 235000001727 glucose Nutrition 0.000 claims 1
- 229920001596 poly (chlorostyrenes) Polymers 0.000 claims 1
- 239000004575 stone Substances 0.000 claims 1
- 230000005518 electrochemistry Effects 0.000 abstract description 2
- XUIMIQQOPSSXEZ-UHFFFAOYSA-N Silicon Chemical compound [Si] XUIMIQQOPSSXEZ-UHFFFAOYSA-N 0.000 description 15
- 229910052710 silicon Inorganic materials 0.000 description 15
- 239000010703 silicon Substances 0.000 description 15
- 239000010410 layer Substances 0.000 description 8
- 238000002156 mixing Methods 0.000 description 7
- 235000019441 ethanol Nutrition 0.000 description 6
- 238000004321 preservation Methods 0.000 description 6
- 238000010792 warming Methods 0.000 description 6
- 238000005516 engineering process Methods 0.000 description 5
- 239000002245 particle Substances 0.000 description 5
- HMDDXIMCDZRSNE-UHFFFAOYSA-N [C].[Si] Chemical compound [C].[Si] HMDDXIMCDZRSNE-UHFFFAOYSA-N 0.000 description 4
- 239000003575 carbonaceous material Substances 0.000 description 4
- 230000000052 comparative effect Effects 0.000 description 3
- 150000001875 compounds Chemical class 0.000 description 3
- 239000003792 electrolyte Substances 0.000 description 3
- 239000000843 powder Substances 0.000 description 3
- WHXSMMKQMYFTQS-UHFFFAOYSA-N Lithium Chemical compound [Li] WHXSMMKQMYFTQS-UHFFFAOYSA-N 0.000 description 2
- AFCARXCZXQIEQB-UHFFFAOYSA-N N-[3-oxo-3-(2,4,6,7-tetrahydrotriazolo[4,5-c]pyridin-5-yl)propyl]-2-[[3-(trifluoromethoxy)phenyl]methylamino]pyrimidine-5-carboxamide Chemical compound O=C(CCNC(=O)C=1C=NC(=NC=1)NCC1=CC(=CC=C1)OC(F)(F)F)N1CC2=C(CC1)NN=N2 AFCARXCZXQIEQB-UHFFFAOYSA-N 0.000 description 2
- 239000011149 active material Substances 0.000 description 2
- 239000010426 asphalt Substances 0.000 description 2
- 239000007767 bonding agent Substances 0.000 description 2
- 239000003610 charcoal Substances 0.000 description 2
- 239000003795 chemical substances by application Substances 0.000 description 2
- 239000002131 composite material Substances 0.000 description 2
- -1 graphite Alkene Chemical class 0.000 description 2
- 229910052744 lithium Inorganic materials 0.000 description 2
- 239000003595 mist Substances 0.000 description 2
- 230000010287 polarization Effects 0.000 description 2
- RSWGJHLUYNHPMX-UHFFFAOYSA-N 1,4a-dimethyl-7-propan-2-yl-2,3,4,4b,5,6,10,10a-octahydrophenanthrene-1-carboxylic acid Chemical compound C12CCC(C(C)C)=CC2=CCC2C1(C)CCCC2(C)C(O)=O RSWGJHLUYNHPMX-UHFFFAOYSA-N 0.000 description 1
- NIXOWILDQLNWCW-UHFFFAOYSA-M Acrylate Chemical compound [O-]C(=O)C=C NIXOWILDQLNWCW-UHFFFAOYSA-M 0.000 description 1
- 239000006245 Carbon black Super-P Substances 0.000 description 1
- RYGMFSIKBFXOCR-UHFFFAOYSA-N Copper Chemical compound [Cu] RYGMFSIKBFXOCR-UHFFFAOYSA-N 0.000 description 1
- 229910005001 Li12Si7 Inorganic materials 0.000 description 1
- 229910005025 Li13Si4 Inorganic materials 0.000 description 1
- 229910010661 Li22Si5 Inorganic materials 0.000 description 1
- 229910011184 Li7Si3 Inorganic materials 0.000 description 1
- 229910001290 LiPF6 Inorganic materials 0.000 description 1
- 241000282320 Panthera leo Species 0.000 description 1
- 229920003171 Poly (ethylene oxide) Polymers 0.000 description 1
- 239000004743 Polypropylene Substances 0.000 description 1
- 235000009754 Vitis X bourquina Nutrition 0.000 description 1
- 235000012333 Vitis X labruscana Nutrition 0.000 description 1
- 240000006365 Vitis vinifera Species 0.000 description 1
- 235000014787 Vitis vinifera Nutrition 0.000 description 1
- 238000002441 X-ray diffraction Methods 0.000 description 1
- QCWXUUIWCKQGHC-UHFFFAOYSA-N Zirconium Chemical compound [Zr] QCWXUUIWCKQGHC-UHFFFAOYSA-N 0.000 description 1
- 150000001336 alkenes Chemical class 0.000 description 1
- 239000000956 alloy Substances 0.000 description 1
- 229910045601 alloy Inorganic materials 0.000 description 1
