CN109110744A - A kind of preparation method of hollow tubular polyaniline carbon material - Google Patents
A kind of preparation method of hollow tubular polyaniline carbon material Download PDFInfo
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Abstract
The present invention discloses a kind of preparation method of hollow tubular polyaniline carbon material, include the following steps: to take two parts of acid solutions, aniline is added in portion, hydrogen peroxide is added after stirring and dissolving, stands reaction 1-5h, ammonium persulfate is added in another, two parts of solution are mixed rapidly after mixing evenly, reaction 1-48h is stood, is separated by solid-liquid separation, solid is through dry persursor material；The persursor material is heat-treated 0.5-24h at inert atmosphere, 400-1000 DEG C, obtains polyaniline carbon material.The present invention is easy to control with easy to operate, at low cost, product purity, pollutant is few, prepares resulting materials in hollow tubular structures and has a large amount of micropore and the good beneficial effect of chemical property.
Description
Technical field
The present invention relates to carbon material technical fields, and in particular to a kind of preparation side of hollow tubular polyaniline carbon material
Method.
Background technique
The energy is that the mankind participate in the indispensable material base of social activities, with the sharply consumption of global energy and environment
Continuous deterioration, the energy seems of crucial importance.Supercapacitor is as one of energy storage device, the strong, environment with charging and discharging capabilities
Friendly, the advantages that having extended cycle life, possess market potential and application value.According to active material difference, supercapacitor can divide
For carbon material, metal oxide, conducting polymer supercapacitor.Carbon aerogels belong to typical amorphous carbon material, specific surface
Product height (600 ~ 1000 m2·g-1), itself hole is that nanoscale, even aperture distribution, but preparation cost are high, and hardly possible realizes scale
Production.Carbon nanotube application study is active, but specific surface area is low, and electrolyte is difficult to enter in pipe, easy to reunite to be not easy to disperse, cost
It is high.To meet higher commercial requirements, need to improve carbon material capacitive property.There are two ways to improving specific capacitance, first is that excellent
Polarizing electrode material structure, second is that introducing fake capacitance in electric double layer capacitance.N doping has caused researcher's extensive concern.In element
In periodic table, nitrogen and carbon are adjacent, and atomic diameter is close, when nitrogen replaces carbon, material structure will not be caused significantly abnormal
Deformation.
Introducing nitrogen-atoms, there are mainly two types of methods: rich nitrogen presoma direct carborization and post treatment method.Polyaniline is a kind of
Outstanding rich nitrogen is carbonized presoma, nitrogen containing about 15% and 79% carbon.Its preparation cost is low, generate technical maturity,
Synthesis process is simple, environmental stability is high, and chemical structure is controllable, carbonization rate is high, hole is abundant, impurity content is low, is
Pyrolysis prepares the ideal persursor material of nitrogen-doped carbon material.
The synthesis of polyaniline is with a long history, and preparation process is simple, and adjusting synthesis condition can control the pattern of polyaniline.Again
Using polyaniline as rich nitrogen carbonization presoma, the nitrogen-doped carbon material with pattern Modulatory character can be obtained.First synthesize polyphenyl
Amine, then pyrolysis processing is carried out, ingredient unstable in carbon skeleton is removed, nitrogen-doped carbon material can be obtained.
Yang Miao seedling et al. is published an article in Electrochimica Acta, using polyaniline nanotube as presoma, with KOH
A kind of nitrogen-doped carbon material is prepared through carbonization treatment for activator, using the material as the electrode material of supercapacitor
Material is 0.1 Ag in current density-1When specific capacitance be 163 Fg-1；It has however been found that destroy polyaniline original for high temperature
Pattern.
Yuan Ding victory et al. is delivered in Electrochemistry Communications does dopant acid using sulfuric acid, synthesizes
Polyaniline nano-line as the carbon matrix precursor under different temperatures, rich nitrogen carbon nanocoils are prepared using direct carborization.Correspond to
Its higher middle boring ratio and N doping appropriate, 700 DEG C of carbonized product have optimal chemical property, which are made
It is 0.1 Ag in current density for the electrode material of supercapacitor-1When specific capacitance be 329 Fg-1.But above-mentioned side
Method needs to use during synthesized polyaniline CTAB as antistructurizing agent, very high to requirements such as the mixed uniformitys,
Very high to the operation level requirement of operator when being especially mass produced, product purity is difficult to control, and side reaction is more.In addition,
CTAB itself is not involved in reaction, eventually generates a large amount of pollutant, and environment is unfriendly, and cost is very high.
Summary of the invention
It is an object of the present invention in view of the above shortcomings of the prior art, propose it is a kind of it is easy to operate, at low cost,
Product purity is easy to control, pollutant is few, prepares resulting materials in hollow tubular structures and has a large amount of micropore and electrochemistry
The preparation method of hollow tubular polyaniline carbon material of good performance.
The present invention solve technical problem the technical solution adopted is that, propose a kind of system of hollow tubular polyaniline carbon material
Preparation Method, it is characterised in that the following steps are included:
Step 1: taking two parts of acid solutions, and portion is added aniline, hydrogen peroxide is added after stirring and dissolving, stands reaction 1-5h, another
Ammonium persulfate is added, after mixing evenly mixes two parts of solution rapidly, stands reaction 1-48h, is separated by solid-liquid separation, solid is through dry
Persursor material；The acid solution is one of phosphoric acid, oxalic acid, citric acid, tartaric acid, sulfuric acid, p-methyl benzenesulfonic acid or several
Any mixed solution of ratio of kind；
Step 2: the persursor material is heat-treated 0.5-24h at inert atmosphere, 400-1000 DEG C, obtains polyaniline
Carbon material.
