CN102218545B - Method for preparing nano aluminum by utilizing chemical method - Google Patents
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- CN102218545B CN102218545B CN201110142205XA CN201110142205A CN102218545B CN 102218545 B CN102218545 B CN 102218545B CN 201110142205X A CN201110142205X A CN 201110142205XA CN 201110142205 A CN201110142205 A CN 201110142205A CN 102218545 B CN102218545 B CN 102218545B
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Abstract
The invention relates to a method for preparing nano aluminum by utilizing a chemical method. With respect to the chemical method, the nano aluminum is prepared by mainly using a method for thermal decomposition of aluminum compounds, wherein the particle diameter of the prepared nano aluminum is within 10-100nm, and five characteristic diffraction peaks of elementary aluminum substance are represented in an X-ray powder diffraction diagram. The method provided by the invention has the advantages of low cost, high safety, simplicity and convenience for operation and controllable product particle size.
Description
Technical field
The present invention relates to a kind of method for preparing nanometer aluminum (hereinafter to be referred as nano aluminum), in particular to utilizing chemical method, mainly is to adopt the method for thermal decomposition aluminium compound to prepare nano aluminum.The present invention has low cost, safe, easy and simple to handle, advantage that product granularity is controlled.
Background technology
The content of aluminium is only second to the content of iron in earth's crust metallic element, be positioned at second.In daily life, various aluminum products are used by people in a large number.And nano aluminum is to obtain broad research and in addition practical successively new material in recent years.The using value of nano aluminum at aspects such as propellant, gunpowder, medicine and solar cells just it is found that and reused, and below specifically describes the application of these several respects respectively.
Nano aluminum is in the application in propellant: because the density of aluminium is high, oxygen demand is low, and high enthalpy of combustion is arranged, and making can have higher content of aluminium powder in solid propellant, and is quite remarkable to the effect that improves specific impulse.Add abundant raw materials, cost is lower, and therefore the additive as energy material is widely used in the propellant.Compare with common aluminium powder, nanometer aluminium powder has the advantages that burning is faster, thermal discharge is bigger, if in the solid fuel propellant, add the ultra micro alumina particles of 1% mass ratio, the combustion heat of fuel can increase by 1 times.The research report is abroad arranged, in the HTPB composite propellant, add 20%Alex (ARGONIDE Company products nanometer aluminium powder), compare with the common aluminium powder of same content, burn rate can improve 70%.
The application of nano aluminum in fiery explosive: the metal dust that in explosive, adds high heating value is one of approach that improves power.Aluminum composition has been widely used in underawater ordnance and the air weapon ammunition as one type of high density, high quick-fried heat, high explosive.Thisly cooperate successful high explosive with metal oxide by nanometer aluminium powder, because its surface area is more much bigger than conventional thermite powder, thereby it can provide and is equivalent to existing ten times of high burning velocities of power propellant.
The application of nano aluminum aspect medicine: nano aluminum and other metal oxide nano-material self assembly after-combustion speed can reach 1500-2300m/s, and the shock wave maximum can reach 3 Mach." the intelligent bomb " of this nano-scale is expected targeted drug is transported to cancer cell, do not damage healthy cell simultaneously.Perhaps, the breakthrough that the power of this nano bomb will bring cancer and AIDS-treating medicine to transmit.At first, this medicine can be used needle injection, and then is diffused into whole body.Then, utilize the hand-held device of aiming tumour to send pulse to tumour, this pulse lures that the nana intelligent bomb produces directed shock wave into, and the cell that will be aimed at breaks a duck eye, and medicine gets into tumour cell thus.In addition, the strength of shock wave can push cell with medicine in several milliseconds.The experiment of in animal tissue, carrying out shows that the success rate of this method is up to 99%, and nearly all cell all can successfully receive medicine.On the other hand, experiment confirms that also traditional remedies such as this method and chemotherapy compare, and the side effect of healthy cell is wanted much little.For conventional explosives, surge waveform is formed in the blast process.In the nano aluminum thermit powder, the quick propagation of chemical reaction makes that under situation about need not explode, forming shock wave becomes possibility.Do not explode and to produce the key point that shock wave then is this technology.Except biomedical sector, nano bomb also has wide application prospects at other fields such as geology and seismology.
