CN105839078A - Method for preparing graphene nano-composite energetic material through atomic-layer deposition technology - Google Patents

Method for preparing graphene nano-composite energetic material through atomic-layer deposition technology Download PDF

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CN105839078A
CN105839078A CN201610228290.4A CN201610228290A CN105839078A CN 105839078 A CN105839078 A CN 105839078A CN 201610228290 A CN201610228290 A CN 201610228290A CN 105839078 A CN105839078 A CN 105839078A
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graphene
layer deposition
atomic layer
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energetic materials
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CN105839078B (en
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闫宁
冯昊
秦利军
龚婷
惠龙飞
李建国
黄钰
张王乐
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Xian Modern Chemistry Research Institute
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    • C—CHEMISTRY; METALLURGY
    • C23—COATING METALLIC MATERIAL; COATING MATERIAL WITH METALLIC MATERIAL; CHEMICAL SURFACE TREATMENT; DIFFUSION TREATMENT OF METALLIC MATERIAL; COATING BY VACUUM EVAPORATION, BY SPUTTERING, BY ION IMPLANTATION OR BY CHEMICAL VAPOUR DEPOSITION, IN GENERAL; INHIBITING CORROSION OF METALLIC MATERIAL OR INCRUSTATION IN GENERAL
    • C23C—COATING METALLIC MATERIAL; COATING MATERIAL WITH METALLIC MATERIAL; SURFACE TREATMENT OF METALLIC MATERIAL BY DIFFUSION INTO THE SURFACE, BY CHEMICAL CONVERSION OR SUBSTITUTION; COATING BY VACUUM EVAPORATION, BY SPUTTERING, BY ION IMPLANTATION OR BY CHEMICAL VAPOUR DEPOSITION, IN GENERAL
    • C23C16/00—Chemical coating by decomposition of gaseous compounds, without leaving reaction products of surface material in the coating, i.e. chemical vapour deposition [CVD] processes
    • C23C16/44—Chemical coating by decomposition of gaseous compounds, without leaving reaction products of surface material in the coating, i.e. chemical vapour deposition [CVD] processes characterised by the method of coating
    • C23C16/455—Chemical coating by decomposition of gaseous compounds, without leaving reaction products of surface material in the coating, i.e. chemical vapour deposition [CVD] processes characterised by the method of coating characterised by the method used for introducing gases into reaction chamber or for modifying gas flows in reaction chamber
    • C23C16/45523—Pulsed gas flow or change of composition over time
    • C23C16/45525—Atomic layer deposition [ALD]
    • B—PERFORMING OPERATIONS; TRANSPORTING
    • B82—NANOTECHNOLOGY
    • B82Y—SPECIFIC USES OR APPLICATIONS OF NANOSTRUCTURES; MEASUREMENT OR ANALYSIS OF NANOSTRUCTURES; MANUFACTURE OR TREATMENT OF NANOSTRUCTURES
    • B82Y40/00—Manufacture or treatment of nanostructures
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    • C23—COATING METALLIC MATERIAL; COATING MATERIAL WITH METALLIC MATERIAL; CHEMICAL SURFACE TREATMENT; DIFFUSION TREATMENT OF METALLIC MATERIAL; COATING BY VACUUM EVAPORATION, BY SPUTTERING, BY ION IMPLANTATION OR BY CHEMICAL VAPOUR DEPOSITION, IN GENERAL; INHIBITING CORROSION OF METALLIC MATERIAL OR INCRUSTATION IN GENERAL
    • C23C—COATING METALLIC MATERIAL; COATING MATERIAL WITH METALLIC MATERIAL; SURFACE TREATMENT OF METALLIC MATERIAL BY DIFFUSION INTO THE SURFACE, BY CHEMICAL CONVERSION OR SUBSTITUTION; COATING BY VACUUM EVAPORATION, BY SPUTTERING, BY ION IMPLANTATION OR BY CHEMICAL VAPOUR DEPOSITION, IN GENERAL
    • C23C16/00—Chemical coating by decomposition of gaseous compounds, without leaving reaction products of surface material in the coating, i.e. chemical vapour deposition [CVD] processes
    • C23C16/22—Chemical coating by decomposition of gaseous compounds, without leaving reaction products of surface material in the coating, i.e. chemical vapour deposition [CVD] processes characterised by the deposition of inorganic material, other than metallic material
    • C23C16/30—Deposition of compounds, mixtures or solid solutions, e.g. borides, carbides, nitrides
    • C23C16/40—Oxides
    • C—CHEMISTRY; METALLURGY
    • C23—COATING METALLIC MATERIAL; COATING MATERIAL WITH METALLIC MATERIAL; CHEMICAL SURFACE TREATMENT; DIFFUSION TREATMENT OF METALLIC MATERIAL; COATING BY VACUUM EVAPORATION, BY SPUTTERING, BY ION IMPLANTATION OR BY CHEMICAL VAPOUR DEPOSITION, IN GENERAL; INHIBITING CORROSION OF METALLIC MATERIAL OR INCRUSTATION IN GENERAL
    • C23C—COATING METALLIC MATERIAL; COATING MATERIAL WITH METALLIC MATERIAL; SURFACE TREATMENT OF METALLIC MATERIAL BY DIFFUSION INTO THE SURFACE, BY CHEMICAL CONVERSION OR SUBSTITUTION; COATING BY VACUUM EVAPORATION, BY SPUTTERING, BY ION IMPLANTATION OR BY CHEMICAL VAPOUR DEPOSITION, IN GENERAL
    • C23C16/00—Chemical coating by decomposition of gaseous compounds, without leaving reaction products of surface material in the coating, i.e. chemical vapour deposition [CVD] processes
    • C23C16/44—Chemical coating by decomposition of gaseous compounds, without leaving reaction products of surface material in the coating, i.e. chemical vapour deposition [CVD] processes characterised by the method of coating
    • C23C16/4417—Methods specially adapted for coating powder

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Abstract

The invention discloses a method for preparing a graphene nano-composite energetic material through an atomic-layer deposition technology. The method includes the steps that graphene loaded nanometer metal compound powder is prepared through an ultrasonic-assisted solution mixing and in-situ reduction method, so that even scattering of nanometer metal on the surface of graphene is achieved; and then, the gas-phase atomic-layer deposition technology is adopted, two different precursors pass through a reaction cavity alternately, the precursors make contact with the surface of the graphene/nanometer metal compound powder fully, a chemical reaction is set off, and oxides are generated. By means of the method, the oxides wrap the graphene surface and the nanometer metal surface evenly. According to the graphene nano-composite energetic material prepared through the method, the affinity between the oxides and the nanometer metal surface is increased, and spatial arrangement is improved. Due to the addition of the graphene, the scattering situation of the nanometer metal is improved, and the energy release rate of the energetic material is increased. The method is high in automation degree and good in safety, the material can be directly used without after-treatment, and mass production of the graphene nano-composite energetic material is achieved easily.

