CN107556473A - The preparation method of graphene film polyaniline composite material with Specific surface area - Google Patents
The preparation method of graphene film polyaniline composite material with Specific surface area Download PDFInfo
- Publication number
- CN107556473A CN107556473A CN201710801326.8A CN201710801326A CN107556473A CN 107556473 A CN107556473 A CN 107556473A CN 201710801326 A CN201710801326 A CN 201710801326A CN 107556473 A CN107556473 A CN 107556473A
- Authority
- CN
- China
- Prior art keywords
- surface area
- specific surface
- graphene
- polyaniline
- preparation
- Prior art date
- Legal status (The legal status is an assumption and is not a legal conclusion. Google has not performed a legal analysis and makes no representation as to the accuracy of the status listed.)
- Pending
Links
Abstract
The invention discloses a kind of preparation method of the graphene film polyaniline composite material with Specific surface area.The composite has two-stage microstructure, the nanometer layer stacked configuration unit of layer composition, and the Specific surface area obtained by nanometer layer stacked configuration unit by the interaction stack assembly straggly including conjugation are sprawled including the nano-graphene piece as template and the polyaniline for being deposited on its surface.The preparation method is that using different sized nanostructures graphene films as template, polyaniline is deposited in its surface in situ controllable polymerization, obtain nanometer layer stacked configuration unit, this nanometer layer stacked configuration unit assembles the graphene film polyaniline composite material with Specific surface area by the interaction stacking straggly including conjugation.The composite of the present invention has two-stage microstructure and a large amount of nanoscale holes, can both improve the microstructure of polyaniline, the specific surface area of material can be significantly increased again, can effectively improve electrode material energy density and power density, extends cycle life.
Description
Technical field
The present invention relates to a kind of preparation method of energy device electrode material, more particularly to one kind to have Specific surface area
Graphene film-polyaniline composite material preparation method.
Background technology
In today of resource increasingly depleted, energy device has the function that very important during social development is promoted.
And the research emphasis of energy device is the improvement and innovation of electrode material, a kind of electrode material with unique texture how is designed
Material, energy density and can be improved and improve power density, turn into the task of top priority of energy device research.Graphene and polyaniline
It is still the key object of research as generally acknowledged excellent partner.
Graphene, numerous areas is related to by called optical imaging, its application as a kind of excellent conductive material:Energy
Source, sensing, corrosion etc..And in energy field, now widely used is graphene oxide and redox graphene, this
Although class graphene has, dissolubility is good, and the advantages such as price is low, it is good that contained a large amount of oxygen-containing functional groups limit its
The performance of electric conductivity.In addition to the influence of functional group, it there is also an issue:Big size graphene based composites intensive heap layer by layer
It is folded, reduce specific surface area, be unfavorable for the absorption of ion.And by based on the nano-graphene piece without oxygen-containing functional group,
Problem above can then be solved by constructing a kind of multi-pore structure.
Polyaniline is known as a kind of conducting polymer, excellent fake capacitance, good environmental stability etc.
It is set to be received much concern in energy field.But aniline to form bulk deposition because self assembly acts in the course of the polymerization process, is unfavorable for
Charge transfer, it is also easy to produce overpotential and polarizes, cause the peroxidating of polyaniline, influences its cycle life.Therefore, conduction is utilized
Property good graphene film controllable deposition polyaniline, change the microstructure of polyaniline, have for the performance for improving electrode material
Significance.
In recent years, the research for graphene-polyaniline composite material is numerous, has also made significant headway.Min Yonggang
Et al.(CN 104558597 A)Using graphene oxide as raw material, by compound with aniline under carbonate effect, one is constructed
Gel graphene oxide-polyaniline material of the kind with loose structure.Further above material is reduced in the basic conditions,
Oxygen-containing functional group is removed, obtains a kind of graphene-polyaniline porous material.This porous material has high specific surface area, ion
The advantages such as transmission speed is fast.But due to it is raw materials used be graphene oxide, even if being reduced by alkali, surface certainly exists portion
Divide oxygen-containing functional group, so as to influence its electric conductivity.Again because it selects large stretch of graphene, the hole of construction is mostly micron order rather than received
Meter level, the raising of specific surface area is limited, better performance can not be played.
The content of the invention
In view of the above-mentioned problems, it is an object of the invention to provide a kind of graphene film-polyaniline with Specific surface area
The preparation method of composite, the composite have a large amount of nanoscale holes being made up of two-stage microstructure, can both changed
The microstructure of kind polyaniline, the specific surface area of material can be significantly increased again, effectively improve the performance of electrode material.