The application of nano aluminum in solar cell: along with the material of present solar cell and improving constantly of production technique; The minority carrier life time of solar cell also constantly increases; Promptly the diffusion length of few son constantly increases; When the thickness of the diffusion length of minority carrier and silicon chip quite or when surpassing silicon wafer thickness, the recombination velocity on back of the body surface to the influence of solar cell characteristic just clearly.From present commercial solar cell, in order to reduce the cost of solar cell, raise the efficiency, manufacturer is also constantly reducing the thickness of silicon chip, to reduce raw-material price.Therefore,, must consider to reduce the recombination velocity on battery back of the body surface, improve the long wave spectral response in order to improve the efficient of battery.So the quality of aluminium back of the body field will directly have influence on the output characteristics of solar cell.Particle is little, and aluminium paste contacts better with silicon chip, and particle is big, exists bigger space between zone that has and silicon face, has the cavity, and aluminium paste contacts relatively poor with silicon chip, and this just makes some zone not form aluminium back of the body field.So the granular size of aluminium paste all has very important relation for the formation and the quality of aluminium back of the body field.Alumina particles is more little, and fusing point is low more, is easy to more form the sial composite bed with silica-base material at a certain temperature, helps the output characteristics that aluminium is carried on the back the formation of field and improved solar cell more.Therefore, preparing nano level aluminium powder is extremely important for the making of the solar panel aluminum back of the body.
But the method general cost that obtains nano aluminum at present is higher, and occurs safety problem in the production process easily, and complex operation, and in addition, the granularity of the nanometer aluminum of acquisition is difficult to control.
Summary of the invention
How to realize that it is present problem demanding prompt solution that low cost, high security, easy and simple to handle, product controllably obtain nano aluminum, be the direction that the scientific research personnel makes great efforts also always, has important social benefit and economic benefit.
The inventor utilizes chemical method through discovering with keen determination, adopts the method for thermal decomposition aluminium compound can prepare nano aluminum.The inventive method is under the atmospheric low-temperature condition, to prepare nano aluminum by chemical method, has low cost, safe, easy and simple to handle, advantage that product granularity is controlled.
Particularly, preparation method of the present invention may further comprise the steps:
Step 1) under the situation of inert gas shielding, adds raw material inorganic aluminate compound, lithium aluminium hydride and phosphor-included additive and organic solvent in the reactor, adopts stirring or ultrasonic method to be distributed to raw material in the organic solvent;
Step 2), slowly be promoted to 140-200 ℃ at the following temperature of reactor of stirring condition, constantly feed inert gas in the course of reaction, the reaction time is 5 minutes-2 hours, and heating rate is controlled at 0.5-10 ℃/minute; Keep to stir the not open close inert gas of going in the course of reaction, finish, lower the temperature keeping feeding under the condition of inert gas up to reaction;
Step 3) is taken out the back centrifugal treating with product, outwells the back to supernatant and adds the organic solvent washing product repeatedly, and sealing is preserved after the product vacuum drying that obtains at last.
Description of drawings
The transmission electron microscope photo of the nano aluminum particle that Fig. 1 makes for embodiment 1;
The XRD diffraction pattern of the nano aluminum particle that Fig. 2 makes for embodiment 1.
The specific embodiment
The following specifically describes preparation in accordance with the present invention.
Step 1) under the situation of inert gas shielding, adds raw material inorganic aluminate compound, lithium aluminium hydride and phosphor-included additive and organic solvent in the reactor, adopts stirring or ultrasonic method to be distributed to raw material in the organic solvent.
In preparation method of the present invention; The main effect of this step is: will be distributed in the organic solvent as reaction medium as the raw material inorganic aluminate compound and the lithium aluminium hydride of reactant; And the phosphor-included additive that plays a protective role is distributed in the organic solvent; Make reactive material and protective substance in medium, be uniformly dispersed, so that follow-up reacting by heating is carried out.
The inorganic aluminate compound is the primary raw material of the inventive method; Can use in principle can with lithium aluminium hydride all inorganic aluminate compounds of reaction decomposes under heating; Like anhydrous Aluminum chloride, anhydrous aluminum perchlorate, anhydrous slufuric acid aluminium, acetic anhydride aluminium, preferably use anhydrous Aluminum chloride.Can use a kind of in these aluminium salt compounds separately, also can use wherein multiple arbitrarily of combination.
In this application, use anhydrous aluminium salt compound to be very important,, can cause the danger of blasting, and can cause reaction process slowly even the adverse consequences that can't react because calorize salt compound is in a single day moisture.
In this article, lithium aluminium hydride and tetrahydro lithium aluminium are equivalent in meaning, and the expression chemical structural formula is LiAlH
4Material.
