CN108394889A - A kind of method and apparatus extracting carbon material from plastics - Google Patents
A kind of method and apparatus extracting carbon material from plastics Download PDFInfo
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- CN108394889A CN108394889A CN201810533244.4A CN201810533244A CN108394889A CN 108394889 A CN108394889 A CN 108394889A CN 201810533244 A CN201810533244 A CN 201810533244A CN 108394889 A CN108394889 A CN 108394889A
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- C—CHEMISTRY; METALLURGY
- C01—INORGANIC CHEMISTRY
- C01B—NON-METALLIC ELEMENTS; COMPOUNDS THEREOF; METALLOIDS OR COMPOUNDS THEREOF NOT COVERED BY SUBCLASS C01C
- C01B32/00—Carbon; Compounds thereof
- C01B32/15—Nano-sized carbon materials
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- C—CHEMISTRY; METALLURGY
- C01—INORGANIC CHEMISTRY
- C01B—NON-METALLIC ELEMENTS; COMPOUNDS THEREOF; METALLOIDS OR COMPOUNDS THEREOF NOT COVERED BY SUBCLASS C01C
- C01B32/00—Carbon; Compounds thereof
- C01B32/15—Nano-sized carbon materials
- C01B32/182—Graphene
- C01B32/184—Preparation
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- C—CHEMISTRY; METALLURGY
- C01—INORGANIC CHEMISTRY
- C01B—NON-METALLIC ELEMENTS; COMPOUNDS THEREOF; METALLOIDS OR COMPOUNDS THEREOF NOT COVERED BY SUBCLASS C01C
- C01B32/00—Carbon; Compounds thereof
- C01B32/20—Graphite
- C01B32/205—Preparation
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- C—CHEMISTRY; METALLURGY
- C01—INORGANIC CHEMISTRY
- C01B—NON-METALLIC ELEMENTS; COMPOUNDS THEREOF; METALLOIDS OR COMPOUNDS THEREOF NOT COVERED BY SUBCLASS C01C
- C01B2204/00—Structure or properties of graphene
- C01B2204/04—Specific amount of layers or specific thickness
Abstract
The present invention proposes a kind of method and apparatus extracting carbon material from plastics; this method is be heat-treated on the fusing point for reaching fuse salt at least one plastic material (such as poly- terephthalate) at least one fuse salt (such as NaCl) forming nanostructured carbon material; wherein salt is in molten condition, and carbonaceous material will be protected from oxidation；Secondly, fused salt promotes the further graphitization of carbon material, and product is the graphite nanosheets with high conductivity and high surface area；This method provides simple, economic, efficient method for production conductive carbon material.It produces significant actively impact also by converting hardly degredation plastic waste to the conductive carbon material of high value to environment.
Description
Technical field
The invention belongs to carbon material preparation fields, are related to a kind of method for extracting carbon material from plastics.Specially generate
The method of the nano-graphite carbon of high conductivity and high surface area.
Background technology
Global yield was up to 3.35 hundred million tons in 2016 for plastics, since production cost is low, durability, density are low, chemical resistance
By force, spatial stability is low etc., and various structure applications are increasingly being applied in the modern life.
Poly- terephthalate ((C10H8O4)n, PET) and it is most common plastics, the cost that can be born due to it, excellent machine
Tool performance, shielding properties and the high grade of transparency are often used as the container of bottling liquid and other food.Its radioresistance characteristic
Insulating materials and core tracking detector for nuclear power station and nuclear equipment.
In fact, the ever-increasing demand to bottled water, the plastic bottle consumption figure for keeping the whole world annual has reached 50,000,000,000 U.S.s
Member or so.The plastics not utilized in only about 9% new water bottle are recovered, and about 80% old water bottle can be landfilled or launch
In ocean.Therefore, the plastics in ocean are put into there are about upper hundreds of millions tons, the micro-structure of plastics is taken the photograph by birds, fish and other biological
It takes, and is finally eaten up in the form of seafood by the mankind, form a global waste management and serious, the current weather of environmental crisis
Perhaps, variation experiencings the consequence of same levels.Currently, in 20 years time, the plastics cumulant that the whole world uses is about
120000000 tons.
, may be in the time of centuries in view of the retrogression of nature of PET takes a long time, its cycle or conversion is
It is vital.As hydrocarbon, plastics have high fever magnitude, therefore are widely regarded as generating H2With diving for synthesis gas
In raw material.On the other hand, due to the high-carbon content that it has about 45%, and lack inorganic constituents, PET is considered height
The reliable sources of pure solid carbon material.It is noted that due to carbon material energy storage system, conducing composite material and
The application of the different fields such as solar energy acquisition is increasing, and the carbon material with high surface area and electric conductivity is with important meaning
Justice.
In some traditional carbon nanomaterial production methods, PET is utilized as carbon source.Heating is cut in a nitrogen atmosphere
Broken mineral water bottle generates the high carbon polymer of black to 815 DEG C, is then inserted hollow carbon pipe, in rotating cathode electricity
Anode is used as in arc discharge equipment, this is conventionally used for the method for preparing multi-walled carbon nanotube (MWCNTs).In cigarette ash middle-jiao yang, function of the spleen and stomach
The different zones that pole and cathode heating temperature are about 1700-2600 DEG C form the carbon ball and MWCNTs of nanoscale.
As evidence feasibility (C.Lius of the PET as carbon source is used in tangible conventional chemical vapor deposit (CVD) growing method
andHui-Ming Cheng,Carbon nanotubes:controlled growth and application,
Materials Today 16 (2013) 19-28.), CVD stones are added as carbon source in PET and high density polyethylene (HDPE) by Hatta et al.