Composite two-stage microstructure prepared by the present invention is shown as:As template nano-graphene piece and be deposited on
The polyaniline on its surface sprawl layer composition nanometer layer stacked configuration unit, and by nanometer layer stacked configuration unit by including
The Specific surface area that interaction stack assembly straggly including conjugation obtains.
Nanometer layer stacked configuration unit be using size as(10~200)nm ×(10~200)Nm, thickness are 1 ~ 3 layer of nanometer
Graphene film is template, deposits to form polyaniline and sprawl layer and obtain in its surface in situ controllable polymerization;And this nanometer of layered laminate
By the interaction stacking straggly including conjugation between construction unit, assembling obtain containing a large amount of yardsticks 10 ~
The Specific surface area of 400nm holes, thus construct out graphene film-polyaniline composite material of Specific surface area.
The flatness for being unique in that nano-graphene piece is good and electric conductivity of nanometer layer stacked configuration unit make to gather
Aniline can controllable polymerization in situ deposition spread over nano-graphene piece surface, so as to rapid dispersion electric charge, reduce polyphenyl
The overpotential of amine, polarization is eliminated, the peroxidating of polyaniline is prevented, increases the service life;And nanometer layer stacked configuration unit assembles
Into Specific surface area, then the specific surface area of material can be significantly increased, be advantageous to the abundant contact between electrolyte and material,
The absorption of ion is effectively increased, reduces interface impedance.
Preparation method of the present invention comprises the following steps that:
1. the preparation of nano-graphene piece:
(1)Compound concentration is 0.001~0.01mg/mL metabisulfite solution, is placed in thermostatic mixer;Electrode uses commercially available stone
Black paper, cleaned, dried repeatedly using absolute ethyl alcohol and deionized water;The graphite paper curled is placed in metabisulfite solution and soaked
Moisten, more than 30min is electrolysed under subsequent 5~20V of constant potential;
(2)Neopelex is added in above-mentioned electrolyte or 1-METHYLPYRROLIDONE, stirring are sufficiently mixed, after mixing
Its concentration is 0.5~10mg/mL, and then ultrasound is peeled off, 200~1800W of power, to prevent temperature is too high from causing solution to evaporate,
Ultrasound is carried out under water conservation, and ultrasonic time is not less than 10min;By aforesaid liquid high speed centrifugation, rotating speed is not less than 9000 r/
Min, time are not less than 10min, take supernatant, obtain the mixed liquor containing different sized nanostructures graphene films;
2. the preparation of Specific surface area graphene film-polyaniline composite material:
(1)The mixed liquor of above-mentioned different sized nanostructures graphene films is taken, is separately added into aniline and sulfuric acid, stirring makes it fully mixed
Close, the concentration of aniline in mixed liquor is 0.0001~1mol/L;Sulfuric acid concentration is 0.1~1mol/L;
(2)It will be added dropwise to dropwise in above-mentioned mixed liquor with the oxidant of aniline equimolar concentration, more than polyase 13 0min, reaction temperature
0~20 DEG C of degree, obtains the graphene film-polyaniline composite material with Specific surface area.
Advantages of the present invention:
(1)Prepared graphene is to be without oxygen-containing functional group, nano level graphene film, size(10~200)nm ×(10~
200)Nm, thickness are 1 ~ 3 layer, have good flatness and electric conductivity, as the template for preparing nanometer layer stacked configuration unit.
(2)The nanometer layer stacked configuration unit formed has given full play to the plane template and electric action of nano-graphene piece, can be with
Avoid the polarization of polyaniline itself.(3)The Specific surface area formed shows a large amount of nanoscale holes, can both improve poly-
The microstructure of aniline, the specific surface area of material can be significantly increased again, effectively increase the performance of electrode material.In this, as
Electrode material is applied to be beneficial to the energy density and power density that improve device in energy storage device, extends cycle life, this
Development for new energy materialses is significant.
Brief description of the drawings
Fig. 1 is the preparation process schematic diagram of the present invention.
Fig. 2 is the TEM figures of nano-graphene piece prepared by the present invention.
Fig. 3 is the AFM figures of nano-graphene piece prepared by the present invention.
Fig. 4 is the SEM figures of graphene film-polyaniline composite material of Specific surface area prepared by the present invention.
Fig. 5 is the TEM figures of graphene film-polyaniline composite material of Specific surface area prepared by the present invention.
Fig. 6 is the CV figures of graphene film-polyaniline composite material of Specific surface area prepared by the present invention.
Embodiment
Describe the present invention in detail below in conjunction with the accompanying drawings and by specific embodiment.