Polyaniline carbon material of the present invention refers to, using polyaniline as presoma, the carbon that is prepared through high temperature pyrolysis
Material.
Preferably, the concentration of the acid solution is calculated as 0.01-0.1 mol/L with hydrionic concentration in step 1.Institute
It states hydrionic concentration to refer to, acid is considered as strong acid, the hydrionic concentration generated when ionizing completely in aqueous solution.
Preferably, the additional amount of the hydrogen peroxide is calculated as mL/100 (2-5) with the volume of acid solution in step 1
mL。
Preferably, the additional amount of the aniline is calculated as (1-4) mL/100 mL with the volume of acid solution in step 1.
Preferably, in step 1, the additional amount of the ammonium persulfate with the volume of acid solution be calculated as (2.35-9.4) g/
100 mL。
Preferably, solvent used by the acid solution is the aqueous solution of ethyl alcohol in step 1；The water of the ethyl alcohol
In solution, the volume ratio of ethyl alcohol and water is (0.1-1): 1.
Preferably, two parts of acid solutions are p-methyl benzenesulfonic acid solution in step 1.
Preferably, described first time for standing reaction is 2-4h in step 1.
Preferably, described second time for standing reaction is 12-24h in step 1.
Preferably, the method for the separation of solid and liquid is filtering or centrifugation in step 1.
Preferably, the drying is to dry 12-24h at air atmosphere, 50-60 DEG C in step 1.
Preferably, the condition of the heat treatment is to be heat-treated 2h at nitrogen atmosphere, 600-800 DEG C in step 2.
A kind of preparation method of hollow tubular polyaniline carbon material provided by the invention has the following beneficial effects:
1, using direct mixing method, with a variety of acid for dopant, in-situ polymerization prepares polyaniline fiber presoma, and passes through a step
Carbonization obtains polyaniline carbon material, easy to operate and safe, at low cost, product purity is high；It can be by selecting different acid
For dopant, the persursor material of control synthesis different-shape；It is not required to use the constitution controllers such as CTAB, pollutant is few；It is in situ
Polymerization reaction carries out under static conditions, without stirring for significantly reducing energy consumption.
2, oxidant is added using two-stage method, a small amount of hydrogen peroxide is added in the first stage, and oxidability is low, and early period generates polyphenyl
Amine intermediate oxidation state forms oligomer, increases reaction system activated centre, second stage ammonium persulfate causes long chain polymeric, raw
At uniform long tubular structure.
3, the persursor material thermal stability being prepared using this method is good, still maintains original after 800 DEG C of high-temperature process
Some tubular structures.
4, preparation gained polyaniline carbon material is in hollow tubular structures, is conducive to the transmission and infiltration of electrolyte；Moreover,
There are a large amount of micropore, central hole structure on tube wall, pore-size distribution is wide, and specific surface area is up to 1025 m2·g-1, reaction active site
Point is more；When being applied to supercapacitor as electrode material, high specific capacitance is shown, in 5 mV s-1Current potential is swept under speed, than electricity
Appearance reaches 180 Fg-1；Good capacity retention is shown, is had extended cycle life, than electricity after 1000 charge and discharge cycles
Holding conservation rate is more than 97 %；In addition, electrochemical impedance is low, high rate performance is good, and current density is from 0.5 A g-1 Increase to 5
A g-1, it is smaller that specific capacitance reduces amplitude.
5, solvent used by acid solution is the aqueous solution of ethyl alcohol, and the volume ratio of ethyl alcohol and water is (0.1-1): 1, in solution
Contain suitable ethyl alcohol, on the one hand, be conducive to the dissolution of organic acid and participate in reacting as dopant acid, on the other hand, Ke Yigai
Become the rate of in-situ polymerization, and then changes the pattern of the persursor material of synthesis.
Detailed description of the invention
Fig. 1 is the XRD diagram of PANI, PANI-C600, PANI-C700, PANI-C800 in the embodiment of the present invention 1.
Fig. 2 is the SEM figure of PANI-C800 in the embodiment of the present invention 1.
Fig. 3 is the TEM figure of PANI-C800 in the embodiment of the present invention 1.
Fig. 4 (a) is the isothermal nitrogen adsorption desorption curve of PANI, PANI-C600, PANI-C700, PANI-C800；Fig. 4 (b)
It is the graph of pore diameter distribution of PANI-C600, PANI-C700, PANI-C800.
It is in the embodiment of the present invention 1 that Fig. 5 a, which is the cyclic voltammetry curve figure of PANI-C700 in the embodiment of the present invention 1, Fig. 5 b,
The cyclic voltammetry curve figure of PANI-C800.
Fig. 6 is the SEM figure of material 3 in comparative example 2 of the present invention, material 4, material 5, material 6, material 11.
Fig. 7 is cyclic voltammetry curve figure of the material 3 under different scanning rates in comparative example 2 of the present invention.
Fig. 8 is cyclic voltammetry curve figure of the material 4 under different scanning rates in comparative example 2 of the present invention.
Fig. 9 is cyclic voltammetry curve figure of the material 5 under different scanning rates in comparative example 2 of the present invention.
