CN110299519A - A kind of crystalline silicon/oxygen silicon/carbon coating composite negative pole material and preparation method thereof - Google Patents
A kind of crystalline silicon/oxygen silicon/carbon coating composite negative pole material and preparation method thereof Download PDFInfo
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- CN110299519A CN110299519A CN201910526701.1A CN201910526701A CN110299519A CN 110299519 A CN110299519 A CN 110299519A CN 201910526701 A CN201910526701 A CN 201910526701A CN 110299519 A CN110299519 A CN 110299519A
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- silicon
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- carbon coating
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- 229910052710 silicon Inorganic materials 0.000 title claims abstract description 83
- 239000010703 silicon Substances 0.000 title claims abstract description 83
- 239000001301 oxygen Substances 0.000 title claims abstract description 79
- 229910052760 oxygen Inorganic materials 0.000 title claims abstract description 79
- 239000000463 material Substances 0.000 title claims abstract description 71
- 229910021419 crystalline silicon Inorganic materials 0.000 title claims abstract description 69
- OKTJSMMVPCPJKN-UHFFFAOYSA-N Carbon Chemical compound [C] OKTJSMMVPCPJKN-UHFFFAOYSA-N 0.000 title claims abstract description 50
- 229910052799 carbon Inorganic materials 0.000 title claims abstract description 40
- 239000011248 coating agent Substances 0.000 title claims abstract description 28
- 238000000576 coating method Methods 0.000 title claims abstract description 28
- 239000002131 composite material Substances 0.000 title claims abstract description 28
- 238000002360 preparation method Methods 0.000 title claims abstract description 13
- MYMOFIZGZYHOMD-UHFFFAOYSA-N Dioxygen Chemical compound O=O MYMOFIZGZYHOMD-UHFFFAOYSA-N 0.000 title 1
- XUIMIQQOPSSXEZ-UHFFFAOYSA-N Silicon Chemical compound [Si] XUIMIQQOPSSXEZ-UHFFFAOYSA-N 0.000 claims abstract description 93
- QVGXLLKOCUKJST-UHFFFAOYSA-N atomic oxygen Chemical compound [O] QVGXLLKOCUKJST-UHFFFAOYSA-N 0.000 claims abstract description 78
- OBNDGIHQAIXEAO-UHFFFAOYSA-N [O].[Si] Chemical group [O].[Si] OBNDGIHQAIXEAO-UHFFFAOYSA-N 0.000 claims abstract description 19
- 239000002245 particle Substances 0.000 claims abstract description 19
- 238000000227 grinding Methods 0.000 claims abstract description 8
- 239000013078 crystal Substances 0.000 claims abstract description 7
- 239000010406 cathode material Substances 0.000 claims description 26
- 238000000034 method Methods 0.000 claims description 22
- 239000007773 negative electrode material Substances 0.000 claims description 20
- 239000007788 liquid Substances 0.000 claims description 19
- 239000006185 dispersion Substances 0.000 claims description 15
- 239000010410 layer Substances 0.000 claims description 15
- 229910052744 lithium Inorganic materials 0.000 claims description 15
- WHXSMMKQMYFTQS-UHFFFAOYSA-N Lithium Chemical compound [Li] WHXSMMKQMYFTQS-UHFFFAOYSA-N 0.000 claims description 14
- 238000000498 ball milling Methods 0.000 claims description 13
- 238000003763 carbonization Methods 0.000 claims description 11
- 238000003860 storage Methods 0.000 claims description 11
- MHAJPDPJQMAIIY-UHFFFAOYSA-N Hydrogen peroxide Chemical group OO MHAJPDPJQMAIIY-UHFFFAOYSA-N 0.000 claims description 10
- 239000011261 inert gas Substances 0.000 claims description 10
- 239000010439 graphite Substances 0.000 claims description 9
- 238000003756 stirring Methods 0.000 claims description 9
- 238000001035 drying Methods 0.000 claims description 8
- 229910002804 graphite Inorganic materials 0.000 claims description 8
- 229910021421 monocrystalline silicon Inorganic materials 0.000 claims description 6
- 239000011247 coating layer Substances 0.000 claims description 5
- 239000002194 amorphous carbon material Substances 0.000 claims description 3
- 239000007800 oxidant agent Substances 0.000 claims description 3
- 230000001590 oxidative effect Effects 0.000 claims description 3
- 238000005255 carburizing Methods 0.000 claims description 2
- 238000007580 dry-mixing Methods 0.000 claims description 2
- 229910021420 polycrystalline silicon Inorganic materials 0.000 claims description 2
- 239000000126 substance Substances 0.000 claims 4
- 229910001416 lithium ion Inorganic materials 0.000 abstract description 15
- 238000005253 cladding Methods 0.000 abstract description 2
- 238000002156 mixing Methods 0.000 abstract description 2
- HMDDXIMCDZRSNE-UHFFFAOYSA-N [C].[Si] Chemical compound [C].[Si] HMDDXIMCDZRSNE-UHFFFAOYSA-N 0.000 description 18
- 239000000203 mixture Substances 0.000 description 16
- 238000005303 weighing Methods 0.000 description 15
- 239000011863 silicon-based powder Substances 0.000 description 13
- HBBGRARXTFLTSG-UHFFFAOYSA-N Lithium ion Chemical compound [Li+] HBBGRARXTFLTSG-UHFFFAOYSA-N 0.000 description 12
- 238000004519 manufacturing process Methods 0.000 description 12
- 238000001514 detection method Methods 0.000 description 10
- KXGFMDJXCMQABM-UHFFFAOYSA-N 2-methoxy-6-methylphenol Chemical compound [CH]OC1=CC=CC([CH])=C1O KXGFMDJXCMQABM-UHFFFAOYSA-N 0.000 description 9
