CN110212191A - A kind of graphene/SnO2The preparation method of/Si@PPy composite material - Google Patents
A kind of graphene/SnO2The preparation method of/Si@PPy composite material Download PDFInfo
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- CN110212191A CN110212191A CN201910556794.2A CN201910556794A CN110212191A CN 110212191 A CN110212191 A CN 110212191A CN 201910556794 A CN201910556794 A CN 201910556794A CN 110212191 A CN110212191 A CN 110212191A
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- OKTJSMMVPCPJKN-UHFFFAOYSA-N Carbon Chemical compound [C] OKTJSMMVPCPJKN-UHFFFAOYSA-N 0.000 title claims abstract description 126
- 229910021389 graphene Inorganic materials 0.000 title claims abstract description 100
- 239000002131 composite material Substances 0.000 title claims abstract description 75
- 238000002360 preparation method Methods 0.000 title claims abstract description 30
- XOLBLPGZBRYERU-UHFFFAOYSA-N SnO2 Inorganic materials O=[Sn]=O XOLBLPGZBRYERU-UHFFFAOYSA-N 0.000 claims abstract description 63
- 239000011863 silicon-based powder Substances 0.000 claims abstract description 22
- 239000000463 material Substances 0.000 claims abstract description 13
- 238000003756 stirring Methods 0.000 claims description 35
- XLYOFNOQVPJJNP-UHFFFAOYSA-N water Chemical compound O XLYOFNOQVPJJNP-UHFFFAOYSA-N 0.000 claims description 33
- ROOXNKNUYICQNP-UHFFFAOYSA-N ammonium persulfate Chemical compound [NH4+].[NH4+].[O-]S(=O)(=O)OOS([O-])(=O)=O ROOXNKNUYICQNP-UHFFFAOYSA-N 0.000 claims description 28
- 229910002804 graphite Inorganic materials 0.000 claims description 27
- 239000010439 graphite Substances 0.000 claims description 27
- 239000008367 deionised water Substances 0.000 claims description 25
- 229910021641 deionized water Inorganic materials 0.000 claims description 25
- LFQSCWFLJHTTHZ-UHFFFAOYSA-N Ethanol Chemical compound CCO LFQSCWFLJHTTHZ-UHFFFAOYSA-N 0.000 claims description 17
- 229960000935 dehydrated alcohol Drugs 0.000 claims description 17
- 239000005457 ice water Substances 0.000 claims description 15
- 229910001870 ammonium persulfate Inorganic materials 0.000 claims description 14
- QAOWNCQODCNURD-UHFFFAOYSA-N Sulfuric acid Chemical compound OS(O)(=O)=O QAOWNCQODCNURD-UHFFFAOYSA-N 0.000 claims description 12
- 238000000498 ball milling Methods 0.000 claims description 11
- 239000012286 potassium permanganate Substances 0.000 claims description 10
- VWDWKYIASSYTQR-UHFFFAOYSA-N sodium nitrate Chemical compound [Na+].[O-][N+]([O-])=O VWDWKYIASSYTQR-UHFFFAOYSA-N 0.000 claims description 10
- 238000000967 suction filtration Methods 0.000 claims description 10
- 238000013019 agitation Methods 0.000 claims description 9
- 238000010792 warming Methods 0.000 claims description 9
- CSCPPACGZOOCGX-UHFFFAOYSA-N Acetone Chemical compound CC(C)=O CSCPPACGZOOCGX-UHFFFAOYSA-N 0.000 claims description 8
- IJGRMHOSHXDMSA-UHFFFAOYSA-N Atomic nitrogen Chemical compound N#N IJGRMHOSHXDMSA-UHFFFAOYSA-N 0.000 claims description 8
- 239000006185 dispersion Substances 0.000 claims description 8
- 238000005406 washing Methods 0.000 claims description 8
- 238000010008 shearing Methods 0.000 claims description 7
- TXUICONDJPYNPY-UHFFFAOYSA-N (1,10,13-trimethyl-3-oxo-4,5,6,7,8,9,11,12,14,15,16,17-dodecahydrocyclopenta[a]phenanthren-17-yl) heptanoate Chemical compound C1CC2CC(=O)C=C(C)C2(C)C2C1C1CCC(OC(=O)CCCCCC)C1(C)CC2 TXUICONDJPYNPY-UHFFFAOYSA-N 0.000 claims description 6
- 229910021626 Tin(II) chloride Inorganic materials 0.000 claims description 6
- 235000011150 stannous chloride Nutrition 0.000 claims description 6
- 239000001119 stannous chloride Substances 0.000 claims description 6
- 238000002604 ultrasonography Methods 0.000 claims description 6
- 238000007792 addition Methods 0.000 claims description 5
- 239000012153 distilled water Substances 0.000 claims description 5
- 238000001035 drying Methods 0.000 claims description 5
- 235000010344 sodium nitrate Nutrition 0.000 claims description 5
- 239000004317 sodium nitrate Substances 0.000 claims description 5
- 238000002525 ultrasonication Methods 0.000 claims description 5
- 238000000227 grinding Methods 0.000 claims description 4
- 229910052757 nitrogen Inorganic materials 0.000 claims description 4
- 239000002253 acid Substances 0.000 claims description 3
- QGZKDVFQNNGYKY-UHFFFAOYSA-O Ammonium Chemical compound [NH4+] QGZKDVFQNNGYKY-UHFFFAOYSA-O 0.000 claims description 2
- 229910001220 stainless steel Inorganic materials 0.000 claims description 2
- 239000004575 stone Substances 0.000 claims description 2
- 229910001416 lithium ion Inorganic materials 0.000 abstract description 23
- HBBGRARXTFLTSG-UHFFFAOYSA-N Lithium ion Chemical compound [Li+] HBBGRARXTFLTSG-UHFFFAOYSA-N 0.000 abstract description 22
- 238000007600 charging Methods 0.000 abstract description 16
- 238000000034 method Methods 0.000 abstract description 15
- XUIMIQQOPSSXEZ-UHFFFAOYSA-N Silicon Chemical compound [Si] XUIMIQQOPSSXEZ-UHFFFAOYSA-N 0.000 abstract description 14