Figure 10 is cyclic voltammetry curve figure of the material 6 under different scanning rates in comparative example 2 of the present invention.
Specific embodiment
Following is a specific embodiment of the present invention in conjunction with the accompanying drawings, technical scheme of the present invention will be further described,
However, the present invention is not limited to these examples.
Embodiment 1
Configure two parts of concentration be 0.05mol/L(with hydrionic densimeter) 500 mL p-methyl benzenesulfonic acid solution；Portion adds
Enter 10 mL aniline monomers, 10 mL hydrogen peroxide are added after stirring and dissolving, stand reaction 3h, 23.9 g persulfuric acid are added in another
Ammonium, 10 min of magnetic agitation is to being completely dissolved.Above-mentioned two parts of solution is mixed rapidly, stands 24 h of reaction at room temperature.It will be abundant
The sample of reaction carries out decompression suction filtration, and is repeatedly washed with deionized water, and until filtrate becomes colorless, obtained solid product is 60
It is dried for standby at DEG C, obtains blackish green persursor material, be labeled as PANI.Gained persursor material is divided into three parts, respectively
It is put into graphite crucible, is passed through nitrogen and is protected, control heating rate is 7 DEG C of min-1, it is warming up to 600 DEG C, 700 respectively
DEG C, 800 DEG C, heat preservation 2 h obtain the polyaniline carbon material of three parts of black, be respectively labeled as PANI-C600, PANI-C700,
PANI-C800。
Above-mentioned polyaniline carbon material, acetylene black and the PVDF being prepared is weighed by the mass ratio of 8:1:1,
Few drops of N-Methyl pyrrolidone reagents are added after mixed grinding, magnetic agitation handles 8 h, obtains active material slurry.By one
Quantitative slurry is coated uniformly in the titanium sheet through cleaning, 1 × 1 cm of coated area2.By the electrode prepared in 80 DEG C of drums
Dry 12 h in wind baking oven.
PANI, PANI-C600, PANI-C700, PANI-C800 material being prepared using the above method are carried out X to penetrate
Line diffraction analysis (abbreviation XRD, similarly hereinafter), the X ' Pert PRO type X-ray that experiment is produced using PANalytical company of Holland
Diffraction spectrometers result is as shown in Figure 1.As can see from Figure 1: there is polyaniline fibre at 2 θ=18 °, 20 °, 25 ° in PANI
The characteristic peak of dimension, respectively corresponds (011), (020), (200) three crystal faces of polyaniline, and the characteristic peak at 2 θ=18 ° is
Due to polyaniline molecule pi-pi accumulation interplanar distance from.Characteristic peak at 2 θ=20 ° is the period due to main polymer chain
Property parallel construction, the characteristic peak at 2 θ=25 ° is the periodic vertical structure due to main polymer chain, is shown to methylbenzene sulphur
The polyaniline crystallinity of acid doping is preferable.PANI-C600, PANI-C700, PANI-C800 material after being carbonized under different temperatures,
The characteristic peak of polyaniline disappears, and two wider diffraction maximums occurs all at 24 ° and 43 ° in polyaniline fiber carbonized product, this two
A peak respectively represents (002) and (101) crystal face of graphite type material, shows that preparing resulting polyaniline carbon material is mainly nothing
The carbon of sizing, degree of graphitization are low.
The PANI-C800 being prepared using the above method is subjected to pattern table using scanning electron microscope (abbreviation SEM, similarly hereinafter)
Sign studies its microscopic appearance, the Hitachi S4700 type scanning electron microscope of Hitachi company of Japan, knot is used in experiment
Fruit is as shown in Figure 2.From Fig. 2, a, b are respectively the SEM characterization result of PANI-C800 material under different enlargement ratios, Ke Yiqing
See clearly, tubular structure is still kept after 800 DEG C of high-temperature process, and surface is more smooth, and average diameter is between 100-200 nm.
Original pattern is still kept after polyaniline fiber carbonization, there is no melt simultaneously phenomenon.
In order to be best understood from polyaniline carbon material carbonized product internal structure, will be prepared into using the above method
The PANI-C800 arrived is characterized using transmission electron microscope (abbreviation TEM, similarly hereinafter), studies its microscopic appearance feature.It is used in experiment
The Tecnai G2 F30 S-Twin high resolution transmission electron microscopy of Dutch Philips-FEI company, as a result as shown in Figure 3.
In Fig. 3, a, b are respectively the TEM characterization result of PANI-C800 under different enlargement ratios, it may be clearly seen that, PANI-C800
For hollow tubular structure；Moreover, tube wall surface hole is flourishing, there is microcellular structure abundant.
