CN109540941A - A method of detection carbon material type - Google Patents
A method of detection carbon material type Download PDFInfo
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- G01N23/00—Investigating or analysing materials by the use of wave or particle radiation, e.g. X-rays or neutrons, not covered by groups G01N3/00 – G01N17/00, G01N21/00 or G01N22/00
- G01N23/20—Investigating or analysing materials by the use of wave or particle radiation, e.g. X-rays or neutrons, not covered by groups G01N3/00 – G01N17/00, G01N21/00 or G01N22/00 by using diffraction of the radiation by the materials, e.g. for investigating crystal structure; by using scattering of the radiation by the materials, e.g. for investigating non-crystalline materials; by using reflection of the radiation by the materials
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- G01N21/17—Systems in which incident light is modified in accordance with the properties of the material investigated
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- G01N21/31—Investigating relative effect of material at wavelengths characteristic of specific elements or molecules, e.g. atomic absorption spectrometry
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- G01N21/62—Systems in which the material investigated is excited whereby it emits light or causes a change in wavelength of the incident light
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- G01N21/35—Investigating relative effect of material at wavelengths characteristic of specific elements or molecules, e.g. atomic absorption spectrometry using infrared light
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Abstract
The present invention provides a kind of methods for detecting carbon material type.The method includes the steps: the first, second, and third sample is separated from carbon material, the first, second sample is heat-treated in the first, second temperature, obtains the first, second heat treated sample；X-ray diffraction test is carried out to the first, second heat treated sample and third sample, obtains the first, second, and third ray test result, Raman spectrum test is carried out to the first and second heat treated samples, obtains the first and second Raman test results；Judge whether carbon material is graphene oxide according to the first, second, and third ray test result and the first and second Raman test results, in the case where judging the carbon material for graphene oxide, the type and quantity of functional group and the number of plies of carbon material on the carbon material are determined.Beneficial effects of the present invention can include: method is easy and effective, can efficiently and accurately identify carbon material.
Description
Technical field
The present invention relates to measuring for materials fields, particularly, be related to it is a kind of it is simple and feasible judge carbon material whether be
The method of graphene oxide.
Background technique
Graphene is sp2The two-dimensional atomic crystal of the hexagonal honeycomb shape structure of the tightly packed formation of carbon atom, can be with heap
Pile forms three-dimensional graphite, curls into one-dimensional carbon nanotube, can also be wrapped to form the fullerene of zero dimension, is carbon material man
One nova of race.But until 2004, the Geim and Novoselov of Univ Manchester UK etc. removed skill using adhesive tape
Art just successfully prepares single-layer graphene for the first time, this discovery has also overthrown scientist about ideal two dimensional crystal material
It existing at room temperature cannot be foretold due to thermodynamic phase.As a kind of ideal two-dimensional atomic crystal, graphene
Conductivity and thermal conductivity, huge theoretical specific surface area with superelevation, high Young's modulus and tensile strength, it is expected to micro-
It is answered in the wide field of nanometer electronic device, Photoelectric Detection and transition material, structure and function enhancing composite material and energy storage etc.
With.
Currently, the preparation method of graphene is numerous, it is basically divided into two class method of Top-down and Bottom-up, wherein
Top-down method includes mechanical phonograph recorder separation and graphite oxide reduction method etc., and Bottom-up method includes chemical vapor deposition
(CVD) method, epitaxial growth method etc..The size that graphene is made in every kind of method is all different, and each method has respectively
Advantage and drawback.Most common is exactly to pass through intercalation, removing, oxidation stone using oxidation-reduction method (such as improvement Hummers method)
The obtained graphite oxide of ink, then graphene oxide solution is made by removing to graphite oxide suspension ultrasound, finally using various
Reducing agent, which restores graphene oxide, just can be obtained redox graphene, this method is meeting us to graphene product as far as possible
While matter requires, production technology is also simplified as far as possible.Based on this method, the technology of preparing of graphene oxide is gradually at this stage
Maturing, but still need to continue to explore, one of maximum bottleneck is just structure-controllable and the rule of the graphene oxide before reduction
Modelling preparation.
Generally, it is considered that the only number of plies in 10 layers of graphite below just can be regarded as two-dimensional structure, titled with the title of graphene
Meaning.According to the difference of the graphene oxide number of plies, significant changes can occur for electronic structure, to influence its electric conductivity, this is in lithium
The application field of ion battery is very crucial.In addition, some researches show that, the thermal conductivity of single-layer graphene oxide, translucency is more preferable,
Multilayer graphene oxide is higher to the disposal efficiency of organic dyestuff.Therefore, to the research of graphene oxide number of plies measurement method
Facilitate the deep relationship understood between graphene oxide performance and microstructure.
In order to which it plays bigger effect in the related art, people go to understand graphene oxide with furtheing investigate in recent years
Structural property (such as number of plies), and the structural property of graphene oxide and the type and quantity of its functional group are closely related, because
This, the identification to graphene oxide, especially the identification of functional group's type and quantity and the number of plies is highly important thereon.
And utilize different characterization method realizations to the identification of product graphene oxide to the controllable of the above graphene oxide
Metaplasia, which produces, can play crucial directive function, and obtained characterization result is combined the knot analyzed, obtained with basic theory
By for exploring graphene oxide physicochemical characteristics, improving its technology of preparing and further investigation mechanism has important value
And meaning.Accordingly, we have proposed a kind of identification methods of simple and feasible graphene oxide.
Summary of the invention
For the deficiencies in the prior art, it is an object of the invention to solve above-mentioned one existing in the prior art
Or multiple problems.For example, one of the objects of the present invention is to provide a kind of methods of simple and feasible detection carbon material type.