Description

A kind of method using technique for atomic layer deposition to prepare graphene nano Composite Energetic Materials
Technical field
The present invention relates to the preparation method of a kind of graphene nano Composite Energetic Materials, belong to technical field of nanometer material preparation.
Background technology
Propellant adds Nano metal powder, propellant burning property can be improved, and significantly improve its energy level.Nm of gold Belong to and oxidant, catalyst and propellant respectively containing can affinity between component and spatial arrangement to the combustibility of propellant and Kinetics of combustion has significant impact.Nano-metal particle is the biggest with the contact area of the components such as oxidant, and combustion reaction is the most abundant, Propellant energy level is the highest.But, the specific surface area that Nano metal powder is high, typically result in powder reuniting and make reactivity drop Low, constrain its further application in propellant field to a certain extent.Solving the scattered conventional method of Nano metal powder is Use surfactant, polymer or end-capping reagent by the parcel of Nano metal powder, hinder nano particle to reunite.But auxiliary agent Addition may cause nano particle chemism to reduce, and affects the actual application of nano particle.
Graphene is the carbonaceous material with bi-dimensional cellular shape lattice structure that monolayer carbon atom packing becomes, and it has many excellences Performance: specific surface area (2630m greatly2/ g), the combustion reaction enthalpy (carbon-oxygen 32.8kJ/g, carbon-aluminium 1.6KJ/g) of superelevation and High heat conduction, electric conductivity.At present, there are research team (Li, N.；Gong,Z.F.；Cao,M.H.；Ren,L.；Zhao,X.Y.； Liu,B.；Tian,Y.；Hu,C.W.,Well-dispersed ultrafine Mn3O4nanoparticles on graphene as a promising catalyst for the thermal decomposition of ammonium perchlorate.Carbon2013,54,124 –132.)(Dey,A.；Athar,J.；Varma,P.；Prasant,H.；Sikder A.K.；Chattopadhyay,S.,Graphene-iron oxide nanocomposite(GINC):an efficient catalyst for ammonium perchlorate(AP)decomposition And burn rate enhancer for AP based composite propellant.RSC Advance.2015,5,1950 1960.) logical Cross and either physically or chemically nano metal or oxide be fixed on graphenic surface, can effectively prevent nano particle from reuniting, Keep high-specific surface area and the reactivity of particle.But, above method all lacks the nano metal being supported on graphenic surface Or effective control of oxide particle size, distribution and load density.Meanwhile, above method cannot regulate and control metal fuel and oxidation The affinity of agent and spatial arrangement.
Summary of the invention
The shortcomings and deficiencies existed for prior art, the invention provides a kind of employing ald (Atomic Layer Deposition, is called for short ALD) the technology method of preparing graphene nano Composite Energetic Materials.Use the mixing of ultrasonic wave added solution Method prepares graphene-supported nano metal composite granule, then by gas phase technique for atomic layer deposition on above-mentioned composite granule surface Synthesis oxide.Through Composite Energetic Materials prepared by the present invention, compared with traditional energetic material preparation method, effectively change Be apt to Nano metal powder dispersion and with the surface affinity of oxide, it is high, anti-that the energetic material of preparation has energy release rate Performance characteristics should be waited completely.