In preferred embodiments; The mol ratio of inorganic aluminate compound and lithium aluminium hydride meets the following conditions: the molal quantity of inorganic aluminate compound (in aluminium ion): the molal quantity of lithium aluminium hydride=1: 3, thus make inorganic aluminate compound and lithium aluminium hydride react completely and do not have residual.
In the method for the invention, used phosphor-included additive is meant the reproducibility organic phosphine, and its middle finger contains phosphorus and do not contain aerobic, makes phosphor-included additive to play a protective role to the nano aluminum that reaction forms, and prevents that it is oxidized.As phosphor-included additive; Preferred triaryl phosphine and the trialkyl phosphine of adopting; Wherein triaryl phosphine such as triphenylphosphine; Alkyl is that carbon number is 1～30 alkyl in the trialkyl phosphine; Preferred carbon number is 2～25 alkyl, like triethyl phosphine, tripropyl phosphine, tributylphosphine, three amyl group phosphines, three hexyl phosphines, three heptyl phosphines, tri octyl phosphine, three nonyl phosphines, three decyl phosphines, three (undecyl) phosphine, three (dodecyl) phosphine, three (tridecyl) phosphine, three (myristyl) phosphine, three (pentadecyl) phosphine, three (cetyl) phosphine, three (heptadecyl) phosphine, three (octadecyl) phosphine, three (nonadecyl) phosphine, three (eicosyl) phosphine, three (heneicosyl) phosphine, three (docosyl) phosphine, three (tricosyl) phosphine, three (tetracosyl) phosphine, three (pentacosyl) phosphine.Can use a kind of in these phosphor-included additives separately, perhaps also can any combination use wherein multiple.
In the method for the invention, the phosphor-included additive consumption is preferably 1-10 times of lithium aluminium hydride mole, and more preferably 2-5 times, most preferably from about 5 times.
In the step 1) of the inventive method, used organic solvent is non-oxidizable organic solvent.In the methods of the invention, organic solvent plays the effect of decentralized medium and reaction medium, because the very easily oxidation of product nano aluminum, it is non-oxidizable therefore requiring used organic solvent.In preferred embodiments, said organic solvent can be varsol such as toluene, xylenes; Alcohols solvent such as methyl alcohol, ethanol, n-butanol, the tert-butyl alcohol, ethylene glycol, propane diols, oxolane; Ether solvent such as ether; Other atent solvents such as dimethyl formamide (DMF), dimethyl sulfoxide (DMSO) (DMSO).Can use in these solvents any separately, perhaps combination in any is used multiple in these solvents.
In the method for the invention, the consumption of organic solvent is to disperse, to flood raw material inorganic aluminate compound and phosphor-included additive is as the criterion, not other special requirements.For raw material is distributed in the organic solvent better, the consumption of preferred organic solvent is 50 times-200 times of lithium aluminium hydride quality.
In the method for the invention, inert gas is meant any gas that does not react with reactive material inorganic aluminate compound and lithium aluminium hydride and phosphor-included additive, nitrogen.
Preferred embodiment a kind of according to the present invention, the reaction system that step 1) adopts can be operated in glove box.
Step 2), slowly be promoted to 140-200 ℃ at the following temperature of reactor of stirring condition, constantly feed inert gas in the course of reaction, the reaction time is 5 minutes-2 hours, and heating rate is controlled at 0.5-10 ℃/minute; Keep to stir the not open close inert gas of going in the course of reaction, finish, lower the temperature keeping feeding under the condition of inert gas up to reaction.
In preparation method of the present invention; The main effect of this step is: under the condition of inert gas shielding, react under heating as the inorganic aluminate and the lithium aluminium hydride of reactant, form nano aluminum and products such as hydrogen and lithium salts; Hydrogen is selected, and lithium salts is at subsequent step 3) in by being washed off.
Preferred embodiment a kind of according to the present invention, under stirring condition, with 0.5-10 ℃/minute; Preferred 1-8 ℃/minute, more preferably 2-6 ℃/minute, 3-5 ℃/minute heating rate most preferably; Temperature of reactor is risen to 140-200 ℃, preferred 145-190 ℃, more preferably 150-180 ℃; Most preferably 155-170 ℃, constantly feed inert gas in the course of reaction.
The reaction time of this temperature reaction process is 5 minutes-2 hours, preferred 15 minutes-1 hour 45 minutes, and more preferably 30 minutes-1 hour 30 minutes, most preferably 45 minutes-1 hour 15 minutes.The color of observing response solution gradually becomes black until solution by grey in course of reaction, and till color no longer deepens.Reaction time decides according to the solution colour situation of change basically.