To achieve the goals above, the present invention provides a kind of methods for detecting carbon material type.The method may include
Following steps: separating the first sample, the second sample and third sample from carbon material, carries out hot place in the first temperature to the first sample
Reason, obtains the first heat treated sample, is heat-treated to the second sample in second temperature, obtains the second heat treated sample, wherein
First temperature selects within the scope of 450~700 DEG C, and second temperature selects within the scope of 850~1150 DEG C；To the first heat treatment sample
Product, the second heat treated sample and third sample carry out X-ray diffraction test, accordingly obtain the first ray test result, second penetrate
Line test result and third ray test result carry out Raman spectrum survey to the first heat treated sample and the second heat treated sample
Examination, it is corresponding to obtain the first Raman test result and the second Raman test result；Carbon material is judged according to third ray test result
Lamella it is whether peeling-off, according to the first, second, and third ray test result and the first and second Raman test results
Judge whether carbon material has oxygen-containing functional group, if judging result be carbon material piece interlayer it is peeling-off and have oxygen-containing official
It can roll into a ball, then the carbon material is that graphene oxide determines the carbon in the case where judging the carbon material for graphene oxide
The type and quantity of functional group and the number of plies of carbon material on material, wherein whether the lamella for judging carbon material is shelled
From the step of include: the crystal parameter of third sample to be obtained according to the third ray test result, and then obtain third sample
Interplanar distance, if the interplanar distance of third sample is greater than the interplanar distance of graphite, and the X ray diffracting spectrum phase with graphite
Than, there is new diffraction maximum on the diffracting spectrum of third ray test result, then concludes that the piece interlayer of carbon material is peeling-off, it is no
It not can determine that the piece interlayer of carbon material is peeling-off then；It is described to judge whether carbon material there is the step of oxygen-containing functional group to include:
If occurring in the diffracting spectrum of the first ray test result and the second ray test result respectively compared with third test result
Diffraction peaks broadening and peak position are deviated to wide-angle, and the second ray test result is than wideization of the first ray test result and inclined
Shifting becomes apparent from, moreover, the intensity ratio at the peak D and the peak G is surveyed greater than the first Raman in the Raman spectrogram of the second Raman test result
Test result, then concluding has oxygen-containing functional group in carbon material, otherwise not can determine that carbon material has oxygen-containing functional group；The determination
The step of type and quantity of functional group includes: to separate the 4th sample and the 5th sample from carbon material on carbon material, to the 4th sample
Product carry out ftir analysis test, obtain the infrared spectrogram of carbon material, carry out X-ray light to the 5th sample
Electron spectroscopy analysis test, obtains the x-ray photoelectron spectroscopy figure of carbon material；According to the infrared spectrogram and the energy spectrum diagram
Determine the type and quantity of functional group on carbon material；The step of determining carbon material number of plies includes: to separate the 6th from carbon material
Sample carries out Raman spectrum test to the 6th sample, obtains third Raman test result；According to the drawing of third Raman test result
Graceful spectrogram calculates IG/I2D, work as IG/I2DWhen less than 1.0, tentatively judge carbon material for single or double layer structure；Work as IG/I2DFor
When 1.0~1.5, tentatively judge carbon material for 3 layers or 4 layers of structure；Work as IG/I2DWhen greater than 1.5, tentatively judge carbon material for 5 layers
The above structure, wherein the IGIndicate G peak intensity, the I2DIndicate 2D peak intensity.
In an exemplary embodiment of the present invention, the carbon material can be to obtain according to graphene oxide preparation method
The product arrived, or can be for according to product obtained from redox graphene preparation method.
In an exemplary embodiment of the present invention, the graphite-phase should be the graphene oxide preparation method or
The interplanar distance of the raw material of the redox graphene preparation method, the graphite can be prepared by the following: to described
Graphite carries out X-ray diffraction test, obtains the crystal parameter of graphite, and then obtain the interplanar distance of graphite.
In an exemplary embodiment of the present invention, the crystal parameter may include the indices of crystallographic plane or the angle of diffraction.
In an exemplary embodiment of the present invention, described to obtain in the case where the crystal parameter is the angle of diffraction
The step of interplanar distance can include: interplanar distance, the formula 1 are obtained by formula 1 are as follows: 2dsin θ=n λ, in formula, d is crystalline substance
Interplanar distance, λ are the wavelength of X-ray, and n is diffraction progression, and θ is the 1/2 of the angle of diffraction, i.e. 2 θ are the angle of diffraction.
In an exemplary embodiment of the present invention, diffraction maximum new on the X ray diffracting spectrum may include (100)
Crystallographic plane diffraction peak.
In an exemplary embodiment of the present invention, first temperature can select within the scope of 500~600 DEG C, institute
Stating second temperature can select within the scope of 900~1100 DEG C.
In an exemplary embodiment of the present invention, on the determining carbon material the step of functional group's type can include:
Middle infrared is searched in the infrared spectrogram, obtains the corresponding wave number of absorption peak on the middle infrared, by the wave number
It is compared with ir data library, determines the type of functional group on carbon material；
On the determining carbon material the step of number of functional groups can include: judge the energy spectrum diagram according to the size in conjunction with energy
The above corresponding element in each peak, is modified by peak intensity of the sensitivity factor to peak corresponding to each element, by each after amendment
Ratio between peak peak intensity corresponding to element obtains the relative amount ratio of each element, according to the relative amount ratio, determines carbon materials
The quantity of Liao Shang functional group.
In an exemplary embodiment of the present invention, the functional group's type, quantity on the determining carbon material the step of
Later, the method may also include that the functional group's type and number of functional groups according to the determination, obtain each on the carbon material
The quantity of functional group.
In an exemplary embodiment of the present invention, the wavelength of middle infrared described in oxygen-containing functional group is 2.5~25 μm.
The middle infrared may include characteristic frequency area and fingerprint region.The wavelength in the characteristic frequency area can be 2.5~7.7 μm, described
The wavelength of fingerprint region is greater than 7.7 μm, not larger than 25 μm.
Described the step of obtaining the corresponding wave number of absorption peak on the middle infrared can include: can be in the characteristic frequency area
The corresponding wave number of upper acquisition absorption peak obtains the corresponding wave number of absorption peak on the fingerprint region.
In an exemplary embodiment of the present invention, if element corresponds to multiple peaks in the energy spectrum diagram, with described
The peak intensity of highest peak is as the modified object in multiple peaks.
In an exemplary embodiment of the present invention, the area or intensity for choosing highest peak are as the base quantitatively calculated
Plinth, and intensity is modified using sensitivity factor.
An exemplary embodiment according to the present invention, the ftir analysis is surveyed and X-ray photoelectricity
Requirement of the sub- energy spectrum analysis test to graphene oxide is: graphene oxide powder is carried out tabletting by the powder of tabletting.
An exemplary embodiment according to the present invention is tentatively judging the carbon material for the feelings of single or double layer structure
Under condition, the 7th sample is separated from the carbon material, the 7th sample is tested using atomic force microscope, described in determination
Carbon material is single or double layer structure；
In the case where judging the carbon material tentatively for 3 layers or 4 layers of structure, calculates the third Raman test result and draw
The Lorentz force peak number of the peak the 2D fitting of graceful spectrogram, differentiating carbon material is 3 layers or 4 layers of structure；Tentatively judging the carbon materials
In the case that material is 5 layers or more structure, the 8th sample is separated from the carbon material, obtains the by high resolution TEM
The electron micrograph image of eight samples, observation determine the specific number of plies of carbon material.
In an exemplary embodiment of the present invention, described using atomic force microscope the 7th sample to be tested
Step can include: obtain the three-dimensional image of the 7th sample using atomic force microscope, and by the three-dimensional image
The thickness of display and the graphene oxide thickness of single layer compare, so that it is determined that the carbon material number of plies is single or double layer.
In an exemplary embodiment of the present invention, described preliminary to judge the step of carbon material is single or double layer structure
Can include: the halfwidth at the peak 2D is 28cm-1~32cm-1And IG/I2DIn the case that the intensity ratio at peak is less than 0.7, just
Step judges carbon material for single layer structure；Halfwidth at the peak 2D is 48cm-1~52cm-1And IG/I2DThe intensity ratio at peak is
More than or equal to 0.7 less than 1.0 in the case where, tentatively judge carbon material for double-layer structure.
Compared with prior art, beneficial effects of the present invention can include: method is easy and effective, can be efficiently and accurately
Identify whether carbon material is graphene oxide and the specific number of plies of graphene oxide, the type and quantity of functional group.