- 238000007599 discharging Methods 0.000 abstract description 11
- 229910052710 silicon Inorganic materials 0.000 abstract description 10
- 239000010703 silicon Substances 0.000 abstract description 10
- 239000007773 negative electrode material Substances 0.000 abstract description 8
- 239000000758 substrate Substances 0.000 abstract description 8
- 239000000126 substance Substances 0.000 abstract description 2
- 229920000128 polypyrrole Polymers 0.000 description 76
- 239000007772 electrode material Substances 0.000 description 6
- VYZAMTAEIAYCRO-UHFFFAOYSA-N Chromium Chemical compound [Cr] VYZAMTAEIAYCRO-UHFFFAOYSA-N 0.000 description 5
- 229910052804 chromium Inorganic materials 0.000 description 5
- 239000011651 chromium Substances 0.000 description 5
- KAESVJOAVNADME-UHFFFAOYSA-N Pyrrole Chemical compound C=1C=CNC=1 KAESVJOAVNADME-UHFFFAOYSA-N 0.000 description 4
- 230000000694 effects Effects 0.000 description 4
- 150000003233 pyrroles Chemical class 0.000 description 4
- 239000002210 silicon-based material Substances 0.000 description 4
- 229910052744 lithium Inorganic materials 0.000 description 3
- 206010011224 Cough Diseases 0.000 description 2
- WHXSMMKQMYFTQS-UHFFFAOYSA-N Lithium Chemical compound [Li] WHXSMMKQMYFTQS-UHFFFAOYSA-N 0.000 description 2
- 229910052799 carbon Inorganic materials 0.000 description 2
- 239000010406 cathode material Substances 0.000 description 2
- 238000005336 cracking Methods 0.000 description 2
- 125000004122 cyclic group Chemical group 0.000 description 2
- 230000007423 decrease Effects 0.000 description 2
- 230000007547 defect Effects 0.000 description 2
- 238000010586 diagram Methods 0.000 description 2
- 230000005611 electricity Effects 0.000 description 2
- 238000004146 energy storage Methods 0.000 description 2
- 150000002576 ketones Chemical class 0.000 description 2
- 229920001296 polysiloxane Polymers 0.000 description 2
- 239000007784 solid electrolyte Substances 0.000 description 2
- 241000208340 Araliaceae Species 0.000 description 1
- 235000005035 Panax pseudoginseng ssp. pseudoginseng Nutrition 0.000 description 1
- 235000003140 Panax quinquefolius Nutrition 0.000 description 1
- ZLMJMSJWJFRBEC-UHFFFAOYSA-N Potassium Chemical compound [K] ZLMJMSJWJFRBEC-UHFFFAOYSA-N 0.000 description 1
- 239000011149 active material Substances 0.000 description 1
- 150000001336 alkenes Chemical class 0.000 description 1
- 239000010405 anode material Substances 0.000 description 1
- 230000009286 beneficial effect Effects 0.000 description 1
- 230000015572 biosynthetic process Effects 0.000 description 1
- 150000001875 compounds Chemical class 0.000 description 1
- 238000010276 construction Methods 0.000 description 1
- 230000003247 decreasing effect Effects 0.000 description 1
- 238000010410 dusting Methods 0.000 description 1
- 238000004108 freeze drying Methods 0.000 description 1
- 235000008434 ginseng Nutrition 0.000 description 1
- -1 graphite Alkene Chemical class 0.000 description 1
- 238000011065 in-situ storage Methods 0.000 description 1
- 230000002427 irreversible effect Effects 0.000 description 1
- 230000014759 maintenance of location Effects 0.000 description 1
- 230000005012 migration Effects 0.000 description 1
- 238000013508 migration Methods 0.000 description 1
- 229910052700 potassium Inorganic materials 0.000 description 1
- 239000011591 potassium Substances 0.000 description 1
- 238000005215 recombination Methods 0.000 description 1
- 238000010025 steaming Methods 0.000 description 1
- 239000002023 wood 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
-
- 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
- H01M4/36—Selection of substances as active materials, active masses, active liquids
- H01M4/48—Selection of substances as active materials, active masses, active liquids of inorganic oxides or hydroxides
- H01M4/483—Selection of substances as active materials, active masses, active liquids of inorganic oxides or hydroxides for non-aqueous cells
-
- H—ELECTRICITY
- H01—ELECTRIC ELEMENTS
- H01M—PROCESSES OR MEANS, e.g. BATTERIES, FOR THE DIRECT CONVERSION OF CHEMICAL ENERGY INTO ELECTRICAL ENERGY
- H01M4/00—Electrodes
- H01M4/02—Electrodes composed of, or comprising, active material
- H01M4/36—Selection of substances as active materials, active masses, active liquids
- H01M4/58—Selection of substances as active materials, active masses, active liquids of inorganic compounds other than oxides or hydroxides, e.g. sulfides, selenides, tellurides, halogenides or LiCoFy; of polyanionic structures, e.g. phosphates, silicates or borates
- H01M4/583—Carbonaceous material, e.g. graphite-intercalation compounds or CFx
-
- 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
- H01M4/60—Selection of substances as active materials, active masses, active liquids of organic compounds
- H01M4/602—Polymers
- H01M4/606—Polymers containing aromatic main chain polymers
- H01M4/608—Polymers containing aromatic main chain polymers containing heterocyclic rings
-
- H—ELECTRICITY
- H01—ELECTRIC ELEMENTS
