CN110148743A - A kind of silicon-carbon composite cathode material and preparation method thereof and lithium ion battery - Google Patents
A kind of silicon-carbon composite cathode material and preparation method thereof and lithium ion battery Download PDFInfo
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- CN110148743A CN110148743A CN201910606247.0A CN201910606247A CN110148743A CN 110148743 A CN110148743 A CN 110148743A CN 201910606247 A CN201910606247 A CN 201910606247A CN 110148743 A CN110148743 A CN 110148743A
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- 239000010406 cathode material Substances 0.000 title claims abstract description 46
- 239000002153 silicon-carbon composite material Substances 0.000 title claims abstract description 44
- 238000002360 preparation method Methods 0.000 title claims abstract description 32
- 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
- OKTJSMMVPCPJKN-UHFFFAOYSA-N Carbon Chemical compound [C] OKTJSMMVPCPJKN-UHFFFAOYSA-N 0.000 claims abstract description 79
- 239000002131 composite material Substances 0.000 claims abstract description 70
- 238000005253 cladding Methods 0.000 claims abstract description 57
- 239000002041 carbon nanotube Substances 0.000 claims abstract description 44
- 239000005543 nano-size silicon particle Substances 0.000 claims abstract description 43
- 229910021393 carbon nanotube Inorganic materials 0.000 claims abstract description 40
- 229910052799 carbon Inorganic materials 0.000 claims abstract description 37
- XUIMIQQOPSSXEZ-UHFFFAOYSA-N Silicon Chemical compound [Si] XUIMIQQOPSSXEZ-UHFFFAOYSA-N 0.000 claims abstract description 27
- 229910052710 silicon Inorganic materials 0.000 claims abstract description 26
- 239000010703 silicon Substances 0.000 claims abstract description 26
- 239000011247 coating layer Substances 0.000 claims abstract description 3
- 239000000463 material Substances 0.000 claims description 54
- VYPSYNLAJGMNEJ-UHFFFAOYSA-N Silicium dioxide Chemical compound O=[Si]=O VYPSYNLAJGMNEJ-UHFFFAOYSA-N 0.000 claims description 48
- LFQSCWFLJHTTHZ-UHFFFAOYSA-N Ethanol Chemical compound CCO LFQSCWFLJHTTHZ-UHFFFAOYSA-N 0.000 claims description 33
- 239000000843 powder Substances 0.000 claims description 33
- XKRFYHLGVUSROY-UHFFFAOYSA-N Argon Chemical compound [Ar] XKRFYHLGVUSROY-UHFFFAOYSA-N 0.000 claims description 26
- 239000007789 gas Substances 0.000 claims description 26
- 239000000377 silicon dioxide Substances 0.000 claims description 25
- 239000011248 coating agent Substances 0.000 claims description 24
- 238000000576 coating method Methods 0.000 claims description 24
- 229960000935 dehydrated alcohol Drugs 0.000 claims description 21
- 230000009977 dual effect Effects 0.000 claims description 20
- BOTDANWDWHJENH-UHFFFAOYSA-N Tetraethyl orthosilicate Chemical compound CCO[Si](OCC)(OCC)OCC BOTDANWDWHJENH-UHFFFAOYSA-N 0.000 claims description 16
- 238000001035 drying Methods 0.000 claims description 16
- 235000012239 silicon dioxide Nutrition 0.000 claims description 15
- XLYOFNOQVPJJNP-UHFFFAOYSA-N water Substances O XLYOFNOQVPJJNP-UHFFFAOYSA-N 0.000 claims description 14
- 229910052786 argon Inorganic materials 0.000 claims description 13
- 229910052681 coesite Inorganic materials 0.000 claims description 13
- 229910052906 cristobalite Inorganic materials 0.000 claims description 13
- 229910052682 stishovite Inorganic materials 0.000 claims description 13
- 229910052905 tridymite Inorganic materials 0.000 claims description 13
- KRHYYFGTRYWZRS-UHFFFAOYSA-N Fluorane Chemical compound F KRHYYFGTRYWZRS-UHFFFAOYSA-N 0.000 claims description 12
- 235000011114 ammonium hydroxide Nutrition 0.000 claims description 12
- 239000002002 slurry Substances 0.000 claims description 12
- 238000001354 calcination Methods 0.000 claims description 10
- VNWKTOKETHGBQD-UHFFFAOYSA-N methane Chemical compound C VNWKTOKETHGBQD-UHFFFAOYSA-N 0.000 claims description 10
- 239000000654 additive Substances 0.000 claims description 9
- 230000000996 additive effect Effects 0.000 claims description 9
- 239000003054 catalyst Substances 0.000 claims description 8
- 238000004519 manufacturing process Methods 0.000 claims description 8
- 238000003756 stirring Methods 0.000 claims description 8
- HSFWRNGVRCDJHI-UHFFFAOYSA-N alpha-acetylene Natural products C#C HSFWRNGVRCDJHI-UHFFFAOYSA-N 0.000 claims description 7
- 125000002534 ethynyl group Chemical group [H]C#C* 0.000 claims description 7
- 239000012298 atmosphere Substances 0.000 claims description 6
- 238000005229 chemical vapour deposition Methods 0.000 claims description 6
- 238000005530 etching Methods 0.000 claims description 6
- 239000010410 layer Substances 0.000 claims description 6
- 238000005406 washing Methods 0.000 claims description 6
- 239000003792 electrolyte Substances 0.000 claims description 4
- 239000011261 inert gas Substances 0.000 claims description 4
- 239000011259 mixed solution Substances 0.000 claims description 4
- RMAQACBXLXPBSY-UHFFFAOYSA-N silicic acid Chemical compound O[Si](O)(O)O RMAQACBXLXPBSY-UHFFFAOYSA-N 0.000 claims description 4
- 235000007164 Oryza sativa Nutrition 0.000 claims description 3
- 235000009566 rice Nutrition 0.000 claims description 3