Detailed description of the invention
By the description carried out with reference to the accompanying drawing, above and other purpose of the invention and feature will become more clear
Chu, in which:
Fig. 1 shows the XRD spectra of crystalline flake graphite；
Fig. 2 shows the XRD spectras for the carbon material not being heat-treated；
Fig. 3 shows the XRD spectra of carbon material after 550 degree of heat treatments；
Fig. 4 shows the XRD spectra of carbon material after 1000 degree of heat treatments；
Fig. 5 shows the Raman spectrogram of crystalline flake graphite；
Fig. 6 shows the Raman spectrogram for the carbon material not being heat-treated；
Fig. 7 shows the Raman spectrogram of carbon material after 550 degree of heat treatments；
Fig. 8 shows the Raman spectrogram of carbon material after 1000 degree of heat treatments；
Fig. 9 shows the FTIR spectrum figure for the carbon material not being heat-treated；
Figure 10 shows the xps energy spectrum figure for the carbon material not being heat-treated；
Figure 11 shows the high resolution TEM figure of carbon material.
Specific embodiment
Hereinafter, the side of detection carbon material type of the invention will be described in detail in conjunction with attached drawing and exemplary embodiment
Method.Of the invention first, second, third, fourth, the five, the six, the 7th and 8th etc. does not indicate sequencing, is only used for phase
Mutually difference.
When a branch of homogeneous X-ray is irradiated on the crystal of material, the electronics in crystal around atom is become by the X-ray period
The electric field action of change and vibrate, thus make each electronics become emit spherical electromagnetic wave secondary wave source.Emitted spherical wave
Frequency it is consistent with incident X-ray.Periodicity based on crystal structure, each atom (electronics on atom) in crystal
Scattered wave can be interfered and is superimposed, referred to as coherent scattering or diffraction.Diffraction phenomena of the X-ray in crystal, substantially
The result that a large amount of atomic scattering waves interfere.Diffraction pattern caused by every kind of crystal all reflects the atom point of crystals
Cloth rule.According to above-mentioned principle, the feature of the diffraction pattern of certain crystal is most importantly two: 1) distribution of the diffracted ray in space
Rule；2) intensity of diffraction harness.Wherein, the regularity of distribution of diffracted ray is by unit cell dimension, shape, position to and interplanar distance determine
Fixed, diffracted ray intensity then depends on the type, number and arrangement mode of atom in structure cell.Therefore, different crystal has different
Diffracting spectrum.When meeting diffraction conditions, bragg's formula: 2dsin θ=n λ can be applied, is come using the X-ray of known wavelength
The angle θ is measured, to calculate interplanar distance d, this is for crystal structure analysis；The other is being surveyed using the crystal of known d
The angle θ is measured, to calculate the wavelength of characteristic X-ray, and then element contained in sample can be found in existing data.
Raman spectrum is the effective tool for characterizing carbon nanomaterial structure feature and performance.It is imitated using Raman scattering
It answers, the scattering spectrum different from incident light frequency is analyzed to obtain molecular vibration, rotation aspect information, and be applied to divide
A kind of analysis method of minor structure research.So-called Raman scattering is a kind of inelastic scattering effect of the molecule to photon, when with
The exciting light sub-irradiation period of the day from 11 p.m. to 1 a.m of certain frequency, the frequency of a part scattering light and the frequency of incident light are equal.This scattering is point
A kind of elastic scattering of the son to photon.Collision only between molecule and photon is elastic collision, when not having energy exchange, can just be gone out
Existing this scattering, the scattering are known as Rayleigh scattering.The frequency of some scattering light and the frequency of exciting light differ, this to dissipate
Penetrating becomes Raman scattering (and being divided into stockes line and anti-stockes line).And the Raman scattering signal is received and drawn
The method of spectrum analysis can be described as Raman spectrum analysis, and common scattered signal is stockes line.Carbon nanomaterial Raman light
The peak G (1580cm in spectrum-1Near) represent sp2The E of carbon atom2gModel of vibration represents orderly sp2Bond structure, the peak D
(1350cm-1Near) defect and amorphous structure for being located at graphene edge are then represented, usually use the intensity ratio at the peak D and the peak G
ID/IGTo evaluate the degree of graphitization of nano-carbon material, ID/IGIt is worth smaller, shows that the order degree of graphite is higher, ratio is bigger,
Show that the unordered degree of graphite is bigger.Moreover, when being characterized to graphene oxide, wave crest formed in Raman map
The features such as shape, position and intensity all corresponding change can occur with the increase of the graphene oxide number of plies.
When Infrared irradiation of the material by frequency consecutive variations, molecule can absorb the radiation of certain frequencies, and by
It is vibrated or rotational motion causes the net change of dipole moment, generates the jump of molecular vibration and rotational energy level from ground state to excitation state
It moves, weakens the transmitted intensity corresponding to these absorption regions.The percentage transmittance and wave number or wavelength for recording infrared light are closed
It is curve, just obtains infrared spectroscopy.It is abscissa that infrared spectrogram, which leads to common wavelengths (λ) or wave number (σ), indicates the position of absorption peak
It sets, is ordinate with light transmittance (T%) or absorbance (A), indicates absorption intensity.In organic molecule, constitutional chemistry key
Or the atom of functional group is in the state constantly vibrated, vibration frequency is suitable with the vibration frequency of infrared light.Therefore, use is infrared
When light irradiates organic molecule, absorption of vibrations, different chemical bonds or official can occur for chemical bond or functional group in molecule
Absorption frequency difference can be rolled into a ball, different location will be on infrared spectroscopy, thus can get in molecule containing which kind of chemical bond or
The information of functional group.
X-ray photoelectron spectroscopic analysis (X-ray photoelectron spectroscopy, XPS) is gone with X-ray
Radiation sample comes out the inner electron of atom or molecule or valence electron stimulated emission.It is known as by the electronics that photon excitation comes out
Photoelectron can measure photoelectronic energy, and using photoelectronic kinetic energy as abscissa, relative intensity (pulse/s) is that ordinate can
Make photoelectron spectroscopy figure.It can analyze reaction of atomic according to photoelectron the intensity of spectral line in energy spectrum diagram (area of Photoelectron peak)
Content or relative concentration.
Atomic force microscope (AFM) is observed and is analyzed using interaction force generally existing between sample and scanning needle point
Object surface appearance feature.It has a nanoscale probe, and being fixed on can be on the micron order elastic cantilever of sensitive manipulation.When
When probe is very close to sample, the atom and the interatomic active force of sample surfaces on top can make cantilever bending, deviate original flat
Weighing apparatus position.3-D image is rebuild according to the spatial offset amount or vibration frequency of probe, pattern, the atom of sample surfaces can be obtained
Ingredient, mechanical property or other properties.
Transmission electron microscope (TEM) can directly observe sample structure feature, such as the number of plies by the full resolution pricture of sample
And size.
