CN105958036A - Preparation method for carbon-coated silicon negative electrode material for lithium ion battery - Google Patents
Preparation method for carbon-coated silicon negative electrode material for lithium ion battery Download PDFInfo
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- CN105958036A CN105958036A CN201610527851.0A CN201610527851A CN105958036A CN 105958036 A CN105958036 A CN 105958036A CN 201610527851 A CN201610527851 A CN 201610527851A CN 105958036 A CN105958036 A CN 105958036A
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- ion battery
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- OKTJSMMVPCPJKN-UHFFFAOYSA-N Carbon Chemical compound [C] OKTJSMMVPCPJKN-UHFFFAOYSA-N 0.000 title claims abstract description 173
- 229910052799 carbon Inorganic materials 0.000 title claims abstract description 135
- XUIMIQQOPSSXEZ-UHFFFAOYSA-N Silicon Chemical compound [Si] XUIMIQQOPSSXEZ-UHFFFAOYSA-N 0.000 title claims abstract description 37
- 238000002360 preparation method Methods 0.000 title claims abstract description 29
- HBBGRARXTFLTSG-UHFFFAOYSA-N Lithium ion Chemical compound [Li+] HBBGRARXTFLTSG-UHFFFAOYSA-N 0.000 title claims abstract description 26
- 229910001416 lithium ion Inorganic materials 0.000 title claims abstract description 26
- 229910052710 silicon Inorganic materials 0.000 title claims abstract description 26
- 239000010703 silicon Substances 0.000 title claims abstract description 26
- 239000007773 negative electrode material Substances 0.000 title abstract 5
- 239000000463 material Substances 0.000 claims abstract description 93
- 239000006185 dispersion Substances 0.000 claims abstract description 36
- 239000011247 coating layer Substances 0.000 claims abstract description 31
- 238000000034 method Methods 0.000 claims abstract description 30
- 239000002904 solvent Substances 0.000 claims abstract description 20
- 239000002270 dispersing agent Substances 0.000 claims abstract description 8
- 238000003763 carbonization Methods 0.000 claims abstract description 7
- 239000002994 raw material Substances 0.000 claims abstract description 5
- 239000007788 liquid Substances 0.000 claims description 29
- 229910021389 graphene Inorganic materials 0.000 claims description 27
- 239000007787 solid Substances 0.000 claims description 26
- XLYOFNOQVPJJNP-UHFFFAOYSA-N water Substances O XLYOFNOQVPJJNP-UHFFFAOYSA-N 0.000 claims description 25
- VYPSYNLAJGMNEJ-UHFFFAOYSA-N Silicium dioxide Chemical compound O=[Si]=O VYPSYNLAJGMNEJ-UHFFFAOYSA-N 0.000 claims description 20
- 238000010438 heat treatment Methods 0.000 claims description 16
- XKRFYHLGVUSROY-UHFFFAOYSA-N Argon Chemical compound [Ar] XKRFYHLGVUSROY-UHFFFAOYSA-N 0.000 claims description 12
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- 239000000377 silicon dioxide Substances 0.000 claims description 10
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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
- 239000002202 Polyethylene glycol Substances 0.000 claims description 6
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- 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 6
- 229910052786 argon Inorganic materials 0.000 claims description 6
- KRKNYBCHXYNGOX-UHFFFAOYSA-N citric acid Chemical compound OC(=O)CC(O)(C(O)=O)CC(O)=O KRKNYBCHXYNGOX-UHFFFAOYSA-N 0.000 claims description 6
- 239000001257 hydrogen Substances 0.000 claims description 6
- 229910052739 hydrogen Inorganic materials 0.000 claims description 6
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- 229910052757 nitrogen Inorganic materials 0.000 claims description 5
- IAZDPXIOMUYVGZ-UHFFFAOYSA-N Dimethylsulphoxide Chemical compound CS(C)=O IAZDPXIOMUYVGZ-UHFFFAOYSA-N 0.000 claims description 4
- LRHPLDYGYMQRHN-UHFFFAOYSA-N N-Butanol Chemical compound CCCCO LRHPLDYGYMQRHN-UHFFFAOYSA-N 0.000 claims description 4
- NBBJYMSMWIIQGU-UHFFFAOYSA-N Propionic aldehyde Chemical compound CCC=O NBBJYMSMWIIQGU-UHFFFAOYSA-N 0.000 claims description 4
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- 239000004584 polyacrylic acid Substances 0.000 claims description 4
- 239000002356 single layer Substances 0.000 claims description 4
- QVGXLLKOCUKJST-UHFFFAOYSA-N atomic oxygen Chemical compound [O] QVGXLLKOCUKJST-UHFFFAOYSA-N 0.000 claims description 3
- 238000002156 mixing Methods 0.000 claims description 3
- 239000001301 oxygen Substances 0.000 claims description 3
- 229910052760 oxygen Inorganic materials 0.000 claims description 3
- 239000000843 powder Substances 0.000 claims description 3
- 238000003756 stirring Methods 0.000 claims description 3