In order to realize above-mentioned technical assignment, the present invention adopts the following technical scheme that amendment is unified with claim
A kind of method using technique for atomic layer deposition to prepare graphene nano Composite Energetic Materials, comprises the following steps:
Step one, the preparation of graphene-supported nano metal composite granule
(1) graphene oxide 0.01-100 mass parts and solvent 100-10000 mass parts are added in ultrasonic reactor, ultrasonic merit Rate is 10-5000W, and frequency is 10-10000Hz, temperature 20-100 DEG C, ultrasonic disperse 5 minutes-10 hours, it is thus achieved that oxidation stone Ink alkene suspension；
(2) 100-10000 mass parts solvent orange 2 A, 100-10000 mass parts solvent B are mixedly configured into cosolvent, by nanometer Metal powder 1-100 mass parts adds cosolvent, ultrasonic disperse 5 minutes-10 hours, obtains the nano metal suspension of stable dispersion； Ultrasonic power 10-5000W, frequency is 10-10000Hz, temperature 20-100 DEG C；1-100 mass parts graphene oxide is suspended Liquid adds in 10-1000 mass parts nano metal suspension, and ultrasonic disperse 5 minutes-5 hours adds reducing agent 1-5000 mass Part, continue ultrasonic disperse 5 minutes-10 hours, it is thus achieved that stable graphene/nanometer metal material composite suspension liquid；
(3) by above-mentioned graphene/nanometer metal material composite suspension liquid high speed rotor centrifuge 10 minutes-2 hours, temperature Spending 0-100 DEG C, rotating speed 3000-20000rpm, product is dried to constant weight in vacuum 0.01kPa-0.1MPa, it is thus achieved that Graphene is received Rice metal composite powder；
The solvent of described graphene oxide suspension be water, ethanol, isopropanol, methyl acetate, toluene, oxolane, third At least one in ketone, hexane, hexamethylene and N, dinethylformamide；
The solvent orange 2 A of described Nano metal powder suspension is N, dinethylformamide, dimethyl sulfoxide (DMSO), N-crassitude At least one in ketone；Solvent B is at least one in ethylene glycol, isopropanol, glycerine；
Described nano metal is at least one in nanometer aluminium powder, nanometer Mg powder, nano boron powder, nanometer zirconium powder；
Described Graphene is single or multiple lift, monolithic graphite alkene a size of micron order and submicron order；
The reducing agent of described graphene oxide be in hydrazine hydrate, ascorbic acid, sodium borohydride, hydroiodic acid and sodium citrate extremely Few one.
Step 2: ald prepares graphene nano Composite Energetic Materials
(1) graphene nano metal composite powder is placed in gas phase atomic layer deposition system reaction chamber, seals reaction chamber, to gas Being passed through inert carrier gas in phase depositing system and vacuumize, cavity pressure controls at 133Pa-1000Pa, and temperature controls at 25-400 DEG C；
(2) graphene nano metal composite powder is carried out ald and forms coating film, a week of ald growth Phase includes following four link: inject the first precursors of excess in reaction chamber；It is passed through inert carrier gas；To reaction chamber The interior the second precursors injecting excess；Again it is passed through inert carrier gas；Repeat the ald of respective cycle number, The oxide coating film making deposition, is obtained by described process at 0.1-1.0 with the mol ratio of nano metal content in composite granule Graphene nano Composite Energetic Materials.
The first described precursors is ferrocene, nickel acetylacetonate, tetraphernl-lead, double (hexafluoroacetylacetone conjunction copper) Close copper (II) hydrate, double (DPM dpm,dipivalomethane acid) cobalt, double (DPM dpm,dipivalomethane acid) Lead, three (2,2,6,6-tetramethyl-3, the acid of 5-heptadione) bismuth, at least in double (2,2,6,6-tetramethyl hept-3,5-bis-ketone acid) copper Kind；
Described the second precursors is at least one in deionized water, hydrogen peroxide, oxygen, ozone；
Described inert carrier gas is at least one in nitrogen, argon gas, helium；
Each described ald growth cycle time is 1-10000s；
Described atomic layer deposition cycle number is 1-5000；
Present invention Advantageous Effects compared with prior art:
1. the ultrasonic wave added solution process for dispersing that the present invention uses makes Nano metal powder be dispersed in have the two of high-specific surface area Dimension graphenic surface, compared with tradition process for dispersing, the present invention effectively solves the scattering problem of Nano metal powder.
2. the present invention uses gas phase technique for atomic layer deposition at graphene-supported nano metal composite granule surface synthesis oxide.Oxygen Thin film is uniformly covered on nano metal surface and by chemical bond compact siro spinning technology.Compared with conventional art, oxidant with receive Spatial arrangement and the affinity of rice metal powder improve, and energetic material combustion reaction is more complete, and energy release rate significantly improves.
3. the present invention is simple to operate, and security is high, and the product of preparation has controllability and the reappearance of height.In addition the method is certainly Dynamicization degree is high, and security performance is good, and synthesis step is simple, it is easy to industrially realizes and promotes.This energetic material is for improving Propellant burning property and raising energy level have important practical significance.
Accompanying drawing explanation
Fig. 1 is the transmission electricity of the graphene-supported nanometer aluminium powder GO/Al using ultrasonic wave added solution blended process to prepare in embodiment 1 Sub-microscope (TEM) figure.
Fig. 2 is the Al@Fe of stoichiometric proportion Φ=1.0 using technique for atomic layer deposition to prepare in embodiment 12O3With GO/Al@Fe2O3Composite Energetic Materials, and x-ray photoelectron power spectrum (XPS) figure of GO/Al composite granule.
Fig. 3 is the GO/Al@Fe of stoichiometric proportion Φ=1.0 using technique for atomic layer deposition to prepare in embodiment 12O3It is combined and contains SEM (SEM) photo of energy material.
Fig. 4 is the GO/Al@Fe of stoichiometric proportion Φ=1.0 using technique for atomic layer deposition to prepare in embodiment 12O3It is combined and contains Transmission electron microscope (TEM) photo of energy material.
Fig. 5 is the GO/Al@Fe of stoichiometric proportion Φ=1.0 using technique for atomic layer deposition to prepare in embodiment 12O3It is combined and contains Can material and Raman spectrum (Raman) figure of GO/Al composite granule.
Fig. 6 is the GO/Al@Fe of stoichiometric proportion Φ=1.0 using technique for atomic layer deposition to prepare in embodiment 12O3It is combined and contains Can material and FTIR spectrum (FTIR) figure of GO/Al composite granule.