Therefore, the reasonable combination of X-ray diffraction analysis (XRD) and Raman spectrum analysis (Raman) can be used to judge carbon
Whether material is graphene oxide；After determining that carbon material is graphene oxide, ftir analysis
(FTIR) each peak in infrared spectroscopy is able to reflect the vibration of chemical bond and functional group in graphene oxide, each peak of xps energy spectrum
It is able to reflect the relative amount of element in graphene oxide.High resolution transmission electron microscope (HRTEM), Raman spectrum
(Raman), atomic force microscope (AFM), which combines, to identify the number of plies of graphene oxide.As a result,
The present invention judges the type of carbon material by be reasonably applied in combination above-mentioned test analysis.Carbon material can be for according to oxygen
Product obtained from graphite alkene preparation method, or for according to product obtained from redox graphene preparation method.
In an exemplary embodiment of the present invention, the method for the detection carbon material type can comprise the following steps that
The test method can comprise the following steps that
(1) judge whether the carbon material is graphene oxide.Whether the present invention mainly sends out from piece interlayer relative to graphite
Whether raw removing there is oxygen-containing group to identify whether carbon material is graphene oxide.For this purpose, the present invention mainly passes through reasonable group
The X-ray diffraction analysis (XRD) used and Raman spectrum analysis (Raman) are closed to judge whether carbon material is graphene oxide.
The step of whether carbon material is graphene oxide judged can include:
The first sample, the second sample and third sample are separated from carbon material, hot place is carried out in the first temperature to the first sample
Reason, obtains the first heat treated sample, is heat-treated to the second sample in second temperature, obtains the second heat treated sample.Wherein,
First temperature can select within the scope of 450~700 DEG C, and second temperature can select within the scope of 850~1150 DEG C.As wait judge
The carbon material of object can be for by treated the graphite type material of the oxidation operation in graphene processing technology.
X-ray diffraction test is carried out to the first heat treated sample, the second heat treated sample and third sample, accordingly obtains the
One ray test result, the second ray test result and third ray test result, at the first heat treated sample and the second heat
It manages sample and carries out Raman spectrum test, it is corresponding to obtain the first Raman test result and the second Raman test result.Wherein, described
One ray test result, the second ray test result and third ray test result may include X-ray diffractogram, and the first Raman is surveyed
Test result and the second Raman test result may include Raman spectrogram.
Judge whether the lamella of carbon material is peeling-off according to third ray test result, according to first, second, and third
Ray test result and the first and second Raman test results judge whether carbon material has oxygen-containing group (alternatively referred to as oxygen-containing
Functional group), if judging result be carbon material piece interlayer it is peeling-off and have oxygen-containing functional group, the carbon material be oxygen
Graphite alkene.Wherein,
The third ray test result judges that the whether peeling-off step of the lamella of carbon material includes: according to described
Trilete rays test result, obtains the crystal parameter of third sample, and then obtains the interplanar distance of third sample, if third sample
Interplanar distance is greater than the interplanar distance of graphite, and compared with the X ray diffracting spectrum of graphite, the diffraction of third ray test result
Occur new diffraction maximum on map, then concludes that the piece interlayer of carbon material is peeling-off, otherwise not can determine that the piece interlayer of carbon material
It is peeling-off.Wherein, crystal parameter may include 2 θ of the indices of crystallographic plane or the angle of diffraction.The interplanar of carbon material is obtained according to crystal parameter
Away from.In the case where crystal parameter is 2 θ of the angle of diffraction, interplanar distance, formula 1 can be obtained by formula 1 are as follows: 2dsin θ=n λ, formula
In, d is interplanar distance, and λ is the wavelength of X-ray, and n is diffraction progression.Wherein, the interplanar distance of graphite can be known data,
It can also obtain by the same method.New diffraction maximum may include (100) crystallographic plane diffraction peak on the carbon material diffracting spectrum.
Described, if to judge whether carbon material has the step of oxygen-containing group include: respectively compared with third test result
There is diffraction peaks broadening in the diffracting spectrum of one ray test result and the second ray test result and peak position is inclined to wide-angle
It moves, the second ray test result becomes apparent from than wideization of the first ray test result and offset, moreover, the second Raman is tested
As a result in Raman spectrogram the intensity ratio at the peak D and the peak G be greater than the first Raman test result, then conclude in carbon material have contain
Oxygen groups (i.e. oxygen-containing functional group) otherwise not can determine that carbon material has oxygen-containing group.
(2) in the case where judging the carbon material for graphene oxide, the type of functional group on the carbon material is determined
And quantity.The graphene oxide functional group that the present invention is analyzed by the way that FTIR and XPS test is applied in combination.
Specifically, the step of detection carbon material functional group type and quantity can include:
The 4th sample and the 5th sample are separated from carbon material, ftir analysis survey is carried out to the 4th sample
Examination, obtains the infrared spectrogram of carbon material, carries out X-ray photoelectron spectroscopic analysis test to the 5th sample, obtains the X of carbon material
X-ray photoelectron spectroscopy X figure.
The type and quantity of functional group on carbon material are determined according to the infrared spectrogram and the energy spectrum diagram.Wherein,
On the determining carbon material the step of functional group's type can include: infrared in being searched in the infrared spectrogram
Area obtains the corresponding wave number of absorption peak on the middle infrared, and the wave number is compared with ir data library, determines
The type of functional group on carbon material.
On the determining carbon material the step of number of functional groups can include: judge the energy spectrum diagram according to the size in conjunction with energy
The above corresponding element in each peak, is modified by peak intensity of the sensitivity factor to peak corresponding to each element, by each after amendment
Ratio between peak peak intensity corresponding to element obtains the relative amount ratio of each element, according to the relative amount ratio, determines carbon materials
The quantity of Liao Shang functional group.
(3) after determining that the carbon material is graphene oxide, the number of plies of the carbon material is detected.
Method of the invention can be by high resolution transmission electron microscope (HRTEM), Raman spectrum
(Raman), atomic force microscope (AFM) combines, i.e., first primarily determines oxidation with Raman spectrum
The number of plies of graphene, if the number of plies at 1~2 layer, further determines its number of plies using atomic force microscope；If the number of plies is 3~4
Layer is then determined by the Lorentz force peak number that the peak Raman spectrum 2D fits；High-resolution is used if 5 layers or more if the number of plies
Transmission electron microscope intuitively obtains its number of plies, is capable of the number of plies of the determination graphene oxide of system perfecting.
Determine the specific steps of the number of plies can include:
1) the graphene oxide number of plies is primarily determined by Raman spectrum.The present invention mainly utilizes Raman scattering i.e. Stokes
Scattering primarily determines the graphene oxide number of plies.When inelastic scattering has energy exchange, wavelength shift is changed, and most of frequency is not
It changes, only fraction shifts, and this scattering is known as Raman scattering.When energy is reduced, wave number displacement becomes smaller, and generates
Stockes line；When energy increases, wave number displacement becomes larger, and generates anti-stockes line, they are symmetrically dispersed in Rayleigh scattering
The two sides of line are respectively corresponding to obtain or lose the energy of 1 vibration quantum.When being characterized to graphene oxide,
The features such as shape, position and the intensity of wave crest formed in Raman map can all occur with the increase of the graphene oxide number of plies
Corresponding change.According to these variations, then preliminary judgement can be carried out to the graphene oxide number of plies.