- 230000001681 protective effect Effects 0.000 claims description 2
- 239000002071 nanotube Substances 0.000 claims 2
- 240000007594 Oryza sativa Species 0.000 claims 1
- 238000009833 condensation Methods 0.000 claims 1
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- 239000002023 wood Substances 0.000 claims 1
- 238000000034 method Methods 0.000 abstract description 5
- 239000002245 particle Substances 0.000 abstract description 2
- 239000002210 silicon-based material Substances 0.000 abstract description 2
- KRKNYBCHXYNGOX-UHFFFAOYSA-N citric acid Chemical compound OC(=O)CC(O)(C(O)=O)CC(O)=O KRKNYBCHXYNGOX-UHFFFAOYSA-N 0.000 description 33
- 238000004140 cleaning Methods 0.000 description 6
- 238000010792 warming Methods 0.000 description 6
- WHXSMMKQMYFTQS-UHFFFAOYSA-N Lithium Chemical compound [Li] WHXSMMKQMYFTQS-UHFFFAOYSA-N 0.000 description 5
- HMDDXIMCDZRSNE-UHFFFAOYSA-N [C].[Si] Chemical compound [C].[Si] HMDDXIMCDZRSNE-UHFFFAOYSA-N 0.000 description 5
- 238000005119 centrifugation Methods 0.000 description 5
- 238000006243 chemical reaction Methods 0.000 description 5
- 239000008367 deionised water Substances 0.000 description 5
- 229910021641 deionized water Inorganic materials 0.000 description 5
- 229910052744 lithium Inorganic materials 0.000 description 5
- 239000003575 carbonaceous material Substances 0.000 description 4
- 229960004756 ethanol Drugs 0.000 description 4
- 235000019441 ethanol Nutrition 0.000 description 4
- IDGUHHHQCWSQLU-UHFFFAOYSA-N ethanol;hydrate Chemical compound O.CCO IDGUHHHQCWSQLU-UHFFFAOYSA-N 0.000 description 4
- VCJMYUPGQJHHFU-UHFFFAOYSA-N iron(3+);trinitrate Chemical compound [Fe+3].[O-][N+]([O-])=O.[O-][N+]([O-])=O.[O-][N+]([O-])=O VCJMYUPGQJHHFU-UHFFFAOYSA-N 0.000 description 4
- ARUVKPQLZAKDPS-UHFFFAOYSA-L copper(II) sulfate Chemical compound [Cu+2].[O-][S+2]([O-])([O-])[O-] ARUVKPQLZAKDPS-UHFFFAOYSA-L 0.000 description 3
- 238000007599 discharging Methods 0.000 description 3
- 238000005538 encapsulation Methods 0.000 description 3
- 239000012530 fluid Substances 0.000 description 3
- 229910002804 graphite Inorganic materials 0.000 description 3
- 239000010439 graphite Substances 0.000 description 3
- 239000004615 ingredient Substances 0.000 description 3
- 239000007924 injection Substances 0.000 description 3
- 238000002347 injection Methods 0.000 description 3
- 239000007788 liquid Substances 0.000 description 3
- 239000007773 negative electrode material Substances 0.000 description 3
- 239000000126 substance Substances 0.000 description 3
- 238000002604 ultrasonography Methods 0.000 description 3
- 238000004804 winding Methods 0.000 description 3
- 229920002134 Carboxymethyl cellulose Polymers 0.000 description 2
- 241000209094 Oryza Species 0.000 description 2
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- 150000001875 compounds Chemical class 0.000 description 2
- 238000005520 cutting process Methods 0.000 description 2
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- 238000009830 intercalation Methods 0.000 description 2
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- 230000014759 maintenance of location Effects 0.000 description 2
- 238000002156 mixing Methods 0.000 description 2
- 239000011943 nanocatalyst Substances 0.000 description 2
- 239000000243 solution Substances 0.000 description 2
- 239000000758 substrate Substances 0.000 description 2
- KXGFMDJXCMQABM-UHFFFAOYSA-N 2-methoxy-6-methylphenol Chemical compound [CH]OC1=CC=CC([CH])=C1O KXGFMDJXCMQABM-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
- 230000001476 alcoholic effect Effects 0.000 description 1
- 239000010405 anode material Substances 0.000 description 1
- 239000012300 argon atmosphere Substances 0.000 description 1
- 230000009286 beneficial effect Effects 0.000 description 1
- WQZGKKKJIJFFOK-VFUOTHLCSA-N beta-D-glucose Chemical compound OC[C@H]1O[C@@H](O)[C@H](O)[C@@H](O)[C@@H]1O WQZGKKKJIJFFOK-VFUOTHLCSA-N 0.000 description 1
- 239000001768 carboxy methyl cellulose Substances 0.000 description 1
- 235000010948 carboxy methyl cellulose Nutrition 0.000 description 1
- 239000008112 carboxymethyl-cellulose Substances 0.000 description 1
- 230000010261 cell growth Effects 0.000 description 1
- 239000003795 chemical substances by application Substances 0.000 description 1
- 238000001816 cooling Methods 0.000 description 1
- 238000010410 dusting Methods 0.000 description 1
- 230000000694 effects Effects 0.000 description 1
- 238000004146 energy storage Methods 0.000 description 1
- 150000002148 esters Chemical class 0.000 description 1
- 239000008103 glucose Substances 0.000 description 1
- 239000007770 graphite material Substances 0.000 description 1
- 150000002500 ions Chemical class 0.000 description 1
- 238000002955 isolation Methods 0.000 description 1
- 239000000203 mixture Substances 0.000 description 1
- 238000011056 performance test Methods 0.000 description 1
- 239000005011 phenolic resin Substances 0.000 description 1
- 229920001568 phenolic resin Polymers 0.000 description 1
- 230000010287 polarization Effects 0.000 description 1
- 239000001267 polyvinylpyrrolidone Substances 0.000 description 1
- 229920000036 polyvinylpyrrolidone Polymers 0.000 description 1