Quartzy tube hub is added by the upper end of English pipe for the hydroxide of iron.Under an argon atmosphere, which is heated to
700-900 DEG C, grow on a catalyst Nano carbon balls and nanofiber (M.N.M.Hatta, M.S.Hashim, R.Hussin,
S.Aida,Z.Kamdi,A.R.Ainunddin and M.Z.Yunos,Synthesis of carbon nanostructures
from high density polyethylene(HDPE)and polyethylene terephthalate(PET)waste
by chemical vapour deposition,Journal of Physics:Conference Series 914(2017)
012029.)。
PET bottle is converted into solid carbon nanotube, chance can be provided for agricultural and environment.However, in order to assess pyrolysis PET
Prepare the value of carbon material product, it is contemplated that the economic feasibility of its process not only considers shape in description carbon material characteristic
Looks have more necessity in the characterization of crystallinity, Level, specific surface area and electric conductivity.These characteristics are in various application processes
In it is all critically important, usually utilize the technologies such as electron microscope, conductivity measurement and x-ray diffraction and Raman spectrum carry out table
Sign.Raman spectrum is widely used in that carbon material is qualitative and quantitatively characterizing, because it is layer structure, crystallinity and defect characterization
It provides and clearly studies.For example, in graphite material, it is understood that so-called Raman G bands in hexagonal lattice
sp2The vibration of key carbon atom is related, and Raman D bands are then caused by fault of construction.In addition, Raman 2D bands to the quantity of layer very
It is sensitive.Therefore, in graphene-based material, Raman 2D/G (I2D/IG) and D/G (ID/IG) ratio of intensity corresponds respectively to defect
Density and graphene platelet quality, to influence the electric conductivity of material.In general, I2D/IGValue and conductivity are lower
Graphite material has higher ID/IGValue.For example, ID/IGValue is respectively the graphene oxide of 1.02,1.19 and 1.55 reduction
(RGO) I of material2D/IGValue is respectively 0.14,0.07 and 0.01, and conductivity is respectively 166,133 and 69Sm-1.With this trend
It is consistent, there is lower I using RGO foams prepared by GO and NiD/IGIt is worth (0.92), lacking has higher conductivity
1600Sm-1。
The quality of carbon material from document to being prepared by PET is looked back.El Essawy et al. one it is closed not
Broken PET water bottle is heated in rust steel autoclave, 1h is heated at 800 DEG C, forms a kind of highly disordered carbon material, is had weak
Raman G and D band, ID/IGValue is 1.13.PET be used as preparing activated carbon carbon matrix precursor (N.A.El Essawy,
S.M.Ali,H.A.Farag,A.H.Konsowa,M.Elnouby and H.A.Hamad,Green synthesis of
graphene from recycled PET bottle wastes for use in the adsorption of dyes in
aqueous solution,Ecotoxicology and Environmental Safety 145(2017)57–68.)。Rai
Et al. in N2PET is pyrolyzed under atmosphere, pyrolysis procedure is 400 DEG C of pyrolysis 1h, 725 DEG C of pyrolysis 2h.Then obtained carbon material is ground
It is broken and in N2925 DEG C of pyrolysis 1h of atmosphere, then pass to CO2 activation 2h.In N2The specific surface area of the activated carbon obtained after atmosphere cooling
For 659.6m2g-1, ID/IGValue be 1.04, and have there are one very weak 2D Ramans band (P.Rai and K.P.Singh,
Valorization of Poly(ethylene)terephthalate(PET)wastes into magnetic carbon
for adsorption of antibiotic from water:Characterization and application,
Journal of Environmental Management 207(2018)249-261.)。
In another study, at 725 DEG C PET in N2In atmosphere by pyrolytic formed gaseous compound (58%, an oxygen
Change carbon, carbon dioxide and hydrocarbon), terephthalic acid (TPA) (20%) and the black solid residue extracted from reactor bottom.
Black residue is ground, in N2In 925 DEG C pyrolysis 1h, then activated in CO2, loss on ignition is in the range of 12-76%.Gained
The BET specific surface area of the activated carbon arrived ranging from 340-2468m2g-1, ID/IGValue ranging from 0.76~1.24 (J.B.Parra,
C.O.Ania,A.Arenillas,F.Rubiera,J.J.Pis andJ.M.Palacios,Structuralchanges in
polyethylene terepthalate(PET)waste materials caused by pyrolysis and
CO2activation,Adsorption Science&Technology 24(2006)439-449.)。
Document is summarized it is found that although PET is a beneficial source of carbon material, carbon material is prepared and needs at many steps
Reason, and the formation of the carbon material of low degree of graphitization is often led to, this inevitably brings low electric conductivity, greatly limits
The possible application of carbon material, also limits feasibilities of the PET as High-conductivity carbon material carbon source.This is one and bad shows
As because more and more rubbish PET are considered as the carbon source of low cost.It more refers to high additional less than plastic wastes are converted to
Very positive environment can be brought to influence while value material.
The present invention is proposed prepares high performance carbon nano material using fused salt processing PET, and obtained material has a variety of excellent
Different characteristic such as high-specific surface area (522.54m2g-1), low ID/IGIt is worth (0.47) and high I2D/IGIt is worth (0.52) 6.13MPa's
(corresponding volume density is 1.04g cm to pressure-3) test material have excellent conductivity be up to 1143Sm-1Conductivity.It
It is the carbon material for the best quality for using a step fused salt technique to be obtained from plastics so far.
Invention content
The present invention for overcome the deficiencies in the prior art, uses very effective method, nano junction is prepared from plastics
The graphitized carbon material of structure.This method is by a kind of plastics or different types of plastic hybrid and a kind of inorganic metal halogenation
Object or different types of inorganic metal hal ide mixture are heated, and heating temperature is higher than a kind of inorganic metal halogen
The fusing point of compound or different types of inorganic metal hal ide mixture.
Specific technical solution is：
A method of it extracting carbon material from plastics, nanostructured carbon material is generated by heating mixture, it is described mixed
Object is closed to be made of at least one plastics and at least one metal halide salt；Its heating temperature is：The fusing point of metal halide salt
≤ heating temperature≤+ 50 DEG C of boiling point.
Further, above-mentioned metal halide salt is hydrated metal halides salt.
Further, above-mentioned heating temperature is the fusing point of metal halide salt or more, when being less than boiling point, generates nanostructure
The mixture of carbon material and salt is used water dissolution salt therein after cooling, and is filtered, and the filtrate recycling containing salt is filtered
Object dries to obtain nanostructured carbon material.
Further, the conductivity of the nanostructured carbon material of above-mentioned generation is more than 1000S m-1Or Raman ID/IG's
Value is less than 0.5.