- OWEGMIWEEQEYGQ-UHFFFAOYSA-N 100676-05-9 Natural products OC1C(O)C(O)C(CO)OC1OCC1C(O)C(O)C(O)C(OC2C(OC(O)C(O)C2O)CO)O1 OWEGMIWEEQEYGQ-UHFFFAOYSA-N 0.000 claims description 2
- KXGFMDJXCMQABM-UHFFFAOYSA-N 2-methoxy-6-methylphenol Chemical compound [CH]OC1=CC=CC([CH])=C1O KXGFMDJXCMQABM-UHFFFAOYSA-N 0.000 claims description 2
- GUBGYTABKSRVRQ-XLOQQCSPSA-N Alpha-Lactose Chemical compound O[C@@H]1[C@@H](O)[C@@H](O)[C@@H](CO)O[C@H]1O[C@@H]1[C@@H](CO)O[C@H](O)[C@H](O)[C@H]1O GUBGYTABKSRVRQ-XLOQQCSPSA-N 0.000 claims description 2
- VEXZGXHMUGYJMC-UHFFFAOYSA-M Chloride anion Chemical compound [Cl-] VEXZGXHMUGYJMC-UHFFFAOYSA-M 0.000 claims description 2
- 229920000858 Cyclodextrin Polymers 0.000 claims description 2
- GUBGYTABKSRVRQ-QKKXKWKRSA-N Lactose Natural products OC[C@H]1O[C@@H](O[C@H]2[C@H](O)[C@@H](O)C(O)O[C@@H]2CO)[C@H](O)[C@@H](O)[C@H]1O GUBGYTABKSRVRQ-QKKXKWKRSA-N 0.000 claims description 2
- GUBGYTABKSRVRQ-PICCSMPSSA-N Maltose Natural products O[C@@H]1[C@@H](O)[C@H](O)[C@@H](CO)O[C@@H]1O[C@@H]1[C@@H](CO)OC(O)[C@H](O)[C@H]1O GUBGYTABKSRVRQ-PICCSMPSSA-N 0.000 claims description 2
- IKHGUXGNUITLKF-XPULMUKRSA-N acetaldehyde Chemical compound [14CH]([14CH3])=O IKHGUXGNUITLKF-XPULMUKRSA-N 0.000 claims description 2
- HSFWRNGVRCDJHI-UHFFFAOYSA-N alpha-acetylene Natural products C#C HSFWRNGVRCDJHI-UHFFFAOYSA-N 0.000 claims description 2
- 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 2
- GUBGYTABKSRVRQ-QUYVBRFLSA-N beta-maltose Chemical compound OC[C@H]1O[C@H](O[C@H]2[C@H](O)[C@@H](O)[C@H](O)O[C@@H]2CO)[C@H](O)[C@@H](O)[C@@H]1O GUBGYTABKSRVRQ-QUYVBRFLSA-N 0.000 claims description 2
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- 238000004108 freeze drying Methods 0.000 claims description 2
- HYBBIBNJHNGZAN-UHFFFAOYSA-N furfural Chemical compound O=CC1=CC=CO1 HYBBIBNJHNGZAN-UHFFFAOYSA-N 0.000 claims description 2
- 239000008101 lactose Substances 0.000 claims description 2
- 229920005610 lignin Polymers 0.000 claims description 2
- WSFSSNUMVMOOMR-NJFSPNSNSA-N methanone Chemical compound O=[14CH2] WSFSSNUMVMOOMR-NJFSPNSNSA-N 0.000 claims description 2
- 239000000203 mixture Substances 0.000 claims description 2
- 229920001568 phenolic resin Polymers 0.000 claims description 2
- 239000005011 phenolic resin Substances 0.000 claims description 2
- 229920001197 polyacetylene Polymers 0.000 claims description 2
- 229920000767 polyaniline Polymers 0.000 claims description 2
- 229920000647 polyepoxide Polymers 0.000 claims description 2
- 229920006389 polyphenyl polymer Polymers 0.000 claims description 2
- 229920000128 polypyrrole Polymers 0.000 claims description 2
- 229920000123 polythiophene Polymers 0.000 claims description 2
- 229920002635 polyurethane Polymers 0.000 claims description 2
- 239000004814 polyurethane Substances 0.000 claims description 2
- BDERNNFJNOPAEC-UHFFFAOYSA-N propan-1-ol Chemical compound CCCO BDERNNFJNOPAEC-UHFFFAOYSA-N 0.000 claims description 2
- HFHDHCJBZVLPGP-UHFFFAOYSA-N schardinger α-dextrin Chemical compound O1C(C(C2O)O)C(CO)OC2OC(C(C2O)O)C(CO)OC2OC(C(C2O)O)C(CO)OC2OC(C(O)C2O)C(CO)OC2OC(C(C2O)O)C(CO)OC2OC2C(O)C(O)C1OC2CO HFHDHCJBZVLPGP-UHFFFAOYSA-N 0.000 claims description 2
- 238000005507 spraying Methods 0.000 claims description 2
- 238000001291 vacuum drying Methods 0.000 claims description 2
- CSCPPACGZOOCGX-UHFFFAOYSA-N Acetone Chemical compound CC(C)=O CSCPPACGZOOCGX-UHFFFAOYSA-N 0.000 claims 3
- 239000002210 silicon-based material Substances 0.000 abstract description 15
- 239000011248 coating agent Substances 0.000 abstract description 2
- 238000000576 coating method Methods 0.000 abstract description 2
- 239000011863 silicon-based powder Substances 0.000 abstract 3
- 239000007791 liquid phase Substances 0.000 abstract 1
- 238000004519 manufacturing process Methods 0.000 abstract 1
- 230000001105 regulatory effect Effects 0.000 abstract 1
- 239000011343 solid material Substances 0.000 abstract 1
- 238000005253 cladding Methods 0.000 description 11
- 239000010406 cathode material Substances 0.000 description 7
- 235000013339 cereals Nutrition 0.000 description 7
- 229910052744 lithium Inorganic materials 0.000 description 7
- 239000012299 nitrogen atmosphere Substances 0.000 description 7
- WHXSMMKQMYFTQS-UHFFFAOYSA-N Lithium Chemical compound [Li] WHXSMMKQMYFTQS-UHFFFAOYSA-N 0.000 description 6
- 230000000694 effects Effects 0.000 description 5
- 239000005543 nano-size silicon particle Substances 0.000 description 4
- 239000002033 PVDF binder Substances 0.000 description 3
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- 241001597008 Nomeidae Species 0.000 description 2