- 235000013855 polyvinylpyrrolidone Nutrition 0.000 description 1
- 239000007774 positive electrode material Substances 0.000 description 1
- 230000008439 repair process Effects 0.000 description 1
- 239000004065 semiconductor Substances 0.000 description 1
- 239000011856 silicon-based particle Substances 0.000 description 1
- 238000005245 sintering Methods 0.000 description 1
- 239000011343 solid material Substances 0.000 description 1
- 238000006467 substitution reaction Methods 0.000 description 1
- 230000008961 swelling Effects 0.000 description 1
- 238000003466 welding Methods 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
- 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
-
- 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
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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)
- Silicon Compounds (AREA)
- Battery Electrode And Active Subsutance (AREA)
Abstract
The present invention provides a kind of silicon-carbon composite cathode material and preparation method thereof and lithium ion battery, belong to technical field of lithium ion, specific technical solution is as follows: a kind of silicon-carbon composite cathode material, including nucleome and shell, the nucleome is located at the inside of the shell, it is cavity structure between the nucleome and shell, the nucleome includes the nanometer silicon composite material of carbon nanotube cladding, and the shell is carbon coating layer.The cavity of silicon-carbon composite cathode material internal reservation can effectively improve that silicon materials stress caused by volume change in charge and discharge process is concentrated, particle crushes, and then the case where cause capacity attenuation, pole piece to thicken；The surface coated carbon nanotube of nano-silicon is capable of providing good electric conductivity, promotes the conductive capability of silicon-carbon composite cathode material, improves the power-performance of lithium ion battery.
Description
Technical field
The invention belongs to technical field of lithium ion more particularly to a kind of silicon-carbon composite cathode material and preparation method thereof
And lithium ion battery.
Background technique
Lithium ion battery is long extensive at present because having many advantages, such as big platform voltage height, energy density, memory-less effect, service life
Applied to fields such as consumer electronics, electric car, energy storage.The lithium ion battery being commercialized at present mainly uses graphite material conduct
Cathode, because its theory gram volume only has 372mAh/g, the limit has been arrived in the promotion of energy density, it is difficult to meet application end to lithium ion
The higher and higher energy density demand of battery.In other kinds of negative electrode material, silica-base material is because having high gram volume
(4200mAh/g), lower intercalation potential are not easy the ideal that the advantages that analysing lithium, rich reserves is considered as substitution graphite cathode
Material, at present Preliminary Applications in field of lithium ion battery.
Compared to graphite cathode, silicon-based anode is maximum the disadvantage is that there are serious Volumetric expansions in process of intercalation
(300%), cause silicon particle that rupture dusting occurs, cause negative electrode material structure collapses, be detached from conductive grid, the internal resistance of cell is anxious
Increase severely and add, polarization increases.Furthermore volume expansion leads to the destruction of SEI film duration, repairs, and consumes active lithium, capacity is caused to damage
It loses, it is poor to will lead to silicon substrate cycle performance of lithium ion battery above.Silicon based anode material has another disadvantage that silicon is semiconductor material,
Poorly conductive causes the power-performance of silicon substrate lithium ion battery insufficient, disadvantage mentioned above limits silicium cathode material in lithium in graphite
The large-scale application of ion battery field.
Summary of the invention
The first purpose of this invention is the cyclical stability in order to improve lithium ion battery, provides a kind of silicon-carbon Compound Negative
Pole material.
A second object of the present invention is to provide a kind of preparation methods of silicon-carbon composite cathode material；
Third object of the present invention is to provide a kind of lithium ion batteries containing above-mentioned silicon-carbon composite cathode material；
To achieve the goals above, the present invention adopts the following technical scheme that:
A kind of silicon-carbon composite cathode material, including nucleome and shell, the nucleome are located at the inside of the shell, the core
It is cavity structure between body and shell, the nucleome includes the composite material of carbon nanotube cladding nano-silicon, and the shell is carbon
Clad.
Further, the mass percent of nano-silicon is 10%~35%, the mass percent of carbon nanotube is 5%~
15%, the mass percent of carbon is 50%~85%.