Further, above-mentioned metal halide salt is LiCl, NaCl, KCl, MgCl2、CaCl2、NaF、ZnCl2In one
Kind or a variety of mixing；The hydrate metal halide salt is LiCl, NaCl, KCl, MgCl2、CaCl2、NaF、ZnCl2In
The hydrate of one or more mixing.
Further, above-mentioned plastics include polyethylene (PE, C2H4), polypropylene (PP, (C3H6)n), poly terephthalic acid second
Diol ester (PET, (C10H8O4)n), polystyrene (PS, (C8H8)n), polyvinyl chloride (PVC, (C2H3Cl)n), polylactic acid (PLA,
(C3H4O2)n), makrolon (PC, C16H18O5), acrylic acid (PMMA, (C5O2H8)n), nylon (PA, (C12H22N2O2)n) or ABS
Resin (ABS, (C8H8·C4H6·C3H3N) n) or one in the synthetic polymer (such as synthetic rubber) that is made of carbon-carbon bond of skeleton
Kind is two or more.
Further, it is heated in air, under atmosphere of inert gases, nitrogen atmosphere or vacuum condition.Described
When heating atmosphere is inert gas or nitrogen atmosphere, wherein containing the H higher than 0.1% volume fraction2。
Further, the product nano structure carbon material of this method has one or more of characteristic：Large specific surface area
In 500m2g-1；Specific capacitance value is more than 70F g-1；With graphite-structure；There are one symmetrical Raman 2D bands for tool；Containing less than 20 layers
Graphene nano lamella, every layer of thickness is less than 10nm.
Further, above-mentioned metal halide salt is NaCl, and plastics are polyethylene terephthalate (PET), heating
Temperature is 1100 DEG C or more.Preferably 1300 DEG C or more.
The above-mentioned method that carbon material is extracted from plastics is carried out based on following equipment, which includes one with mobile negative
Carry the continuous tunnel furnace of holder；The mobile load bracket is made of refractory material or is laid on metal rail alumina fragments；Tunnel
The setting of stove top is mounted on the heating element at refractory material tomography；The heating element is provided anti-by gas or electrically driven (operated)
Answer required heating temperature；The top of continuous tunnel furnace is equipped with the hole being connected with gas blow-off system, is discharged for collecting in reaction process
Gaseous matter；Refractory container is set in mobile load bracket, wherein installing salt and plastics, is loaded with mobile in reaction process
Holder moves, and from one end of tunnel smelting furnace to the other end, temperature finally goes out continuous tunnel furnace from reduction is increased to；Post-processing and cycle
Device is used to the reaction product in refractory container after heat treatment being dissolved in water, filters the nanostructure carbon materials of suspended state
Material, and it is dried to obtain final product, filtrate is recycled using recycling reacting salt after continuous tunnel furnace waste heat evaporation excessive moisture.
Beneficial effects of the present invention are：It can be in the case where not being limited by mechanical device, plastics and metal halide salt
Together in heating process, wherein salt is in molten condition, and carbonaceous material will be protected, from oxidation；Secondly, fused salt promotes
The further graphitization of carbon material.NaCl in metal halide salt is cheap and easily-available, and has very high boiling point, becomes best choosing
It selects.The nano-carbon material that this method is formed has high-crystallinity and high conductivity, the electricity of high-purity and high surface area and appropriateness
Hold.These characteristics keep the carbon products electric suitable for the conductive carbonaceous additive, ultracapacitor and lithium sulphur being included in energy storage device
Electrode material, hydrogen storage adsorbent, photocatalysis support material, the adsorbent in pond etc. are applied on a large scale.
Description of the drawings
Fig. 1 is the XRD spectrum on PET water bottle fritter.Wide diffraction maximum in the collection of illustrative plates corresponds to anorthic system C10H8O4's
(100) crystal face.
Fig. 2 is the XRD spectrum of sample after PET plastic bottle heats one the whole night at a temperature of 250 DEG C.Diffraction maximum pair in the figure
It should be in crystalline PET (oblique) structure.
Fig. 3 is in 100ml min-1Air mass flow in, heating speed be 40 DEG C of min-1DSC the and TGA heat analysis of PET
Curve.
Fig. 4 is (a) XRD spectrum that PET material is heated to 620 DEG C and 850 DEG C in air；(b) 620 DEG C of SEM pictures；
(c) the SEM partial enlargement pictures of 850 DEG C of SEM pictures and 850 DEG C of (d).
Fig. 5 is PET and NaCl Hybrid Heatings to 1100 DEG C and 1300 DEG C, the product analysis after then cooling and cleaning, (a)
XRD spectrum and (b) Raman spectrum.
The SEM pictures for the carbon material that Fig. 6 is obtained by PET and NaCl Hybrid Heatings to 1100 DEG C.(a) surface is smooth not
The edge of rule particle；(b) presence of graphene nanometer sheet in carbon particle is shown；(c) it is low power SEM image, is graphitized band
It is dispersed in the carbon particle surface of irregular shape；(d) some regions by highly crystalline at graphene nanoplatelets.
Fig. 7 is optical photograph of the PET and NaCl Hybrid Heatings to 1300 DEG C of gained solidification carbon and NaCl.(a) aluminium oxide earthenware
Mixture inside crucible, the mixture (b) taken out from crucible.
Fig. 8 is the SEM pictures for the nanostructured carbon material that PET and NaCl Hybrid Heatings are obtained to 1300 DEG C.(a) see stone
Layer of ink；(b) see that the surface of the graphite linings of carbon material is peeled off, form the nano flake of graphene；(c) it can be become apparent from after amplifying
Ground sees that the surface of the graphite linings of carbon material is peeled off, and forms the nano flake of graphene；(d) it can be more clearly visible that after amplifying
Graphite linings.
Fig. 9 is HRTEM picture of the PET and NaCl Hybrid Heatings to 1300 DEG C of acquisition carbon materials.(a) it is low amplification factor figure
Picture, the hierarchical structure that display material is made of the nano flake of nanometer sheet and fragmentation；(b) it is the shape of the nano flake of fragmentation
Looks magnification at high multiple image；(b) illustration in is the fft analysis of some sheet shaped pieces；(c) sample high-resolution TEM pictures, in figure
It is the FFT patterns on a carbon plate in black rectangle, it is shown that spot corresponding with Nano graphite structure；(d) it is identified in figure
Two thickness out are 5.6nm and 8.5nm.