All under the situation that stirs and constantly feed inert gas, carry out in the entire reaction course, with reaction raw materials in the guard reactor and product.
After reaction finishes, reduce reaction temperature, preferably temperature is reduced to room temperature.
Step 3) is taken out the back centrifugal treating with product, outwells the back to supernatant and adds the organic solvent washing product repeatedly, and sealing is preserved after the product vacuum drying that obtains at last.
In the step 3) of the inventive method, used organic solvent is the non-oxidizable organic solvent that does not react with nano aluminum.Preferred embodiment a kind of according to the present invention, said organic solvent is one or more in methyl alcohol, ethanol, n-butanol, the tert-butyl alcohol, ether, toluene, xylenes, oxolane or the acetone.
To not restriction of washing times, preferred 2-6 time, more preferably 3-5 time, the solvent of using when at every turn washing can be different, for example wash with methyl alcohol, oxolane and acetone respectively.
Preferred embodiment a kind of according to the present invention, the product that obtains is carried out drying, for fear of by airborne dioxygen oxidation or for fear of moisture absorption, preferred vacuum drying, vacuum is preferably 0～10KPa.From similar reason, dried product sealing is preserved.
The outward appearance of the nano aluminum that obtains according to the inventive method is a Dark grey, and particle diameter changes with the change of reaction condition to some extent, and particle diameter is from 10-100nm, and its electromicroscopic photograph is as shown in Figure 1.The X-ray powder diffraction pattern is as shown in Figure 2, from figure, can see five characteristic diffraction peaks of aluminium simple substance, and its peak position is respectively 38.30 ° (111), 44.54 ° (200), 64.94 ° (220), 78.08 ° (311), 82.22 ° (222); Explain that the product that obtains is an aluminium simple substance.
The nano aluminum product that does not also have the chemical method preparation at present on the domestic and international market, and the inventive method belongs to chemical method, the method for employing thermal decomposition aluminium compound has made and has met nano level aluminium simple substance.Compare with existing other production methods, the inventive method just can prepare nano aluminum under condition of normal pressure under relatively low temperature, therefore has the advantage that cost is low, safe, easy and simple to handle, product granularity is controlled.
Below come further to explain or explanation content of the present invention through embodiment.But the embodiment that is provided should not be understood that protection domain of the present invention is constituted restriction.
Embodiment 1
Under the situation of nitrogen protection, the anhydrous AlCl of 0.267g (2mmol) packs in three mouthfuls of round-bottomed flasks
3, 0.2277g (6mmol) LiAlH
4, 7.869g (30mmol) TPP (triphenylphosphine) and 20ml xylenes constantly stir.With three mouths of rubber stopper sealing; Carry out ultrasonic dispersion 10-120 minute.
Under stirring condition, slowly be promoted to 160 ℃ to temperature with 2 ℃/minute heating rates, constantly feed nitrogen in the course of reaction; Reaction time is 1 hour, and observing solution colour has grey to become black, and reaction finishes; Stop heating, constantly under the feeding nitrogen situation temperature is being reduced to room temperature.
Put into centrifuge tube after product taken out and carry out centrifugally, after outwelling supernatant, use methyl alcohol, oxolane and washing with acetone product respectively, the sealing bag of packing into after the product vacuum drying that obtains.
The transmission electron microscope photo of the aluminium simple substance particle that makes according to embodiment 1 is seen Fig. 1, and its particle diameter major part is between between the 30nm to 70nm.
The XRD diffraction pattern of this nano aluminum particle is as shown in Figure 2, from figure, can see five characteristic diffraction peaks of aluminium simple substance, and its peak position is respectively 38.30 ° (111), 44.54 ° (200), 64.94 ° (220), 78.08 ° (311), 82.22 ° (222).
Embodiment 2
Under the situation of nitrogen protection, the anhydrous AlCl of 0.267g (2mmol) packs in three mouthfuls of round-bottomed flasks
3, 0.2277g (6mmol) LiAlH
4, 7.869g (30mmol) TPP (triphenylphosphine) and 20ml xylenes constantly stir.With three mouths of rubber stopper sealing; Carry out ultrasonic dispersion 10-120 minute.
Under stirring condition; Slowly be promoted to 170 ℃ to temperature with 3 ℃/minute heating rates, constantly feed nitrogen in the course of reaction, the reaction time is 1 hour 30 minutes; Observing solution colour has grey to become black; Reaction finishes, and stops heating, constantly under the feeding nitrogen situation temperature is being reduced to room temperature.