Fig. 7 is the Al@Fe of stoichiometric proportion Φ=1.0 using technique for atomic layer deposition to prepare in comparative example 12O3Aluminothermy SEM (SEM) photo of agent energetic material.
Fig. 8 is the GO/Al@Fe of stoichiometric proportion Φ=1.0 using technique for atomic layer deposition to prepare in embodiment 12O3It is combined and contains The Al@Fe of stoichiometric proportion Φ=1.0 prepared by employing technique for atomic layer deposition in energy material and comparative example 12O3Thermite Means of differential scanning calorimetry (DSC) curve of energetic material.
Fig. 9 is the GO/Al@Fe of stoichiometric proportion Φ=1.0 using technique for atomic layer deposition to prepare in embodiment 12O3It is combined and contains Energy material and comparative example 2 use GO/Al-Fe prepared by physical blending process2O3The means of differential scanning calorimetry of Composite Energetic Materials (DSC) curve.
Detailed description of the invention
Below by embodiment and accompanying drawing, the present invention is specifically described.It is important to point out that following example are served only for this Invention is further described, it is impossible to be interpreted as limiting the scope of the invention, and the researcher in this field can be according to upper State present invention and the present invention is made some nonessential improvement and adjustment.
Embodiment 1
This gives a kind of method using technique for atomic layer deposition to prepare graphene-supported nanometer aluminium powder Composite Energetic Materials, The method specifically includes following steps:
Step one: the preparation of graphene-supported nanometer aluminium powder
(1) by graphene oxide 0.1g and DMF 100g, add in ultrasonic reactor, at ultrasonic power be 1000W, frequency is 200Hz, temperature 60 C, ultrasonic disperse time 2 h, it is thus achieved that graphene oxide suspension.
(2) configuration DMF (100g), isopropanol (100g) cosolvent, by nanometer aluminium powder 2g, add altogether In solvent, being disperseed by ultrasonic wave added, ultrasonic power 1000W, frequency is 200Hz, temperature 60 C, the ultrasonic disperse time 2 Hour, obtain the nanometer aluminium powder suspension of stable dispersion.Graphene oxide suspension 100g is added nanometer aluminium powder cosolvent suspend In liquid 200g, ultrasonic disperse 5 hours, add hydrazine hydrate 0.5g, continue ultrasonic disperse 1 hour, it is thus achieved that stable Graphene is born Carry nanometer aluminium powder composite suspension liquid.
(3) above-mentioned graphene-supported nanometer aluminium powder composite suspension liquid is placed in high speed rotor centrifuge, in temperature 25 DEG C, rotating speed 12000rpm, centrifugal 20 minutes, product was dried to constant weight in vacuum 0.1kPa, it is thus achieved that graphene-supported nanometer aluminium powder is multiple Close powder.Utilizing transmission electron microscope (TEM) to characterize product morphology, result is as it is shown in figure 1, nanometer aluminium powder is equal Even it is dispersed on Graphene.
Step 2: ald prepares graphene nano Composite Energetic Materials
Graphene-supported nanometer aluminium powder is placed in gas phase atomic layer deposition system reaction chamber, seals reaction chamber.To vapour deposition Being passed through nitrogen in system and vacuumize, control pressure is at 133Pa, and temperature controls at 350 DEG C.
Graphene-supported nanometer aluminium powder carrying out ald and forms coating film, a cycle of ald growth includes Following four link:
(1) in reaction chamber, inject the first presoma ferrocene (FeCp2), it is allowed to multiple with graphene-supported nanometer aluminium powder Closing powder surface saturated chemical reaction occurs and replaces surface functional group, concrete chemical equation is as follows:
||-O*+FeCp2→||-OFeCp+Cp
In the present invention " | | " represent substrate material surface, the most graphene-supported nanometer aluminium powder composite granule；
(2) it is passed through nitrogen and cleans unreacted ferrocene and accessory substance；
(3) in reaction chamber, inject oxygen, occur surface to react with the absorption ferrocene presoma on graphene composite powder surface, Again replacing surface functional group, concrete chemical equation is as follows:
| | - O F e C p + O 2 → | | - O F e O x * + C p
(4) it is passed through nitrogen and cleans unreacted oxygen precursor and accessory substance.
(1) arrives (4) as procedure described above, and reaction precursor pulse sequence represents with t1-t2-t3-t4, wherein: t1 is the first reaction The injection length of presoma, t3 is the injection length of the second precursors, t2 and t4 is the scavenging period of nitrogen.This reality Testing the pulse sequence used in example is 90s-60s-90s-60s.Repeat the ald of respective cycle number, make the oxygen of deposition Compound coating film is respectively 1:2,1:2.2,1:2.4,1:2.6,1:2.8,1:3.0 with the mol ratio of nanometer aluminium powder in composite granule, 1:3.2.Obtain stoichiometric proportion and be respectively Φ=1.0, the GO/Al@Fe of 1.1,1.2,1.3,1.4,1.5 and 1.62O3It is combined and contains Can material.