Figure 10 is N2 adsorption-desorption isotherm of the PET and NaCl Hybrid Heatings to 1300 DEG C of acquisition carbon materials.
Figure 11 is electric conductivity performance of the supercapacitor test of the PET and NaCl Hybrid Heatings to 1300 DEG C of acquisition carbon materials：
(a) V-I relationships, (b) conductivity and density of carbon material and the relationship of pressure, (c) cyclic voltammetric under different scanning rates
(CV) characteristic, (d) electrode manufactured with the carbon material constant current charge-discharge performance under different current densities.
Figure 12 is that Hybrid Heating is to 1300 DEG C in air by PET plastic bottle and NaF, with the carbon materials of postcooling and cleaning acquisition
The Raman spectrum of material.
Figure 13 is PET plastic bottle and MgCl2·6H2Hybrid Heating is obtained to 1300 DEG C with postcooling and cleaning O in a vacuum
The Raman spectrum of the carbon material obtained.
Figure 14 is a preferred reaction process flow chart for being used for continuous production nanostructure graphitized carbon.In figure：1 movement
Load bracket；2 continuous tunnel furnace tops；3 holes being connected with gas blow-off system；Temperature profile in 4 continuous tunnel furnaces；5 from nano junction
The salt recycled in the carbon and salt mixture of structure；6 refractory containers；The crucible of the mixture of 7 loaded plastics and salt；8 plastic materials melt
Change；9 solid salt particles；10 nanostructured carbon materials are dispersed in fuse salt；11 crucibles are cooling enough；The carbon materials of 12 nanostructures
Material.
Specific implementation mode
In order to enable the invention to be proved, it is easier to understand and be easy to be implemented by those skilled in the art, with non-limit
The example of system is described in conjunction with corresponding picture, chart and microphoto, wherein：
As shown in figure 14, preferred reactor includes a tunnel smelting furnace with mobile load bracket.Mobile load branch
Frame 1 is made of refractory material, and alumina fragments are such as laid on metal rail.Controllers can change its speed and enter tunnel
Stove.Continuous tunnel furnace top 2 includes the heating element being mounted at refractory material tomography.Heating element is gas or electrically driven (operated).Tunnel
The top of stove sets that there are one the holes 3 that are connected with gas blow-off system.Temperature profile Fig. 4 out of continuous tunnel furnace find out temperature gradually from
Room temperature T1Increase to adjustable maximum temperature Tmax.Maximum temperature TmaxIt is 1100 DEG C or more, wherein preferably greater than 1200 DEG C, then it is excellent
Choosing is more than 1300 DEG C.Temperature is continuously decreased from maximum temperature later, and the other end temperature that load bracket is moved on to continuous tunnel furnace is T2,
T2Less than 500 DEG C, wherein preferably smaller than 400 DEG C, it is further preferably no larger than 300 DEG C.
In refractory container 6, salt is a kind of metal halide or various metals halide for salt and plastic material fragment
Mixture.It is preferred that salt is NaCl or the salt-mixture containing NaCl.Because NaCl is cheap, and easily obtains.In addition, sodium chloride
Fusing point and boiling point respectively may be about 800 DEG C and 1400 DEG C, show melt NaCl can protect carbonaceous at a high temperature of more than 900 DEG C
Material is from severe oxidation.In addition, the solubility of NaCl in water is very high, therefore can relatively easily be removed simultaneously from system
Recycling.Refractory container 6 is ceramic crucible, such as aluminium oxide (Al2O3)；Or carbon crucible, such as graphite crucible, but need reaction process
It is carried out under protectiveness atmosphere, such as argon gas or nitrogen atmosphere, to avoid the oxidation of carbon crucible.Start heat treatment process, passes through shifting
The crucible 7 of loaded plastics and the mixture of salt is sent into continuous tunnel furnace by dynamic load holder 1.Temperature in stove is by being arranged on continuous tunnel furnace
The heating element in portion 2 controls.Temperature gradually increases, as shown in temperature profile Fig. 4 in continuous tunnel furnace.When the temperature in continuous tunnel furnace is super
When crossing the fusing point of plastic material in crucible, plastic material fusing 8, by continuous tunnel furnace further mobile crucible, temperature be more than
The decomposition point of plastic material.Therefore, plastic material resolves into gas phase, is separated in crucible, solid carbonaceous particles with it is solid
Body salt particle 9 mixes, and gas phase is discharged from the hole that continuous tunnel furnace is connected with gas blow-off system 3.When crucible continues to move along,
Temperature has been more than the fusing point of salt.The further mobile crucible in continuous tunnel furnace, carbonaceous material pass through the promotion of fused salt, graphitization are made to increase
By force.In TmaxWhen, graphitizing process is accelerated, and carbonaceous material forms a kind of carbon material of nanostructure and is dispersed in 10 in fuse salt.
Continuous tunnel furnace is moved further across by crucible, temperature is reduced to the temperature T in exit2.When crucible enough cooling 11, Xiang Qi
Water is added in inside, salt is dissolved in water, crucible internal component includes the liquid phase and nanostructured carbon material being made of water and salt
Suspended phase.The carbon material of nanostructure can be extracted by filter paper.Skilled in the art realises that how by nanostructure
Carbon material (12) is separated from suspended phase.Then,.Salt can be recycled by evaporating moisture in liquid phase.From continuous tunnel furnace
Heat, can be used for evaporating moisture content.The salt 5 recycled from the carbon and salt mixture of nanostructure is passed to starting point and plastics
Material mixes.