- YZCKVEUIGOORGS-IGMARMGPSA-N Protium Chemical compound [1H] YZCKVEUIGOORGS-IGMARMGPSA-N 0.000 description 2
- 241000720974 Protium Species 0.000 description 2
- HMDDXIMCDZRSNE-UHFFFAOYSA-N [C].[Si] Chemical compound [C].[Si] HMDDXIMCDZRSNE-UHFFFAOYSA-N 0.000 description 2
- 150000001336 alkenes Chemical class 0.000 description 2
- 239000012300 argon atmosphere Substances 0.000 description 2
- 230000004888 barrier function Effects 0.000 description 2
- 230000003139 buffering effect Effects 0.000 description 2
- 239000006258 conductive agent Substances 0.000 description 2
- 239000003792 electrolyte Substances 0.000 description 2
- 239000002245 particle Substances 0.000 description 2
- -1 polyethylene Polymers 0.000 description 2
- 229920000642 polymer Polymers 0.000 description 2
- 239000002002 slurry Substances 0.000 description 2
- RYGMFSIKBFXOCR-UHFFFAOYSA-N Copper Chemical compound [Cu] RYGMFSIKBFXOCR-UHFFFAOYSA-N 0.000 description 1
- 229910001290 LiPF6 Inorganic materials 0.000 description 1
- 206010054949 Metaplasia Diseases 0.000 description 1
- SECXISVLQFMRJM-UHFFFAOYSA-N N-Methylpyrrolidone Chemical compound CN1CCCC1=O SECXISVLQFMRJM-UHFFFAOYSA-N 0.000 description 1
- 240000007594 Oryza sativa Species 0.000 description 1
- 235000007164 Oryza sativa Nutrition 0.000 description 1
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- 239000013543 active substance Substances 0.000 description 1
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- 238000009830 intercalation Methods 0.000 description 1
- 150000002500 ions Chemical class 0.000 description 1
- 150000002576 ketones Chemical class 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
-
- 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
- H01M4/13—Electrodes for accumulators with non-aqueous electrolyte, e.g. for lithium-accumulators; Processes of manufacture thereof
- H01M4/134—Electrodes based on metals, Si or alloys
-
- 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
- H01M4/13—Electrodes for accumulators with non-aqueous electrolyte, e.g. for lithium-accumulators; Processes of manufacture thereof
- H01M4/139—Processes of manufacture
- H01M4/1395—Processes of manufacture of electrodes based on metals, Si or alloys
-
- H—ELECTRICITY
- H01—ELECTRIC ELEMENTS
- H01M—PROCESSES OR MEANS, e.g. BATTERIES, FOR THE DIRECT CONVERSION OF CHEMICAL ENERGY INTO ELECTRICAL ENERGY
- H01M4/00—Electrodes
- H01M4/02—Electrodes composed of, or comprising, active material
- H01M4/36—Selection of substances as active materials, active masses, active liquids
- H01M4/38—Selection of substances as active materials, active masses, active liquids of elements or alloys
- H01M4/386—Silicon or alloys based on silicon
-
- H—ELECTRICITY
- H01—ELECTRIC ELEMENTS
- H01M—PROCESSES OR MEANS, e.g. BATTERIES, FOR THE DIRECT CONVERSION OF CHEMICAL ENERGY INTO ELECTRICAL ENERGY
- H01M4/00—Electrodes
- H01M4/02—Electrodes composed of, or comprising, active material
- H01M4/62—Selection of inactive substances as ingredients for active masses, e.g. binders, fillers
- H01M4/624—Electric conductive fillers
- H01M4/625—Carbon or graphite
-
- 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
- H01M4/628—Inhibitors, e.g. gassing inhibitors, corrosion inhibitors
-
- Y—GENERAL TAGGING OF NEW TECHNOLOGICAL DEVELOPMENTS; GENERAL TAGGING OF CROSS-SECTIONAL TECHNOLOGIES SPANNING OVER SEVERAL SECTIONS OF THE IPC; TECHNICAL SUBJECTS COVERED BY FORMER USPC CROSS-REFERENCE ART COLLECTIONS [XRACs] AND DIGESTS
- Y02—TECHNOLOGIES OR APPLICATIONS FOR MITIGATION OR ADAPTATION AGAINST CLIMATE CHANGE
- Y02E—REDUCTION OF GREENHOUSE GAS [GHG] EMISSIONS, RELATED TO ENERGY GENERATION, TRANSMISSION OR DISTRIBUTION
- Y02E60/00—Enabling technologies; Technologies with a potential or indirect contribution to GHG emissions mitigation
- Y02E60/10—Energy storage using batteries
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- Chemical & Material Sciences (AREA)
- Chemical Kinetics & Catalysis (AREA)
- Electrochemistry (AREA)
- General Chemical & Material Sciences (AREA)
- Engineering & Computer Science (AREA)
- Materials Engineering (AREA)
- Manufacturing & Machinery (AREA)
- Composite Materials (AREA)
- Battery Electrode And Active Subsutance (AREA)
Abstract