- H01M—PROCESSES OR MEANS, e.g. BATTERIES, FOR THE DIRECT CONVERSION OF CHEMICAL ENERGY INTO ELECTRICAL ENERGY
- H01M4/00—Electrodes
- H01M4/02—Electrodes composed of, or comprising, active material
- H01M4/62—Selection of inactive substances as ingredients for active masses, e.g. binders, fillers
- H01M4/624—Electric conductive fillers
- H01M4/625—Carbon or graphite
-
- H—ELECTRICITY
- H01—ELECTRIC ELEMENTS
- H01M—PROCESSES OR MEANS, e.g. BATTERIES, FOR THE DIRECT CONVERSION OF CHEMICAL ENERGY INTO ELECTRICAL ENERGY
- H01M4/00—Electrodes
- H01M4/02—Electrodes composed of, or comprising, active material
- H01M2004/026—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
Abstract
A kind of graphene/SnO2The preparation method of/Si@PPy composite material, it is related to the negative electrode material of lithium ion battery.It will solve the problems, such as the existing silicon substrate lithium ion battery using the preparation of micron order silicon powder, and that there are charging and discharging capacities is low, cycle life is short.Method.The surface coated PPy of Si powder can provide constraints to expansion of the Si in charge and discharge process in the present invention, the graphene/SnO on surface2Composite material can increase the specific capacity of negative electrode material, in graphene/SnO2When/Si@PPy material contacts with each other, graphene/SnO2Electronics can be quickly transmitted, graphene/SnO is improved2The chemical property of/Si@PPy composite material.This graphene/SnO2/ Si@PPy cathode and its special structure can be improved the charging and discharging capacity of lithium ion battery, extend cycle life, and cost is greatly reduced in micron order Si powder.The present invention is suitable for the negative electrode material of silicon substrate lithium ion battery.
Description
Technical field
The present invention relates to the negative electrode materials of lithium ion battery, and in particular to a kind of graphene/SnO2/ Si@PPy composite material
Preparation method.
Background technique
Since nineteen ninety lithium ion battery is commercialized for the first time, lithium ion battery is widely used in digital product, electronic
The fields such as tool, new-energy automobile, energy-storage system.Traditional graphite cathode is since its theoretical capacity is lower, only 372mAh/g,
Lead to the replacement upgrading of digital product, electric tool, the development of new-energy automobile, energy-storage system field is increasingly by lithium ion
The limitation of battery capacity.The method that tradition improves capacity of lithium ion battery is mainly series-connected cell packet, but this method is simultaneously
Also the volume and weight that will increase battery is not often applicable in generally, therefore the battery core capacity density for improving battery is only lithium ion
The deciding factor of battery development.Silicon has the theoretical specific capacity of 4200mAh/g, is that next-generation lithium ion battery is ideal negative
Pole material.But the defect of silicon materials is also particularly pertinent, defect mainly has at 3 points.First, the conductivity of silicon materials is lower, very
Difficulty is directly applied separately as electrode material；Second, the activity of silicon materials is poor, it is more difficult to reacted with other materials construct it is compound
Material；Third, silicon materials are in lithium ion battery charge and discharge process, since the de- lithium formation solid electrolyte interface of embedding lithium-is adjoint
Huge volume expansion and structure change, easily cause electrode active material dusting cracking fall off from collector, Er Qiekai
The active material split, which will continue to form new solid electrolyte interface at slight crack, makes capacity of lithium ion battery significantly decay, and makes
It is reduced at cycle life, these problems become the main problem for restricting silicon substrate lithium ion battery applications.Silicon substrate lithium ion at present
Cell negative electrode material mostly uses greatly nano silicone, obtains excellent performance of lithium ion battery with this, and the use of nano silicone
It will definitely increase the cost of negative electrode material, this is also the key factor for restricting the development of silicon substrate lithium ion battery.And use micron order
Although the cost of material can be greatly lowered in silicon powder, the service life for extending silicon based anode material is also micron order silicon powder
Critical issue urgently to be resolved in practical applications.
Summary of the invention
The invention aims to solve the existing silicon substrate lithium ion battery using the preparation of micron order silicon powder, there are charge and discharge
The problem that specific capacity is low, cycle life is short, and a kind of graphene/SnO is provided2The preparation method of/Si@PPy composite material.
