CN108417810A - Preparation method of polyaniline/graphene/silicon composite material with three-dimensional network structure - Google Patents
Preparation method of polyaniline/graphene/silicon composite material with three-dimensional network structure Download PDFInfo
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- 229910052710 silicon Inorganic materials 0.000 title claims abstract description 65
- 239000010703 silicon Substances 0.000 title claims abstract description 64
- OKTJSMMVPCPJKN-UHFFFAOYSA-N Carbon Chemical compound [C] OKTJSMMVPCPJKN-UHFFFAOYSA-N 0.000 title claims abstract description 57
- 229910021389 graphene Inorganic materials 0.000 title claims abstract description 55
- 229920000767 polyaniline Polymers 0.000 title claims abstract description 46
- 239000002131 composite material Substances 0.000 title claims abstract description 44
- 238000002360 preparation method Methods 0.000 title claims abstract description 20
- XUIMIQQOPSSXEZ-UHFFFAOYSA-N Silicon Chemical compound [Si] XUIMIQQOPSSXEZ-UHFFFAOYSA-N 0.000 claims abstract description 59
- QAOWNCQODCNURD-UHFFFAOYSA-N Sulfuric acid Chemical compound OS(O)(=O)=O QAOWNCQODCNURD-UHFFFAOYSA-N 0.000 claims abstract description 42
- 239000000017 hydrogel Substances 0.000 claims abstract description 35
- VEXZGXHMUGYJMC-UHFFFAOYSA-N Hydrochloric acid Chemical compound Cl VEXZGXHMUGYJMC-UHFFFAOYSA-N 0.000 claims abstract description 32
- PAYRUJLWNCNPSJ-UHFFFAOYSA-N Aniline Chemical compound NC1=CC=CC=C1 PAYRUJLWNCNPSJ-UHFFFAOYSA-N 0.000 claims abstract description 18
- XLYOFNOQVPJJNP-UHFFFAOYSA-N water Substances O XLYOFNOQVPJJNP-UHFFFAOYSA-N 0.000 claims abstract description 15
- 239000005457 ice water Substances 0.000 claims abstract description 14
- 238000001027 hydrothermal synthesis Methods 0.000 claims abstract description 13
- CBCKQZAAMUWICA-UHFFFAOYSA-N 1,4-phenylenediamine Chemical compound NC1=CC=C(N)C=C1 CBCKQZAAMUWICA-UHFFFAOYSA-N 0.000 claims abstract description 9
- 239000000178 monomer Substances 0.000 claims abstract description 9
- LPXPTNMVRIOKMN-UHFFFAOYSA-M sodium nitrite Substances [Na+].[O-]N=O LPXPTNMVRIOKMN-UHFFFAOYSA-M 0.000 claims abstract description 9
- ROOXNKNUYICQNP-UHFFFAOYSA-N ammonium persulfate Chemical compound [NH4+].[NH4+].[O-]S(=O)(=O)OOS([O-])(=O)=O ROOXNKNUYICQNP-UHFFFAOYSA-N 0.000 claims abstract description 8
- 238000003756 stirring Methods 0.000 claims abstract description 8
- 238000006116 polymerization reaction Methods 0.000 claims abstract description 7
- 229910004039 HBF4 Inorganic materials 0.000 claims abstract description 6
- 229910001870 ammonium persulfate Inorganic materials 0.000 claims abstract description 4
- 238000002791 soaking Methods 0.000 claims abstract description 3
- 238000006243 chemical reaction Methods 0.000 claims description 23
- 230000035484 reaction time Effects 0.000 claims description 12
- 239000006185 dispersion Substances 0.000 claims description 10
- 239000008367 deionised water Substances 0.000 claims description 7
- 229910021641 deionized water Inorganic materials 0.000 claims description 7
- 239000005543 nano-size silicon particle Substances 0.000 claims description 7
- 229910002804 graphite Inorganic materials 0.000 claims description 5
- 239000010439 graphite Substances 0.000 claims description 5
- 239000007788 liquid Substances 0.000 claims description 5
- 230000003647 oxidation Effects 0.000 claims description 5
- 238000007254 oxidation reaction Methods 0.000 claims description 5
- 239000002070 nanowire Substances 0.000 claims description 3
- -1 oxygen Graphite alkene Chemical class 0.000 claims description 3
- 229910052760 oxygen Inorganic materials 0.000 claims description 2
- 239000001301 oxygen Substances 0.000 claims description 2
- 239000010409 thin film Substances 0.000 claims description 2
- BFNBIHQBYMNNAN-UHFFFAOYSA-N ammonium sulfate Chemical compound N.N.OS(O)(=O)=O BFNBIHQBYMNNAN-UHFFFAOYSA-N 0.000 claims 1
- 229910052921 ammonium sulfate Inorganic materials 0.000 claims 1