The invention provides a preparation method for a carbon-coated silicon negative electrode material for a lithium ion battery. The negative electrode material for the lithium ion battery with excellent performance is obtained from silicon powder by two times of carbon coating; the preparation method comprises the following steps of carrying out liquid phase dispersion on the silicon powder, then carrying out dispersion on the silicon powder, the first carbon coating layer and a dispersing agent; removing the solvent, and carrying out high-temperature carbonization treatment on the obtained solid material to obtain primary carbon-coated silicon negative electrode material; preparing a dispersion solution of a second carbon-coated material, dispersing the primary carbon-coated silicon material to the dispersion solution of the second carbon-coated material, and then removing the solvent and carrying out secondary roasting to obtain the secondary carbon-coated silicon negative electrode material. According to the preparation method, the raw materials are low in cost and easily available; the ratio of silicon to carbon can be optionally regulated and controlled; and the preparation method is simple in equipment, easy to implement the technological process, and suitable for scale production.
Description
Technical field
The present invention relates to field of lithium ion battery material, be specifically related to the carbon coated Si of a kind of lithium ion battery
The preparation method of negative material.
Background technology
Due to the development of electronic product, especially smart mobile phone and new-energy automobile, to lithium ion battery
Energy density requires the highest, and the current lithium battery with material with carbon elements such as graphite as negative pole is because of energy density,
Theoretical specific capacity only 375mAh/g, poor safety performance, far from meeting the demand that people increase day by day.
Such as, current smart mobile phone was fast due to the many power consumptions of function, almost will fill once electricity every several hours,
Trip and life for people bring a lot of inconvenience.Environmental problem and energy crisis promote various countries to send out energetically
Exhibition new-energy automobile, but continual mileage is short, be short of power, dangerous and cost is high hampers newly always
The development of energy automobile.Therefore, the lithium cell negative pole material of exploitation high-energy-density has far-reaching economic effect
Benefit and social meaning.
Silicon is considered as most potential negative material, because silicon can form alloy cpd Li with lithiumxSi
(0 < x≤4.4), i.e. one silicon can combine with most 4.4 lithiums, and specific capacity reaches as high as 4200mAh/g,
It is more than 11 times of graphite cathode, and the intercalation potential of silicon is higher than the deposition potential of lithium, improves high power
The safety of rate discharge and recharge.But, silicium cathode distance large-scale commercial application is the most far, traces it to its cause
Mainly silicon materials change in volume during embedding de-lithium is very big, and up to 300%, huge body
Long-pending change cause solid liquid interface film persistently rupture with formed again, electrolyte decomposition, cause active substance easy
Between efflorescence, collector, electrical contact deteriorates, thus causes that capacity attenuation is fast, cycle performance is poor, and these are
Silicium cathode problem demanding prompt solution；Additionally, it is well known that, silicon materials are quasiconductors, therefore its electric conductivity
Not as graphite cathode, which has limited its high rate performance, if silicium cathode therefore can be solved in embedding de-lithium process
Change in volume and the problem of electric conductivity, for the silicium cathode application paving in electronic product and new-energy automobile field
Level line road, is beneficial to improve the life of people and environment.
Summary of the invention
The technical problem to be solved in the present invention be to provide to solve the technical problem that be to provide one can scale
Metaplasia is produced, is improved silicium cathode material conductivity and circulative ion cathode material lithium and preparation method thereof.
For solving above-mentioned technical problem, the technical scheme that the present invention proposes is to provide a kind of lithium ion battery
Carbon coated Si negative material, the clad on silicon power raw material surface is by the first carbon coating layer and the second carbon coating layer
Composition, the first carbon coating layer is wrapped in the outside of silicon power raw material, and the second carbon coating layer is wrapped in the first carbon bag
The outside of coating.