Further, the partial size of the nano-silicon is 30-150nm.
A kind of preparation method of the silicon-carbon composite cathode material, comprising the following steps:
Step 1: nano-silicon, catalyst, additive being mixed with dehydrated alcohol, prepare slurry, then by slurry 100~
150 DEG C of 5~10h of drying obtain dried powder, dried powder are placed in 600~800 DEG C of 2~15h of calcining in tube furnace, furnace is interior certainly
It is so cooled to room temperature, then heats to 500~900 DEG C, be passed through carbon-source gas and protection gas carries out 2~4h of chemical vapor deposition,
Then in-furnace temperature drops to room temperature, and material is taken out and is ground, and crosses 200 mesh screens, obtains carbon nanotube cladding nano-silicon
Composite material；
Step 2: by carbon nanotube cladding nano-silicon composite material mix with water and dehydrated alcohol, addition concentrated ammonia liquor with
Tetraethyl orthosilicate stirring, tetraethyl orthosilicate hydrolyzes under alkaline condition generates SiO2, 60 DEG C~120 DEG C drying after washing
8~for 24 hours, it then smashes and grinds, crosses 200 mesh screens, and then obtain the dual of coating carbon nano-tube with silicon dioxide cladding nano-silicon
Clad composite material；
Step 3: the dual cladding composite material of step 2 preparation and organic carbon source material are added to absolute ethanol, so
The powder body material dry with dry powder manufacturing apparatus preparation afterwards, then by powder body material 400~1000 in the atmosphere of inert gas
DEG C roasting 4~10h, drop to room temperature, will material take out grind, and cross 200 mesh screens, obtain carbon coating silica packet
Cover triple clad composite materials of carbon nanotube cladding nano-silicon；
Step 4: triple clad composite materials prepared by step 3 are added in hydrofluoric acid, and etching removes composite material
In SiO2Layer, clean rear 60 DEG C~120 DEG C drying 8 of washing~for 24 hours, obtain silicon-carbon composite cathode material.
Further, the mass percent of nano-silicon is 85-96% in step 1, and the mass percent of catalyst is 2-
10%, the mass percent of additive is 2-5%, and the quality of dehydrated alcohol is three kinds of nano-silicon, catalyst and additive substances
1~10 times of quality sum.
Further, carbon-source gas is one of methane, acetylene in step 1, and the protective gas is argon gas, described
The throughput of carbon-source gas is 2~4L/min, and the throughput of the protection gas is 1~5L/min.
Further, the mass ratio of carbon nanotube cladding nanometer silicon composite material and positive silicic acid tetraacethyl is 1 in step 2:
0.2-1:2.0, the concentration of the concentrated ammonia liquor are 25%, and the volume of the concentrated ammonia liquor is 2 times of tetraethyl orthosilicate；Water and anhydrous
The volume ratio of ethyl alcohol is 1:4, and the mass ratio of carbon nanotube cladding nanometer silicon composite material and water and dehydrated alcohol mixed solution is
1:99。
Further, the mass ratio of dual cladding composite material and organic carbon source material is 1:1-1:5 in step 3, anhydrous
The quality of ethyl alcohol is 3~10 times of two kinds of material masses of dual cladding composite material and organic carbon source.
Further, the quality of HF described in step 4 is 10~50 times of triple clad composite material quality, the HF
Concentration be 5~30%, etch period be 6~for 24 hours.
A kind of lithium ion battery containing the silicon-carbon composite cathode material, the lithium ion battery include positive, negative
Pole, electrolyte and diaphragm, the cathode include negative current collector and the silicon-carbon composite cathode material.
Beneficial effects of the present invention:
(1) cavity of silicon-carbon composite cathode material internal reservation can effectively improve silicon materials volume in charge and discharge process and become
The case where changing caused stress concentration, particle crushing, and then capacity attenuation, pole piece caused to thicken.
(2) the surface coated carbon nanotube of nano-silicon is capable of providing good electric conductivity, promotes silicon-carbon composite cathode material
Conductive capability, improve the power-performance of lithium ion battery.
(3) contact of the carbon coating layer isolation silicon with electrolyte, forms stable SEI film, promotes the circulation of lithium ion battery
Stability.
(4) compared with the existing technology, silicon-carbon composite cathode material structural stability of the invention is good, conductive capability is strong, group
At the lithium ion battery cyclical stability and high rate performance that have had.
Detailed description of the invention
Fig. 1: the preparation method flow chart of silicon-carbon composite cathode material；
Fig. 2: lithium ion battery circulation volume conservation rate line chart；
Fig. 3: high temperature circulation battery core thickness swelling line chart.
Specific embodiment
1-3 and the present invention is described further by specific embodiment with reference to the accompanying drawing.Implement in detail below
In mode, the ingredient that is related to, coating, roll-in, cutting, film-making, winding, encapsulation, fluid injection, chemical conversion, sorting be prepare lithium from
Conventional technology in sub- battery.
Specific embodiment one
A kind of silicon-carbon composite cathode material, including nucleome and shell, the nucleome are located at the inside of the shell, the core
It is cavity structure between body and shell, the nucleome includes the nanometer silicon composite material of carbon nanotube cladding, and the shell is carbon
Clad.
Further, the mass percent of nano-silicon is 10%~35%, the mass percent of carbon nanotube is 5%~
15%, the mass percent of carbon is 50%~85%.