- 235000011130 ammonium sulphate Nutrition 0.000 claims 1
- 239000000243 solution Substances 0.000 abstract 5
- 239000011259 mixed solution Substances 0.000 abstract 4
- 238000006193 diazotization reaction Methods 0.000 abstract 1
- 239000000463 material Substances 0.000 description 25
- 239000002210 silicon-based material Substances 0.000 description 11
- 238000000034 method Methods 0.000 description 10
- 239000003643 water by type Substances 0.000 description 8
- 230000008569 process Effects 0.000 description 7
- 230000008859 change Effects 0.000 description 6
- HBBGRARXTFLTSG-UHFFFAOYSA-N Lithium ion Chemical compound [Li+] HBBGRARXTFLTSG-UHFFFAOYSA-N 0.000 description 5
- 230000000052 comparative effect Effects 0.000 description 5
- 238000001035 drying Methods 0.000 description 5
- 229910001416 lithium ion Inorganic materials 0.000 description 5
- 239000012954 diazonium Substances 0.000 description 4
- IJGRMHOSHXDMSA-UHFFFAOYSA-O diazynium Chemical compound [NH+]#N IJGRMHOSHXDMSA-UHFFFAOYSA-O 0.000 description 4
- 230000005540 biological transmission Effects 0.000 description 3
- 239000003575 carbonaceous material Substances 0.000 description 3
- 239000011248 coating agent Substances 0.000 description 3
- 238000000576 coating method Methods 0.000 description 3
- 230000010287 polarization Effects 0.000 description 3
- 239000011856 silicon-based particle Substances 0.000 description 3
- 239000006245 Carbon black Super-P Substances 0.000 description 2
- 102000004310 Ion Channels Human genes 0.000 description 2
- 229910001290 LiPF6 Inorganic materials 0.000 description 2
- 150000001875 compounds Chemical class 0.000 description 2
- 238000010410 dusting Methods 0.000 description 2
- 230000000694 effects Effects 0.000 description 2
- 239000003792 electrolyte Substances 0.000 description 2
- 239000010408 film Substances 0.000 description 2
- 239000002002 slurry Substances 0.000 description 2
- 238000005406 washing Methods 0.000 description 2
- 239000002023 wood Substances 0.000 description 2
- 101000911390 Homo sapiens Coagulation factor VIII Proteins 0.000 description 1
- WHXSMMKQMYFTQS-UHFFFAOYSA-N Lithium Chemical compound [Li] WHXSMMKQMYFTQS-UHFFFAOYSA-N 0.000 description 1
- 229910000676 Si alloy Inorganic materials 0.000 description 1
- HMDDXIMCDZRSNE-UHFFFAOYSA-N [C].[Si] Chemical compound [C].[Si] HMDDXIMCDZRSNE-UHFFFAOYSA-N 0.000 description 1
- 239000003082 abrasive agent Substances 0.000 description 1
- 150000001412 amines Chemical class 0.000 description 1
- QVGXLLKOCUKJST-UHFFFAOYSA-N atomic oxygen Chemical compound [O] QVGXLLKOCUKJST-UHFFFAOYSA-N 0.000 description 1
- 239000003610 charcoal Substances 0.000 description 1
- 125000004122 cyclic group Chemical group 0.000 description 1
- 230000001351 cycling effect Effects 0.000 description 1
- 230000006378 damage Effects 0.000 description 1
- 230000007423 decrease Effects 0.000 description 1
- 230000007547 defect Effects 0.000 description 1
- 230000005611 electricity Effects 0.000 description 1
- 238000005469 granulation Methods 0.000 description 1
- 230000003179 granulation Effects 0.000 description 1
- 102000057593 human F8 Human genes 0.000 description 1
- 230000006872 improvement Effects 0.000 description 1
- 150000002500 ions Chemical class 0.000 description 1
- 239000007791 liquid phase Substances 0.000 description 1
- 229910052744 lithium Inorganic materials 0.000 description 1
- 230000014759 maintenance of location Effects 0.000 description 1
- 230000035800 maturation Effects 0.000 description 1
- 239000002905 metal composite material Substances 0.000 description 1
- 239000007769 metal material Substances 0.000 description 1
- 229910021471 metal-silicon alloy Inorganic materials 0.000 description 1
- 239000000203 mixture Substances 0.000 description 1
- 239000012071 phase Substances 0.000 description 1
- 229920006389 polyphenyl polymer Polymers 0.000 description 1
- 229940047431 recombinate Drugs 0.000 description 1