Its preparation method comprises the following steps:
1) in the silica flour that granular size is 1-100 μm, add solvent, disperse, continue 3-20h,
First silica flour dispersion is made the silicon grain of nanorize, alleviates silicon materials greatly in charge and discharge process
Change in volume；
2) adding in solvent by first carbon encapsulated material of 1-50wt%, the dispersant adding 0.2-5wt% enters
Row dispersion, obtains the first carbon encapsulated material dispersion liquid；
3) by first carbon encapsulated material dispersion liquid add step 1) in proceed dispersion；
4) removing step 3) in solvent, the solid obtained is risen to the heating rate of 1-20 DEG C/min
500-1400 DEG C carries out carbonization treatment 1-20h, obtains primary carbon coated Si negative material；
5) second carbon encapsulated material of 0.1-10wt% is dispersed in solvent, disperses, obtain second
Carbon encapsulated material dispersion liquid；
6) the second carbon encapsulated material dispersion liquid and primary carbon coated Si negative material are stirred mixing；
7) removing step 6) in solvent, the solid obtained is risen to the heating rate of 1-20 DEG C/min
500-1400 DEG C carries out carbonization treatment 1-20h, obtains secondary carbon coated Si negative material.
Wherein, described first carbon encapsulated material is graphite, sucrose, glucose, maltose, lactose, shallow lake
Powder, formaldehyde, acetaldehyde, propionic aldehyde, phenolic resin, epoxy resin, Polyethylene Glycol, cellulose, lignin,
In polyvinyl alcohol, polrvinyl chloride, polyethylene glycol oxide, polyurethane, poly-furfural, citric acid, cyclodextrin
At least one；Preferably, described first carbon encapsulated material is in graphite, starch, sucrose, polyvinyl alcohol
At least one, above-mentioned carbon encapsulated material is containing the organic molecule such as oxygen element, protium or polymer
As clad, the material with carbon element of the porous formed after roasting is uniformly wrapped on nano-silicon surface, plays buffering
Silicon materials are the effect of change in volume in discharge and recharge；Preferably, the weight of described first carbon encapsulated material is divided
Number is 5-20%, and amount is coated with insufficient less, has measured the advantage not embodying silicon materials more.
Described second carbon encapsulated material be multi-layer graphene, single-layer graphene, graphene oxide, polypyrrole,
Polythiophene, polyphenyl, polyacetylene, polyaniline, redox graphene at least one；Preferably, institute
Stating the second carbon encapsulated material is multi-layer graphene, single-layer graphene, graphene oxide, reduction-oxidation graphite
At least one in alkene, uses its derivant graphene-based as the second clad, the graphite of high-crystallinity
The material with carbon element electric conductivity of alkene structure is high, and electrochemical stability is good, and beneficially high rate charge-discharge, circulation are surely
Qualitative good；Preferably, the part by weight of the second carbon encapsulated material is 1-5%, both can guarantee that second time bag
Cover completely, can guarantee that again electric conductivity.
Described dispersant is in polyvinyl alcohol, polyethylene glycol oxide, polyacrylic acid, LA132, LA135
Kind or multiple combination.
Wherein, described solvent be water, methanol, ethanol, propanol, isopropanol, butanol, ethylene glycol, third
At least one in ketone, dimethylformamide, dimethyl sulfoxide, ethyl acetate, it is preferable that preparation process
Described in solvent be at least one in water, ethanol, isopropanol, ethyl acetate, it is highly preferred that preparation
During described solvent be water and ethanol.
Wherein it is preferred to, step 1) in the particle diameter of silica flour be 5-30 μm.
Wherein it is preferred to, step 1) in jitter time be 5-10h.
Wherein it is preferred to, the weight fraction of described dispersant is 0.5-2%, and dispersant major function is auxiliary
Helping covering material and solvent to mix, content is low, mixes uneven, and content is high causes covering material
Relative amount reduces.
Wherein, step 2) employed in process for dispersing be ultrasonic, stirring, one or several in ball milling
Being used in conjunction of the method for kind.
Wherein, step 4) and step 7) in the used method removing solvent be vacuum drying, spray dried
Being used in conjunction of one or more methods in dry, lyophilization, filtration drying, preferred method is for for spraying
It is dried.
Wherein it is preferred to, the temperature that high temperature cabonization processes is 700-1200 DEG C, and temperature is the lowest, and carbonization is not
Thoroughly；The highest, there is side reaction and waste the energy.
Wherein, high temperature cabonization heating rate is 5-10 DEG C/min, and this heating rate has taken into account efficiency and effect.
Wherein, the high temperature cabonization time is 3-10h.
Wherein, the atmosphere of high temperature cabonization is nitrogen, argon, nitrogen hydrogen mixed gas, the mixing of argon hydrogen
One in gas, it is preferable that high temperature cabonization atmosphere is for nitrogen, argon hydrogen mixed gas, these atmosphere
There is provided inert environments during carbonization, it is ensured that covering material is coated on silicon materials surface.