Further, the partial size of the nano-silicon is 30-150nm.
A kind of preparation method of the silicon-carbon composite cathode material, comprising the following steps:
Step 1: carbon nanotube cladding mixes nano-silicon powder, catalyst, additive with dehydrated alcohol, preparation slurry
Slurry, is then placed in baking oven, 100~150 DEG C of 5~10h of drying obtain dried powder, powder is placed in tube furnace by material
600~800 DEG C of 2~15h of calcining, wherein the revolving speed of tube furnace is 0.5~2r/min, then cooled to room temperature in furnace rises
Temperature is passed through carbon-source gas and protection gas carries out 2~4h of chemical vapor deposition, then in-furnace temperature drops to room to 500~900 DEG C
Material is taken out and is ground by temperature, and crosses 200 mesh screens, obtains composite material (the CNTs@of carbon nanotube cladding nano-silicon
Si)；
Step 2: SiO2Cladding, the carbon nanotube cladding nanometer silicon composite material and volume ratio that step 1 is prepared
Ethanol solution for 75% is the ratio mixing of 1:99 in mass ratio, and concentrated ammonia liquor and tetraethyl orthosilicate stirring, positive silicic acid is added
Tetra-ethyl ester hydrolyzes under alkaline condition generates SiO2, after washing 60~120 DEG C drying 8~for 24 hours, then smash and grind, cross 200
Mesh screen, and then obtain the dual cladding composite material (SiO of coating carbon nano-tube with silicon dioxide cladding nano-silicon2@CNTs@
Si)；
Step 3: C cladding the dual cladding composite material of step 2 preparation and organic carbon source material is added together anhydrous
In ethyl alcohol, dry powder body material then is prepared with dry powder manufacturing apparatus, then by powder body material in the atmosphere of inert gas
400~1000 DEG C of 4~10h of roasting are carried out, room temperature is then dropped to, material is taken out and is ground, and cross 200 mesh screens, are obtained
To triple clad composite materials (C@SiO of carbon coating coating carbon nano-tube with silicon dioxide cladding nano-silicon2@CNTs@Si)。
Step 4: triple clad composite materials prepared by step 3 are added in hydrofluoric acid, etch by silica etching
Remove the SiO in composite material2Layer, clean rear 60~120 DEG C of drying 8 of washing~for 24 hours, obtain carbon coating cavity carbon coated nanometer
Pipe coats nanometer silicon composite material (C@cavity@CNTs@Si), i.e. silicon-carbon composite cathode material.
Preferably, the quality accounting of nano-silicon described in step 1 is 85~96%, the quality accounting 2 of catalyst~
10%, additive quality accounting is 2~5%, and the quality of dehydrated alcohol is three kinds of nano-silicon, catalyst and additive material masses
1~10 times of sum.
Preferably, catalyst described in step 1 is the combination of one or both of ferric nitrate, copper sulphate, the addition
Agent is the combination of one or both of carboxyl methyl cellulose, citric acid.
Preferably, the throughput of carbon-source gas described in step 1 is 2~4L/min, and the throughput of the protection gas is
1~5L/min, the carbon-source gas are the combination of one or both of methane, acetylene, the protection gas
Body is argon gas.
Preferably, the mass ratio of the cladding of carbon nanotube described in step 2 nanometer silicon composite material and tetraethyl orthosilicate
For 1:0.2~1:2.0.
Preferably, the concentration of the concentrated ammonia liquor is 25%, and the volume of the concentrated ammonia liquor is the 2 of tetraethyl orthosilicate volume
Times.
Preferably, organic carbon source described in step 3 is citric acid, glucose, phenolic resin, polyvinylpyrrolidone
One of or a variety of combinations.
Preferably, the mass ratio of dual cladding composite material described in step 3 and organic carbon source is 1:1~1:5, nothing
The quality of water-ethanol is 3~10 times of dual cladding composite material and organic carbon source gross mass.
Preferably, inert gas described in step 3 is argon gas.
Preferably, the quality of HF described in step 4 is 10~50 times of triple clad composite material quality, the HF
Concentration be 5~30%, etch period be 6~for 24 hours.
A kind of lithium ion battery containing the silicon-carbon composite cathode material, including anode, cathode, electrolyte and diaphragm,
The cathode includes the silicon-carbon composite cathode material, it is described anode include lithium source material, through ingredient, coating, roll-in, film-making,
Winding, welding, encapsulation, fluid injection, chemical conversion, partial volume prepare the lithium ion battery of high-energy density.
Preferably, the positive electrode is one of NCM, NCA, NCMA, LCO, LFP, LMO or a variety of combinations.
Embodiment 1:
A kind of preparation method of the silicon-carbon composite cathode material, comprising the following steps:
Step 1: the partial size for taking quality accounting 96% is 30nm nano-silicon powder, 2% ferric nitrate, 2% carboxymethyl cellulose
It is mixed with according to solid-liquid mass ratio 1:5 with dehydrated alcohol, according to 1000W/m in ultrasonic pond21~5h of power ultrasound prepare slurry
Slurry, is then placed in baking oven and dries by material, and 100~150 DEG C of baking temperature, 5~10h of baking time obtains dried powder, will
Powder is placed in tube furnace, is heated up with 5 DEG C/min, is warming up to 600 DEG C, calcines 15h, natural cooling in furnace after calcining
To room temperature, material is crushed and screened, smashed partial size is in 100~200nm, and then 5 DEG C/min is warming up to 600 DEG C, leads to
Enter acetylene and argon gas carries out 2~4h of chemical vapor deposition, acetylene flow is 2L/min, argon flow 1.5L/min, tubular type turn
The revolving speed of furnace is 0.5r/min.In-furnace temperature is dropped into room temperature, material is taken out and is ground, and crosses 200 mesh screens, is obtained
The composite material (CNTs@Si) of carbon nanotube cladding nano-silicon.