Utilize XPS, SEM, TEM, Raman, FTIR GO/Al@Fe to stoichiometric proportion Φ=1.02O3Surface composition, Pattern and structure characterize, and result is shown in Fig. 2, Fig. 3, Fig. 4, Fig. 5 and Fig. 6.As in figure 2 it is shown, from XPS spectrum figure Al The disappearance of elemental signals, the appearance of Fe elemental signals can illustrate nanometer Fe2O3The most complete is coated on nanometer GO/Al surface. As shown in Figure 3 and Figure 4, Fe2O3It is uniformly coated on graphene-supported nanometer aluminium powder surface, GO/Al@Fe2O3Surface shape Looks are coarse, and nanometer aluminium powder size increases.As it is shown in figure 5, through Fe2O3The uniformly GO/Al composite granule of cladding, Graphene D peak (1341cm-1) and G peak (1575cm-1) etc. Raman characteristic signal peak disappear, Fe is described2O3Completely, uniformly Be coated on GO/Al surface.As shown in Figure 6, through Fe2O3The uniformly GO/Al composite granule of cladding, Graphene infrared Characteristic absorption peak C-O/C-OH (1100cm-1) and C=O (1595cm-1) disappear, Fe is described2O3Completely, wrap uniformly Overlay on GO/Al surface.
Embodiment 2
This gives a kind of method using technique for atomic layer deposition to prepare graphene-supported nanometer aluminium powder Composite Energetic Materials, The step one of the method is identical with the step one of embodiment 1, and difference is step 2.
Step 2: ald prepares graphene nano Composite Energetic Materials
Graphene-supported nanometer aluminium powder is placed in gas phase atomic layer deposition system reaction chamber, seals reaction chamber.To vapour deposition Being passed through nitrogen in system and vacuumize, control pressure is at 133Pa, and temperature controls at 200 DEG C.
Graphene-supported nanometer aluminium powder carrying out ald and forms coating film, a cycle of ald growth includes Following four link:
(1) in reaction chamber, three (DPM dpm,dipivalomethane acid bismuth) Bi (thd) is injected3, it is allowed to be combined with Graphene There is saturated surface chemical reaction and replace surface functional group in powder surface, concrete chemical equation is as follows:
||-O*+Bi(thd)3→||-OBi(thd)x+thd
(2) it is passed through nitrogen and cleans the first presoma unreacted and accessory substance；
(3) in reaction chamber, inject deionized water, with absorption the first presoma on graphene composite powder surface, surface occurs Reaction, replaces surface functional group again；Concrete chemical equation is as follows:
| | - O B i ( t h d ) x + H 2 O → | | - O B i O x * + ( t h d ) 3
(4) it is passed through nitrogen and cleans unreacted oxygen precursor and accessory substance.
(1) arrives (4) as procedure described above, and reaction precursor pulse sequence represents with t1-t2-t3-t4, wherein: t1 is the first reaction The injection length of presoma, t3 is the injection length of the second precursors, t2 and t4 is the scavenging period of nitrogen.This reality Testing presoma pulse sequence in example is 60s-30s-60s-30s.Repeat the ald of respective cycle number, make the oxygen of deposition Change bismuth coating film and be respectively 1:2 with the mol ratio of nanometer aluminium powder in composite granule, i.e. stoichiometric proportion Φ=1.0.
Embodiment 3
This gives a kind of method using technique for atomic layer deposition to prepare graphene-supported nanometer aluminium powder Composite Energetic Materials, The step one of the method is identical with the step one of embodiment 1, and difference is step 2.
Step 2: ald prepares graphene nano Composite Energetic Materials
Graphene-supported nanometer aluminium powder is placed in gas phase atomic layer deposition system reaction chamber, seals reaction chamber.To vapour deposition It is passed through nitrogen in system and vacuumizes, controlling pressure and control in room temperature in 133Pa, temperature.
Graphene-supported nanometer aluminium powder carries out cycle of ald includes following four link:
(1) in reaction chamber, inject the first presoma butter of tin (SnCl4) it is allowed to multiple with graphene-supported nanometer aluminium powder
Closing powder surface saturated surface chemical reaction occurs and replaces surface functional group, concrete chemical equation is as follows:
||-OH+SnCl4→||-OSnCl3+HCl
(2) it is passed through nitrogen and cleans the first presoma unreacted and accessory substance；
(3) in reaction chamber, the second presoma hydrogen peroxide (H is injected2O2), with absorption on the of graphene composite powder surface There is surface reaction in a kind of presoma, again replaces surface functional group, and concrete chemical equation is as follows:
||-OSnCl3+3H2O→||-OSn(OH)3+3HCl+3/2O2
(4) it is passed through nitrogen and cleans unreacted oxygen precursor and accessory substance.
(1) arrives (4) as procedure described above, and reaction precursor pulse sequence represents with t1-t2-t3-t4, wherein: t1 is the first The injection length of precursors, t3 is the injection length of the second precursors, t2 and t4 is the scavenging period of nitrogen. In this experimental example, presoma pulse sequence is 30s-10s-30s-10s.Repeat the ald of respective cycle number, make deposition Tin oxide coating film and composite granule in the mol ratio of nanometer aluminium powder be respectively 1:2, i.e. stoichiometric proportion Φ=1.
Embodiment 4
This gives a kind of method using technique for atomic layer deposition to prepare graphene-supported nanometer aluminium powder Composite Energetic Materials, The step one of the method is identical with the step one of embodiment 1, and difference is step 2.
Step 2: ald prepares graphene nano Composite Energetic Materials
Graphene-supported nanometer aluminium powder is placed in gas phase atomic layer deposition system reaction chamber, seals reaction chamber.To vapour deposition Being passed through nitrogen in system and vacuumize, control pressure is at 133Pa, and temperature controls at 190 DEG C.