Put into centrifuge tube after product taken out and carry out centrifugally, after outwelling supernatant, use ethanol, toluene and ether washing reaction product respectively, the sealing bag of packing into after the product vacuum drying that obtains.
The transmission electron microscope photo of the aluminium simple substance particle that makes according to embodiment 2 shows that its particle diameter major part is between between the 20nm to 60nm.Can see five characteristic diffraction peaks of aluminium simple substance from the XRD diffraction pattern of this nano aluminum particle.
Embodiment 3
Under the situation of nitrogen protection, the anhydrous Al (ClO of 0.651g (2mmol) packs in three mouthfuls of round-bottomed flasks
4)
3, 0.2277g (6mmol) LiAlH
4, 7.869g (30mmol) TPP (triphenylphosphine) and 20ml xylenes constantly stir.With three mouths of rubber stopper sealing; Carry out ultrasonic dispersion 10-120 minute.
Under stirring condition; Slowly be promoted to 180 ℃ to temperature with 4 ℃/minute heating rates, constantly feed nitrogen in the course of reaction, the reaction time is 50 minutes; Observing solution colour has grey to become black; Reaction finishes, and stops heating, constantly under the feeding nitrogen situation temperature is being reduced to room temperature.
Put into centrifuge tube after product taken out and carry out centrifugally, after outwelling supernatant, use ethanol, acetone and ether washing reaction product respectively, the sealing bag of packing into after the product vacuum drying that obtains.
The transmission electron microscope photo of the aluminium simple substance particle that makes according to embodiment 3 shows that its particle diameter major part is between between the 40nm to 90nm.Can see five characteristic diffraction peaks of aluminium simple substance by the XRD diffraction pattern of this nano aluminum particle.
Embodiment 4
Under the situation of nitrogen protection, 0.342g (1mmol) the anhydrous slufuric acid aluminium of in three mouthfuls of round-bottomed flasks, packing into, 0.2277g (6mmol) LiAlH
4, 6.070g (30mmmo) tributylphosphine and 20ml xylenes constantly stir.With three mouths of rubber stopper sealing; Carry out ultrasonic dispersion 10-120 minute.
Under stirring condition; Slowly be promoted to 150 ℃ to temperature with 3 ℃/minute heating rates, constantly feed nitrogen in the course of reaction, the reaction time is 90 minutes; Observing solution colour has grey to become black; Reaction finishes, and stops heating, constantly under the feeding nitrogen situation temperature is being reduced to room temperature.
Put into centrifuge tube after product taken out and carry out centrifugally, after outwelling supernatant, use methyl alcohol, methyl ether and washing with acetone product respectively, the sealing bag of packing into after the product vacuum drying that obtains.
The transmission electron microscope photo of the aluminium simple substance particle that makes according to embodiment 4 shows that its particle diameter major part is between between the 20nm to 100nm.Can see five characteristic diffraction peaks of aluminium simple substance by the XRD diffraction pattern of this nano aluminum particle.
According to the above embodiments the present invention has been made detailed description.What need explanation is that above embodiment is just to illustrating the present invention.Under the prerequisite that does not depart from spirit of the present invention and essence, those skilled in the art can design multiple alternative of the present invention and improvement project, and it all should be understood to be within protection scope of the present invention.
Claims (12)
1. method for preparing nano aluminum may further comprise the steps:
Step 1); Under the situation of inert gas shielding; The anhydrous inorganic aluminate compound of raw material, lithium aluminium hydride and non-oxidizable organic phosphine and non-oxidizable organic solvent are added in the reactor, adopt stirring or ultrasonic method to be distributed to raw material in the non-oxidizable organic solvent;
Step 2), slowly be promoted to 140-200 ℃ at the following temperature of reactor of stirring condition, constantly feed inert gas in the course of reaction, the reaction time is 5 minutes-2 hours, and heating rate is controlled at 0.5-10 ℃/minute; Keep to stir the not open close inert gas of going in the course of reaction, finish, lower the temperature keeping feeding under the condition of inert gas up to reaction;
Step 3) is taken out the back centrifugal treating with product, outwells the back to supernatant and adds non-oxidizable organic solvent washing product repeatedly, and sealing is preserved after the product vacuum drying that obtains at last.