- 239000010405 anode material Substances 0.000 description 1
- 239000002969 artificial stone Substances 0.000 description 1
- 238000000889 atomisation Methods 0.000 description 1
- 239000006257 cathode slurry Substances 0.000 description 1
- 239000011247 coating layer Substances 0.000 description 1
- 239000011889 copper foil Substances 0.000 description 1
- 230000001351 cycling effect Effects 0.000 description 1
- 239000008367 deionised water Substances 0.000 description 1
- 229910021641 deionized water Inorganic materials 0.000 description 1
- 238000001035 drying Methods 0.000 description 1
- 238000010410 dusting Methods 0.000 description 1
- 230000000694 effects Effects 0.000 description 1
- 239000011267 electrode slurry Substances 0.000 description 1
- 150000002085 enols Chemical class 0.000 description 1
- 238000000227 grinding Methods 0.000 description 1
- 230000008676 import Effects 0.000 description 1
- 238000002955 isolation Methods 0.000 description 1
- 239000007788 liquid Substances 0.000 description 1
- 230000014759 maintenance of location Effects 0.000 description 1
- 238000004519 manufacturing process Methods 0.000 description 1
- 229910052751 metal Inorganic materials 0.000 description 1
- 239000002184 metal Substances 0.000 description 1
- 239000002048 multi walled nanotube Substances 0.000 description 1
- 239000002086 nanomaterial Substances 0.000 description 1
- 125000000914 phenoxymethylpenicillanyl group Chemical group CC1(S[C@H]2N([C@H]1C(=O)*)C([C@H]2NC(COC2=CC=CC=C2)=O)=O)C 0.000 description 1
- 229920002239 polyacrylonitrile Polymers 0.000 description 1
- 229920001155 polypropylene Polymers 0.000 description 1
- 238000004080 punching Methods 0.000 description 1
- 230000001105 regulatory effect Effects 0.000 description 1
- 230000002441 reversible effect Effects 0.000 description 1
- 239000004576 sand Substances 0.000 description 1
- 239000004065 semiconductor Substances 0.000 description 1
- 239000002210 silicon-based material Substances 0.000 description 1
- 239000011856 silicon-based particle Substances 0.000 description 1
- 239000002002 slurry Substances 0.000 description 1
- 239000007787 solid Substances 0.000 description 1
- 239000002904 solvent Substances 0.000 description 1
- 239000000126 substance Substances 0.000 description 1
- 239000000758 substrate Substances 0.000 description 1
- 239000002562 thickening agent Substances 0.000 description 1
- XLYOFNOQVPJJNP-UHFFFAOYSA-N water Chemical compound O XLYOFNOQVPJJNP-UHFFFAOYSA-N 0.000 description 1
- 239000002023 wood Substances 0.000 description 1
- 229910052726 zirconium Inorganic materials 0.000 description 1
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
-
- 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
- H01M4/587—Carbonaceous material, e.g. graphite-intercalation compounds or CFx for inserting or intercalating light metals
-
- H—ELECTRICITY
- H01—ELECTRIC ELEMENTS
- H01M—PROCESSES OR MEANS, e.g. BATTERIES, FOR THE DIRECT CONVERSION OF CHEMICAL ENERGY INTO ELECTRICAL ENERGY
- H01M4/00—Electrodes
- H01M4/02—Electrodes composed of, or comprising, active material
- H01M4/62—Selection of inactive substances as ingredients for active masses, e.g. binders, fillers
- H01M4/624—Electric conductive fillers
- H01M4/625—Carbon or graphite
-
- H—ELECTRICITY
- H01—ELECTRIC ELEMENTS
- H01M—PROCESSES OR MEANS, e.g. BATTERIES, FOR THE DIRECT CONVERSION OF CHEMICAL ENERGY INTO ELECTRICAL ENERGY
- H01M4/00—Electrodes
- H01M4/02—Electrodes composed of, or comprising, active material
- H01M2004/021—Physical characteristics, e.g. porosity, surface area
-
- 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
- H01M2004/026—Electrodes composed of, or comprising, active material characterised by the polarity
- H01M2004/027—Negative electrodes
-
- 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
Landscapes
- Chemical & Material Sciences (AREA)