Graphene-supported nanometer aluminium powder carries out cycle of ald includes following four link:
(1) in reaction chamber, acetylacetone,2,4-pentanedione nickel (acac) is injected2, it is allowed to and graphene-supported nanometer aluminium powder composite granule surface Saturated surface chemical reaction occurring and replaces surface functional group, concrete chemical equation is as follows:
||-OH+Ni(acac)2→||-ONi(acac)*+H(acac)
(2) it is passed through nitrogen and cleans the first presoma unreacted and accessory substance；
(3) in reaction chamber, deionized water is injected, with absorption the first presoma acetylacetone,2,4-pentanedione on graphene composite powder surface There is surface reaction in nickel, again replaces surface functional group, and concrete chemical equation is as follows:
||-ONi(acac)*+H2O→||-ONiOX+H2O+CO2
(4) it is passed through nitrogen and cleans unreacted oxygen precursor and accessory substance.
In this experimental example, presoma pulse sequence is 30s-10s-30s-10s.Repeat the ald of respective cycle number, make The nickel oxide coating film of deposition is respectively 1:2 with the mol ratio of nanometer aluminium powder in composite granule, i.e. stoichiometric proportion Φ=1.
Embodiment 5
This gives a kind of method using technique for atomic layer deposition to prepare graphene-supported nanometer aluminium powder Composite Energetic Materials, The step one of the method is identical with the step one of embodiment 1, and difference is step 2.
Step 2: ald prepares graphene nano Composite Energetic Materials
Graphene-supported nanometer aluminium powder is placed in gas phase atomic layer deposition system reaction chamber, seals reaction chamber.To vapour deposition Being passed through nitrogen in system and vacuumize, control pressure is at 133Pa, and temperature controls at 200 DEG C.
Graphene-supported nanometer aluminium powder carries out cycle of ald includes following four link:
(1) in reaction chamber, inject the first presoma tetraphernl-lead (PbPh4), it is allowed to multiple with graphene-supported nanometer aluminium powder Closing powder surface saturated surface chemical reaction occurs and replaces surface functional group, concrete chemical equation is as follows:
||-O*+PbPh4→||-OPbPh*+H(Ph)X
(2) it is passed through nitrogen and cleans the first presoma unreacted and accessory substance；
(3) injection of ozone in reaction chamber, occurs surface to react with absorption the first presoma on graphene composite powder surface, Again replacing surface functional group, concrete chemical equation is as follows:
||-OPbPh*+O3→||-OPbOX+Ph4
(4) it is passed through nitrogen and cleans unreacted oxygen precursor and accessory substance.In this experimental example, presoma pulse sequence is 30s-10s-30s-10s.Repeat the ald of respective cycle number, make the lead oxide coating film of deposition receive in composite granule The mol ratio of rice aluminium powder is respectively 1:2, i.e. stoichiometric proportion Φ=1.
Embodiment 6
This gives a kind of method using technique for atomic layer deposition to prepare graphene-supported nanometer aluminium powder Composite Energetic Materials, The step one of the method is identical with the step one of embodiment 1, and difference is step 2.
Step 2: ald prepares graphene nano Composite Energetic Materials
Graphene-supported nanometer aluminium powder is placed in gas phase atomic layer deposition system reaction chamber, seals reaction chamber.To vapour deposition Being passed through nitrogen in system and vacuumize, control pressure is at 133Pa, and temperature controls at 250 DEG C.
The cycle that graphene-supported nanometer aluminium powder carries out ald includes following four link: (1) is to reaction chamber Interior injection the first presoma acetyl acetone copper (Cu (acac)2), it is allowed to and graphene-supported nanometer aluminium powder composite granule surface Saturated surface chemical reaction occurring and replaces surface functional group, concrete chemical equation is as follows:
||-OH+Cu(acac)2→||-OCu(acac)*+H(acac)
(2) it is passed through nitrogen and cleans the first presoma unreacted and accessory substance；
(3) in reaction chamber, the second precursors ozone (O is injected3), with absorption on the of graphene composite powder surface There is surface reaction in a kind of presoma, again replaces surface functional group, and concrete chemical equation is as follows:
||-OCu(acac)*+O3→||-OCuOX+H2O+CO2
(4) it is passed through nitrogen and cleans unreacted oxygen precursor and accessory substance.In this experimental example, presoma pulse sequence is 30s-10s-30s-10s.Repeat the ald of respective cycle number, make the cupric oxide coating film of deposition receive in composite granule The mol ratio of rice aluminium powder is respectively 1:2, i.e. stoichiometric proportion Φ=1.
Embodiment 7
This gives a kind of method using technique for atomic layer deposition to prepare graphene-supported nanometer Mg powder energetic material, should Method specifically includes following steps:
Step one: the preparation of graphene-supported nanometer Mg powder
(1) by graphene oxide 0.1g and methyl acetate 100g, add in ultrasonic reactor, be 500w at ultrasonic power, frequently Rate is 100Hz, temperature 50 C, the 5 hours ultrasonic disperse time, it is thus achieved that graphene oxide suspension.
(2) configuration methyl acetate quality (100g), glycerine (100g) cosolvent, nanometer Mg powder 2g is added in cosolvent, Being disperseed by ultrasonic wave added, ultrasonic power 500W, frequency is 200Hz, temperature 50 C, ultrasonic disperse time 2 h, Nanometer Mg powder suspension to stable dispersion.Graphene oxide suspension 100g is added 200g nanometer Mg powder cosolvent suspension In, ultrasonic disperse 5 hours, add ascorbic acid 1g, continue ultrasonic disperse 2 hours, it is thus achieved that stable graphene/nanometer magnesium powder Composite suspension liquid.