- 229920001568 phenolic resin Polymers 0.000 description 9
- 239000005011 phenolic resin Substances 0.000 description 9
- 239000000843 powder Substances 0.000 description 9
- 239000002994 raw material Substances 0.000 description 9
- XLYOFNOQVPJJNP-UHFFFAOYSA-N water Chemical compound O XLYOFNOQVPJJNP-UHFFFAOYSA-N 0.000 description 9
- 229910021383 artificial graphite Inorganic materials 0.000 description 8
- 239000010426 asphalt Substances 0.000 description 8
- 230000000052 comparative effect Effects 0.000 description 8
- 238000001816 cooling Methods 0.000 description 8
- 238000011049 filling Methods 0.000 description 8
- 238000010438 heat treatment Methods 0.000 description 8
- 238000011056 performance test Methods 0.000 description 8
- 239000002210 silicon-based material Substances 0.000 description 8
- 238000005507 spraying Methods 0.000 description 8
- 238000012360 testing method Methods 0.000 description 8
- -1 polypropylene Polymers 0.000 description 7
- 238000011160 research Methods 0.000 description 4
- LIVNPJMFVYWSIS-UHFFFAOYSA-N silicon monoxide Chemical compound [Si-]#[O+] LIVNPJMFVYWSIS-UHFFFAOYSA-N 0.000 description 4
- 239000002086 nanomaterial Substances 0.000 description 3
- 230000003647 oxidation Effects 0.000 description 3
- 238000007254 oxidation reaction Methods 0.000 description 3
- IJGRMHOSHXDMSA-UHFFFAOYSA-N Atomic nitrogen Chemical compound N#N IJGRMHOSHXDMSA-UHFFFAOYSA-N 0.000 description 2
- LFQSCWFLJHTTHZ-UHFFFAOYSA-N Ethanol Chemical compound CCO LFQSCWFLJHTTHZ-UHFFFAOYSA-N 0.000 description 2
- 238000009831 deintercalation Methods 0.000 description 2
- 239000003792 electrolyte Substances 0.000 description 2
- 238000005516 engineering process Methods 0.000 description 2
- 239000002070 nanowire Substances 0.000 description 2
- 239000011856 silicon-based particle Substances 0.000 description 2
- 239000002002 slurry Substances 0.000 description 2
- 238000001238 wet grinding Methods 0.000 description 2
- 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 description 1
- ZTQSAGDEMFDKMZ-UHFFFAOYSA-N Butyraldehyde Chemical compound CCCC=O ZTQSAGDEMFDKMZ-UHFFFAOYSA-N 0.000 description 1
- RYGMFSIKBFXOCR-UHFFFAOYSA-N Copper Chemical compound [Cu] RYGMFSIKBFXOCR-UHFFFAOYSA-N 0.000 description 1
- PXGOKWXKJXAPGV-UHFFFAOYSA-N Fluorine Chemical compound FF PXGOKWXKJXAPGV-UHFFFAOYSA-N 0.000 description 1
- 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 description 1
- 229910001290 LiPF6 Inorganic materials 0.000 description 1
- 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 description 1
- 240000007594 Oryza sativa Species 0.000 description 1
- 235000007164 Oryza sativa Nutrition 0.000 description 1
- 240000003936 Plumbago auriculata Species 0.000 description 1
- 239000004743 Polypropylene Substances 0.000 description 1
- 239000004372 Polyvinyl alcohol Substances 0.000 description 1
- 229920002472 Starch Polymers 0.000 description 1
- 229910000831 Steel Inorganic materials 0.000 description 1
- 229930006000 Sucrose Natural products 0.000 description 1
- 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 description 1
- ZVLDJSZFKQJMKD-UHFFFAOYSA-N [Li].[Si] Chemical compound [Li].[Si] ZVLDJSZFKQJMKD-UHFFFAOYSA-N 0.000 description 1
- 150000001336 alkenes Chemical class 0.000 description 1
- 239000010405 anode material Substances 0.000 description 1
- 238000013459 approach Methods 0.000 description 1
- 230000009286 beneficial effect Effects 0.000 description 1
- 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 description 1
- 239000011230 binding agent Substances 0.000 description 1
- 239000002041 carbon nanotube Substances 0.000 description 1
- 229910021393 carbon nanotube Inorganic materials 0.000 description 1
- 239000003575 carbonaceous material Substances 0.000 description 1
- 235000013339 cereals Nutrition 0.000 description 1
- 238000006243 chemical reaction Methods 0.000 description 1
- 239000003153 chemical reaction reagent Substances 0.000 description 1
- 239000003795 chemical substances by application Substances 0.000 description 1
- 150000001875 compounds Chemical class 0.000 description 1
- 239000006258 conductive agent Substances 0.000 description 1
- 239000011889 copper foil Substances 0.000 description 1
- 125000004122 cyclic group Chemical group 0.000 description 1
- 230000000694 effects Effects 0.000 description 1
- 239000008151 electrolyte solution Substances 0.000 description 1
- 238000005265 energy consumption Methods 0.000 description 1
- 239000003822 epoxy resin Substances 0.000 description 1
- 235000019441 ethanol Nutrition 0.000 description 1
- 229910052731 fluorine Inorganic materials 0.000 description 1
- 239000011737 fluorine Substances 0.000 description 1
- 239000008103 glucose Substances 0.000 description 1
- 239000008187 granular material Substances 0.000 description 1
- 238000011835 investigation Methods 0.000 description 1
- 239000012528 membrane Substances 0.000 description 1
- 238000012986 modification Methods 0.000 description 1
- 230000004048 modification Effects 0.000 description 1
- DOTMOQHOJINYBL-UHFFFAOYSA-N molecular nitrogen;molecular oxygen Chemical compound N#N.O=O DOTMOQHOJINYBL-UHFFFAOYSA-N 0.000 description 1