Embodiment 1:
(1)The metabisulfite solution that 80mL concentration is 0.01mg/mL is prepared, is placed in thermostatic mixer 25 DEG C of stirring 30min, it is standby
With;Using two 70 × 80mm commercially available graphite paper as electrode, cleaned, dried repeatedly using absolute ethyl alcohol and deionized water;
The graphite paper curled is placed in metabisulfite solution and infiltrates 20min, 5h is electrolysed under subsequent constant potential 10V.(2)In above-mentioned electrolyte
Middle addition neopelex, stirring are sufficiently mixed, and its concentration is 1mg/mL after mixing, and then ultrasound is peeled off, and power is
1600W, to prevent temperature is too high from causing solution to evaporate, ultrasound is carried out under water conservation, ultrasonic time 1h.Electrolyte exists
Ultracentrifugation under 13000r/min rotating speeds, centrifugation time 60min.Supernatant is taken, is obtained containing different sized nanostructures graphite
The mixed liquor of alkene piece.(3)The mixed liquor of the above-mentioned different sized nanostructures graphene films of 15mL is taken, aniline and sulfuric acid is separately added into, stirs
Mixing is sufficiently mixed it, and the concentration of aniline in mixed liquor is 0.02mol/L, sulfuric acid concentration 0.25mol/L.(4)Will be with aniline
The oxidant of equimolar concentration is added dropwise in above-mentioned mixed liquor dropwise, polymerize 10h at 0 DEG C, obtains having Specific surface area
Graphene film-polyaniline composite material.
Embodiment 2:
(1)The metabisulfite solution that 80mL concentration is 0.005mg/mL is prepared, is placed in thermostatic mixer 25 DEG C of stirring 30min, it is standby
With;Using two 70 × 80mm commercially available graphite paper as electrode, cleaned, dried repeatedly using absolute ethyl alcohol and deionized water;
The graphite paper curled is placed in metabisulfite solution and infiltrates 20min, 5h is electrolysed under subsequent constant potential 10V.(2)In above-mentioned electrolyte
Middle addition neopelex, stirring are sufficiently mixed, and its concentration is 1mg/mL after mixing, and then ultrasound is peeled off, and power is
1600W, to prevent temperature is too high from causing solution to evaporate, ultrasound is carried out under water conservation, ultrasonic time 1h.Electrolyte exists
Ultracentrifugation under 13000r/min rotating speeds.Supernatant is taken, obtains the mixed liquor containing different sized nanostructures graphene films.(3)
The mixed liquor of the above-mentioned different sized nanostructures graphene films of 15mL is taken, is separately added into aniline and sulfuric acid, stirring is sufficiently mixed it, mixes
The concentration of aniline closed in liquid is 0.05mol/L, sulfuric acid concentration 0.25mol/L.(4)By the oxidant with aniline equimolar concentration
It is added dropwise to dropwise in above-mentioned mixed liquor, polymerize 10h at 0 DEG C, obtains having graphene film-polyaniline of Specific surface area compound
Material.
Embodiment 3:
(1)The metabisulfite solution that 80mL concentration is 0.001mg/mL is prepared, is placed in thermostatic mixer 25 DEG C of stirring 30min, it is standby
With;Using two 70 × 80mm commercially available graphite paper as electrode, cleaned, dried repeatedly using absolute ethyl alcohol and deionized water;
The graphite paper curled is placed in metabisulfite solution and infiltrates 20min, 5h is electrolysed under subsequent constant potential 10V.(2)In above-mentioned electrolyte
Middle addition 1-METHYLPYRROLIDONE, stirring are sufficiently mixed, and its concentration is 1.5mg/mL after mixing, and then ultrasound is peeled off, and power is
1600W, to prevent temperature is too high from causing solution to evaporate, ultrasound is carried out under water conservation, ultrasonic time 1h.Electrolyte exists
Ultracentrifugation under 90000,11000,15000,18000r/min rotating speeds, centrifugation time 60min.Supernatant is taken, is contained
There is the mixed liquor of different sized nanostructures graphene films(3)The mixed liquor of the above-mentioned different sized nanostructures graphene films of 15mL is taken, respectively
Aniline and sulfuric acid are added, stirring is sufficiently mixed it, and the concentration of aniline in mixed liquor is 0.05mol/L, and sulfuric acid concentration is
0.25mol/L.(4)It will be dropwise added dropwise in above-mentioned mixed liquor with the oxidant of aniline equimolar concentration, polymerize 10h at 0 DEG C, obtain
To graphene film-polyaniline composite material with Specific surface area.