- 230000009467 reduction Effects 0.000 description 1
- 238000000926 separation method Methods 0.000 description 1
- 238000005245 sintering Methods 0.000 description 1
- 238000001694 spray drying Methods 0.000 description 1
- 239000000126 substance Substances 0.000 description 1
- 238000006467 substitution reaction Methods 0.000 description 1
- 239000000758 substrate Substances 0.000 description 1
Classifications
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- H—ELECTRICITY
- H01—ELECTRIC ELEMENTS
- H01M—PROCESSES OR MEANS, e.g. BATTERIES, FOR THE DIRECT CONVERSION OF CHEMICAL ENERGY INTO ELECTRICAL ENERGY
- H01M4/00—Electrodes
- H01M4/02—Electrodes composed of, or comprising, active material
- H01M4/36—Selection of substances as active materials, active masses, active liquids
- H01M4/362—Composites
-
- H—ELECTRICITY
- H01—ELECTRIC ELEMENTS
- H01M—PROCESSES OR MEANS, e.g. BATTERIES, FOR THE DIRECT CONVERSION OF CHEMICAL ENERGY INTO ELECTRICAL ENERGY
- H01M10/00—Secondary cells; Manufacture thereof
- H01M10/05—Accumulators with non-aqueous electrolyte
- H01M10/052—Li-accumulators
- H01M10/0525—Rocking-chair batteries, i.e. batteries with lithium insertion or intercalation in both electrodes; Lithium-ion batteries
-
- H—ELECTRICITY
- H01—ELECTRIC ELEMENTS
- H01M—PROCESSES OR MEANS, e.g. BATTERIES, FOR THE DIRECT CONVERSION OF CHEMICAL ENERGY INTO ELECTRICAL ENERGY
- H01M4/00—Electrodes
- H01M4/02—Electrodes composed of, or comprising, active material
- H01M4/36—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
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- 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
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- H01M—PROCESSES OR MEANS, e.g. BATTERIES, FOR THE DIRECT CONVERSION OF CHEMICAL ENERGY INTO ELECTRICAL ENERGY
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- H01M4/62—Selection of inactive substances as ingredients for active masses, e.g. binders, fillers
- H01M4/628—Inhibitors, e.g. gassing inhibitors, corrosion inhibitors
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- H—ELECTRICITY
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- 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
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- 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)
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- Carbon And Carbon Compounds (AREA)
- Battery Electrode And Active Subsutance (AREA)
- Silicon Compounds (AREA)
Abstract
The invention discloses a preparation method of a polyaniline/graphene/silicon composite material with a three-dimensional network structure, which comprises the following steps: adding p-phenylenediamine into water, stirring and dissolving in a water bath, adding a silicon source, stirring and dispersing, adding graphene oxide, uniformly dispersing, and carrying out hydrothermal reaction to obtain hydrogel M1; adding hydrogel M1 into hydrochloric acid for precooling, and adding NaNO2Solution and HBF4Respectively precooling the solution, and dropwise adding precooled NaNO into hydrochloric acid containing hydrogel M1 in an ice water bath2Solution and precooled HBF4Carrying out solution and then carrying out diazotization reaction to obtain hydrogel M2; dissolving aniline monomer in sulfuric acid solutionAdding hydrogel M2, soaking, and precooling to obtain a first mixed solution; dissolving ammonium persulfate in a sulfuric acid solution, and precooling to obtain a second mixed solution; and dropwise adding the second mixed solution into the first mixed solution in an ice-water bath, and adjusting the temperature to perform polymerization reaction to obtain the polyaniline/graphene/silicon composite material with the three-dimensional network structure.
Description
Technical field
The present invention relates to technical field of lithium ion more particularly to a kind of three-dimensional net structure polyaniline/graphene/silicons
Composite material and preparation method thereof.