- Chemical Kinetics & Catalysis (AREA)
- Electrochemistry (AREA)
- General Chemical & Material Sciences (AREA)
- Engineering & Computer Science (AREA)
- Composite Materials (AREA)
- Materials Engineering (AREA)
- Manufacturing & Machinery (AREA)
- Inorganic Chemistry (AREA)
- Battery Electrode And Active Subsutance (AREA)
Abstract
The present invention relates to electrochemistry and lithium ion battery negative material field, a kind of Si-C composite material and preparation method thereof and lithium ion battery are disclosed.The Si-C composite material includes basis material, the nano-silicon being carried on described matrix material surface and the cladding carbon-coating for being coated on outer layer, wherein the conductive agent that the cladding carbon-coating includes amorphous carbon layer and is scattered in the amorphous carbon layer.Si-C composite material of the present invention is used as the negative electrode active material of lithium ion battery, and made lithium ion battery has good first charge discharge efficiency and cyclical stability, shows obvious preferable comprehensive performance.
Description
Technical field
The present invention relates to electrochemistry and lithium ion battery negative material fields, and in particular to a kind of Si-C composite material and its
Preparation method and lithium ion battery.
Background technique
In the case where terminal enterprise is constantly evolved to the requirement continuous improvement of lithium ion battery energy density in market, existing city
Main graphite negative electrodes material (theoretical specific capacity only has 372mAh/g) the mentioning for lithium ion battery energy density to be applied in field
It rises and has reached bottleneck, rethink its space of promotion and be difficult to realize.Silicon and lithium can form Li12Si7、Li7Si3、Li13Si4With
Li22Si5Alloy, theoretical specific capacity is up to 4200mAh/g, and its discharge voltage is lower, it is considered to be most potential graphite is negative
One of pole alternative materials.
However silicon based anode material in charge and discharge process along with huge volume expansion (~420%) so that silicon substrate
Negative electrode material is easy dusting in use, causes cyclical stability poor；In repeatedly charge and discharge process, material is continuous
Ground is shunk and expansion so that active material be easy to fall off from collector and active material and conductive agent bonding agent etc. contact it is poor；More
The SEI film that further will lead to negative electrode material surface is constantly consumed and is formed, and forms thicker and non-uniform SEI film, repeatedly
Consumption lithium ion.In addition to this, silicon is as a kind of semiconductor, there are problems that electric conductivity it is insufficient this.
It is swollen by the volume that silicon materials nanosizing, porous, doping vario-property and cladding processing etc. can effectively be solved silicon
Swollen problem.Currently, industrialization technology scheme mainly uses silicon nanoparticle compound with carbon-based material.Liu et al. is the study found that work as silicon
When particle diameter is down to 150nm, volume expansion problem (ACS Nano 2012,6,1522-1531) can be effectively reduced；By nanometer
Silicon is compound with carbon-based material, using graphite as kernel, while providing reversible capacity, keeps the good interior contact of material, guarantees
The electric conductivity of material, while cushion space is provided for the volume expansion of silicon；Increase carbon coating layer on the surface of silicon and graphite again, keeps away
Exempt from silicon and directly contacted with electrolyte, while advantageously forming stable SEI film, the two combines, and effectively improves stability of material.
