CN108423671A - A kind of high thermal stability I2 doping graphene film and preparation method thereof - Google Patents

A kind of high thermal stability I2 doping graphene film and preparation method thereof Download PDF

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CN108423671A
CN108423671A CN201810537263.4A CN201810537263A CN108423671A CN 108423671 A CN108423671 A CN 108423671A CN 201810537263 A CN201810537263 A CN 201810537263A CN 108423671 A CN108423671 A CN 108423671A
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doping
graphene
film
thermal stability
graphene film
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吴彪
张志滨
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Northwest University
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Northwest University
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    • C01INORGANIC CHEMISTRY
    • C01BNON-METALLIC ELEMENTS; COMPOUNDS THEREOF; METALLOIDS OR COMPOUNDS THEREOF NOT COVERED BY SUBCLASS C01C
    • C01B32/00Carbon; Compounds thereof
    • C01B32/15Nano-sized carbon materials
    • C01B32/182Graphene
    • C01B32/194After-treatment
    • CCHEMISTRY; METALLURGY
    • C01INORGANIC CHEMISTRY
    • C01BNON-METALLIC ELEMENTS; COMPOUNDS THEREOF; METALLOIDS OR COMPOUNDS THEREOF NOT COVERED BY SUBCLASS C01C
    • C01B2204/00Structure or properties of graphene
    • C01B2204/20Graphene characterized by its properties
    • C01B2204/24Thermal properties

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Abstract

The invention discloses a kind of high thermal stability I2 doping graphene films, and the multi-layer graphene microplate by being mingled with I2 doping object forms, and multi-layer graphene microplate is along the random stacking of its in-plane.The invention also discloses a kind of preparation method of high thermal stability I2 doping graphene film, graphene microchip first is deposited on substrate to form graphene film, then I2 doping object is deposited on graphene film by this method, obtains I2 doping graphene film.The film of the present invention forms compact texture by multi-layer graphene microplate stacking, enhance the active force between graphene microchip and I2 doping object, so that the steric hindrance of I2 doping object is become larger, be not easy to escape and volatilize, to improve the thermal stability of I2 doping graphene film;The present invention improves the arrangement architecture of graphene and I2 doping object by the method for stepped depositions, and still there is the I2 doping graphene film of preparation thermal stability, significant effect to be suitable for promoting under 500 DEG C of hot conditions.