Background technology
With the development of electric vehicle and portable electrical appliance, the demand of lithium ion battery with high energy density also increasingly increases
Add.Conventional graphite negative material theoretical specific capacity only has 372mAh/g, it is difficult to meet the market demand.The gram volume for the first time of silicon materials
For 4200mAh/g, embedding lithium platform higher, earth's crust storage is abundant, and the advantages such as environmentally friendly gradually cause the extensive pass of researcher
Note.
However the volume expansion of silicon is up to 300%, in cyclic process, not only results in silicon and the conductive charcoal network of surrounding
Separation forms " dead silicon ", it is peeling-off with collector to also result in silicon.Secondly, larger volume expansion also results in surface
SEI films constantly recombinate destruction, keep SEI films more and more thicker, constantly the Li of consumption anode+, coulombic efficiency reduction.Finally, larger
The phase leads to silicon materials dusting after cycling for volume expansion, these problems eventually lead to cycle performance and drastically deteriorate.
Currently, researchers are mainly by the way that silicon and carbon material is compound and metal material is compound or uses the sub- silicon of oxidation
To solve the above problems.In terms of metal silicon alloy, the volume that padded coaming is mainly carried out with metal composites such as Al, Ti, Mg is swollen
It is swollen, the cycle performance of silicon can be greatly promoted, but the common fault of silicon alloy is that material stiffness is too big, later cycles material
Meeting dusting is broken, and performance drastically declines.In terms of silicon carbon material, mainly mix silicon materials and carbon material by solid-liquid,
The means such as liquid phase coating, spray drying granulation, high temperature sintering the shortcomings that improving silicon materials, can not only improve the conductance of material
Property, the volume expansion of padded coaming improves the cyclical stability of material to a certain extent.In addition, there is part research in oxygen
Change on sub- silicon materials, relative to silicon materials, gram volume decreases, but its cycle performance increases.Its maximum problem
It is that first effect is relatively low, only 65~70%, in actual use, need to be to its prelithiation, however prelithiation technique is also not
Maturation is also to be used after so that it is mixed with graphite at present.
Invention content
Technical problems based on background technology, the present invention propose a kind of three-dimensional net structure polyaniline/graphene/
Silicon composite preparation method overcomes defect of the existing technology, can effectively buffer silicon volume expansion, improve material electronics and
Ionic conductivity and improvement material interface properties, gained composite material are in three-dimensional net structure, the not only transmission of lithium ion
Path is provided, and volume deformation of the silicon materials in charge and discharge process can be buffered.In addition polyaniline can not only improve material
Interface performance, in the composite be in chain structure, electronics and ion are provided in charge and discharge process between silicon particle
Channel.Last graphene and polyaniline can also improve the electron conduction of silicon materials, reduce material polarization, to a certain extent
Improve the cyclical stability of silica-base material.
A kind of three-dimensional net structure polyaniline/graphene/silicon composite material and preparation method thereof proposed by the present invention, including it is as follows
Step：
S1, stirring in water bath dissolving in deionized water is added in p-phenylenediamine, adds silicon source and be stirred dispersion, then adds
Enter graphene oxide to be uniformly dispersed, then carries out hydro-thermal reaction and obtain hydrogel M1；
S2, it hydrogel M1 is added in hydrochloric acid is pre-chilled, then by NaNO2Solution and HBF4Solution is pre-chilled respectively, in ice-water bath
The NaNO after precooling is added dropwise into the hydrochloric acid containing hydrogel M12HBF after solution and precooling4Then it is anti-to carry out diazotising for solution
It answers, deionized water washs to obtain hydrogel M2；
S3, aniline monomer is dissolved in sulfuric acid solution, adds hydrogel M2, impregnated, precooling obtains the first mixed liquor；
Ammonium persulfate is dissolved in sulfuric acid solution, is pre-chilled, obtains the second mixed liquor；The second mixed liquor is added dropwise in ice-water bath
In one mixed liquor, adjusts temperature and carry out polymerisation, sulfuric acid solution washing is dried to obtain three-dimensional net structure polyaniline/graphite
Alkene/silicon composite.
Preferably, in S1, silicon source is at least one of silicon nanoparticle, silicon nanowires, silicon nano thin-film, the sub- silicon of oxidation.
Preferably, in S1, the mass ratio of p-phenylenediamine and graphene oxide is 8~12：1.
Preferably, in S1, the mass ratio of silicon source and graphene oxide is 7~57：3.
Preferably, in S1, bath temperature is 50~90 DEG C.
Preferably, in S1, hydrothermal temperature is 120~200 DEG C, and the hydro-thermal reaction time is 0.5~10h.