Firstly, separating the sample of test from carbon material, Raman spectrum test is carried out to the sample, obtains graphite oxide
The Raman spectrogram of alkene (i.e. carbon material).It generally will form 3 main peak types on the Raman spectrogram of graphene oxide, be respectively
The peak D, the peak G and the peak 2D (frequency multiplication peak).Wherein, the peak D represents the sp of aromatic rings in graphene oxide structure2The symmetrical of carbon atom stretches
Vibration (radial breathing), is generally used to measure the order degree of sample structure.The peak G is normally at 1580cm-1Position, peak shape is very
Sharply.That the peak G represents is sp in graphene oxide2The in plane vibration mode of hydbridized carbon atoms.The position at the peak G is to graphene oxide
The number of plies is very sensitive, through the position at the peak G, it can be determined that the number of plies of specific graphene oxide sample.With the increase of the number of plies, G
Peak is mobile towards lower wave number direction, that is, mobile towards low energy direction, shows the weakening of the bond energy between graphene oxide layer.Due to
The peak position of graphene oxide will receive temperature, doping and very faint stress influence, so, when need using Raman into
When the row graphene oxide number of plies calculates, extreme care is answered in operation.The peak 2D represents the vibration mode of two photonic crystal lattices, is the peak D
Frequency multiplication peak.In graphene oxide raman spectrum, even if the peak D is not present, the peak 2D is also always very strong, nor represents defect.
For single-layer graphene oxide sample, the peak 2D is an individual symmetrical peak, halfwidth about 30cm-1.It is right with the increase of the number of plies
Title property reduces, and the peak 2D splits into the peak of multiple overlappings.This apparent peak shape change can effectively distinguish graphene oxide layer number.
Due to the limitation of itself Raman figure, it is only applicable to graphene oxide measurement of the number of plies less than 5 layers.To sum up, it can use IG/I2DPeak
Intensity ratio can primarily determine the number of plies of graphene oxide.IGIndicate G peak intensity, the I2DIndicate 2D peak intensity.
As I in graphene oxide spectrogramG/I2DWhen the intensity ratio at peak is less than 1.0, can tentatively it judge in graphene oxide
There are single layer structure or double-layer structure, if need to determine in graphene oxide is single layer or double-layer structure, needs aobvious with atomic force
Micro mirror does further measurement；Work as IG/I2DIntensity ratio be 1.0~1.5 when, then judge graphene oxide be 3 layers or 4 layers knot
Structure, wherein the peak 2D of 3 layers of graphene oxide can be judged with six Lorentz peaks to be fitted.Work as IG/I2DIntensity > 1.5
When, the Raman spectrum of graphene oxide and the Raman spectrum of graphite are similar, it is difficult to measure the graphene oxide number of plies, need to use at this time
High resolution TEM does further measurement.
2) the system measurement graphene oxide number of plies.
It can use atomic force microscope for the graphene oxide that Preliminary Determination is single or double layer to carry out its number of plies
It is further to determine.After Raman spectrum primarily determines in sample and has single or double layer graphene oxide, atomic force microscope energy
The three-dimensional image for directly obtaining graphene oxide is single layer or the double-deck graphite oxide by the measurement determination to thickness
Alkene.It is described to determine that graphene oxide is single layer or double-layer structure includes the graphene oxide thickness and list that measured by thickness
The graphene oxide thickness of layer compares, and determines the graphene oxide number of plies.For example, for the oxygen being attached in the substrates such as mica sheet
Graphite alkene overburden will increase the about extra play of 0.35nm, so observing the thickness one of single-layer graphene oxide at AFM
As about 0.7~1.2nm.This thickness can be identified into single-layer graphene oxide compared with thickness of sample in afm image, utilize height
Line of writing music, which carries out statistical disposition, can identify the double-deck graphene oxide.
For Preliminary Determination is 3 layers or 4 layers of graphene oxide, it can be fitted by the peak Raman spectrum 2D
Lorentz force peak number determines.For example, can be judged by six Lorentz peaks to be fitted.
The graphene oxide for being 5 layers or more for Preliminary Determination, can use high resolution TEM and does to its number of plies
It is further to determine.It can be by the full resolution pricture at graphene oxide edge or fold come straight using transmission electron microscope (TEM)
The number of plies and size for connecing observation graphene oxide, can directly read the number of plies of graphene oxide directly from image.But
In the less apparent situation of contrast, especially for single layer and the double-deck graphene oxide, high resolution transmission electron microscope
It can not accurately judge the number of plies of graphene oxide.
In the present embodiment, the detection of carbon material functional group type and quantity, the detection of the carbon material number of plies can be in no particular order
Sequentially.
In the present embodiment, the step of detecting carbon material functional group type and quantity may also include that according to the determination
Functional group's type and number of functional groups obtain the quantity of carbon material Shang Ge functional group.Wherein, it needs to combine FTIR carry out official
The differentiation of type can be rolled into a ball.
In the present embodiment, during determining the carbon material number of plies, can use the peak 2D in Raman spectrogram half is high
Wide and IG/I2DThe intensity ratio at peak primarily determines that graphene oxide is single or double layer structure.When the halfwidth at the peak 2D is 28cm-1
~32cm-1And IG/I2DWhen the intensity ratio at peak is less than 0.7, tentatively judge graphene oxide for single layer structure；Half when the peak 2D is high
Width is 48cm-1~52cm-1And IG/I2DWhen the intensity ratio at peak is more than or equal to 0.7 less than 1.0, tentatively judge that graphene oxide is
Double-layer structure.
In the present embodiment, the object carbon material that the present invention identifies may include the doubtful carbon material for graphene oxide.Carbon
Material can be for according to product obtained from graphene oxide preparation method；Carbon material can also be to prepare according to redox graphene
Product obtained from method.I.e. the present invention can be to being prepared whether carbon material is graphene oxide or redox graphene
It is identified.
In the present embodiment, graphite can prepare raw material for carbon material.Graphite may include crystalline flake graphite.
In the present embodiment, the crystal face interlamellar spacing of the graphite can be 0.3~0.4nm.
The crystal face interlamellar spacing of graphite can be obtained by above-mentioned method, i.e., carry out X-ray diffraction test to graphite, obtain stone
The crystal parameter of ink, and then obtain the interplanar distance of graphite.
In the present embodiment, ID/IGNumerical value can be used to indicate the degree of order.The method may further comprise the step of: in oxidation stone
In the qualification process of black alkene, in combination with the obtained Raman spectrum of test, by the strong and weak size at the peak comparative analysis G and the peak D and its
Ratio ID/IG, widthization degree can know lattice defect degree of the carbon material compared to graphite, the variation of structurally ordered degree respectively.
Wherein, the infrared spectrogram of graphite can be obtained by carrying out Raman spectrum test to graphite, with this and carbon material into
Row compares.
In the present embodiment, further, the first temperature and second temperature may respectively be 500~600 DEG C, 900~1100
℃。
For example, described by carbon material includes: the heating prompt drop with 5~10 DEG C/min the step of being heat-treated for 550 DEG C
By carbon material by heat to 550 DEG C, 1~180min, such as 100 ± 20min are kept the temperature, then cooled to room temperature.