Description

A kind of high thermal stability I2 doping graphene film and preparation method thereof
Technical field
The invention belongs to surfacing preparing technical fields, and in particular to a kind of high thermal stability I2 doping graphene film And preparation method thereof.
Background technology
Two-dimensional material is a kind of material of the laminated structure with atomic thickness, because with unique electricity, optics, heat , mechanics and chemical property, have huge application potential in the multiple fields such as material and machinery.Common two-dimensional material includes Graphene, boron nitride, transition metal dichalcogenide such as molybdenum sulfide, tungsten sulfide, selenizing molybdenum, tungsten selenide etc..Wherein, graphene is made For a kind of sp2The carbon material of the two-dimension single layer graphite of hydridization, the hexagon stablized make it have excellent electrically and thermally property Energy.Graphene can be made into transparent conductive film, be applied to touch screen, organic solar batteries, organic luminescent device, intelligent glass etc. Transparent electrode, can also be applied to heat dissipation and electric discharge face coat.Since carrier concentration is limited, the conductivity of graphene Large area film or long conducting wire not high, got up by graphene microchip stacking, conductivity also by graphene microchip it Between contact resistance limitation.So the conductivity for improving graphene is an important task.Current most common raising stone The method of black alkene conductivity is doping.Dopant includes halogens such as chlorine, bromine, iodine and fluorine, alkali metal element such as potassium, lithium and Sodium, acidic materials such as hydrochloric acid, nitric acid and sulfuric acid and some other organic compounds, wherein the iodine in halogens is suitable With the most frequently.However, iodine is that thermal stability is very poor as the problem of dopant maximum, at a temperature of less than 100 DEG C, or Will volatilize disappearance under vacuum conditions, so that doping failure.So for two-dimensional materials such as graphenes, searching one is needed Doping method of the kind with high thermal stability.
There are two main classes for the doping method of two-dimensional material at present.The first kind is that doping is added in two-dimensional material growth course Object participates in the synthesis of two-dimensional material to be doped, and this method complex process, process is not easy to control, at present also in research and skill Art explores state.Second class is post-processed to the two-dimensional material after growth to be doped.The method of post-processing is divided into two Kind, one is dry method doping, i.e., under vacuum in two-dimensional material surface evaporated atom and molecule, or to two-dimensional material into Row plasma treatment, this method can realize the doping to single layer two-dimensional material microplate, but to industrially applying more extensive two It is then invalid to tie up material film.Another kind is wet method doping, i.e., makes dopant and two-dimensional material film phase interaction under liquid-phase condition For being doped, this method is commonly used in the doping of multilayer two-dimension material microplate.
Invention content
Technical problem to be solved by the present invention lies in view of the above shortcomings of the prior art, provide a kind of high heat stability Property I2 doping graphene film.The film is made of the multi-layer graphene microplate for being mingled with I2 doping object, multi-layer graphene microplate Along the random stacking of its in-plane, since stacking forms compact texture to graphene microchip layer by layer, enhance graphene microchip and Active force between I2 doping object, the steric hindrance around I2 doping object also become larger, are not easy to escape under high temperature and high vacuum environment Ease and volatilization, to improve the thermal stability of I2 doping graphene film.
In order to solve the above technical problems, the technical solution adopted by the present invention is:A kind of high thermal stability I2 doping graphene Film, which is characterized in that the multi-layer graphene microplate by being mingled with I2 doping object forms, and multi-layer graphene microplate is along its plane side To random stacking;The I2 doping graphene film still has thermal stability under 500 DEG C of hot conditions.
A kind of above-mentioned high thermal stability I2 doping graphene film, which is characterized in that the I2 doping object with atom and The form of ion exists.
Above-mentioned a kind of high thermal stability I2 doping graphene film, which is characterized in that the I2 doping object is nanometer iodine.
In addition, the present invention also provides a kind of method preparing high thermal stability I2 doping graphene film, feature exists In this approach includes the following steps:
Step 1: substrate is carried out washing and drying treatment successively;The substrate is silicon chip, glass, plastic film or rubber Glue;
Step 2: graphene microchip dispersion is suspended in a solvent, suspension stabilizer is then added, obtains graphene microchip Dispersion liquid;
Step 3: the graphene microchip dispersion liquid obtained in step 2 to be deposited to the lining in step 1 after drying process It on bottom, is then thermally dried, forms graphene microchip film on substrate;
Step 4: iodine solution is deposited in the graphene microchip film formed in step 3, then it is thermally dried, Obtain I2 doping graphene film.
Above-mentioned method, which is characterized in that solvent described in step 2 is water or N-Methyl pyrrolidone;It is described to suspend surely It is cellulose family suspension stabilizer to determine agent.
Above-mentioned method, which is characterized in that the method deposited described in step 3 is drop coating, dip-coating or printing, step 4 Described in the method that deposits be dip-coating or printing.