- 229910021382 natural graphite Inorganic materials 0.000 description 1
- 229910052757 nitrogen Inorganic materials 0.000 description 1
- 235000012149 noodles Nutrition 0.000 description 1
- 229920002239 polyacrylonitrile Polymers 0.000 description 1
- 229920000767 polyaniline Polymers 0.000 description 1
- 229920000647 polyepoxide Polymers 0.000 description 1
- 229920001155 polypropylene Polymers 0.000 description 1
- 229920000128 polypyrrole Polymers 0.000 description 1
- 229920000123 polythiophene Polymers 0.000 description 1
- 229920002451 polyvinyl alcohol Polymers 0.000 description 1
- 229920000036 polyvinylpyrrolidone Polymers 0.000 description 1
- 239000001267 polyvinylpyrrolidone Substances 0.000 description 1
- 235000013855 polyvinylpyrrolidone Nutrition 0.000 description 1
- 239000008213 purified water Substances 0.000 description 1
- 230000002441 reversible effect Effects 0.000 description 1
- 235000009566 rice Nutrition 0.000 description 1
- 239000004065 semiconductor Substances 0.000 description 1
- 239000000243 solution Substances 0.000 description 1
- 239000002904 solvent Substances 0.000 description 1
- 239000008107 starch Substances 0.000 description 1
- 235000019698 starch Nutrition 0.000 description 1
- 239000010959 steel Substances 0.000 description 1
- 239000005720 sucrose Substances 0.000 description 1
- 239000002699 waste material Substances 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
- 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
- H01M4/362—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
- 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
-
- 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)
- Composite Materials (AREA)
- Materials Engineering (AREA)
- Manufacturing & Machinery (AREA)
- Battery Electrode And Active Subsutance (AREA)
Abstract
The invention belongs to the technical fields of high-capacity lithium ion cell material, it is related to a kind of crystalline silicon/oxygen silicon/carbon coating composite negative pole material, the crystalline silicon/oxygen silicon is made using wet ball grinding sub-micron silicon, its inner core is crystalline silicon, outer layer is oxygen silicon, the crystalline silicon/oxygen silicon median particle diameter D50 be 0.16 μm -0.60 μm, preferably 0.10 μm -0.25 μm, oxygen content 3%-18%.The present invention also provides preparation method, by wet ball grinding, mixing char-forming material, high temperature cabonization and etc. preparation complete.Inner core provided by the invention is submicron crystal silicon, and appearance coats oxygen silicon layer, then in the composite material of oxygen silicon layer outer cladding carbon, meets four conditions of industrial applications, and first discharge specific capacity is high, and coulombic efficiency is high for the first time, and cycle performance is high and industrialization is at low cost.
Description
Technical field
The invention belongs to high purity nano material field of material technology, are related to high-purity silicon nanowires, silicon nanometer, and high-purity carbon is received
Rice noodles pipe, carbon nanometer, the device and preparation method thereof of high-purity nm carbofrax material.
Background technique
National Ministry of Industry and Information proposes, needs to reach 300wh/kg to the year two thousand twenty China power battery energy density, strives for reaching
350wh/kg, at the same manufacturing cost be lower than 1 yuan every watt, therefore to lithium ion battery lithium storage content, for the first time coulomb imitate
Rate, cycle-index and cost control propose very high requirement.
The whole world is applied to lithium ion battery negative material to silicon materials since two thousand eight and has made intensive studies, and China is close
The research institutions and manufacturing enterprise of various schools of thinkers also assist in silicon in the application study in negative electrode material, these researchs are from the nanometer of silicon
Change, village hollowing, the microscopic approach of porous and silicon effectively coats breach to find, Lai Jinhang agraphitic carbon cladding, but equal nothing
Method effectively realizes that silicon nanowire material is under the situation of same median diameter d50 size and same unformed carbon amounts covering material
Its carbon coating layer thickness is greatly thickened, and is formed effectively to silicon nano material in the charge expansion of embedding reason process silicon of lithium ion battery
Constraint, while expansive force is had an effect with line direction, can require there are four industrialized silicon-carbon cathode material tools: discharge specific volume for the first time
Amount is high, and coulombic efficiency is high for the first time, and cycle performance is high and industrialization is at low cost, indispensable in four-in-one.More than meeting simultaneously
It is required that seriously annoying high-capacity lithium ion cell industry and China greatly develops new-energy automobile industry, it is super using bend
Vehicle changes the estate planning of the relatively backward status orthodox car industry in China.