Step 2: the second that the carbon nanotube cladding nanometer silicon composite material and volume ratio that step 1 is prepared are 75%
Alcoholic solution is mixed according to the ratio that mass ratio is 1:99, and after ultrasonic disperse 30min, it is compound that addition accounts for carbon nanotube cladding nano-silicon
The concentrated ammonia liquor of 2 times of volumes of tetraethyl orthosilicate of the quality of materials than 0.2% and tetraethyl orthosilicate stirs 12h, positive silicic acid tetrem
Ester hydrolyzes under alkaline condition generates SiO2, after reaction for 24 hours using 60 DEG C of drying after deionized water cleaning centrifugation three times,
Then it smashes and grinds, crosses 200 mesh screens, and then the dual cladding for obtaining coating carbon nano-tube with silicon dioxide cladding nano-silicon is compound
Material (SiO2@CNTs@Si)。
Step 3: nothing is added according to mass ratio 1:1 in the dual cladding composite material of step 2 preparation and citric acid together
In water-ethanol, wherein dehydrated alcohol is 3 times of dual cladding composite material and citric acid gross mass, ultrasonic disperse 30min, so
Powder body material, is then placed in revolvig tubular kiln in the atmosphere of argon gas by the powder body material dry with dry powder manufacturing apparatus preparation afterwards
It is roasted, 400 DEG C of maturing temperature, then calcining time 10h drops to room temperature, material is taken out and is ground, and crosses 200
Mesh screen obtains triple clad composite materials (C@SiO of carbon coating coating carbon nano-tube with silicon dioxide cladding nano-silicon2@
CNTs@Si)。
Step 4: triple clad composite materials prepared by step 3 are added in the hydrofluoric acid of 5% concentration, wherein HF
Quality be 10 times of triple clad composite material quality, for 24 hours, etching removes the SiO in composite material for stirring2Layer, is then used
60 DEG C of drying for 24 hours, obtain carbon coating cavity enveloped carbon nanometer tube cladding nanometer silicon composite material (C@after deionized water cleaning centrifugation
Cavity@CNTs@Si), that is, silicon-carbon composite cathode material sample SC-1.
Embodiment 2:
A kind of preparation method of the silicon-carbon composite cathode material, comprising the following steps:
Step 1: the 150nm nano-silicon powder, 10% copper sulphate, 5% citric acid of quality accounting 85% are taken and according to solid-liquid
Mass ratio 1:5 is mixed with dehydrated alcohol, according to 1000W/m in ultrasonic pond21~5h of power ultrasound prepare slurry, then will
Slurry is placed in baking oven and dries, and 100~150 DEG C of baking temperature, 5~10h of baking time obtains dried powder, and powder is placed in pipe
It in formula furnace, is heated up with 5 DEG C/min, is warming up to 800 DEG C, calcine 2h, cooled to room temperature in furnace after calcining, by material
Material is crushed and screened, and smashed partial size is in 300~800nm, and then 5 DEG C/min is warming up to 800 DEG C, is passed through methane and argon gas
2~4h of chemical vapor deposition is carried out, acetylene flow is 2L/min, and argon flow 1.5L/min, the revolving speed of revolvig tubular kiln is 2r/
min.In-furnace temperature is dropped into room temperature, material is taken out and is ground, and crosses 200 mesh screens, carbon nanotube cladding is obtained and receives
The composite material (CNTs@Si) of rice silicon.
Step 2: the carbon nanotube cladding nanometer silicon composite material and water and dehydrated alcohol (body that step 1 is prepared
Product ratio be 1:4) mixed solution according to the mixing of ratio that mass ratio is 1:99, after ultrasonic disperse 30min, is added and accounts for carbon nanotube packet
The concentrated ammonia liquor of 2 times of volumes of tetraethyl orthosilicate and tetraethyl orthosilicate of nanometer silicon composite material mass ratio 2% is covered, 12h is stirred,
Tetraethyl orthosilicate hydrolyzes under alkaline condition generates SiO2, after being centrifuged three times using deionized water cleaning after reaction
120 DEG C of drying 8h, then smash and grind, and cross 200 mesh screens, and then obtain coating carbon nano-tube with silicon dioxide cladding nano-silicon
Dual cladding composite material (SiO2@CNTs@Si)。
Step 3: nothing is added according to mass ratio 1:5 in the dual cladding composite material of step 2 preparation and citric acid together
In water-ethanol, wherein dehydrated alcohol is 10 times of dual cladding composite material and citric acid gross mass, ultrasonic disperse 30min, so
Powder body material, is then placed in revolvig tubular kiln in the atmosphere of argon gas by the powder body material dry with dry powder manufacturing apparatus preparation afterwards
It is roasted, 1000 DEG C of maturing temperature, then calcining time 4h drops to room temperature, material is taken out and is ground, and crosses 200
Mesh screen obtains triple clad composite materials (C@SiO of carbon coating coating carbon nano-tube with silicon dioxide cladding nano-silicon2@
CNTs@Si)。
Step 4: triple clad composite materials prepared by step 3 are added in the hydrofluoric acid of 30% concentration, wherein HF
Quality be 50 times of triple clad composite material quality, stir 6h, etching removes the SiO in composite material2Layer, then spends
120 DEG C of drying 8h after ionized water cleaning centrifugation, obtaining carbon coating cavity enveloped carbon nanometer tube cladding nanometer silicon composite material, (C@is empty
Chamber@CNTs@Si), that is, silicon-carbon composite cathode material sample SC-2.