Currently employed cladding carbon source mainly includes phenolic resin, PVA, citric acid, stearic acid, glucose, sucrose, poly- second
Enol, polyvinyl chloride, polyethylene glycol, polyethylene oxide, Vingon, acrylate or polyacrylonitrile etc., calcined
Agraphitic carbon is formed in journey, as cladding carbon-coating isolation silicon particle and extraneous electrolyte, improves stability of material.Agraphitic carbon exists
Have the shortcomings that cladding is imperfect, electric conductivity is insufficient, is easy to cause big ohmic polarization during cladding, reduces the electrification of material
Learn performance.
Summary of the invention
It is endless the purpose of the invention is to overcome agraphitic carbon of the existing technology to there is cladding during cladding
Disadvantage whole, electric conductivity is insufficient provides a kind of Si-C composite material and preparation method thereof and lithium ion battery.
To achieve the goals above, the present invention provides a kind of Si-C composite material, which includes matrix material
The nano-silicon that expect, is carried on described matrix material surface and the cladding carbon-coating for being coated on outer layer, wherein the cladding carbon-coating
Including amorphous carbon layer and the conductive agent being scattered in the amorphous carbon layer.
The present invention also provides a kind of preparation methods of Si-C composite material, method includes the following steps:
(1) basis material is added in the alcohol mixture of nano-silicon, it is evenly dispersed, obtain mixed liquor；
(2) mixed liquor is spray-dried, obtains presoma；
(3) presoma, carbon source and conductive agent are mixed, is then once calcined under nitrogen protection；
(4) the once sintered material disintegrating for obtaining step (3), then mixes with carbon source and conductive agent, again in nitrogen
Protection is lower to carry out secondary clacining, is then crushed, and smashed crushed material is mixed with graphite.
The present invention also provides the Si-C composite materials of above-mentioned method preparation.
The present invention also provides a kind of lithium ion battery, the negative electrode active material in the lithium ion battery is the silicon-carbon
Composite material.
In the present invention, by secondary clacining, complete cladding carbon-coating can be formed, this helps to improve silicon-carbon composite wood
The stability of material, while by the dispersed electro-conductive agent in amorphous carbon layer, it may be configured with the conductive network of effect, reduce the Europe of material
Nurse polarization, improves material property.In application process, use Si-C composite material of the present invention as lithium ion battery
The first charge discharge efficiency of negative electrode active material, made lithium ion battery is high, and specific discharge capacity is high, good cycling stability.
Detailed description of the invention
Fig. 1 is the stereoscan photograph of Si-C composite material prepared by embodiment 1；
Fig. 2 is the X-ray diffraction spectrogram of Si-C composite material prepared by embodiment 1.
Specific embodiment
The endpoint of disclosed range and any value are not limited to the accurate range or value herein, these ranges or
Value should be understood as comprising the value close to these ranges or value.For numberical range, between the endpoint value of each range, respectively
It can be combined with each other between the endpoint value of a range and individual point value, and individually between point value and obtain one or more
New numberical range, these numberical ranges should be considered as specific open herein.
The present invention provides a kind of Si-C composite material, which includes basis material, is carried on described matrix
Nano-silicon on material surface and the cladding carbon-coating for being coated on outer layer, wherein the cladding carbon-coating include amorphous carbon layer and
The conductive agent being scattered in the amorphous carbon layer.
In Si-C composite material of the present invention, the mass ratio of the nano-silicon and described matrix material can be 1:
2-20 specifically, such as can be 1:2,1:3,1:4,1:5,1:6,1:7,1:8,1:9,1:10,1:11,1:12,1:13,1:
14, any in the range that any two in 1:15,1:16,1:17,1:18,1:19,1:20 and these point values are constituted
Value.In the preferred case, the mass ratio of the nano-silicon and described matrix material is 1:2-10, most preferably 1:4-5.
In the present invention, described matrix material can be in natural graphite, artificial graphite and carbonaceous mesophase spherules extremely
Few one kind.
In the present invention, the granularity of the nano-silicon can be 20-500nm, specifically, for example, can for 20nm, 50nm,
80nm、110nm、140nm、170nm、200nm、230nm、260nm、290nm、320nm、350nm、380nm、410nm、440nm、
The arbitrary value in range that any two are constituted in 470nm, 500nm and these point values.In the preferred case, the nanometer
The partial size of silicon is 20-200nm.