2. method according to claim 1 is characterized in that,
In the step 1), said anhydrous inorganic aluminate compound is one or more in anhydrous Aluminum chloride, anhydrous aluminum perchlorate, anhydrous slufuric acid aluminium, the acetic anhydride aluminium.
3. method according to claim 1 and 2 is characterized in that, the mol ratio of anhydrous inorganic aluminate compound and lithium aluminium hydride meets the following conditions: the molal quantity of anhydrous inorganic aluminate compound: the molal quantity=1:3 of lithium aluminium hydride, and in aluminium ion.
4. method according to claim 1 and 2; It is characterized in that; Non-oxidizable organic phosphine described in the step 1); Be triaryl phosphine and trialkyl phosphine, alkyl is that carbon number is 1 ~ 30 alkyl in the said trialkyl phosphine, and the 1-10 that said non-oxidizable organic phosphine consumption is the lithium aluminium hydride mole doubly.
5. method according to claim 4; Wherein, Said triaryl phosphine is a triphenylphosphine, and said trialkyl phosphine is triethyl phosphine, tripropyl phosphine, tributylphosphine, three amyl group phosphines, three hexyl phosphines, three heptyl phosphines, tri octyl phosphine, three nonyl phosphines, three decyl phosphines, three (undecyl) phosphine, three (dodecyl) phosphine, three (tridecyl) phosphine, three (myristyl) phosphine, three (pentadecyl) phosphine, three (cetyl) phosphine, three (heptadecyl) phosphine, three (octadecyl) phosphine, three (nonadecyl) phosphine, three (eicosyl) phosphine, three (heneicosyl) phosphine, three (docosyl) phosphine, three (tricosyl) phosphine, three (tetracosyl) phosphine, three (pentacosyl) phosphine.
6. method according to claim 1 and 2 is characterized in that,
In step 1); Said non-oxidizable organic solvent; Be methyl alcohol, ethanol, n-butanol, the tert-butyl alcohol, ether, toluene, xylenes, dimethyl formamide, dimethyl sulfoxide (DMSO), ethylene glycol, propane diols or oxolane, said consumption of organic solvent is 50 times-200 times of lithium aluminium hydride quality.
7. method according to claim 1 and 2 is characterized in that,
Step 2) in, the temperature reaction time is 30 minutes-1 hour 30 minutes.
8. method according to claim 1 and 2 is characterized in that,
Step 2) in, the temperature reaction time is 45 minutes-1 hour 15 minutes.
9. method according to claim 1 and 2 is characterized in that,
Step 2) in, reaction is reduced to room temperature with temperature after finishing.
10. method according to claim 1 and 2 is characterized in that,
In the step 3), said non-oxidizable organic solvent is methyl alcohol, ethanol, n-butanol, the tert-butyl alcohol, ether, toluene, xylenes, oxolane and acetone; Washing times is 2-6 time.
11. method according to claim 1 and 2 is characterized in that,
In the step 3), washing times 3-5 time.
12. the nano aluminum of method preparation according to claim 1 and 2; Its particle diameter is 10-100nm; The X-ray powder diffraction pattern shows five characteristic diffraction peaks of aluminium simple substance, and its peak position is respectively 38.30 ° (111), 44.54 ° (200), 64.94 ° (220), 78.08 ° (311), 82.22 ° (222).
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| CN103042228B (en) * | 2012-12-21 | 2014-12-03 | 江苏大学 | Liquid-phase preparation method for high-quality nano-aluminum particles |
| CN106623901B (en) * | 2016-12-19 | 2021-01-19 | 北京化工大学 | Aluminum nanosheet, and preparation method and application thereof |
| CN107225254A (en) * | 2017-04-01 | 2017-10-03 | 北京化工大学 | A kind of aluminum nanoparticles and preparation method thereof |
| CN109834288B (en) * | 2017-11-24 | 2022-04-29 | 阜阳师范学院 | Preparation method of nano aluminum powder with uniform particle size distribution |
| CN109834289B (en) * | 2017-11-24 | 2022-06-10 | 阜阳师范学院 | Preparation method of nano aluminum powder |
| CN110860696A (en) * | 2018-08-27 | 2020-03-06 | 阜阳师范学院 | Method for preparing nano aluminum powder |
| CN110860697A (en) * | 2018-08-28 | 2020-03-06 | 阜阳师范学院 | Method for preparing nano aluminum powder by using protective agent |
| CN113564382B (en) * | 2021-07-09 | 2022-08-30 | 中南大学 | Method for preparing metal aluminum by reduction at room temperature |
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