A kind of graphene/SnO2The preparation method of/Si@PPy composite material, it is sequentially included the following steps:
One, graphene/SnO is prepared2Composite material:
By the crystalline flake graphite of 10~20g, the potassium permanganate of 1~5g, 10~50mL mass fraction be 98% sulfuric acid successively
It is added in 100mL there-necked flask, carries out washing suction filtration after stirring 1~3h at 25 DEG C of constant temperature, then dry at 60~80 DEG C, be made
Expansible graphite；Expansible graphite is placed in 1~2min of extruding in 1000 DEG C of Muffle furnaces, expanded graphite is made；Take 5~10g swollen
Swollen graphite dispersion in 10~50mL distilled water, then be added 1~5g sodium nitrate, ice-water bath stir 30~90min, 10~
10 additions of the potassium permanganate of 30g point, then 35 DEG C are warming up to, continue 1~8h of stirring, the deionized water of 400~800mL be added,
And 90 DEG C are warming up to, continue 1~3h of stirring, is then cooled to 25 DEG C and the H that 50~200mL mass fraction is 35% is added dropwise2O2,
The HCl solution and deionized water for being again 15% with mass fraction are successively washed to solution and are in neutrality, 6~12h of ultrasonication, then
It is freeze-dried and graphene oxide is made；
It takes 0.1~0.5g stannous chloride to be dissolved in 50~100mL dehydrated alcohol, 1~3g graphene oxide, dispersion is then added
After add 10~50mL deionized water and be fitted into 300mL microwave reaction kettle, control reaction kettle internal pressure is 1.5~2.0MPa,
10min is successively heated at 90 DEG C, 10min is heated at 130 DEG C, and 10min is heated at 150 DEG C, heats 30~60min at 180 DEG C,
Then 2~5h is stirred with high-speed shearing machine, obtained graphene/SnO after freeze-dried2Composite material；
Two, Si@PPy composite material is prepared:
By micron Si powder with speed 1~6h of ball milling of 1000r/min, the Si powder for taking 1g ball milling to cross is added to tri- mouthfuls of 100mL
In bottle；
Under nitrogen environment protection, the pyrroles of 1~2g is dissolved in 10~50mL dehydrated alcohol and obtains chromium solution, by pyrrole
It coughs up solution to be added in above-mentioned 100mL there-necked flask, ice-water bath 30~90min of magnetic agitation, revolving speed 400r/min；
It takes 1~5g ammonium persulfate to be dissolved in the HCl solution that 10~50mL concentration is 1mol/L and forms ammonium persulfate solution, it will
Ammonium persulfate solution is added dropwise in above-mentioned there-necked flask, and continuation ice-water bath stirring 12~for 24 hours, 50~500mL third is then added
Ketone simultaneously stirs 15~60min, then successively alternately wash 3~5 times with dehydrated alcohol and deionized water, and drying obtains after suction filtration
Si@PPy composite material；
Three, graphene/SnO is prepared2/ Si@PPy composite material:
By 1~3g graphene/SnO2Composite material and 1~3g Si@PPy composite material be dispersed in 100~500mL go from
In sub- water, 1~3h of magnetic agitation, then 1~3h of ultrasound, is transferred in microwave reaction kettle, control reaction kettle internal pressure be 1.5~
2.0MPa successively heats 10min at 90 DEG C, and 10min is heated at 130 DEG C, and 10min is heated at 150 DEG C, heats 30 at 180 DEG C
~60min, is cooled to room temperature, and graphene/SnO is obtained after freeze-dried2/ Si@PPy composite material.
The invention has the advantages that
PPy is coated on micron Si powder surface using in-situ oxidizing-polymerizing method and prepares Si@PPy clad structure, Si@by the present invention
The PPy clad of PPy has higher activity compared with Si powder surface, therefore is easy and graphene/SnO2Recombination reaction occurs,
Make graphene/SnO by microwave hydrothermal construction from part2Composite material is dispersed in the surface Si@PPy, acts on forming graphite by assembling
Alkene/SnO2/ Si@PPy lithium ion battery negative material.The surface coated PPy of Si powder can be swollen in charge and discharge process to Si
It bulges to restriction effect, the graphene/SnO on surface2Composite material can not only further increase the specific capacity of negative electrode material, and
In graphene/SnO2When/Si@PPy material contacts with each other, graphene/SnO2Can quickly transmit electronics, improve graphene/
SnO2The chemical property of/Si@PPy composite material.This graphene/SnO2/ Si@PPy cathode and its special structure can be into
One step improves the charging and discharging capacity of lithium ion battery, extends cycle life, and the use of micron order Si powder also can make cost substantially
It reduces, keeps silicon substrate lithium battery further from business application.
The present invention prepares gained graphene/SnO2/ Si@PPy composite material is suitable for the cathode material of silicon substrate lithium ion battery
Material.
Detailed description of the invention
Fig. 1 is graphene/SnO in embodiment2The preparation flow schematic diagram of/Si@PPy composite material；
Fig. 2 is preparation gained graphene/SnO in embodiment2The shape appearance figure of composite material；
Fig. 3 is the shape appearance figure of preparation gained Si@PPy composite material in embodiment；
Fig. 4 is preparation gained graphene/SnO in embodiment2The shape appearance figure of/Si@PPy composite material；
Fig. 5 is graphene/SnO in embodiment2The high rate performance curve graph of/Si@PPy cathode, wherein ★ indicate graphene/
SnO2/ Si@PPy coulombic efficiency, ■ indicate graphene/SnO2/ Si@PPy discharge curve, ● indicate graphene/SnO2/Si@PPy
Charging curve；
Fig. 6 is graphene/SnO in embodiment2Cycle performance of/Si@PPy the cathode in the case where current density is 1000mA/g is bent
Line chart, wherein zero indicates graphene/SnO2/ Si@PPy coulombic efficiency, indicate graphene/SnO2/ Si@PPy discharge curve, △
Indicate graphene/SnO2/ Si@PPy charging curve.
Specific embodiment
The technical solution of the present invention is not limited to the following list, further includes between each specific embodiment
Any combination.