Unless be otherwise noted in this example, what material was characterized in carrying out in accordance with the following methods：Scanning electron microscope
(SEM) 450 instruments of Nova Nano-SEM equipped with energy dispersion X-ray analysis instrument (EDX) are characterized in be tested；High-resolution
It is FEI Tecnai F20 field emission microscopes that transmission electron microscope (HRTEM), which characterizes instrument, and accelerating potential is
200kV.X-ray diffraction (XRD) is characterized on 1710 X-ray diffractometers of Philips, using Cu-K alpha rays (k=
1.54A °), step-length and residence time are respectively 0.05 2 θ and 5s, then use X'Pert High Score Plus softwares pair
XRD spectrum is analyzed.Raman spectrum is at one with the He-Ne ion lasers that wavelength is (red, 1.96eV) 633nm
Renishaw 1000 Ramanscope generate.Thermogravimetric (TG) and differential scanning calorimetry (DSC) are analyzed while using SDT-
Q60 heat analysis is tested, and test airflow speed is 100ml min-1, heating rate is 40 DEG C of min-1。Brunauer-
Emmett-Teller (BET) specific surface areas are calculated by nitrogen adsorption/desorption isotherm, at -196 DEG C using static
Adsorption technology, test equipment model TriStar 3000V 6.04.The measurement of conductivity uses brass on a copper stent
Piston (D=20.05mm, H=85.36mm) is compressed to (ID=20.05mm, H in a propylene acid tube by 0.5 gram of carbon material
=45.37mm).Carbon dust is compressed with hydraulic press, the pressure of carbon is made to rise to 6MPa.At various pressures, in brass piston and
By the different current values within the scope of 0.16~3A between copper seat, and corresponding electricity is recorded at 20 DEG C using four probe direct current methods
Gesture.The resistivity of compression carbon dust is calculated using the equation：
ρ=(S × V)/(I × H) (1)
Wherein, ρ is resistivity (μ Ω m), and S is the surface area (mm of acrylic acid pore2), V is potential difference (mV), and I is electric current
(A), H is the height (mm) of compressed powder.Conductivity is to be calculated as the inverse of resistivity.
The electrochemical capacitor performance of carbon product is evaluated using three-electrode system, by carbon material and 10% conduction
Carbon (SP45, BET surface area 45m2g-1) and 10% binder (polytetrafluoroethylene (PTFE), PTFE) mix be made work electricity
Pole.The mixture is with 3.3mg cm-2In foamed nickel current collector of the load capacity coated in diameter 1.2cm.Electrolyte is 6M KOH.It adopts
With platinum filament and saturated calomel electrode (Hg/HgCl n are saturated KCl) respectively as to electrode and reference electrode.With cyclic voltammetry
(CV), constant current charge-discharge and electrochemical impedance spectroscopy (EIS) measure, to evaluate chemical property.The ratio of ultracapacitor
Capacitance (Fg-1) calculated using following equation：
Cs=(I Δs t)/(m Δ V) (2)
Wherein I is discharge current, and Δ t is discharge time, and m is the quality of active material, and Δ V is voltage window.
Embodiment 1
The description of PET material
Fig. 1 is the XRD spectrum on PET water bottle fritter.Broad peak of the collection of illustrative plates using centered on 2 θ=25.4 ° as characteristic peak,
Show that the PET of short range (100) crystallized domains has three oblique crystal structure (C10H8O4, JCPDS card No.50-2275).Total comes
It says, the XRD spectrum of Fig. 1 illustrates that PET is low crystalline texture.
The PET material of this low crystalline texture heats a whole night 260 DEG C in Muffle furnace (on PET fusing points).It is cooled to
After room temperature, obtained heat treatment material is the crystal grain of white big irregular shape, and XRD analysis is carried out to it..In collection of illustrative plates
In diffraction maximum correspond to anorthic crystal structure PET.Most strong diffraction maximum is corresponding to (100) crystal face at 2 θ=25.4 °.Fig. 2
In illustration be crystalline PET scanning electron microscopic picture, it is observed that grain size is more than 0.5 millimeter, sharp edge and smooth surface it is big
Sized particles.The EDX of crystalline PET is analyzed to obtain C:The value of O is 1.8, is less than atom C in PET molecular cells:The theoretical value of O
2.5。
Gonzalez et al. (E.Gonzalez II, M.D.Barankin, P.C.Guschl, and R.F.Hicks,
Remote Atmospheric-Pressure Plasma Activation of the Surfaces of Polyethylene
24 (2008) 12636-12643. of Terephthalate and Polyethylene Naphthalate, Langmuir) respectively
Using XPS analysis, the C in reset condition and plasma treated PET is calculated:O ratio is respectively 3 and 1.7.Original
The C measured on state PET:Higher O values are considered as due to surface contamination.On the other hand, the C of the PET of corona treatment:O
It is caused by causing pet sheet face to have more C-O and C=O because of corona treatment to be worth relatively low.In the present embodiment, according to
C observed by EDX analyses:The reduction of O ratio is the surface electronic irradiation due to PET under microscope.These observation result cards
Real, PET crystallizations occur in process of setting, and plastic bottle is that therefore this high-carbon content, do not have made of pure PET
The material of inorganic matter ingredient is the beneficial source for preparing solid carbonaceous material.
Fig. 3 is the TGA and DSC curve within the temperature range of 25-900 DEG C.There are three endothermic peaks on DSC curve.First
A endothermic peak is caused by the thawing of PET at 254.1 DEG C.Second endothermic peak is 466.8 DEG C, this is attributed to PET
Decomposition, according to TGA curves, it will be seen that the decomposition that its quality has dropped 84.17%, PET starts from 390 DEG C or so.Last
Endothermic peak may be assigned to the part graphitization of remaining carbon material at 791.2 DEG C.
In order to study this endothermic peak, a fritter PET plastic is heated in resistance furnace, respectively test pyrolysis to 620 DEG C and
The XRD and SEM of the black carbon material of 850 DEG C of acquisitions.Fig. 4 (a) illustrates the XRD spectrum of sample.The sample of 620 DEG C of pyrolysis
XRD shows 2 θ=21.2 ° and the two of 43.4 ° diffraction maximums.First diffraction maximum corresponds to the lonsdaleite atom battle array of shortrange order
(002) crystal face of row, d(002)Interlamellar spacing isIn also referred to as disordered graphite or amorphous carbon.Second 2 θ of broad peak=
40-45 °, maximum value 43.4o, correspond to the superposition crystal face of (100) and (101).