Fig. 2, Fig. 3 are that the TEM and AFM of graphene film scheme.It can be seen that prepared graphene is the few layer of nanometer
Laminated structure, size are(50~100)nm ×(50~100)Nm, because carbon atom thickness in monolayer is 0.33nm, so thickness is 1
~ 3 layers.Fig. 4, Fig. 5 are SEM and the TEM figure of graphene film-polyaniline composite material of Specific surface area.Can from figure
Go out, different size layer stacked configuration unit accumulations straggly, containing a large amount of nanoscale holes, similar network structure.It is more directly perceived in TEM
Show, the pore size of composite is 50 ~ 200nm, is nanometer porous gap structure.Fig. 6 is Specific surface area
The CV figures of graphene film-polyaniline composite material.As shown in fig. 6, graphene film-polyaniline of prepared Specific surface area is multiple
Condensation material shows good chemical property, under high sweep speed, still keeps very perfect peak type, this also mainly with
Electrolyte intermediate ion rapid, high volume absorption under a large amount of pore structures is relevant.
Claims (7)
1. a kind of graphene film-polyaniline composite material with Specific surface area, it is characterised in that composite has two
Level microstructure, including nano-graphene piece as template and be deposited on the polyaniline on its surface and sprawl the nanometer layer of layer composition
Stacked configuration unit, and the interaction stacked group straggly including conjugation is passed through by nanometer layer stacked configuration unit
Fill obtained Specific surface area.
2. composite according to claim 1, it is characterised in that the size of the nano-graphene piece is(10~200)
nm ×(10~200)Nm, thickness are 1~3 layer;The pore size of the network structure is 10~400nm.
3. a kind of preparation method of graphene film-polyaniline composite material of the Specific surface area described in claim 1, it is special
Sign comprises the following steps:
(1)Using graphite paper as electrode, graphite paper is placed in metabisulfite solution and infiltrated as electrolyte by metabisulfite solution, with
More than 30min is electrolysed under 5~20V of constant potential afterwards;
(2)Neopelex is added in above-mentioned electrolyte or 1-METHYLPYRROLIDONE, stirring are sufficiently mixed, Ran Houchao
Sound is peeled off, and 200~1800W of power, the time is not less than 10min;Aforesaid liquid is not less than under 9000 r/min at a high speed with rotating speed
Centrifugation, time are not less than 10min, take supernatant, obtain the mixed liquor containing different sized nanostructures graphene films;
(3)The mixed liquor of above-mentioned different sized nanostructures graphene films is taken, is separately added into aniline and sulfuric acid, stirring makes it fully mixed
Close;
(4)It will be added dropwise to dropwise in above-mentioned mixed liquor with the oxidant of aniline equimolar concentration, more than polyase 13 0min, reaction temperature
0~20 DEG C of degree, obtains the graphene film-polyaniline composite material with Specific surface area.
4. preparation method according to claim 3, it is characterised in that the step(1)Middle sodium sulfate concentration be 0.001~
0.01mg/mL。
5. preparation method according to claim 3, it is characterised in that the step(2)DBSA after middle mixing
Sodium or 1-METHYLPYRROLIDONE concentration are 0.5~10mg/mL.
6. preparation method according to claim 3, it is characterised in that the step(3)Concentration of aniline is after middle mixing
0.0001~1mol/L;Sulfuric acid concentration is 0.1~1mol/L.
7. preparation method according to claim 3, it is characterised in that the step(4)Middle oxidant is ammonium persulfate or double
Oxygen water.