Specific embodiment 1: a kind of graphene/SnO of present embodiment2The preparation method of/Si@PPy composite material, it
It sequentially includes the following steps:
One, graphene/SnO is prepared2Composite material:
By the crystalline flake graphite of 10~20g, the potassium permanganate of 1~5g, 10~50mL mass fraction be 98% sulfuric acid successively
It is added in 100mL there-necked flask, carries out washing suction filtration after stirring 1~3h at 25 DEG C of constant temperature, then dry at 60~80 DEG C, be made
Expansible graphite；Expansible graphite is placed in 1~2min of extruding in 1000 DEG C of Muffle furnaces, expanded graphite is made；Take 5~10g swollen
Swollen graphite dispersion in 10~50mL distilled water, then be added 1~5g sodium nitrate, ice-water bath stir 30~90min, 10~
10 additions of the potassium permanganate of 30g point, then 35 DEG C are warming up to, continue 1~8h of stirring, the deionized water of 400~800mL be added,
And 90 DEG C are warming up to, continue 1~3h of stirring, is then cooled to 25 DEG C and the H that 50~200mL mass fraction is 35% is added dropwise2O2,
The HCl solution and deionized water for being again 15% with mass fraction are successively washed to solution and are in neutrality, 6~12h of ultrasonication, then
It is freeze-dried and graphene oxide is made；
It takes 0.1~0.5g stannous chloride to be dissolved in 50~100mL dehydrated alcohol, 1~3g graphene oxide, dispersion is then added
After add 10~50mL deionized water and be fitted into 300mL microwave reaction kettle, control reaction kettle internal pressure is 1.5~2.0MPa,
10min is successively heated at 90 DEG C, 10min is heated at 130 DEG C, and 10min is heated at 150 DEG C, heats 30~60min at 180 DEG C,
Then 2~5h is stirred with high-speed shearing machine, obtained graphene/SnO after freeze-dried2Composite material；
Two, Si@PPy composite material is prepared:
By micron Si powder with speed 1~6h of ball milling of 1000r/min, the Si powder for taking 1g ball milling to cross is added to tri- mouthfuls of 100mL
In bottle；
Under nitrogen environment protection, the pyrroles of 1~2g is dissolved in 10~50mL dehydrated alcohol and obtains chromium solution, by pyrrole
It coughs up solution to be added in above-mentioned 100mL there-necked flask, ice-water bath 30~90min of magnetic agitation, revolving speed 400r/min；
It takes 1~5g ammonium persulfate to be dissolved in the HCl solution that 10~50mL concentration is 1mol/L and forms ammonium persulfate solution, it will
Ammonium persulfate solution is added dropwise in above-mentioned there-necked flask, and continuation ice-water bath stirring 12~for 24 hours, 50~500mL third is then added
Ketone simultaneously stirs 15~60min, then successively alternately wash 3~5 times with dehydrated alcohol and deionized water, and drying obtains after suction filtration
Si@PPy composite material；
Three, graphene/SnO is prepared2/ Si@PPy composite material:
By 1~3g graphene/SnO2Composite material and 1~3g Si@PPy composite material be dispersed in 100~500mL go from
In sub- water, 1~3h of magnetic agitation, then 1~3h of ultrasound, is transferred in microwave reaction kettle, control reaction kettle internal pressure be 1.5~
2.0MPa successively heats 10min at 90 DEG C, and 10min is heated at 130 DEG C, and 10min is heated at 150 DEG C, heats 30 at 180 DEG C
~60min, is cooled to room temperature, and graphene/SnO is obtained after freeze-dried2/ Si@PPy composite material.
It is ultrasonic after magnetic agitation in present embodiment step 3, it is therefore an objective to make graphene/SnO2Composite material and Si@PPy
Composite material is uniformly mixed.
PPy is the abbreviation of polypyrrole in present embodiment.
Specific embodiment 2: the present embodiment is different from the first embodiment in that, scale stone described in step 1
Ink is 100 mesh.Other steps and parameter are same as the specific embodiment one.
Specific embodiment 3: the present embodiment is different from the first and the second embodiment in that, by 15g's in step 1
Crystalline flake graphite, the potassium permanganate of 2g, the sulfuric acid that 25mL mass fraction is 98% are added sequentially in 100mL there-necked flask, constant temperature 25
Washing suction filtration is carried out after stirring 2h at DEG C, then is dried at 70 DEG C.Other steps and parameter and specific embodiment one or two-phase
Together.
Specific embodiment 4: unlike one of present embodiment and specific embodiment one to three, it will in step 1
Expansible graphite is placed in extruding 1.5min in 1000 DEG C of Muffle furnaces.Other steps and one of parameter and specific embodiment one to three
It is identical.
Specific embodiment 5: being taken in step 1 unlike one of present embodiment and specific embodiment one to four
7g expanded graphite is dispersed in the distilled water of 40mL, and the sodium nitrate of 2g is then added, and ice-water bath stirs 60min, the permanganic acid of 20g
10 additions of potassium point, then 35 DEG C are warming up to, continue to stir 4h, the deionized water of 600mL is added, and be warming up to 90 DEG C, continues to stir
2h is mixed, be then cooled to 25 DEG C and the H that 100mL mass fraction is 35% is added dropwise2O2, then the HCl solution for being 15% with mass fraction
It successively washs to solution and is in neutrality with deionized water, ultrasonication 8h.Other steps and parameter and specific embodiment one to four
One of it is identical.
Specific embodiment 6: being taken in step 1 unlike one of present embodiment and specific embodiment one to five
0.2g stannous chloride is dissolved in 70mL dehydrated alcohol, and 2g graphene oxide is then added, 20mL deionized water is added after dispersion simultaneously
It is fitted into 300mL microwave reaction kettle, control reaction kettle internal pressure is 1.8MPa, and 10min is successively heated at 90 DEG C, is added at 130 DEG C
Hot 10min heats 10min at 150 DEG C, 40min is heated at 180 DEG C, then stirs 3h with high-speed shearing machine.Other steps and ginseng
Number is identical as one of specific embodiment one to five.
Specific embodiment 7: unlike one of present embodiment and specific embodiment one to six, it is high in step 1
The shearing rotating speed of fast cutter is 8000rpm/min.Other steps and parameter are identical as one of specific embodiment one to six.
Specific embodiment 8: unlike one of present embodiment and specific embodiment one to seven, it is micro- in step 2
Rice Si powder is with the speed ball milling 4h of 1000r/min.Other steps and parameter are identical as one of specific embodiment one to seven.