In the negative electrode material research process of lithium ion battery, nanoscale crystalline silicon and the sub- silicon of oxidation successively become research
Popular object.Silicon based anode material with huge lithium storage content (4200mAh/g), the slightly above discharge platform of carbon material, compared with
Low de- lithium current potential (0.5V) becomes next-generation lithium ion battery negative material.However silicon is adjoint in lithium ion charge and discharge process
The volume change of 300%-350%, the coefficient of expansion is high, and the powder of electrode is easily caused in lithium ion deintercalation charge and discharge process
Change, then constantly forms new ESI film, a large amount of electrolyte consumed in battery.Sub- silicon its theoretical capacity 2800mAh/g is aoxidized,
The lithium ion deintercalation coefficient of expansion is lower than crystalline silicon, about 150%-200%, but the material reversible capacity is low.
It is found by further investigation, crystalline silicon material will really be used for lithium ion battery negative material, particle D50 size
It must reach within 100nm, just can be reduced its expansive force, have carbon coating after silicon and available beam is reached to the expansion of crystalline silicon
It ties up.But three-dimensional reaches 100nm silicon nano material manufacturing process complexity, and energy consumption is very big, and manufacturing cost is very high.Three-dimensional dimension at present
D50 is in 100nm, and both at home and abroad and brand with reference to its appearance structure, price is in 3000-10000 member/kilogram differ,
High price can not apply in lithium ion battery material at all.
Summary of the invention
The object of the present invention is to provide a kind of crystalline silicon/oxygen silicon/carbon coating composite negative pole materials and preparation method thereof, make
Four conditions for meeting silicon lithium ion battery cathode material industrialization and using: first discharge specific capacity is high, for the first time coulombic efficiency
Height, cycle performance is high and industrialization is at low cost.
The purpose of the present invention is what is realized by following technological means:
A kind of crystalline silicon/oxygen silicon/carbon coating composite negative pole material, the crystalline silicon/oxygen silicon use wet ball grinding sub-micron
Silicon is made, and inner core is crystalline silicon, and outer layer is oxygen silicon, and the crystalline silicon/oxygen silicon median particle diameter D50 is 0.10 μm -0.60 μm,
Oxygen content is 3%-18%.
Above-mentioned crystalline silicon/oxygen silicon median particle diameter D50 is preferably 0.10 μm -0.25 μm.
Above-mentioned oxygen silicon refers to that the outer layer of crystalline silicon during ball milling is oxidized, due to degree of oxidation difference, thus shape
At different oxygen content.
The above-mentioned sub-micron silicon as raw material be monocrystalline and/or polycrystalline silicon crystal material, median particle diameter D50 be 1 μm-
100μm。
When material of the production compared with low oxygen content, generally carry out wet-milling using the lesser sub-micron silicon of partial size, when production compared with
When the material of rich oxygen content, wet-milling generally is carried out using the biggish sub-micron silicon of partial size.
Above-mentioned crystalline silicon/oxygen silicon is coated with carbon coating layer, and the quality of the carbon coating layer accounts for the siliceous amount of crystalline silicon/oxygen
25%-75%.
Above-mentioned crystalline silicon/oxygen silicon/carbon coating composite negative pole material and graphite cathode material are mixed to get lithium particle battery
The mass ratio of negative electrode material, the crystalline silicon/oxygen silicon/carbon coating composite negative pole material and graphite cathode material is 5%:95%-
35%:65%.
The present invention also provides above-mentioned crystalline silicon/oxygen silicon/carbon coating composite negative pole material preparation method, including it is as follows
Step:
(1) sub-micron silicon and the dispersion of liquid medium uniform stirring are added in ball mill by wet process storage tank, carry out ball milling
1.5-24h, obtaining outer layer is oxygen silicon layer, and inner core is composite material crystalline silicon/oxygen silicon of crystalline silicon；
(2) above-mentioned crystalline silicon/oxygen silicon is added to evenly dispersed containing and forms amorphous carbon material under the high temperature conditions
In solution, by being dried to obtain dry mixing material, drying time 2-10h；
(3) above-mentioned dry mixed material is fitted into closed good high temperature furnace, under the protection of inert gas, is carried out high
Warm carbonization treatment, carburizing temperature are 500-1000 DEG C, carbonization time 2-24h, obtain crystalline silicon/oxygen silicon/carbon coating Compound Negative
Pole material.
Liquid medium refers to purified water or ethyl alcohol in above-mentioned steps (1).
The revolving speed of ball milling is 1000-1800 revs/min in above-mentioned steps (1).
Ball-milling Time in above-mentioned steps (1) can control crystalline silicon/oxygen silicon grain diameter.When crystalline silicon/oxygen silicon D50 size
When 100 nanometers closer, every Ball-milling Time for reducing unit sizes needs is increased more.When close to 100 nanometers, reduce
D50 size 5nm-10nm, it is possible to need to increase Ball-milling Time 12-24 hours.