The present invention has the advantage that with good effect:
1, the technical process that the present invention uses is simple, and device therefor is all conventional disperse equipment, technique
Easily realize, low cost；Silicon materials used are the silica flours of industrialization, low cost, cheap and easily-available, first by silicon
The sphere of powder is milled into the silicon grain of nanorize, alleviates silicon materials volume in charge and discharge process greatly and becomes
Change；
2, the method using twice carbon cladding, carbon cladding uses containing oxygen element, protium etc. for the first time
Organic molecule or polymer are as clad, and the material with carbon element of the porous formed after roasting is uniformly wrapped on to be received
Rice silicon face, plays buffering silicon materials effect of change in volume in discharge and recharge；Carbon cladding uses for the second time
Its derivant graphene-based is as the second clad, the material with carbon element electric conductivity of the graphene-structured of high-crystallinity
Height, electrochemical stability is good, beneficially high rate charge-discharge, good cycling stability.
Accompanying drawing explanation
Fig. 1 is the stereoscan photograph of the secondary carbon coated Si material of example 1.
Fig. 2 is the half-cell charging and discharging curve of the secondary carbon coated Si material of example 1.
Fig. 3 is the cyclic curve under different electric current densities of the secondary carbon coated Si material of example 2.
Fig. 4 is the charging and discharging curve under different electric current densities of the secondary carbon coated Si material of example 3.
Fig. 5 is the cycle charge-discharge curve of the secondary carbon coated Si material of example 2.
Fig. 6 is the cycle charge-discharge curve of the secondary carbon coated Si material of example 4.
Detailed description of the invention
Embodiment 1 one kinds is the first carbon coating layer with sucrose, and Graphene is the lithium ion of the second carbon coating layer
The preparation method of battery silicium cathode material, its step includes:
1) silica flour that 80 gram particle footpaths are 8 μm is added in ball mill, add 160ml water, ball milling 6
Hour；
2) 20g sucrose and 5g polyvinyl alcohol are dissolved in 40ml water, obtain the first carbon coating layer solution；
3) by step 2) the first carbon coating layer solution add step 1) in, continue ball milling 2 hours,
Obtain silicon grain and the dispersion liquid of the first carbon encapsulated material of nanorize；
4) it is spray-dried removing step 3) water of the dispersion liquid of the nano-silicon of gained and the first carbon encapsulated material
Point, obtain solid；
5) by step 4) solid carry out high temperature cabonization process in a nitrogen atmosphere, heating rate is 5 DEG C
/ min, maintains 5 hours at 900 DEG C, obtains primary carbon coated Si negative material；
6) by 0.85g graphene dispersion to 200ml water, the dispersion liquid of the second carbon encapsulated material is obtained；
7) by step 6) the dispersion liquid of the second carbon encapsulated material and step 5) the primary carbon cladding that obtains
Silicium cathode material is thoroughly mixed；
8) removing step 7) in water, obtain solid；
9) by step 8) solid carry out high temperature cabonization process in a nitrogen atmosphere, heating rate is 10 DEG C
/ min, maintains 2 hours at 700 DEG C, obtains secondary carbon coated Si negative material；
As shown in Figure 2, the silicon materials gram volume of secondary carbon cladding is high, and electric discharge first reaches near
1200mAh/g。
Embodiment 2
A kind of is the first carbon coating layer with graphite, and graphene oxide is that the lithium ion battery silicon of the second clad is born
The preparation method of pole material, its step includes:
1) silica flour that 100 grams of D50 are 25 μm is added in ball mill, add 200ml water, ball milling
10 hours；
2) by 10g graphite and 1.1g polyacrylic acid ultrasonic disperse in 30ml water, the first carbon cladding is obtained
Layer dispersion liquid；
3) by step 2) the first carbon coating layer dispersion liquid add step 1) in, continue ball milling 3 hours,
The silicon grain obtaining nanorize is dispersed in the first carbon coating layer；
4) it is spray-dried removing step 3) moisture in gains, obtain solid；
5) by step 4) solid carry out high temperature cabonization process in a nitrogen atmosphere, heating rate is 10 DEG C
/ min, maintains 3 hours at 700 DEG C, obtains primary carbon coated Si negative material；
6) 3.3g graphene oxide is distributed in 100ml water, obtains the solution of the second carbon encapsulated material；
7) by step 6) the solution of the second carbon encapsulated material and step 5) the primary carbon coated Si that obtains
Negative material is thoroughly mixed；
8) removing step 7) in water, obtain solid；
9) by step 8) solid carry out high temperature cabonization process under an argon atmosphere, heating rate is 5 DEG C
/ min, maintains 3 hours at 850 DEG C, obtains secondary carbon coated Si negative material.
As seen from Figure 3, along with the increase of electric current density, gram volume decreases, but protects
Holdup is the highest, Fig. 5 can absolutely prove that carbon cladding can improve the cyclical stability of silicon materials.