Preferably, in S2, precooling temperature is 0 DEG C.
Preferably, in S2, concentration of hydrochloric acid is 0.8~1.2mol/L.
Preferably, in S2, NaNO2NaNO in solution2With HBF4HBF in solution4Mass ratio be 1：1~4.
Preferably, in S2, diazo-reaction temperature is -10~20 DEG C, and the diazo-reaction time is 0.5~4h.
Preferably, in S3, soaking time is 2~10h.
Preferably, in S3, precooling temperature is 0 DEG C.
Preferably, in S3, the molar ratio of aniline monomer and ammonium persulfate is 1：1~4.
Preferably, in S3, a concentration of 0.4~0.6mol/L of sulfuric acid solution.
Preferably, in S3, polymeric reaction temperature is -10~20 DEG C, and polymerization reaction time is 2~12h.
Preferably, in S3, drying temperature is 60~100 DEG C.
Compared with the prior art, the advantages of the present invention are as follows：
(1) present invention gained polyaniline/graphene/silicon composite material is in three-dimensional net structure, can not only buffer silicon substrate
Volume expansion of the material in charge and discharge process, and provide channel for the quick transmission of lithium ion；
(2) interface performance of the invention that can not only improve material using polyaniline, raising interface stability, and due to
It is in chain structure still can provide electronics and ion channel even if part silicon particle ruptures in charge and discharge process for it,
Greatly improve the cycle performance of material；
(3) present invention can improve the electron conduction of silica-base material using graphene and polyaniline, reduce material polarization,
Improve the high rate performance of material；
(4) the method for the present invention is simple, easily controllable and realization industrial operation, gained polyaniline/graphene/silicon composite wood
Material has good cyclical stability and high rate performance.
Description of the drawings
Fig. 1 is that the SEM of 1 gained polyaniline of the embodiment of the present invention/graphene/silicon composite material schemes.
Fig. 2 is TEM figure of 1 gained polyaniline of the embodiment of the present invention/graphene/silicon composite material under low point of multiplying power.
Fig. 3 is TEM figure of 1 gained polyaniline of the embodiment of the present invention/graphene/silicon composite material under high score multiplying power.
Fig. 4 is 1 gained polyaniline of the embodiment of the present invention/graphene/silicon composite material and the first charge-discharge song of comparative example
Line.
Fig. 5 is 1 gained polyaniline of the embodiment of the present invention/graphene/silicon composite material and comparative example in 0.1C current densities
Under cycle performance figure.
Specific implementation mode
In the following, technical scheme of the present invention is described in detail by specific embodiment.
Embodiment 1
A kind of three-dimensional net structure polyaniline/graphene/silicon composite material and preparation method thereof, includes the following steps：
S1,0.288g p-phenylenediamine is added in 100mL deionized waters, 60 DEG C of stirring in water bath dissolvings add 0.684g
Nano-silicon is stirred dispersion, is subsequently added into the graphene oxide dispersion that 12mL mass fractions are 3mg/mL, is uniformly dispersed, so
After carry out hydro-thermal reaction, hydrothermal temperature is 180 DEG C, and the hydro-thermal reaction time 2h obtains hydrogel M1；
S2,0 DEG C will be cooled in advance in the hydrochloric acid of a concentration of 1mol/L of hydrogel M1 addition 100mL；Again by 0.2g NaNO2Add
Enter in 4mL deionized waters, measures the HBF that 8mL mass fractions are 14wt%4The two is cooled to 0 DEG C by solution in advance respectively；In ice water
The NaNO after precooling is added dropwise in bath into the hydrochloric acid containing hydrogel M12HBF after solution and precooling4Then solution carries out diazonium
Change reaction, diazo-reaction temperature is 0 DEG C, and the diazo-reaction time is 2h, and deionized water washs to obtain hydrogel M2；
S3, the sulfuric acid solution that the aniline monomer that 10mL molar concentrations are 0.01mol/L is dissolved in a concentration of 0.5mol/L
In, hydrogel M2 is added, 7h is impregnated, is cooled to 0 DEG C in advance and obtains the first mixed liquor；0.03g ammonium persulfates are dissolved in 3mL moles
In the sulfuric acid solution of a concentration of 0.5mol/L, it is cooled to 0 DEG C in advance, obtains the second mixed liquor；In ice-water bath drop is mixed by second
It adds in the first mixed liquor, then carries out polymerisation, polymeric reaction temperature is 0 DEG C, polymerization reaction time 6h, sulfuric acid solution
Washing 3~5 times is placed in drying in 80 DEG C of baking ovens and completely, obtains three-dimensional net structure polyaniline/graphene/silicon composite material.