It should be mentioned that in graphite hexagonal structure (JCPDS card No.13-0148), (002) diffraction maximum appears in 2 θ
=26.6 °, level spacing isIt is on 42.4 ° and 44.4 ° that diffraction maximum (100) and (101), which respectively appear in 2 θ values,.With
Graphite-phase ratio, the d of unordered carbon material(002)With higher value, this shows that the crystallinity of material is very poor.
A kind of variant of the agraphitic carbon as six purpose square graphites, in this case, the carbon-coating of (002) crystal face can be randomly
It mutually converts, and is rotated around normal graphite linings.
In the XRD spectrum for the PET that 850 DEG C (Fig. 4 a) is decomposed, 2 θ values of the diffraction maximum of (002) and (100)/(101) overlapping
For 25.2 °, (interlamellar spacing is) and 43.2 ° at have maximum value.Compared with the sample of 620 DEG C of pyrolysis, (002) diffraction maximum
Intensity increase, and its transformation to the value of bigger shows the increase of material crystals crystallinity, so as to cause graphited
Occur.
The endothermic peak occurred at 791.2 DEG C in DSC curve is attributed to the graphitization of agraphitic carbon.From the TGA curves of Fig. 3
In as can be seen that residual mass be about 10%.
Further morphology characterization can be obtained from the SEM of sample shown in Fig. 4 b-d.620 DEG C are pyrolyzed obtained carbon
Material, SEM show the particle of a large amount of irregular shapes, have sharp edge, grain size is up to hundreds of microns.As shown,
Although heating in air, the sign not aoxidized on material shows that inoxidizability is very high.EDX to sample analysis shows that,
C:The ratio of O is 5.2, this is higher than 1.8 observed in crystalline PET.However, existing in the agraphitic carbon of 620 DEG C of pyrolysis
Relatively high oxygen content, this may be the complete graphited major obstacle of the material.850 DEG C of pyrolysis (Fig. 4 c and d) obtain
The SEM photograph of carbon material show, it is roughly the same with the pattern that 620 DEG C are pyrolyzed observed by obtained material, it is characterized in that not
The bulky grain of regular shape.However, having small pit on the magnification at high multiple image display surface of Fig. 4, this may be due to slight
Caused by oxidation.Nevertheless, these micrographs show the high antioxidant of this material, even at up to 850 DEG C
Under high temperature.
It is reported that temperature is more than that for air to carbon material with stronger oxidation, this depends on carbon material at 500 DEG C
Property, including degree of graphitization, granularity and porosity (V.Zh.Shemet, A.P.Pomytkin and V.S.Neshpor,
High temperature oxidation behavior of carbon materials in air,Curhon 31
(1993)1-6.).According to Hahn, the thermal oxide of highly oriented pyrolytic graphite is happened at 550-950 DEG C of (H.Pan, J.Li and
Y.P.Feng,Carbon Nanotubes for Supercapacitor,Nanoscale Research Letters 5
(2010)654–668.).At a temperature of less than 875 DEG C, oxidation process is the pit formation by rejected region.However,
At higher temperature, oxidation is happened in defect and base plane.It is well known that the oxidation rate of agraphitic carbon compares graphitized carbon
Material wants high.In the case of not by equipment limit, in air PET pyrolysis generate carbon material high antioxidant mainly by
In its surface defect with huge particle size, low-porosity and low-density.
Embodiment 2
The present embodiment implements the heat treatment situation of PET in NaCl.One plastic water bottle is cut into small pieces (about with scissors
10×5mm).9.83g plastic sheets are placed in an alumina crucible, inside diameter and height be respectively 50mm and
100mm.Then, 50.80gNaCl (NaCl, AladdinC111533, purity 99.5%) is added in crucible.This crucible
It is placed in a Muffle furnace, is heated in air atmosphere, temperature is with 20 DEG C of min-1Rate is warming up to 1100 DEG C, cold immediately after
But get off, rate roughly the same with the rate of heat addition is cooled to room temperature.Including the salt of solidification and the black solid mixture of carbon material
It is placed in enough distilled water, salt is completely dissolved.Then, vacuumizing filtration is carried out with filter paper, by carbon material from mistake
It is recycled in screening, it is then dry at a temperature of 80 DEG C.
Fig. 5 shows the XRD for the PET-NaCl mixtures for being heated to 1100 DEG C and 1300 DEG C (fusing point of NaCl is 801 DEG C)
And Raman spectrum, it is then cooling so that NaCl is deviate from cleaning product.The XRD spectrum of the black solid product obtained at 1100 DEG C is aobvious
Lonsdaleite and the corresponding diffraction maximums of cube NaCl are shown.The latter is remaining NaCl, even if after cleaning process, it is still deposited
It is in carbon material.On the other hand, the diffraction maximum of (002) lonsdaleite structure appears in 2 θ=25.13 °, and interplanar distance is Maximum value in 2 θ=43.18 ° corresponds to (100) and (101) crystal face of overlapping.
As shown in Figure 5 b, 1100 DEG C of Raman spectrums that carbon material is prepared in melting NaCl provide the graphite knot of material
Structure information.The D bands caused by defect and G bands correspond to the stretching vibration of carbon material substrate graphene layer, respectively appear in
1372、1599cm-1Raman shift values on.In addition, low intensive 2D bands, that is, D bands frequency multiplication peak, Raman shift is
2703cm-1。ID/IGCorresponding with defect level or with carbon material degree of graphitization is inversely proportional, and it is 0.94 to be worth..In addition, the production
The I of product2D/IGQuality of the intensity than indicating graphene platelet, value is 0.23.Generally speaking, XRD and Raman analysis show sample
The presence of middle nano-graphite crystallite.Fig. 6 is the SEM pictures of the carbon material of 1100 DEG C of generations.Fig. 6 a show that surface is smooth not
The edge of rule particle.This pattern seems that the air with PET is heated to the substantially phase of observed pattern in 850 DEG C of sample
Seemingly, and in melting NaCl there is a large amount of graphitization bands on the smooth surface of the carbon material generated.Fig. 6 b are clearly illustrated
The presence of graphene nanometer sheet in carbon particle.Fig. 6 c are low power SEM image, show that these graphitization bands are dispersed in irregular shape
The carbon particle surface of shape.As shown in the SEM figures of Fig. 6 d, some regions are by highly crystalline at graphene nanoplatelets.This discovery
Demonstrating can be by being simply heated to prepare the carbon nanometer of carbonization structure close to 1100 DEG C of low temperature in NaCl
Material.