In the present invention, it is preferred to which the amorphous carbon layer is by the way that carbon source is carried out secondary clacining formation, so that carbon
Clad can completely coat described matrix material so that the Si-C composite material have higher energy density,
The comprehensive performances such as first charge discharge efficiency and good cyclical stability.
In the present invention, the carbon source can be selected from pitch, phenolic resin, polyvinyl alcohol, citric acid, stearic acid, grape
At least one of sugar, sucrose, polyvinyl chloride and polyethylene glycol.
In the present invention, the conductive agent can be in conductive black, Ketjen black, carbon nanotube and graphene at least
It is a kind of.Preferably, the conductive agent is conductive black.In a particular embodiment, used conductive black can be city
The Super P sold.By the dispersed electro-conductive agent in cladding carbon-coating, the electric conductivity of the Si-C composite material can be effectively promoted.
The present invention also provides a kind of preparation methods of Si-C composite material, method includes the following steps:
(1) basis material is added in the alcohol mixture of nano-silicon, it is evenly dispersed, obtain mixed liquor；
(2) mixed liquor is spray-dried, obtains presoma；
(3) presoma, carbon source and conductive agent are mixed, is then once calcined under nitrogen protection；
(4) the once sintered material disintegrating for obtaining step (3), then mixes with carbon source and conductive agent, again in nitrogen
Protection is lower to carry out secondary clacining, is then crushed, and smashed crushed material is mixed with graphite.
In method of the present invention, in step (1), described matrix material can be selected from natural graphite, artificial stone
At least one of ink and carbonaceous mesophase spherules.
In method of the present invention, the granularity of the nano-silicon can be 20-500nm, preferably 20-200nm.
Preferably, the mass ratio of the nano-silicon and described matrix material is 1:2-20, specifically for example can for 1:2,
1:3,1:4,1:5,1:6,1:7,1:8,1:9,1:10,1:11,1:12,1:13,1:14,1:15,1:16,1:17,1:18,1:
19, the arbitrary value in the range that any two in 1:20 and these point values are constituted.Under preferable case, the nano-silicon with
The mass ratio of described matrix material is 1:2-10.
In method of the present invention, it is preferable that in the spray-drying process described in step (2), spraying import temperature
Degree is 120-180 DEG C, preferably 120-150 DEG C；Outlet temperature is 70-100 DEG C, preferably 70-90 DEG C；Being atomized disk rotating speed is
10000-30000rpm, preferably 15000-25000rpm；Charging rate is 5-50L/h, preferably 20-30L/h.
In method of the present invention, it is preferable that in step (3), the presoma, the carbon source and the conduction
The mass ratio of agent is 10:(1-10): (0.05-0.5), preferably 10:(3-5): (0.1-0.2).
In method of the present invention, it is preferable that in step (4), the crushed material of once sintered material, carbon source and lead
The mass ratio of electric agent is 10:(0.2-2): (0.001-0.1), more preferably 10:(0.2-1): (0.03-0.05).
Preferably, be sieved after once sintered material disintegrating, after sieving gained crushed material again with carbon source and conductive agent
Mixing.
In method of the present invention, it is preferable that in step (3) and (4), the primary calcining and described secondary forge
The calcinating system of burning is identical, is two sections of calcining at constant temperature, and calcination temperature is respectively 400-600 DEG C, 800-1100 DEG C, heating rate
For 1-5 DEG C/min, soaking time 3-10h, 3-10h.It is highly preferred that calcination temperature is respectively in two sections of calcining at constant temperature
400-500 DEG C, 850-950 DEG C, heating rate are 2-3 DEG C/min, soaking time 4-6h, 4-6h.
In method of the present invention, it is preferable that in step (4), the smashed crushed material of secondary clacining product with
The mixed proportion of graphite is 1:1.5-2.5, most preferably 1:2.
In method of the present invention, the carbon source can be selected from pitch, phenolic resin, polyvinyl alcohol, citric acid, hard
At least one of resin acid, glucose, sucrose, polyvinyl chloride and polyethylene glycol.