Above-mentioned steps (1) ball-grinding machine is stick pin type ball mill or double dynamical centrifugal ball mill.
The solid-to-liquid ratio of above-mentioned steps (1) sub-micron silicon and liquid medium is 15%:85%-35%:65%.
Amorphous carbon material is formed in above-mentioned steps (2) under the high temperature conditions and refers to phenolic resin, polyacrylonitrile, poly- fluorine second
Alkene, polyvinyl alcohol, butyral, polyvinylpyrrolidone, epoxy resin, polyaniline, polythiophene, polypyrrole, pitch, glucose,
One of maltose, sucrose, starch are a variety of.
The quantity number of drying time dried material as needed in above-mentioned steps (2) is adjusted.
Further, in order to accelerate to aoxidize, oxidant, the oxidation can be added in the liquid medium of above-mentioned wet ball grinding
Agent is preferably hydrogen peroxide.
The molar ratio of above-mentioned hydrogen peroxide and liquid medium is 0.001-0.1:1.
Above-mentioned lithium ion battery refers to the lithium ion battery being made of anode, diaphragm, cathode and electrolyte solution.
Above-mentioned graphite cathode material is conventional graphite cathode material, including natural graphite cathode, artificial plumbago negative pole, in
Between phase graphite cathode material.
The present invention having the beneficial effect that compared with the existing technology:
1, the cheap submicron order crystal silicon particle of use cost of the present invention is as raw material, it might even be possible to use semiconductor
The waste silicon powder generated in chip or photovoltaic solar cell piece process of manufacture, middle negative electrode material is direct compared with the prior art
The nanoscalar silicon particles used, greatly reduce production cost, and the industrialization for low cost provides the foundation.
2, the present invention forms oxygen silicon layer and crystalline silicon inner core using submicron crystal silicon wet ball grinding from the outside to the core, has easy
Manufacture, easily dispersion, appearance easily uniformly coat the characteristic of agraphitic carbon, improve lithium storage content and for the first time coulomb using crystalline silicon inner core
Efficiency forms good electric conductivity, using the low-expansion coefficient of oxygen silicon, forms effective constraint of the carbon to silicon expansive force, simultaneously
Without adding the materials such as other carbon nanotubes.Reduce process flow, reduces manufacturing cost, easy industrialized production.
3, the present invention produces crystalline silicon/oxygen silicon by traditional wet ball grinding method, controls oxygen silicon by control Ball-milling Time
The oxygen content of layer, and then crystalline silicon/oxygen silicon property is controlled, simple process, reaction end is easy to control, and guarantees stable production
Quality.
4, crystalline silicon provided by the invention/oxygen silicon/carbon coating composite negative pole material, is pressed compared with ordinary graphite negative electrode material
The uniformly mixing of relative capacity proportion proportion, is tested by half-cell, and first discharge specific capacity is close to theoretical value, coulombic efficiency for the first time
It keeps capacity rate up to 80% or more between 88%-92.5%, in cyclic process in 750-1000 weeks, is a kind of highly desirable silicon-carbon
Cathode four-in-one advantage material.
Detailed description of the invention
Fig. 1 is electromicroscopic photograph of the invention
Specific embodiment
Below by the description of specific embodiment, the invention will be further described, but it is to limit of the invention that this, which is not,
System, those skilled in the art's basic thought according to the present invention, various modifications may be made or improves, but without departing from
Basic thought of the invention, is all within the scope of the present invention.
Various raw materials and reagents used in the embodiment of the present invention are commercially available purchase unless otherwise instructed.
Oxygen content detection of the invention uses nitrogen oxygen analyzer, and specially Beijing steel grinds the ON-3000 type nitrogen that nanogram produces
Oxygen analyzer.
Performance detection is done to cell negative electrode material using button cell in the embodiment of the present invention, used method is as follows:
1) slurrying: negative electrode material, conductive agent, binder are weighed by the mass ratio of 8:0.95:1.05, and solvent adjustment is added
Good slurry viscosity stirs 2.5h.
2) it is coated with: slurry being coated in copper foil current collector with scraper mold.
3) dry: 11 hours dry at 120 DEG C in vacuum oven.
4) cut-parts: it is cut into the circular batteries negative electrode tab of diameter 15mm, is placed in drying box after weighing.
5) it assembles: being assembled into 2025 type button cells by counter electrode of lithium piece in glove box.Electrolyte is 1M's
LiPF6/E DEG C: DM DEG C of (1:1, Vol) mixed liquor, diaphragm are 2300 microporous polypropylene membranes.
6) test: the battery standing 20h that will be sealed is tested using battery performance charge-discharge test and cycle performance.
Embodiment 1: using commercially available median particle diameter D50 for 3.3 μm of monocrystal silicon powder is raw material.
Step 1: weighing above-mentioned monocrystal silicon powder 1100g, be added to according to the solid-to-liquid ratio uniform stirring dispersion of 15%:85%
It in ball mill by wet process storage tank, is carried out ball milling 24 hours with 1000 revs/min of revolving speed, obtaining D50 partial size is 0.10-0.12 μm outer
Table is oxygen silicon layer, and inner core is the material of monocrystalline silicon, and dry drying obtains 1050g crystalline silicon/oxygen silicon, after testing, oxygen content
It is 18%.