Specific embodiment 9: unlike one of present embodiment and specific embodiment one to eight, ball in step 2
Abrading-ball mill uses planetary ball mill, and Material quality of grinding balls is chromium steel ball, and ratio of grinding media to material is 1 ﹕ 1~2.Other steps and parameter and specific reality
It is identical to apply one of mode one to eight.
Specific embodiment 10: unlike one of present embodiment and specific embodiment one to nine, in step 2
The pyrroles of 1.5g, which is dissolved in 25mL dehydrated alcohol, obtains chromium solution.Other steps and parameter and specific embodiment one to nine it
One is identical.
Specific embodiment 11: unlike one of present embodiment and specific embodiment one to ten, in step 2
It takes 2g ammonium persulfate to be dissolved in the HCl solution that 25mL concentration is 1mol/L and forms ammonium persulfate solution.Other steps and parameter with
One of specific embodiment one to ten is identical.
Specific embodiment 12: present embodiment is unlike specific embodiment one to one of 11, step 2
Middle ice-water bath stirs 18h, and 200mL acetone is then added and stirs 40min, then is successively handed over dehydrated alcohol and deionized water
For washing 4 times.Other steps and parameter are identical as specific embodiment one to one of 11.
Specific embodiment 13: present embodiment is unlike specific embodiment one to one of 12, step 3
It is middle by 2g graphene/SnO2Composite material and 2g Si@PPy composite material are dispersed in 300mL deionized water, magnetic agitation 2h,
Then ultrasound 2h.Other steps and parameter are identical as specific embodiment one to one of 12.
Specific embodiment 14: present embodiment is unlike specific embodiment one to one of 13, step 3
Middle supersonic frequency is 45kHz.Other steps and parameter are identical as specific embodiment one to one of 13.
Specific embodiment 15: present embodiment is unlike specific embodiment one to one of 14, step 3
Middle control reaction kettle internal pressure is 1.8MPa, and 10min is successively heated at 90 DEG C, 10min is heated at 130 DEG C, is heated at 150 DEG C
10min heats 40min at 180 DEG C.Other steps and parameter are identical as specific embodiment one to one of 14.
Beneficial effects of the present invention are verified by following embodiment:
Embodiment
A kind of graphene/SnO2The preparation method of/Si@PPy composite material, it is sequentially included the following steps:
One, graphene/SnO is prepared2Composite material:
The crystalline flake graphite of 100 mesh of 10g, the potassium permanganate of 2g, the sulfuric acid that 30mL mass fraction is 98% are added sequentially to
In 100mL there-necked flask, washing suction filtration is carried out after stirring 2h at 25 DEG C of constant temperature, then dry at 60 DEG C, expansible graphite is made；It will
Expansible graphite is placed in extruding 1min in 1000 DEG C of Muffle furnaces, and expanded graphite is made；5g expanded graphite is taken to be dispersed in the steaming of 50mL
In distilled water, the sodium nitrate of 3g is then added, ice-water bath stirs 30min, 10 additions of potassium permanganate point of 15g, then is warming up to 35
DEG C, continue to stir 4h, the deionized water of 400mL is added, and be warming up to 90 DEG C, continues to stir 1h, be then cooled to 25 DEG C and drip
Adding 50mL mass fraction is 35% H2O2, then with mass fraction be 15% HCl solution and deionized water successively wash to solution
It is in neutrality, ultrasonication 6h, is then freeze-dried and graphene oxide is made；
It takes 0.2g stannous chloride to be dissolved in 60mL dehydrated alcohol, 1g graphene oxide is then added, adds 40mL after dispersion
Deionized water is simultaneously fitted into 300mL microwave reaction kettle, and control reaction kettle internal pressure is 2.0MPa, successively heats 10min at 90 DEG C,
10min is heated at 130 DEG C, 10min is heated at 150 DEG C, 30min is heated at 180 DEG C, then stirs 2h, warp with high-speed shearing machine
Graphene/SnO is made after freeze-drying2Composite material；
Two, Si@PPy composite material is prepared:
By micron Si powder with the speed ball milling 6h of 1000r/min, the Si powder for taking 1g ball milling to cross is added to 100mL there-necked flask
In；
Under nitrogen environment protection, the pyrroles of 1g is dissolved in 20mL dehydrated alcohol and obtains chromium solution, by chromium solution
It is added in above-mentioned 100mL there-necked flask, ice-water bath magnetic agitation 30min, revolving speed 400r/min；
It takes 3.4g ammonium persulfate to be dissolved in the HCl solution that 20mL concentration is 1mol/L and forms ammonium persulfate solution, by over cure
Acid ammonium solution is added dropwise in above-mentioned there-necked flask, is continued ice-water bath and is stirred 12h, and 50mL acetone is then added and stirs 15min,
Successively alternately wash 3 times with dehydrated alcohol and deionized water again, drying obtains Si@PPy composite material after suction filtration；
Three, graphene/SnO is prepared2/ Si@PPy composite material:
By 1g graphene/SnO2Composite material and 1g Si@PPy composite material are dispersed in 100mL deionized water, magnetic force
1h is stirred, then ultrasound 1h, transfers in microwave reaction kettle, and control reaction kettle internal pressure is 2.0MPa, successively adds at 90 DEG C
Hot 10min heats 10min at 130 DEG C, 10min is heated at 150 DEG C, 30min is heated at 180 DEG C, is cooled to room temperature, chilled
Graphene/SnO is obtained after drying2/ Si@PPy composite material.
Graphene/SnO in the present embodiment2The preparation flow of/Si@PPy composite material is as shown in Figure 1, this figure is only to simplify
Schematic diagram, specific preparation process in embodiment referring to recording.