Embodiment 3:
A kind of preparation method of the silicon-carbon composite cathode material, comprising the following steps:
Step 1: the 100nm nano-silicon powder, 5% copper sulphate, 3% citric acid of quality accounting 92% are taken and according to solid-liquid
Mass ratio 1:5 is mixed with dehydrated alcohol, according to 1000W/m in ultrasonic pond21~5h of power ultrasound prepare slurry.Then will
Slurry is placed in baking oven and dries, and 100~150 DEG C of baking temperature, 5~10h of baking time obtains dried powder, and powder is placed in pipe
It in formula furnace, is heated up with 5 DEG C/min, is warming up to 700 DEG C, calcine 2h, cooled to room temperature in furnace after calcining, by material
Material is crushed and screened, and smashed partial size is in 300~500nm, and then 5 DEG C/min is warming up to 800 DEG C, is passed through methane and argon gas
2~4h of chemical vapor deposition is carried out, acetylene flow is 2L/min, and argon flow 1.5L/min, the revolving speed of revolvig tubular kiln is 1r/
min.In-furnace temperature is dropped into room temperature, material is taken out and is ground, and crosses 200 mesh screens, carbon nanotube cladding is obtained and receives
The composite material (CNTs@Si) of rice silicon.
Step 2: the composite material and water and dehydrated alcohol for the carbon nanotube cladding nano-silicon that step 1 is prepared
(volume ratio 1:4) mixed solution is mixed according to the ratio of mass ratio 1:99, and after ultrasonic disperse 30min, addition accounts for carbon nanotube
Coat the concentrated ammonia liquor of 2 times of volumes of tetraethyl orthosilicate and tetraethyl orthosilicate of nanometer silicon composite material mass ratio 0.5%, stirring
12h, tetraethyl orthosilicate hydrolyzes under alkaline condition generates SiO2, taken second place after reaction using deionized water cleaning centrifugation three
80 DEG C of drying 12h afterwards, then smash and grind, and cross 200 mesh screens, and then obtain coating carbon nano-tube with silicon dioxide cladding nano-silicon
Dual cladding composite material (SiO2@CNTs@Si).
Step 3: nothing is added according to mass ratio 1:2 in the dual cladding composite material of step 2 preparation and citric acid together
In water-ethanol, wherein dehydrated alcohol is 5 times of dual cladding composite material and citric acid gross mass, ultrasonic disperse 30min, so
Powder body material, is then placed in revolvig tubular kiln in the atmosphere of argon gas by the powder body material dry with dry powder manufacturing apparatus preparation afterwards
It is roasted, 800 DEG C of maturing temperature, then calcining time 6h drops to room temperature, material is taken out and is ground, and crosses 200 mesh
Sieve obtains triple clad composite materials (C@SiO2@CNTs@of carbon coating coating carbon nano-tube with silicon dioxide cladding nano-silicon
Si)。
Step 4: triple clad composite materials prepared by step 3 are added in the hydrofluoric acid of 10% concentration, wherein HF
Quality be 20 times of triple clad composite material quality, stir 12h, etching removes the SiO in composite material2Layer, is then used
80 DEG C of drying 12h after deionized water cleaning centrifugation obtain carbon coating cavity enveloped carbon nanometer tube cladding nanometer silicon composite material (C@
Cavity@CNTs@Si), that is, silicon-carbon composite cathode material sample SC-3.
Comparative example:
Nano-silicon powder body material and citric acid is taken to be added to absolute ethanol together according to mass ratio 1:2, wherein dehydrated alcohol
Quality be 5-10 times, ultrasonic disperse 30min of solid material quality, then with the powder material of dry powder manufacturing apparatus preparation drying
Powder body material, is then placed in revolvig tubular kiln in argon atmosphere and roasts by material, and 800 DEG C of sintering temperature, calcining time 6h,
Then room temperature is dropped to, material is taken out and is ground, and crosses 200 mesh screens, obtains silicon carbon material (the C@of carbon-coated nano silicon
Si) sample DB.
Using the silicon-carbon composite cathode material of above-mentioned three kinds of embodiments and the silicon carbon material of comparative example preparation as negative electrode active
Material, NCM811 material is as positive electrode active materials, through ingredient, coating, roll-in, cutting, film-making, winding, encapsulation, fluid injection, change
Lithium ion battery is prepared at, sorting, and is recycled, the performance tests such as multiplying power discharging.
The result for the lithium ion battery test that each scheme is prepared is as follows:
1. high temperature circulation data of table
2. multiplying power discharging capacity retention ratio of table (opposite 0.5C discharge capacity)
From table 1 it follows that using the lithium ion battery of the silicon-carbon composite cathode material preparation in the present invention compared to normal
There is the silicon carbon material of rule better cyclical stability and smaller circulation to expand.