Fig. 1 be the present embodiment obtained by polyaniline/graphene/silicon composite material SEM figure, by Fig. 1 it can be found that：Graphene
In three-dimensional net structure, in the three-dimensional network channel of nano-silicon dispersed graphite alkene.And Fig. 2 is 1 gained polyphenyl of the embodiment of the present invention
Amine/graphene/silicon composite material under low point of multiplying power TEM figure, Fig. 3 be 1 gained polyaniline of the embodiment of the present invention/graphene/
TEM figure of the silicon composite under high score multiplying power, is can be found that by Fig. 2, Fig. 3：Silicon nanoparticle size about 50~80nm, uniformly
Distribution is on the surface of graphene.
By polyaniline/graphene/silicon composite material, Super-P, LA133 obtained by the present embodiment according to 8:1:1 is ground
Material closes slurry, coating, assembles button CR2016 batteries, selects the EC+DMC solution of 1mol/L LiPF6 as electrolyte, carries out electricity
Chemical property is tested.
Embodiment 2
A kind of three-dimensional net structure polyaniline/graphene/silicon composite material and preparation method thereof, includes the following steps：
S1,0.432g p-phenylenediamine is added in 100mL deionized waters, 50 DEG C of stirring in water bath dissolvings add 0.684g
Silicon nanowires is stirred dispersion, is subsequently added into the graphene oxide dispersion that 12mL mass fractions are 3mg/mL, is uniformly dispersed,
Then hydro-thermal reaction is carried out, hydrothermal temperature is 120 DEG C, and the hydro-thermal reaction time 0.5h obtains hydrogel M1；
S2,0 DEG C will be cooled in advance in the hydrochloric acid of a concentration of 1mol/L of hydrogel M1 addition 100mL；Again by 0.2g NaNO2Add
Enter in 4mL deionized waters, measures the HBF that 32mL mass fractions are 4wt%4The two is cooled to 0 DEG C by solution in advance respectively；In ice water
The NaNO after precooling is added dropwise in bath into the hydrochloric acid containing hydrogel M12HBF after solution and precooling4Then solution carries out diazonium
Change reaction, diazo-reaction temperature is 0 DEG C, and the diazo-reaction time is 4h, and deionized water washs to obtain hydrogel M2；
S3, the sulfuric acid solution that the aniline monomer that 10mL molar concentrations are 0.01mol/L is dissolved in a concentration of 0.5mol/L
In, hydrogel M2 is added, 7h is impregnated, is cooled to 0 DEG C in advance and obtains the first mixed liquor；0.03g ammonium persulfates are dissolved in 3mL moles
In the sulfuric acid solution of a concentration of 0.5mol/L, it is cooled to 0 DEG C in advance, obtains the second mixed liquor；In ice-water bath drop is mixed by second
It adds in the first mixed liquor, then carries out polymerisation, polymeric reaction temperature is 0 DEG C, polymerization reaction time 12h, and sulfuric acid is molten
Liquid washs 3~5 times, is placed in drying in 100 DEG C of baking ovens and completely, obtains three-dimensional net structure polyaniline/graphene/silicon composite wood
Material.
Embodiment 3
A kind of three-dimensional net structure polyaniline/graphene/silicon composite material and preparation method thereof, includes the following steps：
S1,0.432g p-phenylenediamine is added in 100mL deionized waters, 50 DEG C of stirring in water bath dissolvings add 0.684g
The sub- silicon of oxidation is stirred dispersion, is subsequently added into the graphene oxide dispersion that 12mL mass fractions are 3mg/mL, is uniformly dispersed,
Then hydro-thermal reaction is carried out, hydrothermal temperature is 120 DEG C, and the hydro-thermal reaction time 0.5h obtains hydrogel M1；
S2,0 DEG C will be cooled in advance in the hydrochloric acid of a concentration of 1mol/L of hydrogel M1 addition 100mL；Again by 0.2g NaNO2Add
Enter in 4mL deionized waters, measures the HBF that 32mL mass fractions are 4wt%4The two is cooled to 0 DEG C by solution in advance respectively；In ice water
The NaNO after precooling is added dropwise in bath into the hydrochloric acid containing hydrogel M12HBF after solution and precooling4Then solution carries out diazonium
Change reaction, diazo-reaction temperature is 0 DEG C, and the diazo-reaction time is 0.5h, and deionized water washs to obtain hydrogel M2；
S3, the sulfuric acid solution that the aniline monomer that 10mL molar concentrations are 0.01mol/L is dissolved in a concentration of 0.5mol/L
In, hydrogel M2 is added, 6h is impregnated, is cooled to 0 DEG C in advance and obtains the first mixed liquor；0.023g ammonium persulfates are dissolved in 3mL to rub
In the sulfuric acid solution of your a concentration of 0.5mol/L, it is cooled to 0 DEG C in advance, obtains the second mixed liquor；By the second mixed liquor in ice-water bath
It is added dropwise in the first mixed liquor, then carries out polymerisation, polymeric reaction temperature is 0 DEG C, polymerization reaction time 2h, and sulfuric acid is molten
Liquid washs 3~5 times, is placed in drying in 60 DEG C of baking ovens and completely, obtains three-dimensional net structure polyaniline/graphene/silicon composite material.