Embodiment 3
In order to study the influence of temperature, the mixed proportion of PET-NaCl is same as Example 2, and mixture is heated to 1300
DEG C, same heating speed is 20 DEG C of min-1, it is then cooled to room temperature.Fig. 7 a show the mixture of salt and carbon products in crucible.
In order to confirm carbon material distributing position in salt, breaks alumina crucible quilt, the mixture of salt and carbon material is taken from crucible
Go out (Fig. 7 b).As can be seen that carbon material is fully distributed on the NaCl of solidification.Demonstrating height of the carbon product in melting NaCl can
Dispersibility.The solid mixture is added in 500ml distilled water.In the course of dissolution of sodium chloride, carbonizable substance swims in water
On face, indicate it with low density.The obtained suspended substance 20min of stirring, is then filtered, the carbon material on filter paper is dried
Night.The XRD analysis (Fig. 5 a) of obtained sample shows the presence at (002) peak of six purpose square graphites of 2 θ=25.9 °, interlamellar spacing
ForThe diffraction maximum of 2 θ=42.5 ° corresponds to the crystal face of overlapping (100) and (101).As can be seen in the figure, related to NaCl
Diffraction peak almost disappeared from collection of illustrative plates, this may be due to caused by cleaning process.The Raman spectrum of sample is (such as
Fig. 5 b) provide information about generated carbon material quality.The spectrum shows a relatively small D bands to exist
1364cm-1And one drastically G bands outstanding in 1590cm-1。ID/IGRatio can measure and be less than from raman spectrum
0.47.This observed result discloses the presence in the crystal carbon domain with low-defect-density.In addition to this, in 2723cm-1Occur
One symmetrical 2D band, I2D/IGRatio is 0.52.These observation confirms that, carbon material is made of several layer graphenes.
Fig. 8 shows the SEM micrograph of obtained nanostructured carbon material.In Fig. 8 a and d it will be clear that
Graphite linings.It will be clear that the surface of the graphite linings of carbon material is peeled off in Fig. 8 b and c, the nano flake of graphene is formed.
The EDX of carbon material analysis shows that, C:The atom ratio of O is 28.4.
TEM micrograph piece (Fig. 9) provides further evidence for graphitized carbon nano structure.Fig. 9 a are low amplification factor
Image, the hierarchical structure that display material is made of the nano flake of nanometer sheet and fragmentation.Fig. 9 b are that the pattern high power of the latter is put
Big image, it is shown that the crystal edge of nano flake.The illustration of Fig. 9 b is the fft analysis of some sheet shaped pieces.In FFT patterns
The ring of light indicates that interlamellar spacing isCorresponding to the crystal face of the lonsdaleite of (002).The pattern confirms the carbon generated in melting NaCl
The nanocrystalline structure of material.C and d shows sample high-resolution TEM pictures in Fig. 9, there is very high crystallization knot in the sample
Structure.It is the FFT patterns on a carbon plate in black rectangle in 9c, it is shown that spot corresponding with Nano graphite structure.Fig. 9 d
In show some graphite flakes, two be identified in figure thickness be 5.6nm and 8.5nm.Carbon material is carried out
Discovery is gone through, graphite flake is formed by 4-20 layers, and 10 nanometers are less than per layer thickness.
The surface nature of nanostructured carbon material is had studied by N2 adsorption-desorption method, Figure 10 is isothermal curve.According to
IUPAC classifies [40], this curve is II type thermoisopleths, and there is H4 types to lag winding, this shows that there are non-porous or slit-type macropores
Structure.The BET specific surface area of carbon material is 522m2g-1。
As a result, it was confirmed that the PET heat treatments in melting NaCl are used to prepare a kind of carbon nano-structured material, this structure includes
The pieces and a higher specific surface area of kish nanometer sheet and thickness less than 10 nanometers.
It should be noted that together with surface area and crystallinity, conductivity is to determine the property of carbon material in practical applications
One of the most important parameter of energy, such as ultracapacitor, electromagnetic shielding, catalyst and metal ion battery.However, in carbon material
In, with the increase of specific surface area, conductivity would generally reduce.
Embodiment 4
As described in Example 3, the graphite of nanostructure is produced.Using four probe method, caused by under different pressures
The conductivity of carbon material is evaluated.Figure 11 a show the Current Voltage response relation of carbon material at various pressures, 0.5g
Sample shows perfect ohm reaction within the scope of 0.01-6.13MPa.Conductivity and density value are illustrated in Figure 11 b and are applied
The calculating of stressed functional relation, wherein density value is by considering that the pillar height of compressed powder obtains.As it can be seen that in 0.10MPa
Light pressure under, the density of carbon dust is 0.10g cm-3, show 12.53S m-1Conductivity.By the way that pressure is increased to
4.14MPa, density and electric conductivity increase respectively to 0.89g cm-3With 1071.24S m-1.From the figure, it can be seen that density increases
To 1.04g cm-3, pressure is further increased to 5.47MPa, but corresponding conductivity can slightly decrease 1058.43S m-1.From
Figure 11 a similarly increase pressure, the resistance of sample is from 8.76m Ω to 6.79m it is observed that in the slope of I-V curve
Ω.With the increase of pressure and increase that the decline of conductivity is construed to pressure makes the pillar height of compressed powder reduce, according to formula (1)
Conductivity decline can be obtained.As can be seen that increasing pressure to 6.13MPa, the value of density and conductivity increases to 1.06g cm-3With
1150.15S m-1.The significant conductivity obtained.
Embodiment 5
As described in Example 3, nanostructure graphite is produced.Carbon materials are evaluated with the three-electrode system of a KOH containing 6M
The electrochemical behavior of material.It is with 5-200mV s as shown in fig. 11c-1Sweep speed record CV characteristics, show approximate square
The shape of shape shows that carbon material is mainly charged by electrochemical double-layer capacitance mechanism, have preferable high rate performance and
Without fake capacitance effect.It further demonstrates the high-carbon purity and conductivity of sample.