PANI, PANI-C600, PANI-C700, PANI-C800 for being prepared using the above method are subjected to isothermal N2
Adsorption desorption (BET) test, the ASAP2020 type Full-automatic physical chemical adsorption instrument that experiment is produced using Micromeritics company
BET and pore-size distribution analysis are carried out, as a result as shown in Figure 4.Fig. 4 (a) is PANI, PANI-C600, PANI-C700, PANI-
The isothermal nitrogen adsorption desorption curve of C800.The adsorption isotherm of all samples is between I type and IV type thermoisopleth, lower
Relative pressure under have higher adsorbance, be typical pore characteristics, illustrate there is a large amount of micropore in sample.In higher pressure
(P/P within the scope of power0> 0.8) all adsorption curves all strongly enhance, due to N2Capillary condensation in mesoporous and macropore and more
Layer absorbs, but hysteresis loop is very small, shows that the mesoporous content of material is few.Fig. 4 (b) be PANI-C600, PANI-C700,
The graph of pore diameter distribution of PANI-C800, it can be clearly seen that PANI-C600, PANI-C700, PANI-C800 have from figure
Apparent meso-hole structure.Moreover, the temperature of heat treatment is higher, the specific surface area of polyaniline carbon material is in the trend increased,
Tri- kinds of materials of PANI-C600, PANI-C700, PANI-C800, specific surface area are respectively 451 m2·g-1、915 m2·g-1、
1025 m2·g-1.When carburizing temperature is relatively high, the carbon of pyrolytic gasification loss is more, and carbon surface hole is more.Although PANI-
The specific surface area of C800 is high, but its average pore size (2 nm) is less than the average pore size (2.67 nm) of PANI-C700.This attribution
In, as the temperature rises, PANI persursor material melts, although pyrolytic reaction, which persistently occurs, generates more micropores,
Micropore pore volume becomes larger, but melts and phenomenon shrinks the duct of big mesoporous, and average pore size is caused to gradually reduce.Our legal system
The specific surface area data of standby obtained PANI-C600, PANI-C700, PANI-C800 is much higher than carbon nanotube reported in the literature
(BET=100 ~ 400 m2·g-1), and the nitrogen contained has played capacitance bigger positive effect.
Fig. 5 is the cyclic voltammetry result curve figure of PANI-C700, PANI-C800.Experiment using three-electrode system and
CHI660D type electrochemical workstation is tested.The specific capacitance of active material can be calculated according to the following formula by cyclic voltammetry curve
(three-electrode system):
Cm = ∫i(t) dt / (2 × v × m × ΔV)
Wherein: CmFor specific capacitance (Fg-1), v is potential scan rate (mVs-1), Δ V is electric potential scanning range (V), i
It (t) is current value (A) that m is single electrode active material quality (g).The specific capacitance value under different scanning rates is calculated accordingly.
The specific capacitance value of PANI-C800 is all higher than PANI-C700, this is because the specific surface area ratio PANI-C700 of PANI-C800
It is high.But in the 50 mV s of rate that exposes thoroughly-1When, the degree that the CV curve of PANI-C800 deviates is obviously more serious than PANI-C700,
This is because the average pore size of sample P ANI-C800 is small, the content of big mesoporous is small, and when heat treatment temperature is too high, surface is melted
And phenomenon, cause duct to block, is unfavorable for the transmission of electrolyte.
Electrochemical property test is carried out to PANI-C600, PANI-C700, PANI-C800, the results showed that benefit from polyphenyl
The hollow tubular structures of amido carbon material and a large amount of micropore, central hole structure, test electrode specific capacitance with higher and excellent
High rate performance.
PANI-C800 is in 5 mV s-1Current potential is swept under speed, and specific capacitance reaches 180 Fg-1.High rate performance is good, electric current
Density is from 0.5 A g-1 Increase to 5 A g-1, it is smaller that specific capacitance reduces amplitude；Cycle performance is good, by 1000 charge and discharges
Specific capacitance conservation rate is more than 97 % after electricity circulation.
PANI-C700 is in 5 mV s-1Current potential is swept under speed, and specific capacitance reaches 167 Fg-1.High rate performance is good, electric current
Density is from 0.5 A g-1 Increase to 5 A g-1, specific capacitance has the decline of certain amplitude, by 1000 compared with PANI-C800
Specific capacitance conservation rate is more than 87 % after secondary charge and discharge cycles, compared with PANI-C800, also there is the decline of certain amplitude.
PANI-C600 is in 5 mV s-1Current potential is swept under speed, and specific capacitance reaches 149 Fg-1.High rate performance is good, electric current
Density is from 0.5 A g-1 Increase to 5 A g-1, specific capacitance has the decline of certain amplitude, by 1000 compared with PANI-C800
Specific capacitance conservation rate is more than 67 % after secondary charge and discharge cycles, compared with PANI-C800, also there is the decline of certain amplitude.
Embodiment 2
Configuring two parts of concentration is 0.05mol/L(with hydrionic densimeter) 500 mL p-methyl benzenesulfonic acid solution, solvent adopts
With the aqueous solution of ethyl alcohol, the volume ratio of ethyl alcohol and water is 0.2: 1；10 mL aniline monomers are added in portion, are added 10 after stirring and dissolving
ML hydrogen peroxide, stands reaction 3h, and 23.9 g ammonium persulfates are added in another, and 10 min of magnetic agitation is to being completely dissolved.It will be above-mentioned
Two parts of solution mix rapidly, stand 24 h of reaction at room temperature.The sample sufficiently reacted is subjected to decompression suction filtration, and uses deionized water
Repeatedly washing, until filtrate becomes colorless, obtained solid product is dried for standby at 60 DEG C, obtains persursor material.By gained
Persursor material is put into graphite crucible, is passed through nitrogen and is protected, and control heating rate is 5 DEG C of min-1, it is warming up to 800
DEG C, 2 h of heat preservation obtain polyaniline carbon material.