Embodiment 4
A kind of three-dimensional net structure polyaniline/graphene/silicon composite material and preparation method thereof, includes the following steps：
S1,0.288g p-phenylenediamine is added in 100mL deionized waters, 50 DEG C of stirring in water bath dissolvings add 0.684g
The sub- silicon of oxidation is stirred dispersion, is subsequently added into the graphene oxide dispersion that 12mL mass fractions are 3mg/mL, is uniformly dispersed,
Then hydro-thermal reaction is carried out, hydrothermal temperature is 120 DEG C, and the hydro-thermal reaction time 0.5h obtains hydrogel M1；
S2,0 DEG C will be cooled in advance in the hydrochloric acid of a concentration of 1mol/L of hydrogel M1 addition 100mL；Again by 0.2g NaNO2Add
Enter in 4mL deionized waters, measures the HBF that 32mL mass fractions are 4wt%4The two is cooled to 0 DEG C by solution in advance respectively；In ice water
The NaNO after precooling is added dropwise in bath into the hydrochloric acid containing hydrogel M12HBF after solution and precooling4Then solution carries out diazonium
Change reaction, diazo-reaction temperature is 0 DEG C, and the diazo-reaction time is 0.5h, and deionized water washs to obtain hydrogel M2；
S3, the sulfuric acid solution that the aniline monomer that 10mL molar concentrations are 0.01mol/L is dissolved in a concentration of 0.5mol/L
In, hydrogel M2 is added, 6h is impregnated, is cooled to 0 DEG C in advance and obtains the first mixed liquor；0.023g ammonium persulfates are dissolved in 3mL to rub
In the sulfuric acid solution of your a concentration of 0.5mol/L, it is cooled to 0 DEG C in advance, obtains the second mixed liquor；By the second mixed liquor in ice-water bath
It is added dropwise in the first mixed liquor, then carries out polymerisation, polymeric reaction temperature is 0 DEG C, polymerization reaction time 2h, and sulfuric acid is molten
Liquid washs 3~5 times, is placed in drying in 60 DEG C of baking ovens and completely, obtains three-dimensional net structure polyaniline/graphene/silicon composite material.
Comparative example
By nano-silicon, Super-P, LA133 according to 8:1:1 carries out abrasive material, closes slurry, coating, assembles button CR2016 batteries,
It selects the EC+DMC solution of 1mol/L LiPF6 as electrolyte, carries out electrochemical property test.
Fig. 4 and Fig. 5 is the first charge-discharge curve and cycle performance figure that embodiment 1 and comparative example prepare material.In 0.1C
Under current density, present invention gained polyaniline/graphene/silicon composite material initial charge specific capacity is 2685mAh/g, and head effects are
The charge specific capacity of material is 2499mAh/g, capacity retention ratio 93% after 85%, 50 weeks；Nano silicon material used in comparative example
Initial charge specific capacity is 2244mAh/g, and coulombic efficiency is 61.7% for the first time, and the specific capacity after 30 weeks cycles only has 300mAh/
G, it was demonstrated that obtained greatly using polyaniline/graphene/silicon composite material cyclical stability of present invention gained three-dimensional net structure
It improves on ground.