Walk rapid 2: weighing crystalline silicon obtained in step 1/oxygen silicon materials 1000g, is added in pure water and emulsify uniformly
Dispersion, adds asphalt powder 1200g, phenolic resin 300g, further evenly dispersed, by evenly dispersed mixture through spraying dry
It is dry, obtain dry mixed material 2300g.
Step 3: filling this blend into the heating furnace of high-temperature closed, under the conditions of inert gas shielding, carry out at carbonization
Reason, for temperature in 800 degrees Celsius, the time is 3 hours, and by taking out after Temperature fall cooling, the high capacity silicon-carbon for obtaining 1500g is negative
Pole material.
Step 4: the obtained high-capacity cathode material 100g of step 3 uniformly being mixed with artificial graphite 900g, is obtained
To the silicon-carbon cathode material of lithium battery.Performance detection is done to cell negative electrode material using button cell, performance test results are seen below
Table.
Embodiment 2: using commercially available median particle diameter D50 for 10 μm of monocrystal silicon powder is raw material.
Step 1: weighing above-mentioned monocrystal silicon powder 1100g, be added to according to the solid-to-liquid ratio uniform stirring dispersion of 15%:85%
In ball mill by wet process storage tank, carried out ball milling 12 hours with 1200 revs/min of revolving speed, obtaining D50 partial size is 0.15-0.17 μm,
Appearance is oxygen silicon layer, and inner core is the material of monocrystalline silicon, and dry drying obtains 1050g crystalline silicon/oxygen silicon, after testing, oxygen-containing
Amount is 12%.
Walk rapid 2: weighing crystalline silicon obtained in step 1/oxygen silicon materials 1000g, is added in pure water and emulsify uniformly
Dispersion, adds asphalt powder 1200g, phenolic resin 300g, further evenly dispersed, by evenly dispersed mixture through spraying dry
It is dry, obtain dry mixed material 2300g.
Step 3: filling this blend into the heating furnace of high-temperature closed, under the conditions of inert gas shielding, carry out at carbonization
Reason, for temperature in 800 degrees Celsius, the time is 3 hours, and by taking out after Temperature fall cooling, the high capacity silicon-carbon for obtaining 1500g is negative
Pole material.
Step 4: the obtained high-capacity cathode material 100g of step 3 uniformly being mixed with artificial graphite 900g, is obtained
To the silicon-carbon cathode material of lithium battery.Performance detection is done to cell negative electrode material using button cell, performance test results are seen below
Table.
Embodiment 3: using commercially available median particle diameter D50 for 30 μm of monocrystal silicon powder is raw material.
Step 1: weighing above-mentioned monocrystal silicon powder 1100g, be added to according to the solid-to-liquid ratio uniform stirring dispersion of 25%:75%
It in ball mill by wet process storage tank, is carried out ball milling 5 hours with 1400 revs/min of revolving speed, obtaining D50 partial size is 0.18-0.20 μm, outside
Table is oxygen silicon layer, and inner core is the material of monocrystalline silicon, and dry drying obtains 1050g crystalline silicon/oxygen silicon, after testing, oxygen content
It is 8%.
Walk rapid 2: weighing crystalline silicon obtained in step 1/oxygen silicon materials 1000g, is added in pure water and emulsify uniformly
Dispersion, adds asphalt powder 1200g, phenolic resin 300g, further evenly dispersed, by evenly dispersed mixture through spraying dry
It is dry, obtain dry mixed material 2300g.
Step 3: filling this blend into the heating furnace of high-temperature closed, under the conditions of inert gas shielding, carry out at carbonization
Reason, for temperature in 800 degrees Celsius, the time is 3 hours, and by taking out after Temperature fall cooling, the high capacity silicon-carbon for obtaining 1500g is negative
Pole material.
Step 4: the obtained high-capacity cathode material 100g of step 3 uniformly being mixed with artificial graphite 900g, is obtained
To the silicon-carbon cathode material of lithium battery.Performance detection is done to cell negative electrode material using button cell, performance test results are seen below
Table.
Embodiment 4: using commercially available median particle diameter D50 for 50 μm of monocrystal silicon powder is raw material.
Step 1: weighing above-mentioned monocrystal silicon powder 1100g, be added to according to the solid-to-liquid ratio uniform stirring dispersion of 30%:70%
It in ball mill by wet process storage tank, is carried out ball milling 2 hours with 1600 revs/min of revolving speed, obtaining D50 partial size is 0.21-0.23 μm, outside
Table is oxygen silicon layer, and inner core is the material of monocrystalline silicon, and dry drying obtains 1050g crystalline silicon/oxygen silicon, after testing, oxygen content
It is 5.1%.
Walk rapid 2: weighing crystalline silicon obtained in step 1/oxygen silicon materials 1000g, is added in pure water and emulsify uniformly
Dispersion, adds asphalt powder 1200g, phenolic resin 300g, further evenly dispersed, by evenly dispersed mixture through spraying dry
It is dry, obtain dry mixed material 2300g.