Preparation gained graphene/SnO in the present embodiment step 12Composite material, as shown in Figure 2, it is seen that graphene sheet layer
It is relatively thin, nano SnO above lamella2It is evengranular to be distributed on graphene sheet layer.
Preparation gained Si PPy composite material in the present embodiment step 2, as shown in Figure 3, it is seen that uniformly wrap on Si powder surface
One layer of PPy is covered, there is no the Si powder not being wrapped by, and also there is no reuniting by PPy.
Preparation gained graphene/SnO in the present embodiment step 32/ Si PPy composite material, as shown in Figure 4, it is seen that pass through
The spherical morphology of PPy is slightly changed in Si@PPy composite material after microwave reaction, graphene/SnO2It is dispersed in Si@PPy composite wood
Material surface, and the graphene/SnO on surface2Composite material can effectively enhance the electric conductivity and charging and discharging capacity of Si@PPy,
Therefore graphene/SnO2/ Si@PPy composite material has excellent performance of lithium ion battery.
Preparation gained graphene/SnO in the present embodiment2/ Si@PPy composite material is detected:
Graphene/SnO2The high rate performance curve of/Si PPy cathode is as shown in Figure 5, it is seen that graphene/SnO2/ Si@PPy is negative
The first discharge specific capacity and charge specific capacity of pole are respectively 1734mAh/g and 920.38mAh/g, and coulombic efficiency is for the first time
53.08%, and coulombic efficiency is lower for the first time, is declined as forming the irreversible of specific capacity caused by SEI in charge and discharge process
Subtract, graphene/SnO2In initial 5 charge and discharge process, specific capacity is being gradually reduced always/Si@PPy cathode, illustrates graphite
Alkene/SnO2Si continuous cracking when/Si PPy cathode forms SEI, it is therefore desirable to the process of a long period.But with charge and discharge
The continuous progress of electric process, specific capacity also gradually tend towards stability, this illustrates that PPy clad plays restriction effect to Si, prevent
The expansion of Si forms new SEI, therefore capacity keeps stablizing, and coulombic efficiency is also gradually increased.Due to forming specific capacity when SEI
It is higher, remove graphene/SnO2The first charge-discharge specific capacity value of/Si@PPy negative electrode material, graphene/SnO2/ Si@PPy cathode
Material is in 100mA/g, 200mA/g, 300mA/g, 500mA/g, 1000mA/g and turns again to putting for 100mA/g current density
Electric specific capacity average value, charge specific capacity average value and the ratio compared with the charging and discharging capacity average value of initial 100mA/g
Capacity retention ratio is shown in Table 1.As seen from Table 1, graphene/SnO2The charge and discharge at 1000mA/g of/Si@PPy cathode are discharged and are filled
The specific capacity conservation rate of electricity is respectively 69.38% and 74.37%, illustrates graphene/SnO2/ Si@PPy cathode has excellent times
Rate performance.And current density is when turning again to 100mA/g, graphene/SnO2The specific capacity of electric discharge and the charging of/Si@PPy cathode
Conservation rate is respectively 84.56% and 89.73%, this illustrates high current charge-discharge for graphene/SnO2The ratio of/Si@PPy cathode
The influence of capacity is smaller.
1 graphene of table/SnO2The Average specific capacities and Average specific capacities conservation rate of/Si PPy cathode
Graphene/SnO2/ Si@PPy cathode current density be 1000mA/g under cycle performance curve as shown in fig. 6,
It can be seen that under 1000mA/g current density, graphene/SnO2/ Si@PPy cathode first charge-discharge specific capacity is decreased obviously, electric discharge
It is respectively 927.66mAh/g and 681.53mAh/g with charge specific capacity, this is mainly due to non-activated electrode materials in big electricity
Under current density charge and discharge cycles, Li+Migration rate it is slow compared with the delivery rate of electronics, cause embedding lithium-take off lithium process carry out not
Completely, therefore first charge-discharge specific capacity is lower.In preceding 100 cyclic processes, charging and discharging capacity present first increase after by
The trend gradually reduced, charging and discharging capacity gradually decreases after circulation 100 times, this is mainly due in preceding 100 cyclic processes,
Electrode material constantly activates during charge and discharge cycles, therefore charging and discharging capacity gradually increases.Electrode material activates completely
Afterwards, as the carry out electrode material of charge and discharge cycles gradually fails, therefore charging and discharging capacity gradually decreases.
Remove the preceding charging and discharging capacity unstable twice for forming SEI, graphene/SnO through overactivation2/Si@PPy
The specific capacity peak of cathode appear in the 26th time circulation, electric discharge and charging specific capacity be respectively 495.68mAh/g and
500.41mAh/g, at this time graphene/SnO2/ Si@PPy cathode activates completely.After 400 charge and discharge cycles, electric discharge and
The specific capacity of charging is respectively graphene/SnO after 449.51mAh/g and 447.06mAh/g, with complete activation2/ Si@PPy is negative
The charging and discharging capacity of pole is compared, and electric discharge and charge specific capacity conservation rate are respectively 90.69% He after 400 charge and discharge cycles
89.34%, it is seen that graphene/SnO2/ Si@PPy cathode still has preferable under the high current density charge and discharge of 1000mA/g
Cycle life.