Embodiment 3
Configuring two parts of concentration is 0.05mol/L(with hydrionic densimeter) 500 mL p-methyl benzenesulfonic acid solution, solvent adopts
With the aqueous solution of ethyl alcohol, the volume ratio of ethyl alcohol and water is 0.2: 1；10 mL aniline monomers are added in portion, are added 10 after stirring and dissolving
ML hydrogen peroxide, stands reaction 4h, and 23.9 g ammonium persulfates, 10 min of magnetic agitation is added in another.Above-mentioned two parts of solution is fast
Speed mixing stands 24 h of reaction at room temperature.The sample sufficiently reacted is subjected to decompression suction filtration, and is repeatedly washed with deionized water,
Until filtrate becomes colorless, obtained solid product is dried for standby at 60 DEG C, obtains persursor material.By gained presoma material
Material is put into graphite crucible, is passed through argon gas and is protected, and control heating rate is 5 DEG C of min-1, 1000 DEG C are warming up to, heat preservation 2
H obtains polyaniline carbon material.
Embodiment 4
Configuring two parts of concentration is 0.05mol/L(with hydrionic densimeter) 200 mL p-methyl benzenesulfonic acid solution, solvent adopts
With the aqueous solution of ethyl alcohol, the volume ratio of ethyl alcohol and water is 0.2: 1；10 mL aniline monomers are added in portion, are added 10 after stirring and dissolving
ML hydrogen peroxide stands reaction 3 hours, and 9.56 g ammonium persulfates, 10 min of magnetic agitation is added in another.By above-mentioned two parts of solution
Mixing rapidly stands 24 h of reaction at room temperature.The sample sufficiently reacted is subjected to decompression suction filtration, and is repeatedly washed with deionized water
It washs, until filtrate becomes colorless, obtained solid product is dried for standby at 60 DEG C, obtains persursor material.By gained presoma
Material is put into graphite crucible, is passed through nitrogen and is protected, and control heating rate is 5 DEG C of min-1, 800 DEG C are warming up to, heat preservation
2 h obtain polyaniline carbon material.Wherein the amount of ammonium persulfate and the volume ratio of acid solution are the same as embodiment 2.
Embodiment 5
Configuring two parts of concentration is 0.05mol/L(with hydrionic densimeter) 200 mL p-methyl benzenesulfonic acid solution, solvent adopts
With the aqueous solution of ethyl alcohol, the volume ratio of ethyl alcohol and water is 0.2: 1；10 mL aniline monomers are added in portion, are added 10 after stirring and dissolving
ML hydrogen peroxide stands reaction 3 hours, and 9.56 g ammonium persulfates, 10 min of magnetic agitation is added in another.Above-mentioned two parts are clarified
Solution mix rapidly, at room temperature stand reaction 24 h.The sample sufficiently reacted is subjected to decompression suction filtration, and more with deionized water
Secondary washing, until filtrate becomes colorless, obtained solid product is dried for standby at 60 DEG C, obtains persursor material.Before gained
It drives body material to be put into graphite crucible, is passed through nitrogen and is protected, control heating rate is 5 DEG C of min-1, 600 DEG C are warming up to,
It keeps the temperature 4 h and obtains polyaniline carbon material.Wherein the amount of ammonium persulfate and the volume ratio of acid solution are the same as embodiment 2.
Embodiment 6
Configuring two parts of concentration is 0.02mol/L(with hydrionic densimeter) 500 mL p-methyl benzenesulfonic acid solution, solvent adopts
With the aqueous solution of ethyl alcohol, the volume ratio of ethyl alcohol and water is 0.5: 1；20 mL aniline monomers are added in portion, are added 10 after stirring and dissolving
ML hydrogen peroxide stands reaction 3 hours, and 23.9 g ammonium persulfates, 10 min of magnetic agitation is added in another.Remaining step and process
With embodiment 2.Gained carbon material is in hollow tubular through TEM test structure.
Embodiment 7
Configure two parts of concentration be 0.05mol/L(with hydrionic densimeter) 200 mL p-methyl benzenesulfonic acids and phosphoric acid mixing it is molten
Liquid, portion are added 10 mL aniline monomers, 4 mL hydrogen peroxide are added after stirring and dissolving, stand reaction 4 hours, another addition
9.56 g ammonium persulfates, 10 min of magnetic agitation.Remaining step and process are the same as embodiment 2.Gained carbon material tests structure through TEM
In hollow tubular.
Embodiment 8
Configure two parts of concentration be 0.02mol/L(with hydrionic densimeter) 500 mL toluenesulfonic acids and oxalic acid mixing it is molten
Liquid, portion are added 10 mL aniline monomers, 10 mL hydrogen peroxide are added after stirring and dissolving, stand reaction 3 hours, another addition
23.9 g ammonium persulfates, 10 min of magnetic agitation.Remaining step and process are the same as embodiment 1.Gained carbon material tests structure through TEM
In hollow tubular.
Embodiment 9
Configure two parts of concentration be 0.02mol/L(with hydrionic densimeter) 500 mL toluenesulfonic acids and citric acid mixing
Solution, solvent use the aqueous solution of ethyl alcohol, and the volume ratio of ethyl alcohol and water is 0.2: 1, and 10 mL aniline monomers, stirring is added in portion
10 mL hydrogen peroxide are added after dissolution, stand reaction 3 hours, 23.9 g ammonium persulfates, 10 min of magnetic agitation is added in another.
Remaining step and process are the same as embodiment 1.Gained carbon material is in hollow tubular through TEM test structure.