Step 3: filling this blend into the heating furnace of high-temperature closed, under the conditions of inert gas shielding, carry out at carbonization
Reason, for temperature in 800 degrees Celsius, the time is 3 hours, and by taking out after Temperature fall cooling, the high capacity silicon-carbon for obtaining 1500g is negative
Pole material.
Step 4: the obtained high-capacity cathode material 100g of step 3 uniformly being mixed with artificial graphite 900g, is obtained
To the silicon-carbon cathode material of lithium battery.Performance detection is done to cell negative electrode material using button cell, performance test results are seen below
Table.
Embodiment 5: using commercially available median particle diameter D50 for 50 μm of polycrystal silicon powder is raw material.
Step 1: weighing above-mentioned polycrystal silicon powder 1100g, be added to according to the solid-to-liquid ratio uniform stirring dispersion of 25%:75%
In ball mill by wet process storage tank, liquid medium is the hydrogen peroxide solution of molar ratio 0.01:1, carries out ball with 1200 revs/min of revolving speed
Mill 1.5 hours, obtaining D50 partial size is 0.23-0.25 μm, and appearance is oxygen silicon layer, and inner core is the material of crystalline silicon, is dried
To 1050g crystalline silicon/oxygen silicon, after testing, oxygen content 14.5%.
Walk rapid 2: weighing crystalline silicon obtained in step 1/oxygen silicon materials 1000g, is added in pure water and emulsify uniformly
Dispersion, adds asphalt powder 600g, phenolic resin 150g, further evenly dispersed, by evenly dispersed mixture through spraying dry
It is dry, obtain dry mixed material 1750g.
Step 3: filling this blend into the heating furnace of high-temperature closed, under the conditions of inert gas shielding, carry out at carbonization
Reason, for temperature in 1000 degrees Celsius, the time is 3 hours, by taking out after Temperature fall cooling, obtains the high capacity silicon-carbon of 1200g
Negative electrode material.
Step 4: the obtained high-capacity cathode material 300g of step 3 uniformly being mixed with artificial graphite 700g, is obtained
To the silicon-carbon cathode material of lithium battery.Performance detection is done to cell negative electrode material using button cell, performance test results are seen below
Table.
Embodiment 6: using commercially available median particle diameter D50 for 100 μm of polycrystal silicon powder is raw material.
Step 1: weighing above-mentioned polycrystal silicon powder 1100g, be added to according to the solid-to-liquid ratio uniform stirring dispersion of 25%:75%
In ball mill by wet process storage tank, liquid medium is the hydrogen peroxide solution of molar ratio 0.02:1, carries out ball with 1200 revs/min of revolving speed
Mill 2.5 hours, obtaining D50 partial size is 0.58-0.60 μm, and appearance is oxygen silicon layer, and inner core is the material of crystalline silicon, is dried
To 1050g crystalline silicon/oxygen silicon, after testing, oxygen content 18%.
Step 2: weighing crystalline silicon obtained in step 1/oxygen silicon materials 1000g, be added in pure water and emulsify uniformly
Dispersion, adds asphalt powder 600g, phenolic resin 150g, further evenly dispersed, by evenly dispersed mixture through spraying dry
It is dry, obtain dry mixed material 1750g.
Step 3: filling this blend into the heating furnace of high-temperature closed, under the conditions of inert gas shielding, carry out at carbonization
Reason, for temperature in 1000 degrees Celsius, the time is 3 hours, by taking out after Temperature fall cooling, obtains the high capacity silicon-carbon of 1200g
Negative electrode material.
Step 4: the obtained high-capacity cathode material 300g of step 3 uniformly being mixed with artificial graphite 700g, is obtained
To the silicon-carbon cathode material of lithium battery.Performance detection is done to cell negative electrode material using button cell, performance test results are seen below
Table.
Comparative example 1:
Step 1: taking commercially available submicron crystal silicon oxygen particle, D50 partial size is 0.20-0.22 μm, oxygen content 0.5%.
Walk rapid 2: weighing the submicron crystal silicon oxygen material 1000g in step 1, is added in pure water emulsify and uniformly divide
It dissipates, adds asphalt powder 1200g, phenolic resin 300g, it is further evenly dispersed, by evenly dispersed mixture through spraying dry
It is dry, obtain dry mixed material 2300g.
Step 3: filling this blend into the heating furnace of high-temperature closed, under the conditions of inert gas shielding, carry out at carbonization
Reason, for temperature in 800 degrees Celsius, the time is 3 hours, and by taking out after Temperature fall cooling, the high capacity silicon-carbon for obtaining 1500g is negative
Pole material.
Step 4: the obtained high-capacity cathode material 100g of step 3 uniformly being mixed with artificial graphite 900g, is obtained
To the silicon-carbon cathode material of lithium battery.Performance detection is done to cell negative electrode material using button cell, performance test results are seen below
Table.
Comparative example 2:
Step 1: taking commercially available silicon monoxide particle, D50 partial size is 0.20-0.22 μm, oxygen content 36%.
Walk rapid 2: weighing the silicon monoxide granular materials 1000g in step 1, is added in pure water emulsify and uniformly divide
It dissipates, adds asphalt powder 1200g, phenolic resin 300g, it is further evenly dispersed, by evenly dispersed mixture through spraying dry
It is dry, obtain dry mixed material 2300g.