Claims (10)
1. a kind of graphene/SnO2The preparation method of/Si@PPy composite material, it is characterised in that it is sequentially included the following steps:
One, graphene/SnO is prepared2Composite material:
The crystalline flake graphite of 10~20g, the potassium permanganate of 1~5g, the sulfuric acid that 10~50mL mass fraction is 98% are sequentially added
Into 100mL there-necked flask, washing suction filtration is carried out after stirring 1~3h at 25 DEG C of constant temperature, then dry at 60~80 DEG C, being made can be swollen
Swollen graphite；Expansible graphite is placed in 1~2min of extruding in 1000 DEG C of Muffle furnaces, expanded graphite is made；5~10g is taken to expand stone
Ink is dispersed in the distilled water of 10~50mL, and the sodium nitrate of 1~5g is then added, and ice-water bath stirs 30~90min, 10~30g
Points of 10 times additions of potassium permanganate, then be warming up to 35 DEG C, continue 1~8h of stirring, the deionized water of 400~800mL is added, and rise
Temperature continues 1~3h of stirring to 90 DEG C, is then cooled to 25 DEG C and the H that 50~200mL mass fraction is 35% is added dropwise2O2, then use
The HCl solution and deionized water that mass fraction is 15% are successively washed to solution and are in neutrality, then 6~12h of ultrasonication is freezed
Dry obtained graphene oxide；
It takes 0.1~0.5g stannous chloride to be dissolved in 50~100mL dehydrated alcohol, 1~3g graphene oxide is then added, after dispersion again
10~50mL deionized water is added and is fitted into 300mL microwave reaction kettle, control reaction kettle internal pressure is 1.5~2.0MPa, successively
10min is heated at 90 DEG C, 10min is heated at 130 DEG C, and 10min is heated at 150 DEG C, heats 30~60min at 180 DEG C, then
2~5h is stirred with high-speed shearing machine, obtained graphene/SnO after freeze-dried2Composite material；
Two, Si@PPy composite material is prepared:
By micron Si powder with speed 1~6h of ball milling of 1000r/min, the Si powder for taking 1g ball milling to cross is added in 100mL there-necked flask；
Under nitrogen environment protection, the Py of 1~2g is dissolved in 10~50mL dehydrated alcohol and obtains Py solution, Py solution is added
Into above-mentioned 100mL there-necked flask, ice-water bath 30~90min of magnetic agitation, revolving speed 400r/min；
It takes 1~5g ammonium persulfate to be dissolved in the HCl solution that 10~50mL concentration is 1mol/L and forms ammonium persulfate solution, by over cure
Acid ammonium solution is added dropwise in above-mentioned there-necked flask, and continuation ice-water bath stirring 12~for 24 hours, 50~500mL acetone then is added simultaneously
15~60min is stirred, then successively alternately wash 3~5 times with dehydrated alcohol and deionized water, drying obtains Si@after suction filtration
PPy composite material；
Three, graphene/SnO is prepared2/ Si@PPy composite material:
By 1~3g graphene/SnO2Composite material and 1~3g Si@PPy composite material are dispersed in 100~500mL deionized water
In, 1~3h of magnetic agitation, then 1~3h of ultrasound, transfers in microwave reaction kettle, control reaction kettle internal pressure be 1.5~
2.0MPa successively heats 10min at 90 DEG C, and 10min is heated at 130 DEG C, and 10min is heated at 150 DEG C, heats 30 at 180 DEG C
~60min, is cooled to room temperature, and graphene/SnO is obtained after freeze-dried2/ Si@PPy composite material.
2. a kind of graphene/SnO according to claim 12The preparation method of/Si@PPy composite material, it is characterised in that step
Crystalline flake graphite described in rapid one is 100 mesh.
3. a kind of graphene/SnO according to claim 12The preparation method of/Si@PPy composite material, it is characterised in that step
The crystalline flake graphite of 15g, the potassium permanganate of 2g, the sulfuric acid that 25mL mass fraction is 98% are added sequentially to 100mL tri- in rapid one
In mouth bottle, washing suction filtration is carried out after stirring 2h at 25 DEG C of constant temperature, then dry at 70 DEG C.
4. a kind of graphene/SnO according to claim 12The preparation method of/Si@PPy composite material, it is characterised in that step
It takes 0.2g stannous chloride to be dissolved in 70mL dehydrated alcohol in rapid one, 2g graphene oxide is then added, adds 20mL after dispersion and goes
Ionized water is simultaneously fitted into 300mL microwave reaction kettle, and control reaction kettle internal pressure is 1.8MPa, successively heats 10min at 90 DEG C,
10min is heated at 130 DEG C, 10min is heated at 150 DEG C, 40min is heated at 180 DEG C, then stirs 3h with high-speed shearing machine.
5. a kind of graphene/SnO according to claim 12The preparation method of/Si@PPy composite material, it is characterised in that step
Micron Si powder is in rapid two with the speed ball milling 4h of 1000r/min.
6. a kind of graphene/SnO according to claim 12The preparation method of/Si@PPy composite material, it is characterised in that step
Ball milling uses planetary ball mill in rapid two, and Material quality of grinding balls is chromium steel ball, and ratio of grinding media to material is 1 ﹕ 1~2.
7. a kind of graphene/SnO according to claim 12The preparation method of/Si@PPy composite material, it is characterised in that step
It takes 2g ammonium persulfate to be dissolved in the HCl solution that 25mL concentration is 1mol/L in rapid two and forms ammonium persulfate solution.
8. a kind of graphene/SnO according to claim 12The preparation method of/Si@PPy composite material, it is characterised in that step
Ice-water bath stirs 18h in rapid two, is then added and 200mL acetone and stirs 40min, then successively with dehydrated alcohol and deionized water into
Row alternately washing 4 times.
9. a kind of graphene/SnO according to claim 12The preparation method of/Si@PPy composite material, it is characterised in that step
By 2g graphene/SnO in rapid three2Composite material and 2g Si@PPy composite material are dispersed in 300mL deionized water, and magnetic force stirs
2h is mixed, then ultrasound 2h.
10. a kind of graphene/SnO according to claim 12The preparation method of/Si@PPy composite material, it is characterised in that
Supersonic frequency is 45kHz in step 3.
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