Above-mentioned method, which is characterized in that the temperature of heat drying described in step 3 and step 4 is 100 DEG C~ 400℃。
Compared with the prior art, the present invention has the following advantages:
1, I2 doping graphene film of the invention is made of the multi-layer graphene microplate for being mingled with I2 doping object, multilayer stone Black alkene microplate is along the random stacking of its in-plane, and since stacking forms compact texture to graphene microchip layer by layer, I2 doping object is uniform Disperse and is adsorbed in graphene microchip, the interaction force enhancing between I2 doping object and graphene microchip, I2 doping object week The steric hindrance enclosed also becomes larger, and under high temperature and high vacuum environment, I2 doping object is not easy to escape and volatilize, to realize to more The I2 doping of layer graphene microplate improves the thermal stability of I2 doping graphene film, finally obtained I2 doping graphene Film still has thermal stability under 500 DEG C of hot conditions.
2, in I2 doping graphene film of the invention, the graphene microchip that stacking gets up forms the grid of electric current flowing Structure provides access for electric current, and stacking provisions contribute to the minimum of contact resistance between graphene microchip, reduce I2 doping The resistance of graphene film, I2 doping object provide carrier for graphene microchip, improve in I2 doping graphene film Carrier density and the uniformity improve the conductivity and its uniformity of I2 doping graphene film, extend I2 doping stone The service life of black alkene film.
3, graphene microchip is first deposited on substrate by preparation method of the invention, graphene film is formed, then by iodine Dopant is deposited on graphene film, due to being dispersed with the micropore with nano-scale on graphene film, in I2 doping object Deposition process in, I2 doping object can be entered with the diffusion of solution inside film so that graphene microchip is arranged again Cloth, under the action of gravity and hydrodynamic shear, most of graphene microchip meeting parallel arrangement, and structure is formed after the drying The neat and close stacking provisions of arrangement, I2 doping object is sandwiched between graphene microchip, to improve I2 doping object and stone Active force between black alkene microplate, this method obtain having the I2 doping graphene of close stacking provisions thin by stepped depositions Film improves the arrangement architecture of graphene and I2 doping object, improves the thermal stability of I2 doping graphene film, and effect is aobvious It writes, is suitable for promoting.
Invention is further described in detail with reference to the accompanying drawings and examples.
Description of the drawings
Fig. 1 is the schematic cross-section of I2 doping graphene film prepared by the embodiment of the present invention 1.
Fig. 2 is the atomic force microscopy figure of I2 doping graphene film prepared by the embodiment of the present invention 1.
Reference sign:
1-substrate;2-graphene microchips;3-I2 doping objects.
Specific implementation mode
I2 doping graphene film as shown in Figure 1 is formed by 2 stacking of multi-layer graphene microplate and is deposited on substrate 1, It is mingled with I2 doping object 3 between the graphene microchip 2;Graphene microchip 2 indicates that I2 doping object 3 is adopted using grey fill color It is indicated with stain.
Embodiment 1
The high thermal stability I2 doping graphene film of the present embodiment is by being mingled with the multi-layer graphene microplate of I2 doping object Composition, multi-layer graphene microplate exist along the random stacking of its in-plane, the I2 doping object in the form of atom and ion.
The preparation method of the high thermal stability I2 doping graphene film of the present embodiment includes the following steps:
Step 1: glass is carried out washing and drying treatment successively;
Step 2: 50g graphite powders are added in the N-Methyl pyrrolidone of 1L, under conditions of rotating speed is 4000rpm 3h is stood after stirring 30min, obtains graphene microchip suspension, the number of plies of graphene microchip in the graphene microchip suspension It is 2~4 layers, 10g ethyl celluloses is added into graphene microchip suspension, is then centrifuged for removal precipitation particle, obtains supernatant Ethylene glycol adjusting viscosity is added into the supernatant, obtains the graphene microchip dispersion liquid of a concentration of 3.8mg/mL for liquid;
Step 3: the graphene microchip dispersion liquid obtained in step 2 is deposited to step 1 by the method for inkjet printing It on the middle glass after drying process, is then thermally dried under conditions of temperature is 350 DEG C, it is thin to form graphene microchip Film;
Step 4: elemental iodine is dissolved into deionized water, it is configured to the iodine solution of a concentration of 0.5mmol/L, then will The iodine solution is deposited to by the method for dip-coating in the graphene microchip film formed in step 3, then temperature be 300 DEG C Under conditions of be thermally dried, obtain I2 doping graphene film.
Silicon chip, plastic film or rubber also can be used in substrate in the present embodiment.
Printing also can be used in the method that dip-coating also can be used in deposition in the present embodiment step 3, the deposition in step 4 Method.
By I2 doping graphene film manufactured in the present embodiment vacuum degree be 10-6Mbar, temperature be 500 DEG C condition into Row annealing 1h, is then detected to making annealing treatment front and back I2 doping graphene film, x-ray photoelectron spectroscopy knot respectively Fruit, which shows to make annealing treatment, can detect iodine in front and back I2 doping graphene film, illustrate I2 doping stone manufactured in the present embodiment Black alkene film still has thermal stability under 500 DEG C of hot conditions.