The promotion of above-mentioned electrical property be due to polyaniline/graphene/silicon composite material be in three-dimensional net structure,
The transmission for not being only lithium ion provides path, moreover it is possible to buffer volume deformation of the silicon materials in charge and discharge process.In addition polyaniline
The interface performance of material can not only be improved, in the composite be in chain structure, in charge and discharge process for silicon particle it
Between electronics and ion channel are provided.Last graphene and polyaniline can also improve the electron conduction of silicon materials, reduce material
Polarization, improves the cyclical stability of silica-base material to a certain extent.
The foregoing is only a preferred embodiment of the present invention, but scope of protection of the present invention is not limited thereto,
Any one skilled in the art in the technical scope disclosed by the present invention, according to the technique and scheme of the present invention and its
Inventive concept is subject to equivalent substitution or change, should be covered by the protection scope of the present invention.
Claims (10)
1. a kind of three-dimensional net structure polyaniline/graphene/silicon composite material and preparation method thereof, which is characterized in that including walking as follows
Suddenly：
S1, stirring in water bath dissolving in deionized water is added in p-phenylenediamine, adds silicon source and be stirred dispersion, is subsequently added into oxygen
Graphite alkene is uniformly dispersed, and then carries out hydro-thermal reaction and obtains hydrogel M1；
S2, it hydrogel M1 is added in hydrochloric acid is pre-chilled, then by NaNO2Solution and HBF4Solution is pre-chilled respectively, in ice-water bath to containing
Have and the NaNO after precooling is added dropwise in the hydrochloric acid of hydrogel M12HBF after solution and precooling4Then solution carries out diazo-reaction and obtains
To hydrogel M2；
S3, aniline monomer is dissolved in sulfuric acid solution, adds hydrogel M2, impregnated, precooling obtains the first mixed liquor；Incited somebody to action
Ammonium sulfate is dissolved in sulfuric acid solution, and precooling obtains the second mixed liquor；The second mixed liquor first is added dropwise in ice-water bath to mix
It closes in liquid, adjusts temperature progress polymerisation and obtain three-dimensional net structure polyaniline/graphene/silicon composite material.
2. three-dimensional net structure polyaniline/graphene/silicon composite material and preparation method thereof, feature exist according to claim 1
In in S1, silicon source is at least one of silicon nanoparticle, silicon nanowires, silicon nano thin-film, the sub- silicon of oxidation.
3. three-dimensional net structure polyaniline/graphene/silicon composite material and preparation method thereof according to claim 1 or claim 2, feature
It is, in S1, the mass ratio of p-phenylenediamine and graphene oxide is 8~12：1；Preferably, in S1, silicon source and graphene oxide
Mass ratio be 7~57：3.
4. according to any one of the claim 1-3 three-dimensional net structure polyaniline/graphene/silicon composite material and preparation method thereofs,
It is characterized in that, in S1, bath temperature is 50~90 DEG C；Preferably, in S1, hydrothermal temperature is 120~200 DEG C, hydro-thermal
Reaction time is 0.5~10h.
5. according to any one of the claim 1-4 three-dimensional net structure polyaniline/graphene/silicon composite material and preparation method thereofs,
It is characterized in that, in S2, precooling temperature is 0 DEG C；Preferably, in S2, concentration of hydrochloric acid is 0.8~1.2mol/L.
6. according to any one of the claim 1-5 three-dimensional net structure polyaniline/graphene/silicon composite material and preparation method thereofs,
It is characterized in that, in S2, NaNO2NaNO in solution2With HBF4HBF in solution4Mass ratio be 1：1~4.
7. according to any one of the claim 1-6 three-dimensional net structure polyaniline/graphene/silicon composite material and preparation method thereofs,
It is characterized in that, in S2, diazo-reaction temperature is -10~20 DEG C, and the diazo-reaction time is 0.5~4h.
8. according to any one of the claim 1-7 three-dimensional net structure polyaniline/graphene/silicon composite material and preparation method thereofs,
It is characterized in that, in S3, soaking time is 2~10h；Preferably, in S3, precooling temperature is 0 DEG C.
9. according to any one of the claim 1-8 three-dimensional net structure polyaniline/graphene/silicon composite material and preparation method thereofs,
It is characterized in that, in S3, the molar ratio of aniline monomer and ammonium persulfate is 1：1~4；Preferably, in S3, the concentration of sulfuric acid solution
For 0.4~0.6mol/L.
10. according to any one of the claim 1-9 three-dimensional net structure polyaniline/graphene/silicon composite material and preparation method thereofs,
It is characterized in that, in S3, polymeric reaction temperature is -10~20 DEG C, and polymerization reaction time is 2~12h.
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