Described by carbon material includes: with the heating prompt drop of 5~10 DEG C/min the step of being heat-treated for 1000 DEG C by carbon
Heat to 1000 DEG C, is kept the temperature 1~180min, such as 100 ± 20min, then cooled to room temperature by material.
It is in the present embodiment, described that judge whether carbon material has the step of oxygen-containing group further include concluding carbon materials described
With the verification step after oxygen-containing group in material, the verification step can are as follows: according to the absorption peak on the middle infrared come
The carbon material is verified with oxygen-containing group.
In the present embodiment, determine carbon material be graphene oxide after, can by FTIR spectrum test come
Detect the type of functional group on graphene oxide.
It is using the principle that Fourier infrared spectrograph obtains the infrared absorpting light spectra of graphene oxide: by infrared light supply
The infrared light that S is issued is collimated to enter interference system for parallel infrared beam, obtains a branch of interference light after interferometer adjustment system.
Interference light is obtained the interference signal containing spectral information and reached on detector D, become interference signal by D by graphene oxide
For electric signal.Interference signal herein is a function of time, i.e., the interference pattern drawn by interference signal, abscissa is that index glass moves
Dynamic time or index glass moving distance.This interference pattern is sent into computer by A/D converter, carries out Fourier transform by computer
Quick calculating, can be obtained the infrared spectrogram using wave number as abscissa.Then plotter is sent by D/A converter to draw
The standard IR abosrption spectrogram that people are very familiar to out.
The step of determining functional group's type on carbon material can include:
Infrared spectroscopy is divided into three regions: near infrared region (0.75~2.5 μm), middle infrared (2.5~25 μm) and remote
Infrared region (25~300 μm).It is, in general, that near infrared spectrum is generated by the frequency multiplication of molecule, sum of fundamental frequencies；Middle infrared spectrum belongs to
The fundamental vibration spectrum of molecule；Far-infrared spectrum then belongs to the rotation spectrum of molecule and the vibrational spectrum of certain groups.
By the source of absorption peak, mid-infrared light spectrogram (2.5~25 μm) is generally divided into (2.5~7.7 μm of characteristic frequency
That is 4000~1330cm-1) and fingerprint region (7.7~16.7 μm, i.e. 1330~400cm-1) two regions.Wherein characteristic frequency
Absorption peak in area is substantially to be generated by the stretching vibration of group；Fingerprint region is mainly by some singly-bound C-O, C-N and C-X (halogen
Plain atom) etc. stretching vibration and the hydric groups such as C-H, O-H bending vibration and C-C skeletal vibration generate.
Therefore, for the analyzing step of obtained carbon material infrared spectrogram can include: the first step finds graphene oxide
Middle infrared (2.5~25 μm).Second step finds characteristic frequency area (2.5~7.7 μm, i.e. 4000-1330cm-1) and fingerprint
Area (7.7~16.7 μm, i.e. 1330~400cm-1).Step 3: red according to the corresponding wave number comparison of characteristic peak in infrared spectrogram
Outer spectrum library determines what functional group the group is.Such as: 1725cm-1It is the stretching vibration of carbonyl C==O on carboxyl,
1615cm-1It is the stretching vibration of carbon-carbon double bond C==C, 1373cm-1It is the stretching vibration of C-OH, 1078cm-1It is epoxy group C-
The stretching vibration of O-C.
In the present embodiment, the step of determining carbon material number of functional groups can include: since the spectral peak of XPS often compares
Width cannot determine intensity according only to peak heights, generally using the area under spectral peak as intensity, be substantially equal to peak height and multiply half-peak
It is wide.The area or intensity for choosing highest peak mostly use sensitivity factor method as the basis quantitatively calculated, because each element generates
Intensity and content when photoelectron is not necessarily directly proportional, to be modified using sensitivity factor to intensity, way are as follows: with
Peak side, background the point of intersection of tangents subject to background correction, peak area or peak intensity are calculated, then respectively divided by the sensitivity of respective element
The factor, so that it may obtain the relative amount of each element, then obtain each element relative amount ratio.Or using formula ni/nj=
(Ii/Si)/(Ij/Sj) directly seek the relative amount ratios of two elements, wherein ni、njIt may respectively be the atomic concentration of different elements,
Ii、IjIt may respectively be the intensity of spectral line of different elements, Si、SjIt may respectively be the sensitivity factor of different elements.
Quantity according to element relative amount than functional group can be calculated.Such as: when C/O=2:1, oxidation stone can be calculated
The quantity of oxygen-containing functional group in ink.Different elements have fixed combination energy numerical value in corresponding functional group, by tabling look-up
Perhaps it compares with other work or combines FTIR it is determined which kind of functional group, then have stoichiometric relationship, it can be from member
The content of element obtains the content of corresponding functional group.
In the present embodiment, when carrying out FTIR and XPS test, for graphene oxide, it is desirable that be by carbon material
Powder tabletting.
The above exemplary embodiments for a better understanding of the present invention carry out further it below with reference to specific example
Explanation.
Crystalline flake graphite in example is the raw material for preparing graphene oxide, and carbon material is to prepare obtained from graphene oxide
Product.
(1) X-ray diffraction test is carried out to the carbon material after the heat treatment of crystalline flake graphite, carbon material and different temperatures, and obtained
To corresponding XRD spectra.
Fig. 1 shows the XRD spectra of crystalline flake graphite, and Fig. 2 shows the XRD spectra of carbon material, Fig. 3 and Fig. 4 show respectively
Gone out 550 DEG C, 1000 DEG C heat treatment after carbon material XRD spectra.
If Fig. 1 shows, crystalline flake graphite characteristic peak positions are in 2 θ=26.2 °, and corresponding crystal face is (002), in conjunction with Bragg equation
2dsin θ=n λ (d is crystal face interlamellar spacing, and θ is the angle of diffraction, and n is diffraction progression, and λ is the wavelength of X-ray) calculates to obtain interlamellar spacing d
=0.34nm.
What by Fig. 2, we were tested is not heat-treated the XRD spectra of meal material, observes its (001) crystallographic plane diffraction peak angle
Degree is 2 θ=10.4 °, is computed to obtain carbon material layer spacing d=0.85nm at this time, and interlamellar spacing obviously expands compared with crystalline flake graphite,
In addition in the appearance of its 43 ° neighbouring (100) crystallographic plane diffraction peak, illustrate that obvious removing has occurred in carbon material between layers.
After carrying out high-temperature heat treatment to carbon material, if it is graphene oxide, oxygen-containing group therein will be with carbon original
Son reacts, and causes the reduction of oxygen-containing group number and carbon-coating defect increases, the generation of its diffraction maximum is shown as in Fig. 3~Fig. 4
It is significantly broadened, and peak position is deviated to wide-angle direction, and with the raising of heat treatment temperature, the above variation is more obvious.More than
As a result illustrate in the carbon material sample of test piece interlamellar spacing significantly increase and may containing some oxygen-containing groups, after heat treatment with
Oxygen-containing group reduce, graphite flake layer spacing reduction causes crystallite dimension to reduce, while lattice defect increase, and crystal structure to
The transformation of class graphite can also specifically be confirmed in subsequent Raman characterization.