Priority Applications (1)
Application Number | Priority Date | Filing Date | Title |
---|---|---|---|
CN201710801326.8A CN107556473A (en) | 2017-09-07 | 2017-09-07 | The preparation method of graphene film polyaniline composite material with Specific surface area |
Applications Claiming Priority (1)
Application Number | Priority Date | Filing Date | Title |
---|---|---|---|
CN201710801326.8A CN107556473A (en) | 2017-09-07 | 2017-09-07 | The preparation method of graphene film polyaniline composite material with Specific surface area |
Publications (1)
Publication Number | Publication Date |
---|---|
CN107556473A true CN107556473A (en) | 2018-01-09 |
Family
ID=60979681
Family Applications (1)
Application Number | Title | Priority Date | Filing Date |
---|---|---|---|
CN201710801326.8A Pending CN107556473A (en) | 2017-09-07 | 2017-09-07 | The preparation method of graphene film polyaniline composite material with Specific surface area |
Country Status (1)
Country | Link |
---|---|
CN (1) | CN107556473A (en) |
Cited By (1)
Publication number | Priority date | Publication date | Assignee | Title |
---|---|---|---|---|
CN110980707A (en) * | 2019-12-09 | 2020-04-10 | 上海烯望材料科技有限公司 | Method for preparing few-layer graphene through mechanical stripping and few-layer graphene |
Citations (1)
Publication number | Priority date | Publication date | Assignee | Title |
---|---|---|---|---|
CN106169379A (en) * | 2016-09-28 | 2016-11-30 | 唐山学院 | A kind of method preparing graphite paper/CNT graphene/polyaniline flexible compound electrode |
-
2017
- 2017-09-07 CN CN201710801326.8A patent/CN107556473A/en active Pending
Patent Citations (1)
Publication number | Priority date | Publication date | Assignee | Title |
---|---|---|---|---|
CN106169379A (en) * | 2016-09-28 | 2016-11-30 | 唐山学院 | A kind of method preparing graphite paper/CNT graphene/polyaniline flexible compound electrode |
Cited By (1)
Publication number | Priority date | Publication date | Assignee | Title |
---|---|---|---|---|
CN110980707A (en) * | 2019-12-09 | 2020-04-10 | 上海烯望材料科技有限公司 | Method for preparing few-layer graphene through mechanical stripping and few-layer graphene |
Similar Documents
Publication | Publication Date | Title |
---|---|---|
Wang et al. | Cellulose‐based supercapacitors: material and performance considerations | |
Shown et al. | Conducting polymer‐based flexible supercapacitor | |
Yin et al. | Advanced deformable all-in-one hydrogel supercapacitor based on conducting polymer: Toward integrated mechanical and capacitive performance | |
Hu et al. | Binder-free bonding of modularized MXene thin films into thick film electrodes for on-chip micro-supercapacitors with enhanced areal performance metrics | |
Zheng et al. | Nanostructured paper for flexible energy and electronic devices | |
Chang et al. | Polyaniline/carbon nanotube nanocomposite electrodes with biomimetic hierarchical structure for supercapacitors | |
Fan et al. | 3D conductive network-based free-standing PANI–RGO–MWNTs hybrid film for high-performance flexible supercapacitor | |
Yin et al. | Well-constructed CNT mesh/PANI nanoporous electrode and its thickness effect on the supercapacitor properties | |
CN104992853A (en) | Method of preparing flexible bendable thin film electrode of supercapacitor | |
WO2020147567A1 (en) | Functional ink suitable for 3d printing and preparation method thereof | |
CN105118688B (en) | A kind of preparation method and applications of bacteria cellulose/activated carbon fiber/graphene film material | |
Yin et al. | “All-in-Gel” design for supercapacitors towards solid-state energy devices with thermal and mechanical compliance | |
Tang et al. | Scalable manufacturing of leaf‐like MXene/Ag NWs/cellulose composite paper electrode for all‐solid‐state supercapacitor | |
Chen et al. | Robust bioinspired MXene–hemicellulose composite films with excellent electrical conductivity for multifunctional electrode applications | |
Wang et al. | Na-ion conducting gel polymer membrane for flexible supercapacitor application | |
CN108630462A (en) | Nanofiber-based integrated film ultracapacitor of one kind and preparation method thereof | |
WO2009107875A1 (en) | Ionic liquid-containing electrode membrane and electrode, process for producing the electrode membrane and the electrode, and electric storage device | |
Nizam et al. | Nanocellulose-based composites: fundamentals and applications in electronics | |
CN106158405A (en) | A kind of nickel hydroxide/graphene nanocomposite material and preparation method thereof, electrode of super capacitor and ultracapacitor | |
Yu et al. | Solid‐State Hybrid Fibrous Supercapacitors Produced by Dead‐End Tube Membrane Ultrafiltration | |
CN109192543A (en) | A kind of graphene oxide based binder and preparation method thereof and electrode slice | |
CN105271204A (en) | Graphene/graphene nanoribbon compound hydrogel and preparation method thereof | |
Pan et al. | Hierarchical vertically aligned titanium carbide (MXene) array for flexible all-solid-state supercapacitor with high volumetric capacitance | |
CN104979103A (en) | Preparation method of helical line type asymmetric super capacitor | |
Liu et al. | Ti3C2Tx/RGO//PANI/RGO all-solid-state asymmetrical fiber supercapacitor with high energy density and superior flexibility |
Legal Events
Date | Code | Title | Description |
---|---|---|---|
PB01 | Publication | ||
PB01 | Publication | ||
SE01 | Entry into force of request for substantive examination | ||
SE01 | Entry into force of request for substantive examination | ||
RJ01 | Rejection of invention patent application after publication | ||
RJ01 | Rejection of invention patent application after publication |
Application publication date: 20180109 |