(3) above-mentioned graphene/nanometer magnesium powder composite suspension liquid is placed in high speed rotor centrifuge, in temperature 25 DEG C, rotating speed 12000rpm, centrifugal 20 minutes, product was dried to constant weight in vacuum 0.1kPa, it is thus achieved that graphene-supported nanometer Mg powder is combined Material.
Step 2: ald prepares graphene nano Composite Energetic Materials
Graphene-supported nanometer Mg powder is placed in gas phase atomic layer deposition system reaction chamber, seals reaction chamber.To vapour deposition Being passed through nitrogen in system and vacuumize, control pressure is at 133Pa, and temperature controls at 350 DEG C.
Graphene-supported nanometer Mg powder carrying out ald and forms coating film, a cycle of ald growth includes Following four link:
(1) in reaction chamber, ferrocene (FeCp is injected2) be allowed to saturated surface chemical reaction occur also with composite granule surface Displacement surface functional group, concrete chemical equation is as follows:
||-O*+FeCp2→||-OFeCp+Cp
In the present invention " | | " represent substrate material surface, the most graphene-supported nanometer Mg powder composite granule；
(2) it is passed through nitrogen and cleans unreacted ferrocene and accessory substance；
(3) in reaction chamber, inject oxygen, occur surface to react with the absorption ferrocene presoma on graphene composite powder surface, Again replacing surface functional group, concrete chemical equation is as follows:
(4) it is passed through nitrogen and cleans unreacted oxygen precursor and accessory substance.
(1) arrives (4) as procedure described above, and reaction precursor pulse sequence represents with t1-t2-t3-t4, wherein: t1 is the first The injection length of precursors, t3 is the injection length of the second precursors, the scavenging period of the uniform nitrogen of t2 and t4. The pulse sequence used in this experimental example is 90s-60s-90s-60s.Repeat the ald of respective cycle number, make deposition Iron oxide coating film and composite granule in the mol ratio of nanometer Mg powder be respectively 1:2,1:2.2,1:2.4,1:2.6,1:2.8,1:3.0, 1:3.2.I.e. stoichiometric proportion Φ=1,1.1,1.2,1.3,1.4,1.5,1.6.
Comparative example 1
Comparative example gives a kind of method using technique for atomic layer deposition to prepare nano aluminum thermit powder energetic material.
Nanometer aluminium powder is placed in gas phase atomic layer deposition system reaction chamber, seals reaction chamber.Nitrogen it is passed through in gas-phase deposition system Gas also vacuumizes, and control pressure is at 133Pa, and temperature controls at 350 DEG C.
Aluminium powder carrying out ald and forms coating film, a cycle of ald growth includes following four link:
(1) in reaction chamber, ferrocene (FeCp is injected2) be allowed to saturated surface chemical reaction occur also with nanometer aluminium powder surface Displacement surface functional group, concrete chemical equation is as follows:
||-O*+FeCp2→||-OFeCp+Cp；
(2) it is passed through nitrogen and cleans unreacted ferrocene and accessory substance；
(3) in reaction chamber, inject oxygen, occur surface to react, again with the absorption ferrocene presoma on nanometer aluminium powder surface Displacement surface functional group, concrete chemical equation is as follows:
| | - O F e C p + O 2 → | | - O F e O x * + C p ;
(4) it is passed through nitrogen and cleans unreacted oxygen precursor and accessory substance.
(1) arrives (4) as procedure described above, and reaction precursor pulse sequence represents with t1-t2-t3-t4, wherein: t1 is the first The injection length of precursors, t3 is the injection length of the second precursors, t2 and t4 is the scavenging period of nitrogen. The pulse sequence used in this experimental example is 90s-60s-90s-60s.Repeat the ald of respective cycle number, make deposition The mol ratio of iron oxide coating film and nanometer aluminium powder be 1:2, i.e. stoichiometric proportion Φ=1, obtain nano aluminum thermit powder energetic material Al@Fe2O3。
Utilize XPS and the SEM Al@Fe to stoichiometric proportion Φ=1.02O3Surface composition, pattern and structure characterize, Result is shown in Fig. 2 and Fig. 7.As in figure 2 it is shown, from the disappearance of XPS spectrum figure Al elemental signals, the appearance of Fe elemental signals is permissible Nanometer Fe is described2O3The most complete is coated on nanometer Al surface.As it is shown in fig. 7, Fe2O3It is uniformly coated on nanometer aluminium powder Surface, Al@Fe2O3Surface topography is coarse, and nanometer aluminium powder size increases.As shown in Figure 8, DSC test result shows, Under thermit reaction stoichiometric conditions, with the Al Fe of not graphene-containing2O3Sample is compared, and uses technique for atomic layer deposition system Standby GO/Al@Fe2O3Composite Energetic Materials energy release rate improves 60%.
Comparative example 2
The step one of this comparative example is identical with the step one of embodiment 1, and difference is step 2.
Step 2, by graphene-supported nanometer aluminium powder 2g, with Fe2O3Powder 5.9g, by the mixing 1h of mechanical agitation slowly, obtains The thermite of physical blending, nanometer aluminium powder and Fe2O3Mol ratio be 2:1, i.e. stoichiometric proportion Φ=1.
As it is shown in figure 9, DSC test result shows, under thermit reaction stoichiometric conditions, compared to physical blending process, Through graphene nano Composite Energetic Materials GO/Al@Fe prepared by technique for atomic layer deposition2O3, thermit reaction initial reaction temperature 465 DEG C are dropped to by 502 DEG C；Through graphene nano Composite Energetic Materials GO/Al@Fe prepared by technique for atomic layer deposition2O3? Two exothermic peaks of 556 DEG C and 720 DEG C appearance, and Graphene Composite Energetic Materials (GO/Al-Fe prepared by physical blending process2O3) Only one of which exothermic peak；Compared to physical mixed method, through graphene nano Composite Energetic Materials prepared by technique for atomic layer deposition Energy release rate improves 130%.