Embodiment 3
A kind of is the first carbon coating layer with starch, and multi-layer graphene is that the lithium ion battery silicon of the second clad is born
The preparation method of pole material, its step includes:
1) silica flour that 60 grams of D50 are 15 μm is added in ball mill, add 150ml water, ball milling 7
Hour；
2) by 6g starch ultrasonic disperse in 50ml water, the first carbon coating layer dispersion liquid is obtained；
3) by step 2) starch dispersion liquid add step 1) in, continue ball milling 3 hours, received
The silicon grain of riceization is dispersed in the first carbon coating layer solution；
4) it is spray-dried removing step 3) moisture in the nano-silicon of gained and the dispersion liquid of starch, obtain
Solid；
5) by step 4) solid carry out high temperature cabonization process in a nitrogen atmosphere, heating rate is 6 DEG C
/ min, maintains 5 hours at 850 DEG C, obtains primary carbon coated Si negative material；
6) 2g multi-layer graphene is distributed in 200ml water, obtains the dispersion liquid of the second carbon coating layer；
7) by step 6) the dispersion liquid of the second carbon coating layer and step 5) the primary carbon coated Si that obtains
Negative material is thoroughly mixed；
8) removing step 7) in water, obtain solid；
9) by step 8) solid carry out high temperature cabonization process in a nitrogen atmosphere, heating rate is 8 DEG C
/ min, maintains 3 hours at 800 DEG C, obtains secondary carbon coated Si negative material.
As shown in Figure 4, carbon cladding can improve the high rate performance of silicon materials.
Embodiment 4
A kind of is the first carbon coating layer with polyvinyl alcohol, and Graphene is the lithium ion battery silicon of the second carbon coating layer
The preparation method of carbon negative pole material, its step includes:
1) silica flour that 100 grams of D50 are 8 μm is added in ball mill, add 150ml water, ball milling 4
Hour；
2) by 20g polyvinyl alcohol dispersed with stirring in 100ml water, the dispersion liquid of the first carbon coating layer is obtained；
3) by step 2) polyvinyl alcohol dispersion liquid add step 1) in, continue ball milling 2 hours,
Silicon grain to nanorize is dispersed in the dispersion liquid of the first carbon coating layer；
4) it is spray-dried removing step 3) moisture in the nano-silicon of gained and polyvinyl alcohol dispersion liquid,
To solid；
5) by step 4) solid carry out high temperature cabonization process in a nitrogen atmosphere, heating rate is 6 DEG C
/ min, maintains 5 hours at 900 DEG C, obtains primary carbon coated Si negative material；
6) by 1.5g graphene dispersion to 300ml water, the dispersion liquid of the second carbon coating layer is obtained；
7) by step 6) the dispersion liquid of the second carbon coating layer and step 5) the primary carbon coated Si that obtains
Negative material is thoroughly mixed；
8) removing step 7) in water, obtain solid；
9) by step 8) solid under hydrogen/argon mixed atmosphere, carry out high temperature cabonization process, heat up speed
Rate is 10 DEG C/min, maintains 2 hours at 800 DEG C, obtains secondary carbon coated Si negative material.
Can be absolutely proved that carbon cladding can improve the cyclical stability of silicon materials by Fig. 6.
Embodiment 5
A kind of is the first carbon coating layer with glucose, and redox graphene is the lithium ion of the second what is said or talked about clad
The preparation method of battery silicon-carbon cathode material, its step includes:
1) silica flour that 100 grams of D50 are 20 μm is added in ball mill, add 200ml water, ball milling
8 hours；
2) it is dissolved in ultrasonic to 25g glucose and 1.5g polyacrylic acid in 50ml water, obtains the first carbon cladding
Layer solution；
3) by step 2) the first carbon coating layer solution add step 1) in, continue ball milling 2.5 hours,
The silicon grain obtaining nanorize is dispersed in the first carbon coating layer solution；
4) it is spray-dried removing step 3) moisture in gains, obtain solid；
5) by step 4) solid carry out high temperature cabonization process in a nitrogen atmosphere, heating rate is 6 DEG C
/ min, maintains 6 hours at 850 DEG C, obtains primary carbon coated Si negative material；
6) 4g redox graphene is distributed in 100ml water, obtains dividing of the second carbon encapsulated material
Dissipate liquid；
7) by step 6) the dispersion liquid of the second carbon encapsulated material and step 5) the primary carbon cladding that obtains
Silicium cathode material is thoroughly mixed；
8) removing step 7) in water, obtain solid；
9) by step 8) solid carry out high temperature cabonization process under an argon atmosphere, heating rate is 5 DEG C
/ min, maintains 3 hours at 850 DEG C, obtains secondary carbon coated Si negative material
The secondary carbon coated Si negative material of embodiment 1-5 gained is carried out electrical property detection, key step
Including:
1) the N-Methyl pyrrolidone solution of the Kynoar (PVDF) of 5% solid content is configured；
2) weigh a certain amount of secondary carbon coated Si negative material, conductive agent Super-P first grinds mixed
Even, then the N-first class pyrrolidone solution dripping PVDF continues to be ground, and obtains slurry；Silicon-carbon
Material, the part by weight of conductive agent Super-P and PVDF are 80:10:10；
3) slurry is coated on Copper Foil, and vacuum dried, roll-in, cut-parts, it is prepared as pole piece；
4) using lithium sheet as to electrode, barrier film is polyethylene, polypropylene composite materials barrier film, uses 1.2
mol/L LiPF6Three component mixed solvent EC/DMC/EMC (three solvent volume ratios are 1: 1: 1) molten
Liquid is electrolyte, is assembled into button cell.Charging/discharging voltage is limited in 0.05～1.5V.
The amount adjusting glucose in embodiment 5 is 20g, 15g, 10g, repeats the process of step 1-9, system
Standby different silicon and the silicon-carbon cathode material of glucose ratio.