(2) Raman spectrum test is carried out to the carbon material after the heat treatment of crystalline flake graphite, carbon material and different temperatures, and obtained
Corresponding Raman spectrogram.
Fig. 5 shows the Raman spectrogram of crystalline flake graphite, and Fig. 6 shows the Raman spectrogram of carbon material, Fig. 3 and Fig. 4
Respectively illustrate 550 DEG C, 1000 DEG C heat treatment after carbon material Raman spectrogram.
Graphite raw material is 1360,1580cm in the Raman shift of first order Raman Spectrum area as can see from Figure 5-1There are two nearby
Apparent Raman peaks correspond respectively to D band and G band, and the peak D is usually by sp in carbocyclic ring2The mode of atom breathing vibration generates, and the peak G is then
By all sp in carbocyclic ring and long-chain2The extensional motion of atom pair generates, but is both by sp2Caused by chemical bond oscillations.?
It is not in the peak D in the Raman spectrum of complete graphite monocrystalline, and it is defective in graphite sample or disordered structure position is collected
When Raman scattering light, D bands of a spectrum can be just generated in Raman spectrum, as in Fig. 5 crystalline flake graphite in 1360cm-1The Raman nearby occurred
Peak, and no matter be the unordered of which kind of form in structure, D band can all occur, and be interpreted unordered induction Raman mould, by Graphite cloth
Caused by the double resonance Raman scattering processes that the phonon of the area Li Yuan K Near The Critical Point participates in.Second order Raman spectrum region in Fig. 5
2717cm-1Neighbouring stronger peak corresponds to D' band, be the peak D and frequency and frequency multiplication peak, the double resonance drawing participated in originating from biphonon
Graceful scattering, complete graphite crystal and it is defective in the presence of be Raman allow, therefore have stronger Raman signal.
The Raman spectrum (Fig. 5) of graphite is compared, the Raman spectrum of non-heat treated carbon material shows as G peak broadening, D in Fig. 6
Peak broadening and enhancing.The reason of generating this phenomenon may be interpreted as: graphite is after aoxidizing, carbon atom and oxygen-containing group in graphite flake layer
Group is bonded, the opposite disordered structure of carbon atom bonding in the form of sp3 hydridization, the symmetry of graphite lattice, long range order occurs
It is destroyed, this and the available confirmation of XRD spectra result before this.In Fig. 7~Fig. 8, with the raising of heat treatment temperature, the peak D
It gradually increases, R=ID/IGBe gradually increased, and due in the Raman characterization of nano-carbon material the peak G represent orderly sp2Bond
Structure, the peak D then represent the defect and amorphous structure positioned at graphene edge, and R value increase explanation is during heat treatment due to containing
The effect of oxygen groups and carbon causes defect in sheet of material to increase, and opposite disordered structure increases, after this conclusion and above-mentioned heat treatment
Resulting XRD spectra analysis result matches, and then can further verify us and obtain graphene oxide composite material.Heat treatment
Afterwards, R value increase explanation is during heat treatment since the effect of oxygen-containing group and carbon causes defect in sheet of material to increase, i.e., hot
Defect increases after processing, disordered structure increases.
(3) pass through above-mentioned test analysis, it has been determined that carbon material is graphene oxide.
Ftir analysis test and X-ray photoelectron spectroscopic analysis test are carried out to carbon material, and divided
The FTIR spectrum figure and xps energy spectrum figure as shown in Figure 10 of graphene oxide as shown in Figure 9 are not obtained.According to the red of carbon material
External spectrum figure, we not only can be with the presence of verifying oxygen-containing group, can be with the type of qualitative analysis wherein oxygen-containing group.
It can be observed that the position of the absorption peak of part functional group, thus can determine whether there is carbonyl in graphene oxide from Fig. 9
Base, carboxyl, hydroxyl, epoxy group, the functional groups such as carbon-carbon double bond.The presence of these oxygen-containing groups demonstrates carbon material as oxidation stone
Black alkene.The presence of oxygen-containing group illustrates that graphite has been oxidized, and these polar groups especially surface hydroxyl makes to aoxidize stone
Black alkene is easy to form hydrogen bond with hydrone, this is also that graphene oxide has the reason of excellent hydrophilic.The results of FT-IR
Show: graphitic carbon generates on the carbon atom in big pi bond a variety of containing oxygen key, such as C=O and C-O after oxidation, makes part sp2It is miscellaneous
Change track and is changed into sp3Hybridized orbit, this and I in above-mentioned carbon material Raman spectrumD/IGThe result of increase matches.
Wherein, 3397cm-1The wider absorption peak in left and right is the stretching vibration of hydroxyl O-H；1725cm-1It is carbonyl C on carboxyl
The stretching vibration of==O；1615cm-1It is the stretching vibration of carbon-carbon double bond C==C；1373cm-1It is the stretching vibration of C-OH；And
1078cm-1It is the stretching vibration of epoxy group C-O-C.
The intensity that C1s and O1s corresponds to peak can be observed from Figure 10, C:O=2:1 is calculated according to sensitivity factor method.
The quantity of oxygen-containing functional group can be calculated according to carbon-to-oxygen ratio, other elements all calculate its functional group number using sensitivity factor method
Amount, such as sulfur-bearing or the number of functional groups containing halogen etc..
(4) using crystalline flake graphite and the Raman map (i.e. Fig. 5 and Fig. 6) of carbon material comparative analysis to the present invention carry out into
The explanation of one step.As shown in figure 5, crystalline flake graphite is in 1360cm-1Place has a faint absorption peak (peak D), in 1580cm-1Place
There are a point, strong absorption peak (peak G) illustrates the structure of graphite very corresponding to the first-order Raman scattering of E2g optical mode
It is regular.After graphite is oxidized, the peak G of graphite oxide has broadened, and moves to 1590cm-1Place, and also in 1360cm-1Place
There is a stronger peak D, after showing that graphite is oxidized, a part of sp in structure2Hydbridized carbon atoms are converted to sp3Hybrid structure,
C=C double bond i.e. in graphite linings is destroyed.
As shown in fig. 6, graphene oxide is in 1590cm-1There is a stronger absorption peak (peak G) in place, compared to scale
The peak G of graphite occurs illustrating that graphene oxide is reduced compared with the crystalline flake graphite number of plies to the movement of high wave number direction.In 2700cm-1Place
There is the wider peak 2D in a peak (frequency multiplication peak), this is by two in the carbon atom phonon double resonance transition with reversed momentum
Caused by, the movement of this characteristic peak and shape then have close be associated with the graphene oxide number of plies.And IG/I2D> 1.5, it says
The multilayered structure that this bright graphene oxide is 5 layers or more, cannot be further analyzed using Raman spectrum, therefore, I
Sample is measured using high magnification transmission electron microscope.
Transmission electron microscope analysis is done to one region of carbon material and obtains high resolution TEM (HRTEM) figure (Figure 11 a institute
Show), the stacked graph of graphene oxide can be intuitively obtained, the number of plies that this graphene oxide sample can be obtained after statistical counting is 7
Layer.In addition it takes another region of carbon material to do transmission electron microscope analysis and obtains Figure 11 b, can obviously observe that two panels multilayer aoxidizes in Figure 11 b
Graphene lamination is staggered, and the lamination being located above is of five storeys graphene oxide, underlying to have 7 layers.