Fig. 2 is the atomic force microscopy figure after I2 doping graphene film annealing manufactured in the present embodiment, can from Fig. 2 Go out, I2 doping object is contained in I2 doping graphene film manufactured in the present embodiment, I2 doping object is nanometer iodine.
Embodiment 2
The high thermal stability I2 doping graphene film of the present embodiment is by being mingled with the multi-layer graphene microplate of I2 doping object Composition, multi-layer graphene microplate exist along the random stacking of its in-plane, the I2 doping object in the form of atom and ion.
The preparation method of the high thermal stability I2 doping graphene film of the present embodiment includes the following steps:
Step 1: glass is carried out washing and drying treatment successively;
Step 2: 50g graphite powders are added in the N-Methyl pyrrolidone of 1L, under conditions of rotating speed is 4000rpm 3h is stood after stirring 30min, obtains graphene microchip suspension, the number of plies of graphene microchip in the graphene microchip suspension It is 2~4 layers, 10g ethyl celluloses is added into graphene microchip suspension, is then centrifuged for removal precipitation particle, obtains supernatant Ethylene glycol adjusting viscosity is added into the supernatant, obtains the graphene microchip dispersion liquid of a concentration of 3.8mg/mL for liquid;
Step 3: the graphene microchip dispersion liquid obtained in step 2 is deposited to step 1 by the method for inkjet printing It on the middle glass after drying process, is then thermally dried under conditions of temperature is 100 DEG C, it is thin to form graphene microchip Film;
Step 4: elemental iodine is dissolved into deionized water, it is configured to the iodine solution of a concentration of 0.5mmol/L, then will The iodine solution is deposited to by the method for dip-coating in the graphene microchip film formed in step 3, then temperature be 100 DEG C Under conditions of be thermally dried, obtain I2 doping graphene film.
Silicon chip, plastic film or rubber also can be used in substrate in the present embodiment.
Printing also can be used in the method that dip-coating also can be used in deposition in the present embodiment step 3, the deposition in step 4 Method.
Embodiment 3
The high thermal stability I2 doping graphene film of the present embodiment is by being mingled with the multi-layer graphene microplate of I2 doping object Composition, multi-layer graphene microplate exist along the random stacking of its in-plane, the I2 doping object in the form of atom and ion.
The preparation method of the high thermal stability I2 doping graphene film of the present embodiment includes the following steps:
Step 1: glass is carried out washing and drying treatment successively;
Step 2: 50g graphite powders are added in the N-Methyl pyrrolidone of 1L, under conditions of rotating speed is 4000rpm 3h is stood after stirring 30min, obtains graphene microchip suspension, the number of plies of graphene microchip in the graphene microchip suspension It is 2~4 layers, 10g ethyl celluloses is added into graphene microchip suspension, is then centrifuged for removal precipitation particle, obtains supernatant Ethylene glycol adjusting viscosity is added into the supernatant, obtains the graphene microchip dispersion liquid of a concentration of 3.8mg/mL for liquid;
Step 3: the graphene microchip dispersion liquid obtained in step 2 is deposited to step 1 by the method for inkjet printing It on the middle glass after drying process, is then thermally dried under conditions of temperature is 400 DEG C, it is thin to form graphene microchip Film;
Step 4: elemental iodine is dissolved into deionized water, it is configured to the iodine solution of a concentration of 0.5mmol/L, then will The iodine solution is deposited to by the method for dip-coating in the graphene microchip film formed in step 3, then temperature be 400 DEG C Under conditions of be thermally dried, obtain I2 doping graphene film.
Silicon chip, plastic film or rubber also can be used in substrate in the present embodiment.
Printing also can be used in the method that dip-coating also can be used in deposition in the present embodiment step 3, the deposition in step 4 Method.
Embodiment 4
A kind of high thermal stability I2 doping graphene film of the present embodiment is by being mingled with the multi-layer graphene of I2 doping object Microplate forms, and multi-layer graphene microplate is deposited along the random stacking of its in-plane, the I2 doping object in the form of atom and ion .
The preparation method of the high thermal stability doping two-dimensional material film of the present embodiment includes the following steps:
Step 1: glass is carried out washing and drying treatment successively;
Step 2: 50g graphite powders and 0.5 milliliter of bromine to be added in the water of 1L and impregnate for 24 hours, and it is 4000rpm in rotating speed Under conditions of stirring 30min after stand 3h, then be added 10g hypromellose, then centrifuge removal precipitation particle, obtain dense Degree is the graphene microchip dispersion liquid of 3.8mg/mL;
It is passed through Step 3: the graphene microchip dispersion liquid obtained in step 2 is deposited to by the method for drop coating in step 1 It on glass after drying process, is then thermally dried under conditions of temperature is 300 DEG C, forms graphene microchip film;
Step 4: elemental iodine is dissolved into deionized water, it is configured to the iodine solution of a concentration of 0.5mmol/L, then will The iodine solution is deposited to by the method for dip-coating in the graphene microchip film formed in step 3, then temperature be 300 DEG C Under conditions of be thermally dried, obtain I2 doping graphene film.
The above is only presently preferred embodiments of the present invention, is not imposed any restrictions to the present invention.It is every according to invention skill Art essence still falls within technical solution of the present invention to any simple modification, change and equivalence change made by above example Protection domain in.