In method of the present invention, the conductive agent can be selected from conductive black, Ketjen black, carbon nanotube and graphite
At least one of alkene.Preferably, the conductive agent is conductive black.In a particular embodiment, used conductive charcoal
Black can be commercially available Super P.
The present invention also provides the Si-C composite materials prepared by the above method.
The present invention also provides a kind of lithium ion battery, the negative electrode active material in the lithium ion battery is the silicon-carbon
Composite material.
In the lithium ion battery, using above-mentioned Si-C composite material as negative electrode active material lithium ion battery is had
Good chemical property and low in cost, is suitable for industrialization production.
The present invention will be described in detail by way of examples below.
In the following Examples and Comparative Examples, nano-silicon is to be prepared using the grinding thick silicon of micron, and asphalt powder passes through
It is sieved and obtains after crushing pitch particle, specific preparation process is referring to following preparation example.
Preparation example 1
The thick silicon of 1kg (Xuzhou reach the clouds Gui Ye Co., Ltd, 5 μm of average particle size) is dispersed in 9kg ethyl alcohol and is mixed
Liquid is closed, obtained mixed liquor is added to N in nanometer sand mill2Protection is lower to grind 8h, and wherein grinder rotating speed is 1200rpm,
Using 0.1mm zirconium ball, it is 50nm nano-silicon slurry that average particle size, which is made,.
Preparation example 2
1kg pitch particle (Jining time coalification Co., Ltd, softening point: 250 DEG C) is passed through into mechanical crusher coarse crushing
3min (revolving speed 15000rpm) will obtain powder and pass through airslide disintegrating mill finely divided (admission pressure 0.8Mpa, crushing pressure
0.7Mpa), the asphalt powder average grain diameter obtained is 2.5 μm.
Embodiment 1
500g artificial graphite (middle section Star City graphite Co., Ltd, HCG-1C, similarly hereinafter) is added to 100g nano-silicon
In alcohol mixture, it is uniformly mixed；Obtained mixture is spray-dried at 120 DEG C of inlet temperature, 80 DEG C of outlet temperature, mist
Change disk rotating speed is 20000rpm, and charging rate 25L/h obtains presoma；120g presoma, 60g pitch and 1.5g is taken to lead
Electric carbon black Super P (Te Migao graphite Co., Ltd, Super P Li) after mixing, is placed in tube furnace, in N2Guarantor
Under shield, 400 DEG C of heating 4h are warming up to 950 DEG C and Heat preservation 4h with 2.5 DEG C/min heating rate, are once burnt after crushing
Tie material；The once sintered material of gained is crossed into 400 meshes, by gained crushed material 100g, 15g pitch and 0.5g conduction charcoal after sieving
Black Super P after mixing, is placed in tube furnace, in N2Protection under, 400 DEG C of heating 4h, with 2.5 DEG C/min heating rate
950 DEG C and Heat preservation 4h are warming up to, obtained dusty material and artificial graphite 1:2 in mass ratio are mixed to get silicon after crushing
Carbon composite A1.
Embodiment 2
400g carbonaceous mesophase spherules (Bei Terui new energy Co., Ltd, SCMB-2, similarly hereinafter) 100g nanometers have been added to
In the alcohol mixture of silicon, it is uniformly mixed；Obtained mixture is done by spraying at 150 DEG C of inlet temperature, 70 DEG C of outlet temperature
Dry, atomization disk rotating speed is 15000rpm, and charging rate 20L/h obtains presoma；Take 120g presoma, 50g pitch and
1.2g Ketjen black (Aksu (lion king),ECP 600JD), (first rich nano material science and technology has 0.1g carbon nanotube
Limit company, functionalized multi-wall carbonnanotubes) after mixing, it is placed in tube furnace, in N2Protection under, 500 DEG C of heating 6h, with
2 DEG C/min heating rate is warming up to 850 DEG C and Heat preservation 5h, obtains Si-C composite material after crushing；Gained is once sintered
Material crosses 400 meshes, and gained crushed material 100g, 12g pitch and 0.2g carbon nanotube after sieving after mixing, are placed in tubular type
In furnace, in N2Protection under, 500 DEG C of heating 6h are warming up to 850 DEG C and Heat preservation 5h with 2 DEG C/min heating rate, after crushing
Obtained dusty material and carbonaceous mesophase spherules 1:2 in mass ratio are obtained into Si-C composite material A2.