Embodiment 10
Configure two parts of concentration be 0.02mol/L(with hydrionic densimeter) 200 mL p-methyl benzenesulfonic acids and sulfuric acid mixing
Solution, solvent use the aqueous solution of ethyl alcohol, and the volume ratio of ethyl alcohol and water is 0.2: 1, and 10 mL aniline monomers, stirring is added in portion
4 mL hydrogen peroxide are added after dissolution, stand reaction 3 hours, 9.56 g ammonium persulfates, 10 min of magnetic agitation is added in another.Its
Remaining step and process are the same as embodiment 1.Wherein the amount of ammonium persulfate and the volume ratio of acid solution are the same as embodiment 2.Gained carbon material warp
It is in hollow tubular that TEM, which tests structure,.
Embodiment 11
Configure two parts of concentration be 0.02mol/L(with hydrionic densimeter) 200 mL p-methyl benzenesulfonic acids solution, solvent
Using the aqueous solution of ethyl alcohol, the volume ratio of ethyl alcohol and water is 0.5: 1, and 10 mL aniline monomers are added in portion, is added after stirring and dissolving
4 mL hydrogen peroxide stand reaction 2 hours, and 9.56 g ammonium persulfates, 10 min of magnetic agitation is added in another.Remaining step and mistake
Journey is the same as embodiment 1.Wherein the amount of ammonium persulfate and the volume ratio of acid solution are the same as embodiment 2.Gained carbon material tests structure through TEM
In hollow tubular.
Embodiment 12
Configure two parts of concentration be 0.02mol/L(with hydrionic densimeter) 200 mL p-methyl benzenesulfonic acids solution, solvent
Using the aqueous solution of ethyl alcohol, the volume ratio of ethyl alcohol and water is 1: 1, and 10 mL aniline monomers are added in portion, is added 4 after stirring and dissolving
ML hydrogen peroxide stands reaction 3 hours, and 9.56 g ammonium persulfates, 10 min of magnetic agitation is added in another.Above-mentioned two parts are clarified
Solution mix rapidly, at room temperature stand reaction 24 h.The sample sufficiently reacted is subjected to decompression suction filtration, and more with deionized water
Secondary washing, until filtrate becomes colorless, obtained solid product is dried for standby at 60 DEG C, obtains persursor material.Before gained
It drives body material to be put into graphite crucible, is passed through nitrogen and is protected, control heating rate is 5 DEG C of min-1, 800 DEG C are warming up to,
It keeps the temperature 8 h and obtains polyaniline carbon material.Wherein the amount of ammonium persulfate and the volume ratio of acid solution are the same as embodiment 2.Gained carbon materials
Material is in hollow tubular through TEM test structure.
Embodiment 13
Configure two parts of concentration be 0.02mol/L(with hydrionic densimeter) 500 mL p-methyl benzenesulfonic acids solution, solvent
Using the aqueous solution of ethyl alcohol, the volume ratio of ethyl alcohol and water is 1: 1, and 10 mL aniline monomers are added in portion, is added 10 after stirring and dissolving
ML hydrogen peroxide stands reaction 3 hours, and 9.56 g ammonium persulfates, 10 min of magnetic agitation is added in another.Remaining step and process
With embodiment 1.Wherein the amount of ammonium persulfate and the volume ratio of acid solution are the same as embodiment 2.Gained carbon material tests structure through TEM
Hollow tubular.
Comparative example 1
The PANI-C800(abbreviation material 1 that embodiment 1 is prepared), using Yang Miaomiao etc. in International Periodicals electrochemistry journal
Volume 55 page 7021-7027 " preparations of the polyaniline carbon nanotube as electrode material for super capacitor delivered upper 2010 year
And chemical property " method be prepared polyaniline carbon material (abbreviation material 2), using Yuan Dingsheng etc. in International Periodicals
Electrochemistry communicate deliver on volume 13 page 242-246 within 2011 " direct carbonization polyaniline nano-line richness nitrogen carbon nanocoils and its
Electrochemical Properties " method the polyaniline carbon nanocoils material (abbreviation material 3), the commercial activated carbons that are prepared
(XSRC-048) 4 kinds of materials compare experiment, compare specific capacitance, cycle performance and the high rate performance of four kinds of materials.
The parameter comparison of 1 different materials of table
Test condition: the above-mentioned polyaniline being prepared, acetylene black and PVDF are weighed by the mass ratio of 8:1:1, mixing
Few drops of N-Methyl pyrrolidone reagents are added after grinding, magnetic agitation handles 8 h, obtains active material slurry.It will be a certain amount of
Slurry be coated uniformly on through in clean titanium sheet, 1 × 1 cm of coated area2.The electrode prepared is dried in 80 DEG C of air blast
Dry 12 h in case.Using cyclic voltammetry in 2 mV s-1Current potential sweeps the specific capacitance and cycle performance of test material under speed.
The result shows that the specific capacitance for the PANI-C800 that embodiment 1 is prepared is higher, and have good circulation and
High rate performance.
Comparative example 2
Using control variate method, the experiment condition to prepare PANI-C800 in embodiment 1 is basic experimental conditions (that is, if without spy
Different explanation, the experiment condition in addition to variable is with the experiment condition for preparing PANI-C800 in embodiment 1), by adjusting dopant acid kind
11 kinds of tubuloses polyaniline carbon material as shown in table 2 is prepared in class.By comparing experiment, compares and made under different condition
Specific capacitance, cycle performance and the high rate performance of the tubulose polyaniline carbon material obtained, the results are shown in Table 2, test method and ratio
Capacitor, cycle performance and high rate performance calculation method are the same as embodiment 1.