Step 3: filling this blend into the heating furnace of high-temperature closed, under the conditions of inert gas shielding, carry out at carbonization
Reason, for temperature in 800 degrees Celsius, the time is 3 hours, and by taking out after Temperature fall cooling, the high capacity silicon-carbon for obtaining 1900g is negative
Pole material.
Step 4: the obtained high-capacity cathode material 100g of step 3 uniformly being mixed with artificial graphite 900g, is obtained
To the silicon-carbon cathode material of lithium battery.Performance detection is done to cell negative electrode material using button cell, performance test results are seen below
Table.
As seen from the above table, in embodiment 1-5, crystalline silicon prepared by the present invention/oxygen silicon/carbon coating composite negative pole material, oxygen
Content is higher, and coulombic efficiency and battery capacity are lower for the first time, but cycle performance is better, can select according to demand in actually preparation
Select optimal oxygen content.And although oxygen content is very high in embodiment 6, cycle performance is performed poor, and reason is mainly particle
Caused by size is bigger than normal.
Compare the cathode material in crystalline silicon prepared by the present invention/oxygen silicon/carbon coating composite negative pole material and comparative example 1
Material, cycle performance of the invention will be far better than comparative example 1.It is multiple to compare crystalline silicon prepared by the present invention/oxygen silicon/carbon coating
The negative electrode material in negative electrode material and comparative example 2 is closed, battery capacity of the invention and for the first time coulombic efficiency are intended to obvious excellent
In comparative example 2.To sum up, crystalline silicon prepared by the present invention/oxygen silicon/carbon coating composite negative pole material, comprehensive performance want excellent
In comparative example 1 and comparative example 2.
Claims (10)
1. a kind of crystalline silicon/oxygen silicon/carbon coating composite negative pole material, which is characterized in that the crystalline silicon/oxygen silicon uses wet process ball
It grinds sub-micron silicon to be made, inner core is crystalline silicon, and outer layer is oxygen silicon, and the crystalline silicon/oxygen silicon median particle diameter D50 is 0.10 μ
M-0.60 μm, oxygen content 3%-18%.
2. a kind of crystalline silicon according to claim 1/oxygen silicon/carbon coating composite negative pole material, which is characterized in that the crystalline substance
Body silicon/oxygen silicon median particle diameter D50 is preferably 0.10 μm -0.25 μm.
3. a kind of crystalline silicon according to claim 1/oxygen silicon/carbon coating composite negative pole material, which is characterized in that the Asia
Micron silicon is monocrystalline and/or polycrystalline silicon crystal material, and median particle diameter D50 is 1 μm -100 μm.
4. a kind of crystalline silicon according to claim 1/oxygen silicon/carbon coating composite negative pole material, which is characterized in that the crystalline substance
Body silicon/oxygen silicon is coated with carbon coating layer, and the quality of the carbon coating layer accounts for the 25%-75% of the siliceous amount of crystalline silicon/oxygen.
5. a kind of crystalline silicon according to claim 1/oxygen silicon/carbon coating composite negative pole material, which is characterized in that the crystalline substance
Body silicon/oxygen silicon/carbon coating composite negative pole material and graphite cathode material are mixed to get the negative electrode material of lithium particle battery, the crystalline substance
The mass ratio of body silicon/oxygen silicon/carbon coating composite negative pole material and graphite cathode material is 5%:95%-35%:65%.
6. a kind of such as crystalline silicon of any of claims 1-4/oxygen silicon/carbon coating composite negative pole material preparation side
Method, which comprises the steps of:
(1) sub-micron silicon and the dispersion of liquid medium uniform stirring are added in ball mill by wet process storage tank, carry out ball milling 1.5-
For 24 hours, obtaining outer layer is oxygen silicon layer, and inner core is composite material crystalline silicon/oxygen silicon of crystalline silicon；
(2) above-mentioned crystalline silicon/oxygen silicon is added to evenly dispersed containing and forms amorphous carbon material solution under the high temperature conditions
In, by being dried to obtain dry mixing material, drying time 2-10h；
(3) above-mentioned dry mixed material is fitted into closed good high temperature furnace, under the protection of inert gas, carries out pyrocarbon
Change processing, carburizing temperature are 500-1000 DEG C, carbonization time 2-24h, obtain crystalline silicon/oxygen silicon/carbon coating composite negative pole material
Material.
7. a kind of crystalline silicon according to claim 5/oxygen silicon/carbon coating composite negative pole material preparation method, feature
It is, the revolving speed of ball milling is 1000-1800 revs/min in step (1).
8. a kind of crystalline silicon according to claim 5/oxygen silicon/carbon coating composite negative pole material preparation method, feature
It is, the solid-to-liquid ratio of the sub-micron silicon and liquid medium is 15%:85%-35%:65%.
9. a kind of crystalline silicon according to claim 5/oxygen silicon/carbon coating composite negative pole material preparation method, feature
It is, oxidant is added in step (1) in the liquid medium of wet ball grinding, and the oxidant is hydrogen peroxide.
10. a kind of crystalline silicon according to claim 9/oxygen silicon/carbon coating composite negative pole material preparation method, feature
It is, the molar ratio of the hydrogen peroxide and liquid medium is 0.001-0.1:1.
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