Claims (10)

1. one kind uses the method that technique for atomic layer deposition prepares graphene nano Composite Energetic Materials, it is characterised in that step is as follows: Step one: the preparation of graphene-supported nano metal compound
(1) graphene oxide 0.01-100 mass parts and solvent 100-10000 mass parts being added in ultrasonic reactor, ultrasonic power is 10-5000W, frequency is 10-10000Hz, temperature 20-100 DEG C, ultrasonic disperse 5 minutes-10 hours, it is thus achieved that graphene oxide Suspension；
(2) 100-10000 mass parts solvent orange 2 A, 100-10000 mass parts solvent B are mixedly configured into cosolvent, by nano metal Powder 1-100 mass parts adds cosolvent, ultrasonic disperse 5 minutes-10 hours, obtains the nano metal suspension of stable dispersion；Super Acoustical power 10-5000W, frequency is 10-10000Hz, temperature 20-100 DEG C；Described solvent orange 2 A is methyl acetate, N, N-bis- At least one in NMF, dimethyl sulfoxide (DMSO), 1-METHYLPYRROLIDONE, solvent B be ethylene glycol, isopropanol, the third three At least one in alcohol；
(3) 1-100 mass parts graphene oxide suspension is added in 10-1000 mass parts nano metal suspension, ultrasonic disperse 5 Minutes-5 hours, add reducing agent 1-5000 mass parts, continue ultrasonic disperse 5 minutes-10 hours, it is thus achieved that stable Graphene/ Nano metal material composite suspension liquid；
(3) by above-mentioned graphene/nanometer metal material composite suspension liquid high speed rotor centrifuge 10 minutes-2 hours, temperature 0-100 DEG C, rotating speed 3000-20000rpm, product is dried to constant weight in vacuum 0.01kPa-0.1MPa, it is thus achieved that graphene nano Metal composite powder；
Step 2: ald prepares graphene nano Composite Energetic Materials
(1) graphene nano metal composite powder is placed in gas phase atomic layer deposition system reaction chamber, seals reaction chamber, sink to gas phase Being passed through inert carrier gas in long-pending system and vacuumize, cavity pressure controls at 133Pa-1000Pa, and temperature controls at 25-400 DEG C；
(2) graphene nano metal composite powder is carried out ald and forms coating film, a cycle bag of ald growth Include following four link: in reaction chamber, inject the first precursors of excess；It is passed through inert carrier gas；Note in reaction chamber Enter the second precursors of excess；Again it is passed through inert carrier gas；Repeat the ald of respective cycle number so that The oxide coating film of deposition at 0.1-1.0, obtains graphite by described process with the mol ratio of nano metal content in composite granule Alkene Nanocomposite Energetic Materials.
2. the method using technique for atomic layer deposition to prepare graphene nano Composite Energetic Materials as claimed in claim 1, its feature exists In, the solvent of described graphene suspension be water, ethanol, isopropanol, methyl acetate, toluene, oxolane, acetone, At least one in hexane, hexamethylene and N, dinethylformamide.
3. the method using technique for atomic layer deposition to prepare graphene nano Composite Energetic Materials as claimed in claim 1, its feature exists In, described Graphene is single or multiple lift, single-layer graphene a size of micron order and submicron order.
4. the method using technique for atomic layer deposition to prepare graphene nano Composite Energetic Materials as claimed in claim 1, its feature exists In, the reducing agent of described graphene oxide be in hydrazine hydrate, ascorbic acid, sodium borohydride, hydroiodic acid and sodium citrate extremely Few one.
5. the method using technique for atomic layer deposition to prepare graphene nano Composite Energetic Materials as claimed in claim 1, its feature exists In, described nano metal is at least one in nanometer aluminium powder, nanometer Mg powder, nanometer zirconium powder, nanometer beryllium powder.
6. the method using technique for atomic layer deposition to prepare graphene nano Composite Energetic Materials as claimed in claim 1, its feature exists In, the first described precursors is ferrocene, nickel acetylacetonate, tetraphernl-lead, double (hexafluoroacetylacetone conjunction copper) Close copper (II) hydrate, double (DPM dpm,dipivalomethane acid) cobalt, double (DPM dpm,dipivalomethane acid) Lead, three (2,2,6,6-tetramethyl-3, the acid of 5-heptadione) bismuth, at least in double (2,2,6,6-tetramethyl hept-3,5-bis-ketone acid) copper Kind.
7. the method using technique for atomic layer deposition to prepare graphene nano Composite Energetic Materials as claimed in claim 1, its feature exists In, described the second precursors is at least one in deionized water, hydrogen peroxide, oxygen, ozone.
8. the method using technique for atomic layer deposition to prepare graphene nano Composite Energetic Materials as claimed in claim 1, its feature exists In, described inert carrier gas is at least one in nitrogen, argon gas, helium.
9. the method using technique for atomic layer deposition to prepare graphene nano Composite Energetic Materials as claimed in claim 1, its feature exists In, each described ald growth cycle time is 1-10000s.
10. the method using technique for atomic layer deposition to prepare graphene nano Composite Energetic Materials as claimed in claim 1, its feature Being, described atomic layer deposition cycle number is 1-5000.
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