Embodiment 3
500g natural graphite (middle section Star City graphite Co., Ltd, CNG-16F, similarly hereinafter) is added to 120g nano-silicon
In alcohol mixture, it is uniformly mixed；Obtained mixture is spray-dried at 130 DEG C of inlet temperature, 90 DEG C of outlet temperature, mist
Change disk rotating speed is 25000rpm, and charging rate 30L/h obtains presoma；Take 100g presoma, 80g pitch and 1g graphite
Alkene (Xian Feng Nono-material Science & Technology Ltd., carboxylated graphene, similarly hereinafter) after mixing, it is placed in tube furnace, in N2's
Under protection, 450 DEG C of heating 6h are warming up to 900 DEG C and Heat preservation 6h with 3 DEG C/min heating rate, are once burnt after crushing
Tie material；The once sintered material of gained is crossed into 400 meshes, by gained crushed material 100g, 10g pitch and 0.1g graphene after sieving
After mixing, it is placed in tube furnace, in N2Protection under, 450 DEG C of heating 6h are warming up to 900 DEG C with 3 DEG C/min heating rate
And Heat preservation 6h, obtained dusty material and natural graphite 1:2 in mass ratio are obtained into Si-C composite material A3 after crushing.
Reference example 1
It is commercialized silicon carbon material C1 (Bei Terui new energy Co., Ltd, S420-2A).
Reference example 2
It is commercialized silicon carbon material C2 (Jiangxi Zi Chen Science and Technology Ltd., Si/C composites -450mAh/g).
Comparative example 1
Si-C composite material is prepared as described in Example 1, except that it is added without conductive black Super P, thus
Si-C composite material D1 is made.
Comparative example 2
Si-C composite material is prepared as described in Example 1, except that it is compound only to obtain silicon-carbon by primary calcining
Material D2.
Application Example 1
In accordance with the following methods assembly lithium ion battery F1: Si-C composite material A1, thickener (CMC), bonding agent (SBR),
Conductive agent (conductive black Super P) prepares negative electrode slurry according to mass ratio 94:1.5:2.5:2, is adjusted and is starched using deionized water
Expect solid content be 40%, after the silicon-carbon cathode slurry regulated is coated on copper foil, in glove box after drying, roll-in, punching
Middle progress 2032 battery of button assembly, electrolyte are the LiPF6 of 1mol/L, and wherein solvent is EC:DMC:EMC=1:1:1 (volume
Than), diaphragm is Celgard polypropylene screen, uses metal lithium sheet for electrode.
Application Example 2-3, using reference example 1-2 and Comparison study example 1-2
Lithium ion battery is assembled according to Application Example 1, the difference is that using Si-C composite material A2-A3, C1- respectively
C2 and D1-D2 replaces Si-C composite material A1, so that lithium ion battery F2, F3 and CF1, CF2, DF1, DF2 be made respectively.
Test case 1
Above-mentioned lithium ion battery F1-F3 and CF1, CF2, DF1, DF2 is taken to carry out volume test on new prestige tester respectively,
Charge and discharge power range is 0.005-1.5V, and discharge process is that 0.1C is put into 0.01V, after 0.005V is put into 0.01C, charged
Cheng Ze is that 0.1C is charged to 1.5V.
Table 1
| Embodiment number | First charge discharge efficiency (%) | 100 weeks capacity retention ratios (%) |
| F1 | 91.8 | 95.7 |
| F2 | 89.5 | 91.4 |
| F3 | 90.6 | 93.2 |
| CF1 | 89.3 | 95.5 |
| CF2 | 88.4 | 91.6 |
| DF1 | 88.9 | 93.8 |
| DF2 | 88.5 | 88.3 |
It is living to can be seen that cathode of the Si-C composite material of the present invention as lithium ion battery by the result of table 1
Property material, made lithium ion battery has good first charge discharge efficiency and cyclical stability, shows obvious preferable comprehensive
Close performance.
The preferred embodiment of the present invention has been described above in detail, and still, the present invention is not limited thereto.In skill of the invention
In art conception range, can with various simple variants of the technical solution of the present invention are made, including each technical characteristic with it is any its
Its suitable method is combined, and it should also be regarded as the disclosure of the present invention for these simple variants and combination, is belonged to
Protection scope of the present invention.