The result shows that different dopant acids have apparent influence for the pattern and performance of polyaniline carbon material.Such as Fig. 6 (a) (b)
(c) (d) (e) is the SEM figure of material 3, material 4, material 5, material 6, material 11 respectively.Shown in Fig. 6 (e), when in reaction system
Dopant acid is not added, polyaniline carbon material is the non-uniform laminated structure of micron order.And pass through the polyaniline of acid doping
Carbon material is mostly the aggregation of micro-or nano size, show dopant acid be the key that synthetizing micro-nano structure polyaniline base carbon material because
Element.The polyaniline carbon material being prepared after all acid dopings all has duct abundant.The doping of Fig. 6 (a) oxalic acid is prepared into
To the existing nano particle of polyaniline carbon material have nanometer rods again, size is different.Fig. 6 (b) lemon acid doping is prepared
Polyaniline carbon material is mostly graininess, and agglomeration is serious.The polyaniline carbon materials that Fig. 6 (c) winestone acid doping is prepared
Expect that pattern is similar with the Polyaniline of lemon acid doping, same agglomeration is serious, and large particle surface adheres to small nano particle.
The polyaniline carbon material that is prepared of Fig. 6 (d) sulfuric acid doping is mostly nano bar-shape, diameter also more even one.
The Analysis on Mechanism that dopant acid influences polyaniline carbon material pattern: aniline monomer can protonate shape in acid solution
At aniline cation, when the concentration of acid is lower than aniline monomer concentration, proton translocation can occur again for aniline cation, form aniline
With the coherent condition of anilinium ion, stablize to reach thermodynamical equilibrium, coherent condition can turn to the surface lower spherical micelle of energy
Become.The acidity of tartaric acid and citric acid does not have the acidity of oxalic acid and sulfuric acid strong, and the quantity that proton translocation occurs for aniline cation is more,
It is partial to give birth to glomerate condensate, generates the spherical particle of nanometer.
Fig. 7-10 is respectively the cyclic voltammetry curve figure of material 3, material 4, material 5, material 6 under different scanning rates, micro-
The cyclic voltammetry curve of micro-nano structure polyaniline carbon material is in class rectangle shape, has no apparent redox peaks, and sweeping greatly
It retouches speed lower curve and keeps good, show the storage mechanism of micro-nano structure polyaniline carbon material based on electric double layer capacitance.Material
There are lesser redox peaks in material 6, it may be possible to containing more in the polyaniline carbon material being prepared with sulfuric acid doping
There are reversible redox peaks in hetero atom, heteroatom functional group.According to cyclic voltammetry curve calculate each electrode specific capacitance value,
Known to material 3, material 4, material 5, material 6 specific capacitance value be not much different, current density is from 0.5 A g-1 Increase to 5 A
g-1, the specific capacitance of four kinds of materials reduces that amplitude is larger, and capacity retention is not high.This is because expose thoroughly rate when, electrolyte
Ion has little time to cause effective ratio area to reduce into the micropore of material, and electric double layer interface is reduced.Comparatively,
Under same scan speed, the specific capacitance value of micro-nano structure polyaniline carbon material is all higher than gathers without what acid doping was prepared
The specific capacitance value of anilino- carbon material shows that the microstructure of persursor material has significant impact to carbonized product.
The specific capacitance for the hollow tubular polyaniline carbon material that embodiment 1 is prepared is apparently higher than institute under the conditions of others
Material obtained, and there is good circulation and high rate performance.This is attributed to:
(1) when aniline solution and ammonium persulfate solution quickly directly mix, the touch opportunity of reactant and oxidant is impartial, is not easy
There is heterogeneous nucleation, the chain reaction of polyaniline persistently carries out.
(2) macromolecular can directly affect the connection of the construction and interchain of PANI chain, and the anion of p-methyl benzenesulfonic acid can limit
The distortion of PANI chain processed expands the conformation of chain, increases conjugate length.Benzene when p-methyl benzenesulfonic acid doped polyaniline in anion
Ring structure increases space steric effect.
(3) organic sulfonic acid can be improved the dissolubility of polyaniline in aqueous solution, and when direct mixing method does not have mechanical stirring,
Entire reaction system is in static condition, and p-methyl benzenesulfonic acid improves the dissolubility of polyaniline product, ensure that reaction system
Homogeneity.
Comparative example 3
Using the method for control variable, using prepared in embodiment 1 experiment condition of PANI-C800 as basic experimental conditions (that is, if
Without specified otherwise, the experiment condition in addition to variable is with the experiment condition for preparing PANI-C800 in embodiment 1), by changing the step
Two kinds of materials are compared experiment, compare specific capacitance, the cycle performance of two kinds of materials by the additive amount of oxidant hydrogen peroxide in one
And high rate performance.The results are shown in Table 3, and test method and step are the same as embodiment 1.
Test condition: the above-mentioned polyaniline being prepared, acetylene black and PVDF are weighed by the mass ratio of 8:1:1,
Few drops of N-Methyl pyrrolidone reagents are added after mixed grinding, magnetic agitation handles 8 h, obtains active material slurry.By one
Quantitative slurry is coated uniformly in the titanium sheet through cleaning, 1 × 1 cm of coated area2.By the electrode prepared in 80 DEG C of drums
Dry 12 h in wind baking oven.Using cyclic voltammetry in 2 mV s-1Current potential sweeps the specific capacitance and cyclicity of test material under speed
Energy.