From Table 2, it can be seen that using the silicon-carbon composite cathode material of the method production in the present invention compared to conventional silicon
Carbon material has better multiplying power discharging ability.
Emphasis analyzes the cycle performance of embodiment 3, and as shown in Figure 2 and Figure 3, battery has good stable circulation
Property, 300 weeks capacity retention ratios are there are also 89.1%, cell expansion only 7.3%.
Claims (10)
1. a kind of silicon-carbon composite cathode material, including nucleome and shell, the nucleome is located at the inside of the shell, and feature exists
In: it is cavity structure between the nucleome and shell, the nucleome includes the composite material of carbon nanotube cladding nano-silicon, described
Shell is carbon coating layer.
2. a kind of silicon-carbon composite cathode material according to claim 1, it is characterised in that: the mass percent of nano-silicon is
10%~35%, the mass percent of carbon nanotube is 5%~15%, and the mass percent of carbon is 50%~85%.
3. a kind of silicon-carbon composite cathode material according to claim 1, it is characterised in that: the partial size of the nano-silicon is
30-150nm。
4. a kind of preparation method of silicon-carbon composite cathode material described in claim 1-3 any claim, which is characterized in that
The following steps are included:
Step 1: nano-silicon, catalyst, additive being mixed with dehydrated alcohol, prepare slurry, then by 100~150 DEG C of slurry
5~10h of drying obtains dried powder, and dried powder is placed in 600~800 DEG C of 2~15h of calcining in tube furnace, naturally cold in furnace
But to room temperature, 500~900 DEG C are then heated to, carbon-source gas is passed through and protection gas carries out 2~4h of chemical vapor deposition, then
In-furnace temperature drops to room temperature, and material is taken out and is ground, and crosses 200 mesh screens, obtains answering for carbon nanotube cladding nano-silicon
Condensation material；
Step 2: the composite material of carbon nanotube cladding nano-silicon is mixed with water and dehydrated alcohol, concentrated ammonia liquor and positive silicon is added
Sour tetra-ethyl ester stirring, tetraethyl orthosilicate hydrolyzes under alkaline condition generates SiO2, after washing 60 DEG C~120 DEG C drying 8~
For 24 hours, it then smashes and grinds, crosses 200 mesh screens, and then obtain the dual cladding of coating carbon nano-tube with silicon dioxide cladding nano-silicon
Composite material；
Step 3: the dual cladding composite material of step 2 preparation and organic carbon source material are added to absolute ethanol, then used
The dry powder body material of dry powder manufacturing apparatus preparation, then 400~1000 DEG C of roastings in the atmosphere of inert gas by powder body material
4~10h is burnt, room temperature is dropped to, material is taken out and is ground, and crosses 200 mesh screens, obtains carbon coating coated with silica carbon
Triple clad composite materials of nanotube cladding nano-silicon；
Step 4: triple clad composite materials prepared by step 3 are added in hydrofluoric acid, and etching removes in composite material
SiO2Layer, clean rear 60 DEG C~120 DEG C drying 8 of washing~for 24 hours, obtain silicon-carbon composite cathode material.
5. a kind of preparation method of silicon-carbon composite cathode material according to claim 4, it is characterised in that: received in step 1
The mass percent of rice silicon is 85-96%, and the mass percent of catalyst is 2-10%, and the mass percent of additive is 2-
5%, the quality of dehydrated alcohol is nano-silicon, 1~10 times of three kinds of material mass sums of catalyst and additive.
6. a kind of preparation method of silicon-carbon composite cathode material according to claim 4, it is characterised in that: carbon in step 1
Source gas is one of methane, acetylene, and the protective gas is argon gas, and the throughput of the carbon-source gas is 2~4L/min,
The throughput of the protection gas is 1~5L/min.
7. a kind of preparation method of silicon-carbon composite cathode material according to claim 4, it is characterised in that: carbon in step 2
It is 1:0.2-1:2.0, the concentration of the concentrated ammonia liquor that nanotube, which coats nanometer silicon composite material and the mass ratio of positive silicic acid tetraacethyl,
It is 25%, the volume of the concentrated ammonia liquor is 2 times of tetraethyl orthosilicate；The volume ratio of water and dehydrated alcohol is 1:4, carbon nanotube
The mass ratio for coating nanometer silicon composite material and water and dehydrated alcohol mixed solution is 1:99.
8. a kind of preparation method of silicon-carbon composite cathode material according to claim 4, it is characterised in that: double in step 3
The mass ratio of weight clad composite material and organic carbon source material is 1:1-1:5, and the quality of dehydrated alcohol is dual cladding composite wood
3~10 times of material and two kinds of material masses of organic carbon source.
9. a kind of preparation method of silicon-carbon composite cathode material according to claim 4, it is characterised in that: institute in step 4
The quality for stating HF is 10~50 times of triple clad composite material quality, and the concentration of the HF is 5~30%, etch period 6
~for 24 hours.
10. a kind of lithium ion battery containing silicon-carbon composite cathode material described in claim 1-3 any claim, special
Sign is: the lithium ion battery includes anode, cathode, electrolyte and diaphragm, and the cathode includes negative current collector and described
Silicon-carbon composite cathode material.
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