Claims (10)
1. a kind of Si-C composite material, which is characterized in that the Si-C composite material includes basis material, is carried on described matrix material
Expect the nano-silicon on surface and be coated on the cladding carbon-coating of outer layer, wherein the cladding carbon-coating includes amorphous carbon layer and divides
Dissipate the conductive agent in the amorphous carbon layer.
2. Si-C composite material according to claim 1, which is characterized in that the matter of the nano-silicon and described matrix material
Amount is than being 1:2-20, preferably 1:2-10；
Preferably, described matrix material is selected from least one of natural graphite, artificial graphite and carbonaceous mesophase spherules；
Preferably, the granularity of the nano-silicon is 20-500nm, preferably 20-200nm；
Preferably, the amorphous carbon layer is by the way that carbon source is carried out secondary clacining formation；
It is further preferred that the carbon source is selected from pitch, phenolic resin, polyvinyl alcohol, citric acid, stearic acid, glucose, sugarcane
At least one of sugar, polyvinyl chloride and polyethylene glycol；
Preferably, the conductive agent is selected from least one of conductive black, Ketjen black, carbon nanotube and graphene.
3. a kind of preparation method of Si-C composite material, which is characterized in that method includes the following steps:
(1) basis material is added in the alcohol mixture of nano-silicon, it is evenly dispersed, obtain mixed liquor；
(2) mixed liquor is spray-dried, obtains presoma；
(3) presoma, carbon source and conductive agent are mixed, is then once calcined under nitrogen protection；
(4) the once sintered material disintegrating for obtaining step (3), then mixes with carbon source and conductive agent, again in nitrogen protection
Lower carry out secondary clacining, is then crushed, and smashed crushed material is mixed with graphite.
4. according to the method described in claim 3, it is characterized in that, described matrix material is selected from natural stone in step (1)
At least one of ink, artificial graphite and carbonaceous mesophase spherules；
Preferably, the granularity of the nano-silicon is 20-500nm, preferably 20-200nm；
Preferably, the mass ratio of the nano-silicon and described matrix material is 1:2-20, preferably 1:2-10.
5. according to the method described in claim 3, it is characterized in that, in the spray-drying process described in step (2), it is spraying into
Mouth temperature is 120-180 DEG C, preferably 120-150 DEG C；Outlet temperature is 70-100 DEG C, preferably 70-90 DEG C；It is atomized disk rotating speed
For 10000-30000rpm, preferably 15000-25000rpm；Charging rate is 5-50L/h, preferably 20-30L/h.
6. according to the method described in claim 3, it is characterized in that, in step (3), the presoma, the carbon source and institute
The mass ratio for stating conductive agent is 10:(1-10): (0.05-0.5), preferably 10:(3-5): (0.1-0.2).
7. according to the method described in claim 3, it is characterized in that, in step (4), crushed material, the carbon of once sintered material
The mass ratio of source and conductive agent is 10:(0.2-2): (0.001-0.1), more preferably 10:(0.2-1): (0.03-0.05)；
Preferably, it is sieved after once sintered material disintegrating, gained crushed material is mixed with carbon source and conductive agent again after sieving.
8. according to method described in claim 3,6 or 7, which is characterized in that in step (3) and (4), it is described it is primary calcining and
The calcinating system of the secondary clacining is identical, is two sections of calcining at constant temperature, and calcination temperature is respectively 400-500 DEG C, 850-950
DEG C, heating rate is 2-3 DEG C/min, soaking time 4-6h, 4-6h；
Preferably, the carbon source is selected from pitch, phenolic resin, polyvinyl alcohol, citric acid, stearic acid, glucose, sucrose, polychlorostyrene
At least one of ethylene and polyethylene glycol；
Preferably, the conductive agent is selected from least one of conductive black, Ketjen black, carbon nanotube and graphene.
9. the Si-C composite material of the preparation of the method as described in any one of claim 3-8.
10. a kind of lithium ion battery, which is characterized in that the negative electrode active material in the lithium ion battery is claim 1,2
With Si-C composite material described in any one of 9.
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