Figure 11 d show current density in 0.2~20A g-1Between potential-time response for measuring.As can be seen that electric discharge
Time is substantially equal to the charging time, and curve is almost isosceles triangle, indicates high invertibity.According to constant current charge/discharge curve,
Current density is respectively 0.2,0.5,1.0,5.0,10.0 and 20A g-1Corresponding specific capacitance is calculated as 90.2,78.6,73.0,
58.0,50.0 and 40.0F g-1。
Embodiment 6
100gNaF is mixed with 20g PET plastic pieces.The mixture is placed in alumina crucible, is heated to 1300 DEG C,
And keep 1h in aerial electric furnace.Then, crucible is cooled down, is rinsed and then filtered out obtained with enough water
Salt.The dry 2h at a temperature of carbon material obtained on filter paper is at 80 DEG C.The Raman spectrum of the carbon material obtained such as Figure 12 institutes
Show.Raman spectrum is in 1322,1571 and 2640cm-1Place respectively illustrates the presence of D, G and 2D band, the i.e. feature of graphite-structure.
ID/IGIntensity ratio can be calculated as 0.5 from spectrum, indicate the degree of graphitization of height.2D bands in Raman spectrum be it is relatively strong and
Symmetrically, the presence of a small amount of graphene layer is represented.
Embodiment 7
50gMgCl2·6H2O and 10g PET plastic fragments mix, and are placed in alumina crucible, heat treatment and washing
Process is same as Example 6, unique to distinguish, and is heating process 10-2Tube furnace under mbar vacuum carries out.Obtained carbon
The Raman spectrum of material is as shown in figure 13.Respectively in 1307,1567 and 2620cm-1In observe D, G and 2D of graphitic carbon material
Band.Raman I in carbon materialD/IGRatio is calculated as 0.3 from spectrum, indicates the degree of graphitization of height.
The process of production Conducting nanostructures graphitized carbon can in a continuous manner carry out in continuous tunnel furnace, such as Figure 14 institutes
Show.Continuous tunnel furnace provides continuous operation for the preparation of nanostructure carbon.
Claims (10)
1. a kind of method for extracting carbon material from plastics, which is characterized in that generate nanostructure carbon materials by heating mixture
Material, the mixture are made of at least one plastics and at least one metal halide salt；Its heating temperature is：Metal halide
Fusing point≤heating temperature≤+ 50 DEG C of boiling point of salt.
2. a kind of method for extracting carbon material from plastics according to claim 1, which is characterized in that the metal halide
Object salt is hydrated metal halides salt.
3. a kind of method for extracting carbon material from plastics according to claim 1 or 2, which is characterized in that heating temperature
More than the fusing point of metal halide salt, when being less than boiling point, the mixture of nanostructured carbon material and salt is generated, water is used after cooling
Dissolve salt therein, and filter, the filtrate recycling containing salt, filter object dries to obtain nanostructured carbon material.
4. a kind of method for extracting carbon material from plastics according to claim 1 or 2, which is characterized in that generation is received
The conductivity of rice structure carbon material is more than 1000S m-1Or Raman ID/IGValue be less than 0.5.
5. a kind of method for extracting carbon material from plastics according to claim 1 or 2, which is characterized in that the gold
It is LiCl, NaCl, KCl, MgCl to belong to halide salts2、CaCl2、NaF、ZnCl2In one or more mixing；The hydrate
Metal halide salt is LiCl, NaCl, KCl, MgCl2、CaCl2、NaF、ZnCl2In one or more mixing hydrate.
6. a kind of method for extracting carbon material from plastics according to claim 1 or 2, which is characterized in that the plastics
Including polyethylene, polypropylene, polyethylene terephthalate, polystyrene, polyvinyl chloride, polylactic acid, makrolon, propylene
One or more of acid, nylon, ABS resin or synthetic rubber.
7. a kind of method for extracting carbon material from plastics according to claim 1 or 2, which is characterized in that in air, lazy
It is heated under property atmosphere, nitrogen atmosphere or vacuum condition；The heating atmosphere is inert gas or nitrogen atmosphere
When enclosing, wherein containing the H higher than 0.1% volume fraction2。
8. a kind of method for extracting carbon material from plastics according to claim 1 or 2, which is characterized in that this method
Product nano structure carbon material has one or more of characteristic：Surface area is more than 500m2g-1；Capacitance is more than 70F g-1；Tool
There is graphite-structure；There are one symmetrical Raman 2D bands for tool；Containing the graphene nano lamella less than 20 layers, every layer of thickness is less than
10nm。
9. a kind of method for extracting carbon material from plastics according to claim 1 or 2, which is characterized in that metal halide
Object salt is NaCl, and plastics are polyethylene terephthalate (PET), and heating temperature is 1100 DEG C or more.
10. any method for extracting carbon material from plastics described in claim 1-9 is carried out based on following equipment, feature exists
In the equipment includes a continuous tunnel furnace with mobile load bracket；The mobile load bracket be made of refractory material or
Alumina fragments are laid on metal rail；The setting of continuous tunnel furnace top is mounted on the heating element at refractory material tomography；The heating
Element is to provide heating temperature needed for reaction by gas or electrically driven (operated)；The top of continuous tunnel furnace is equipped with to be connected with gas blow-off system
Hole, for collecting the gaseous matter discharged in reaction process；Refractory container is set in mobile load bracket, wherein installing salt
And plastics, it is moved with mobile load bracket in reaction process, from one end of tunnel smelting furnace to the other end, temperature is from being increased to drop
It is low, finally go out continuous tunnel furnace；Post-processing and circulator are for the reaction product in refractory container after heat treatment to be dissolved in
Water, filters the nanostructured carbon material of suspended state, and is dried to obtain final product, and it is extra that filtrate is evaporated using continuous tunnel furnace waste heat
Reacting salt is recycled after moisture to recycle.
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| CN113381005A (en) * | 2021-05-27 | 2021-09-10 | 厦门大学 | Single-crystal ternary cathode material, continuous preparation method and device and application |
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