Specific capacity under the different electric current densities of the secondary carbon coated Si material of table 1 example 5
From test result, along with the raising of glucose content, glucose is as the first clad
Silicon materials gram volume is the lowest, but the capability retention under different electric current density is the highest.
Claims (13)
1. the preparation method of the carbon coated Si negative material of a lithium ion battery, it is characterised in that: bag
Include following steps:
1) in the silica flour that granular size is 1-100 μm, add solvent to disperse, continue 3-20h；
2) first carbon encapsulated material of 1-50wt% is added in solvent, add the dispersant of 0.2-5wt%
Disperse, obtain the first carbon encapsulated material dispersion liquid；
3) by first carbon encapsulated material dispersion liquid add step 1) in proceed dispersion；
4) removing step 3) in solvent, the solid obtained is risen to the heating rate of 1-20 DEG C/min
500-1400 DEG C carries out carbonization treatment 1-20h, obtains primary carbon coated Si negative material；
5) second carbon encapsulated material of 0.1-10wt% is dispersed in solvent, disperses, obtain second
Carbon encapsulated material dispersion liquid；
6) the second carbon encapsulated material dispersion liquid and primary carbon coated Si negative material are stirred mixing；
7) removing step 6) in solvent, the solid obtained is risen to the heating rate of 1-20 DEG C/min
500-1400 DEG C carries out carbonization treatment 1-20h, obtains secondary carbon coated Si negative material.
Wherein, described first carbon encapsulated material is graphite, sucrose, glucose, maltose, lactose, shallow lake
Powder, formaldehyde, acetaldehyde, propionic aldehyde, phenolic resin, epoxy resin, Polyethylene Glycol, cellulose, lignin,
In polyvinyl alcohol, polrvinyl chloride, polyethylene glycol oxide, polyurethane, poly-furfural, citric acid, cyclodextrin
At least one；
Described second carbon encapsulated material be multi-layer graphene, single-layer graphene, graphene oxide, polypyrrole,
Polythiophene, polyphenyl, polyacetylene, polyaniline, redox graphene at least one；
Described dispersant is in polyvinyl alcohol, polyethylene glycol oxide, polyacrylic acid, LA132, LA135
Kind or multiple combination.
The preparation method of the carbon coated Si negative material of lithium ion battery the most according to claim 1,
It is characterized in that: the clad on silicon power raw material surface is made up of the first carbon coating layer and the second carbon coating layer,
First carbon coating layer is wrapped in the outside of silicon power raw material, and the second carbon coating layer is wrapped in the first carbon coating layer
Outside.
The preparation method of the carbon coated Si negative material of lithium ion battery the most according to claim 1,
It is characterized in that: described solvent be water, methanol, ethanol, propanol, isopropanol, butanol, ethylene glycol,
At least one in acetone, dimethylformamide, dimethyl sulfoxide, ethyl acetate.
The preparation method of the carbon coated Si negative material of lithium ion battery the most according to claim 1,
It is characterized in that: step 1) in jitter time be 5-10h.
The preparation method of the carbon coated Si negative material of lithium ion battery the most according to claim 1,
It is characterized in that: preferably, described first carbon encapsulated material is graphite, starch, sucrose, polyvinyl alcohol
In at least one, the weight fraction of described first carbon encapsulated material is 5-20%.
The preparation method of the carbon coated Si negative material of lithium ion battery the most according to claim 1,
It is characterized in that: preferably, the weight fraction of described dispersant is 0.5-2%.
The preparation method of the carbon coated Si negative material of lithium ion battery the most according to claim 1,
It is characterized in that: step 2) employed in process for dispersing be ultrasonic, stirring, one in ball milling or
Being used in conjunction of several method.
The preparation method of the carbon coated Si negative material of lithium ion battery the most according to claim 1,
It is characterized in that: preferably, described second carbon encapsulated material is multi-layer graphene, single-layer graphene, oxygen
At least one in functionalized graphene, redox graphene, the part by weight of described second carbon encapsulated material
For 1-5%.
The preparation method of the carbon coated Si negative material of lithium ion battery the most according to claim 1,
It is characterized in that: step 4) and step 7) in the used method removing solvent be vacuum drying, spraying
Be dried, lyophilization, being used in conjunction of one or more methods in filtration drying.
The preparation side of the carbon coated Si negative material of lithium ion battery the most according to claim 1
Method, it is characterised in that: preferably, the temperature that high temperature cabonization processes is 700-1200 DEG C.
The preparation method of the carbon coated Si negative material of 11. lithium ion batteries according to claim 1,
It is characterized in that: preferably, high temperature cabonization heating rate is 5-10 DEG C/min.
The preparation method of the carbon coated Si negative material of 12. lithium ion batteries according to claim 1,
It is characterized in that: preferably, the high temperature cabonization time is 3-10h.
The preparation method of the carbon coated Si negative material of 13. lithium ion batteries according to claim 1,
It is characterized in that: the atmosphere of high temperature cabonization be nitrogen, argon, nitrogen hydrogen mixed gas, argon hydrogen mix
Close the one in gas.
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