Claims (7)

1. a kind of high thermal stability I2 doping graphene film, which is characterized in that by the multi-layer graphene for being mingled with I2 doping object Microplate forms, and multi-layer graphene microplate is along the random stacking of its in-plane;High temperature of the I2 doping graphene film at 500 DEG C Under the conditions of still have thermal stability.
2. a kind of high thermal stability I2 doping graphene film according to claim 1, which is characterized in that the I2 doping Object exists in the form of atom and ion.
3. a kind of high thermal stability I2 doping graphene film according to claim 1, which is characterized in that the I2 doping Object is nanometer iodine.
4. a kind of high thermal stability I2 doping graphene film prepared as described in any claim in claims 1 to 3 Method, which is characterized in that this approach includes the following steps:
Step 1: substrate is carried out washing and drying treatment successively;The substrate is silicon chip, glass, plastic film or rubber;
Step 2: graphene microchip dispersion is suspended in a solvent, suspension stabilizer is then added, obtains graphene microchip dispersion Liquid;
Step 3: the graphene microchip dispersion liquid obtained in step 2 to be deposited to the substrate in step 1 after drying process On, it is then thermally dried, forms graphene microchip film on substrate;
Step 4: iodine solution is deposited in the graphene microchip film formed in step 3, then it is thermally dried, obtains I2 doping graphene film.
5. according to the method described in claim 4, it is characterized in that, solvent described in step 2 is water or N- crassitudes Ketone;The suspension stabilizer is cellulose family suspension stabilizer.
6. according to the method described in claim 4, it is characterized in that, the method deposited described in step 3 be drop coating, dip-coating or Printing, the method deposited described in step 4 are dip-coating or printing.
7. according to the method described in claim 4, it is characterized in that, the temperature of heat drying described in step 3 and step 4 is equal It is 100 DEG C~400 DEG C.
CN201810537263.4A 2018-05-30 2018-05-30 A kind of high thermal stability I2 doping graphene film and preparation method thereof Pending CN108423671A (en)

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Application publication date: 20180821