The result shows that embodiment 1 adds hydrogen peroxide and does not add obtained polyaniline carbon-based material specific surface area completely
Have a marked difference, add polyaniline carbon-based material obtained by hydrogen peroxide be less than do not add it is obtained, as hydrogen peroxide adds
The specific surface area of the increase of dosage, carbon-based material obtained is also gradually reduced.When preparing at room temperature, the activity of aniline is high, a step
Being directly added into ammonium persulfate is that system is readily synthesized the low-molecular weight polymers such as dimer tripolymer, these molecular weight polymers exist
Cracking gasification is easy when high temperature cabonization.The specific surface area of polyaniline fiber only has 154 m2·g-1, the specific surface area after carbonization
It has greatly changed.
Oxidant is added using two-stage method, a small amount of hydrogen peroxide is added in the first stage, since hydrogen peroxide oxidation is weaker,
The product that the phase mainly generates before the reaction is polyaniline intermediate oxidation state, these intermediate oxidation states are mainly some of polyaniline
Oligomer, these oligomers can be used as the chain carrier of second stage again.Second stage uses ammonium persulfate as oxidation
Agent, first ammonium persulfate are as initiator so that polyaniline chain rapid growth polymerize, in the first stage on the basis of further give birth to
A length of uniform long tubular structure.In the reaction initial stage, aniline monomer is just consumed, to inhibit the secondary of polyaniline
Growth, reacts polyaniline along chain structure itself.When polyaniline high temperature cabonization, pyrolytic reaction gas occurs for oligomer etc.
Change loss, forms hole in carbon surface.The result shows that the PANI-C800 that embodiment 1 is prepared has hollow tubular structures,
As electrode material for having in supercapacitor compared with high specific capacitance, and there is good circulation and high rate performance.
Specific embodiment described herein is only an example for the spirit of the invention.The neck of technology belonging to the present invention
The technical staff in domain can make various modifications or additions to the described embodiments or replace by a similar method
In generation, however, it does not deviate from the spirit of the invention or beyond the scope of the appended claims.
Claims (10)
1. a kind of preparation method of hollow tubular polyaniline carbon material, it is characterised in that the following steps are included:
Step 1: taking two parts of acid solutions, and portion is added aniline, hydrogen peroxide is added after stirring and dissolving, stands reaction 1-5h, another
Ammonium persulfate is added, after mixing evenly mixes two parts of solution rapidly, stands reaction 1-48h, is separated by solid-liquid separation, solid is through dry
Persursor material；The acid solution is one of phosphoric acid, oxalic acid, citric acid, tartaric acid, sulfuric acid, p-methyl benzenesulfonic acid or several
Any mixed solution of ratio of kind；
Step 2: the persursor material is heat-treated 0.5-24h at inert atmosphere, 400-1000 DEG C, obtains polyaniline
Carbon material.
2. a kind of preparation method of hollow tubular polyaniline carbon material as described in claim 1, it is characterised in that:
In step 1, the concentration of the acid solution is calculated as 0.01-0.1 mol/L with hydrionic concentration.
3. a kind of preparation method of hollow tubular polyaniline carbon material as claimed in claim 2, it is characterised in that:
In step 1, the additional amount of the hydrogen peroxide is calculated as (2-5) mL/100 mL with the volume of acid solution.
4. a kind of preparation method of hollow tubular polyaniline carbon material as claimed in claim 3, it is characterised in that:
In step 1, the additional amount of the aniline is calculated as (1-4) mL/100 mL with the volume of acid solution.
5. a kind of preparation method of hollow tubular polyaniline carbon material as claimed in claim 4, it is characterised in that:
In step 1, the additional amount of the ammonium persulfate is calculated as (2.35-9.4) g/100 mL with the volume of acid solution.
6. a kind of preparation method of hollow tubular polyaniline carbon material as claimed in claim 5, it is characterised in that:
In step 1, solvent used by the acid solution is the aqueous solution of ethyl alcohol；In the aqueous solution of the ethyl alcohol, ethyl alcohol and water
Volume ratio be (0.1-1): 1.
7. a kind of preparation method of hollow tubular polyaniline carbon material as claimed in claim 6, it is characterised in that:
In step 1, two parts of acid solutions are p-methyl benzenesulfonic acid solution.
8. such as a kind of preparation method of hollow tubular polyaniline carbon material of any of claims 1-7, feature
It is:
In step 1, the time for standing reaction is 12-24h.
9. such as a kind of preparation method of hollow tubular polyaniline carbon material of any of claims 1-7, feature
It is:
In step 1, the method for the separation of solid and liquid is filtering or centrifugation；The drying is to dry at air atmosphere, 50-60 DEG C
Dry 12-24h.
10. such as a kind of preparation method of hollow tubular polyaniline carbon material of any of claims 1-7, feature
It is:
In step 2, the condition of the heat treatment is to be heat-treated 2h at nitrogen atmosphere, 600-800 DEG C.
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| CN111790241A (en) * | 2020-05-09 | 2020-10-20 | 浙江工业大学 | High-efficiency sulfur dioxide desulfurizer, preparation method and desulfurization method |
| CN112915966A (en) * | 2021-01-28 | 2021-06-08 | 东北大学 | Preparation method and application of polyaniline-based activated carbon |
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