In conclusion the advantages of detection carbon material type method of the invention can include: can be reasonably by a variety of tests
Method combines, and method is easy and effective, can efficiently and accurately judge that the product of different material and method production is
The no number of plies, the type and quantity of functional group for graphene oxide and identification graphene oxide.
Although those skilled in the art should be clear above by combining exemplary embodiment to describe the present invention
Chu can carry out exemplary embodiment of the present invention each without departing from the spirit and scope defined by the claims
Kind modifications and changes.
Claims (10)
1. a kind of method for detecting carbon material type, which is characterized in that the described method comprises the following steps:
The first sample, the second sample and third sample are separated from carbon material, the first sample is heat-treated in the first temperature, is obtained
To the first heat treated sample, the second sample is heat-treated in second temperature, obtains the second heat treated sample, wherein first
Temperature selects within the scope of 450~700 DEG C, and second temperature selects within the scope of 850~1150 DEG C；
X-ray diffraction test is carried out to the first heat treated sample, the second heat treated sample and third sample, first is accordingly obtained and penetrates
Line test result, the second ray test result and third ray test result, to the first heat treated sample and the second heat treatment sample
Product carry out Raman spectrum test, corresponding to obtain the first Raman test result and the second Raman test result；
Judge whether the lamella of carbon material is peeling-off according to third ray test result, according to the first, second, and third ray
Test result and the first and second Raman test results judge whether carbon material has oxygen-containing functional group, if judging result is carbon
The piece interlayer of material is peeling-off and has oxygen-containing functional group, then the carbon material is graphene oxide, is judging the carbon materials
In the case that material is graphene oxide, the type and quantity of functional group and the number of plies of carbon material on the carbon material are determined,
In,
The whether peeling-off step of the lamella for judging carbon material includes: to be obtained according to the third ray test result
The crystal parameter of third sample, and then the interplanar distance of third sample is obtained, if the interplanar distance of third sample is greater than graphite
Interplanar distance, and compared with the X ray diffracting spectrum of graphite, there is new diffraction on the diffracting spectrum of third ray test result
Peak then concludes that the piece interlayer of carbon material is peeling-off, otherwise not can determine that the piece interlayer of carbon material is peeling-off；
Described, if to judge whether carbon material has the step of oxygen-containing functional group include: respectively compared with third test result first
There is diffraction peaks broadening in the diffracting spectrum of ray test result and the second ray test result and peak position deviated to wide-angle,
Second ray test result becomes apparent from than wideization of the first ray test result and offset, moreover, the second Raman test knot
The intensity ratio at the peak D and the peak G is greater than the first Raman test result in the Raman spectrogram of fruit, then concludes in carbon material with oxygen-containing
Otherwise functional group not can determine that carbon material has oxygen-containing functional group；
The step of type and quantity of functional group includes: to separate the 4th sample and the 5th sample from carbon material on the determining carbon material
Product carry out ftir analysis test to the 4th sample, the infrared spectrogram of carbon material are obtained, to the 5th sample
X-ray photoelectron spectroscopic analysis test is carried out, the x-ray photoelectron spectroscopy figure of carbon material is obtained；According to the infrared spectrogram
The type and quantity of functional group on carbon material are determined with the energy spectrum diagram；
The step of determining carbon material number of plies includes: to separate the 6th sample from carbon material, carries out Raman spectrum to the 6th sample
Test obtains third Raman test result；According to the Raman spectrogram of third Raman test result, I is calculatedG/I2D, work as IG/I2D
When less than 1.0, tentatively judge carbon material for single or double layer structure；Work as IG/I2DWhen being 1.0~1.5, tentatively judge that carbon material is
3 layers or 4 layers of structure；Work as IG/I2DWhen greater than 1.5, tentatively judge carbon material for 5 layers or more structures, wherein the IGIndicate the peak G
Intensity, the I2DIndicate 2D peak intensity.
2. the method for detection carbon material type according to claim 1, which is characterized in that
The step of functional group's type includes: that middle infrared is searched in the infrared spectrogram on the determining carbon material, is obtained
The wave number is compared with ir data library, determines carbon material by the corresponding wave number of absorption peak on the middle infrared
The type of upper functional group；
On the determining carbon material the step of number of functional groups include: according in conjunction with can size judge it is each in the energy spectrum diagram
The corresponding element in peak is modified by peak intensity of the sensitivity factor to peak corresponding to each element, passes through each element institute after amendment
Ratio between corresponding peak peak intensity obtains the relative amount ratio of each element, according to the relative amount ratio, determines carbon material Shangguan
The quantity that can be rolled into a ball.
3. the method for detection carbon material type according to claim 1, which is characterized in that
In the case where judging the carbon material tentatively for single or double layer structure, the 7th sample is separated from the carbon material,
The 7th sample is tested using atomic force microscope, using the determination carbon material as single or double layer structure；
In the case where judging the carbon material tentatively for 3 layers or 4 layers of structure, the third Raman test result Raman light is calculated
The Lorentz force peak number of the peak the 2D fitting of spectrogram, differentiating carbon material is 3 layers or 4 layers of structure；
In the case where judging the carbon material tentatively for 5 layers or more structures, the 8th sample is separated from the carbon material, is passed through
High resolution TEM obtains the electron micrograph image of the 8th sample, and observation determines the specific number of plies of carbon material.
4. the method for detection carbon material type according to claim 1, which is characterized in that the carbon material is according to oxidation
Product obtained from graphene preparation method, or for according to product obtained from redox graphene preparation method.
5. the method for detection carbon material type according to claim 4, which is characterized in that the graphite-phase should be the oxygen
The raw material of graphite alkene preparation method or the redox graphene preparation method,
The interplanar distance of the graphite is prepared by the following: being carried out X-ray diffraction test to the graphite, is obtained graphite
Crystal parameter, and then obtain the interplanar distance of graphite.
6. the method for detection carbon material type according to claim 1, which is characterized in that the crystal parameter includes crystal face
Index or the angle of diffraction.
7. it is according to claim 6 detection carbon material type method, which is characterized in that the crystal parameter be diffraction
In the case where angle, described the step of obtaining interplanar distance includes: that interplanar distance is obtained by formula 1, the formula 1 are as follows:
2dsin θ=n λ,
In formula, d is interplanar distance, and λ is the wavelength of X-ray, and n is diffraction progression, and θ is the 1/2 of the angle of diffraction.
8. the method for detection carbon material type according to claim 1, which is characterized in that the new diffraction maximum includes
(100) crystallographic plane diffraction peak.
9. the method for detection carbon material type according to claim 1, which is characterized in that in determining carbon material Shangguan
After the step of type, quantity can be rolled into a ball, the method also includes: according to the functional group's type and number of functional groups of the determination,
Obtain the quantity of carbon material Shang Ge functional group.
10. the method for detection carbon material type according to claim 2, which is characterized in that if element is in the energy spectrum diagram
The upper multiple peaks of correspondence, then using the peak intensity of highest peak in the multiple peak as the modified object.
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